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Identifying Challenges in Safeguards for Metallic Fuel Fabrication Facilities

As new advanced reactors gain popularity, there is an increasing interest in metallic fuel fabrication for fast reactors. While metallic fuels themselves are not a new idea, as many of the first reactors employed metallic fuels, new designs, compositions, and fabrication methods are appearing throughout the nuclear community. As the interest grows and facilities are constructed, both domestic and international safeguards will need to be heavily involved to support safeguards-by-design (SBD) measures from the start. This work compiles a review of historical and modern fuel types and fabrication methods, fabrication processes, safeguards gaps, and potential safeguards solutions. Metallic nuclear fuel types have been around for many decades and were included in some of the first reactors including the Experimental Breeder Reactor (EBR)-I and -II, the Fermi 1 reactor, the Integral Fast Reactor (IFR), and the Dounreay Fast Reactor (DFR). These reactors used various compositions including pure uranium (U) metal, U-zirconium (Zr) alloys, plutonium (Pu)-aluminum (Al) alloys, U-fissium (Fs) alloys, U-Pu-Zr alloys, and U-molybdenum (Mo) alloys [1, 2, 3, 4, 5]. These small alloying additions are included to improve the material properties of the pure U metal. The alpha-phase U (stable below 661C) suffers elongation in one direction causing grain boundary cracking and increasing creep rate due to irradiation growth, thermal cycling, and preferential crystal orientation. It is ideal to utilize the gamma-phase U (typically stable above 769C) by adding small amounts of alloying elements such as Zr or Mo to stabilize this phase down to room temperature [3]. Additionally, some research has been focused on U with transuranic (TRU) elements present, typically coming from the used fuel recycling process. Including these elements in fast reactor fuel can aid in the reduction of nuclear waste by burning minor long-lived actinides. However, the additions of TRU elements can cause concerns to arise when trying to fabrication or safeguard metallic fuels. A typical metallic fuel element is shown in Figure 1. Sodium is added into the cladding to create a thermal bond between the fuel slug and cladding wall. The fuel slug is then inserted and the end plug is welded on to the top of the fuel element. A gas plenum is left to create a headspace for gaseous fission products to escape rather than continue to build in the fuel itself [1, 5]. Other fuel element geometries exist as well, such as the Lightbridge twisted cruciform geometry shown in Figure 2 [6]. This design allows for better cooling performance and provides room for fuel rod swelling without impacting the fuel rod diameter. There are many different fabrication methods for metallic fuels, which is one of the many benefits of these fuel types. Many of these fabrication methods are relatively easy and cost-efficient. The most popular fabrication method is injection casting, sometimes called vacuum induction melting (VIM), shown in Figure 3 [4, 8, 9, 7, 10]. This method was largely used for EBR-II fuel fabrication. The injection casting system is contained inside of a vessel consisting of a Y2O3-coated graphite crucible surrounded by an induction coil with ZrO2-coated quartz molds suspended above the crucible. The fuel feedstock is placed inside of the graphite crucible and melted using the induction furnace. The induction furnace utilizes a dual frequency with the high frequency melting the feedstock and the low frequency causing stirring of the melted feedstock to form a homogeneous mixture. The mixture is heated to approximately 1600C in an argon environment. The vessel is evacuated and then the quartz molds are lowered into the graphite crucible containing the molten metal and the vessel is repressurized to inject the metal fuel upwards into the molds. The molds are removed and then shattered to release the fuel slugs. This fabrication method was used to fabricate 39,000 metallic fuel pins for EBR-II. While injection casting has been the most common metallic fuel fabrication method throughout the decades, many other methods have been explored including low-pressure gravity casting, microwave casting, continuous casting, centrifugal casting, coextrusion, and many others [11, 12, 8, 13, 14, 15]. Some of these methods aim to mitigate challenges that arise with americium (Am) volatilization during the casting process for TRU-containing fuel feedstocks, an issue with injection casting. Coextrusion is one of the methods explored at the Idaho National Laboratory (INL) and has been utilized for the initial fabrication tests of Lightbridge's unique fuels, as well as other metallic fuels with cladding coextruded. In this process, large billets are formed and machined and then inserted into a molten salt bath for approximately 30 minutes. The billets are then loaded into the extrusion press and extruded. This process can be seen in Figure 4 [15].

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Multilane Automated Driving With Optimal Control and Mixed-Integer Programming

Road vehicle lane changes often initiate traffic disturbances and can therefore impact road networks’ energy and time efficiency. Furthermore, unexpected changes in traffic conditions may also render lane changes counterproductive for the lane-changing vehicle. Vehicle-to-vehicle connectivity combined with anticipative control could address these challenges via improved lane change decisions by automated vehicles. In a move toward this objective, receding horizon control cast as a mixed-integer quadratic program is used to plan lane changing and acceleration in a coupled optimization. A long-term pacing module, based on Pontryagin’s minimum principle from optimal control theory, sets terminal and input references for receding horizon control to target a user’s expected travel time. To remove nonlinear vehicle dynamics from the receding horizon controller, lane change commands are passed to a pure pursuit steering module whose response is approximated by a second-order linear model. Here, comparison against a rule-based reactive algorithm in arterial and highway scenarios shows an 8.9%–13.7% reduction in energy consumption and a 5.2%–10.3% reduction in the travel time, along with navigational improvements.

33 ADVANCED PROPULSION SYSTEMS↗

Impact of hydrogen bonding pendant groups in polymer grafted nanoparticles on interlayer adhesion and mechanical properties in material extrusion printing

The addition of nanoparticles or copolymer grafted nanoparticles (CPGNPs) to polymeric matrices greatly improves thermomechanical properties of the resulting nanocomposite, but corresponding studies of nanocomposite systems created by 3D printing are few, especially in the realm of functional polymeric materials. Here we describe how silica nanoparticle-grafted, random copolymers of poly(methyl methacrylate-random-2-uriedo-[1H]-pyrimidinone methacrylate) (P(MMA-r-UPyMA) dramatically increases the mechanical properties of poly(methyl methacrylate) (PMMA) based nanocomposite specimens created by melt extrusion printing. Most notably, when these novel CPGNPs are combined with PMMA matrix chains via a solution-based process, printed specimens containing only 0.5 wt% additive show significant increases in Young’s modulus (90%), storage modulus (93%), tensile modulus (148%) and ultimate tensile strength (110%). These improvements are ascribed to strengthening of adhesion across interfaces due to multi-point hydrogen bonding between UPyMA groups, the reinforcement effect of the P(MMA-r-UPyMA)-grafted silica nanoparticles, as well as hydrogen bonding interactions and entanglements between graft and matrix chains. Imaging of fracture surfaces after tensile testing reveals that in comparison to nanocomposites created by simple mechanical mixing of solids, the solution-casting process improves the dispersion of nanoparticles and reduces the void spaces between printed roads. These studies demonstrate that introducing functionality into polymer grafts, such as hydrogen bonding interactions, and intimate mixing of polymer-modified nanomaterials can greatly improve interlayer adhesion and mechanical properties, thereby advancing this method of polymer additive manufacturing

36 MATERIALS SCIENCE↗

Design and Development of Novel Equiatomic Refractory Multi Principal elemental Alloys Based on MoNbTi System for Use in Irradiation Environments

Multi Principal Elemental Alloys (MPEA) have emerged as promising materials for next-generation nuclear reactors due to their exceptional irradiation resistance. Eight equiatomic MPEA based on the MoNbTi system, comprising of elements with low thermal neutron absorption cross-sections were explored using a combined approach employing empirical parameter estimations, and CALPHAD simulations by which the phases and elemental segregation observed in all the alloys in the as-cast state were predicted. Solution heat treatment at 1500°C transformed five alloys into single-phase matrix materials, enhancing homogeneity and reducing hardness. The densities of the alloys ranged between 6.47 to 7.68 g/cm3, hardness between 472 and 656 VHN, Young’s modulus between 142 GPa to 169 GPa, shear modulus between 54 GPa and 62 GPa, bulk modulus between 117 GPa to 194 GPa and Poisson’s ratio between 0.3 to 0.35. The in-situ high temperature Xray diffraction results, differential scanning calorimetry and dilatometry results up to 1000°C suggested the high temperature phase stability of the MPEA. Subsequent ageing heat treatment at 800 and 1000 oC for 96 hours revealed significant secondary phase precipitation in MoNbTiZr, MoNbTiZrV, and MoNbTiCrA. Oxidation studies at 800 oC for 24 hours in air revealed superior oxidation resistance and cubic rate law dependence in Cr containing MPEA especially in MoNbTiCrAl, while severe mass gain resulting in total disintegration and exfoliation in MoNbTiZr and MoNbTiZrV. This comprehensive study underscores the potential of novel MPEA as promising materials for advanced nuclear reactor applications, shedding light on their microstructural control, mechanical properties, thermal stability, and oxidation resistance.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

A Design and Fabrication Options Trade Study for Metallic Fuel without Internal Sodium Bonding

Nuclear fuels using alloys of uranium, or metallic fuels, have many beneficial properties. The classical metallic fuel design uses a loose fitting cylindrical “slug” of fuel placed inside stainless-steel cladding tubes where the gap is filled with sodium. This sodium bond is liquid at operating temperature and conducts heat from the slug to the cladding, especially in early life before fuel swells into contact with the cladding. Despite the benefits of sodium bonding, there is a desire to develop metallic fuel technologies without it chiefly to reduce chemical reaction hazards in spent fuel storage from sodium fast reactors operating on once-through fuel cycles. Elimination of the sodium bond may also help unlock potential benefits for fuel fabrication, reactor neutronics, and compatibility with other types of reactors. Creating a sodium-free metallic fuel revolves around the problem of manufacturing fuel slug geometries which are in close contact with the cladding at beginning of life to facilitate heat transport while alleviating fuel-cladding chemical interactions (FCCI) at this interface and providing enough free volume to accommodate fuel swelling. Accelerating development and qualification of this fuel system will require careful selection of design and manufacturing options. To this end, a design trade-off study was performed to evaluate candidate options. Several design and manufacturing options were assessed, weighted, scored, and ranked with respect to fabrication, normal reactor operation, off-normal scenarios, and back-end considerations. This effort was performed both for “baseline” needs, which represented a once-through fuel cycle at temperatures and burnups known to be viable for sodium-bonded metallic fuel, and for “enhanced” needs to represent opportunities for closed fuel cycles and/or more aggressive temperatures/burnups. The outcomes of this study prioritized a baseline technology using U-Zr alloy with additives to mitigate FCCI, produced in annular slug geometry by continuous casting, clad in austenitic stainless-steel alloy, and followed by a final step to swage the cladding down to close the gap. This study prioritized an enhanced fuel technology using U-Mo alloy, also produced by continuous casting into an annular geometry, followed by coating/plating with an FCCI barrier on the slug, again with a final step to swage the cladding diameter down using oxide dispersion strengthened steel. It was noted that development of the enhanced fuel technology would entail more risk, thus U-Zr alloy was put forth as a backup to U-Mo if challenges are encountered with FCCI barriers, and advanced ferritic/martensitic steels are put forth as a backup to oxide dispersion strengthened steels if swaging and welding are found unworkable.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Improving Cost and Efficiency of the Scalable Solid Oxide Fuel Cells Power System

The objective of this project was to design and develop a 20kW range small-scale solid oxide fuel cells (SOFC) power system for applications such as data centers and commercial buildings. The original plan included a 5,000 hours demonstration and a Techno-Economic Analysis (TEA) which were dropped as part of project termination. The original project plan was to use a stack with a cross-flow cell design which had previously been tested for 500 hours at a community college in Malta, NY. However, it was decided to move to the advanced R-SOFC co-flow cell developed under Department of Energy Award DE-FE0031971. The advanced cell design has the advantage of a larger active area for the same manufacturing footprint which results in fewer required cells for the same stack power, hence a higher volumetric power density (kW/L) and lower cost per kW than the original cross-flow cell design. A full SOFC system Simulink model was developed and calibrated with testing data from a fuel cell stack and BOP (balance of plant) components. The simulation results from the calibrated model showed an acceptable match with the experimental data. A structural analysis conducted for various load scenarios indicated no high stress areas for all spatial directions. Major electrical system components were acquired, built and successfully tested. System sensors were verified and validated against controls. Safety checks, a diagnostic check, PID tuning, and control software commissioning tasks were also conducted. The power electronics prototype was delivered and trial testing completed. Balance of Plant component testing and simulation work was conducted to characterize Reformer-Heat Exchanger heat transfer and backpressure and reformer catalyst methane conversion and product selectivity. Simulations were conducted to design the Anode and Cathode fluid passages and size the air-air and fuel-fuel heat exchangers. A Burner operation map was created from test data and the Anode Gas Recirculation blower was tested to evaluate its durability. The SOFC system used a horizontal style design where components sit directly on a casting with a direct connection to the skid. This design has efficient packaging and a small footprint with approximate dimensions of 750 mm x 700 mm x 1700 mm. An SOFC system was built and successfully tested at the Malta, NY facility The system for over 500 hours under load of which over 300 hours was at full load of 20 kW.

30 DIRECT ENERGY CONVERSION↗

Roll-to-Roll SOFC Manufacturing for Low Cost Energy Generation

Oak Ridge National Laboratory (ORNL) and Redox Power Systems, LLC. collaborated on this project to develop an integrated, continuous roll-to-toll (R2R) manufacturing processes to produce solid oxide fuel cells (SOFCs). SOFCs are ceramic-based electrochemical devices that efficiently produce electricity from hydrogen-containing fuels, including natural gas. Standard processes for manufacturing SOFCs include tape casting of the anode and electrolyte, followed by stacking of the layers, and lamination using a uniaxial press or isostatic press. After high temperature firing, the cathode and electrical contact are screen printed and fired once again to complete the cell. This effort aimed to further develop R2R tape fabrication processes for green cell fabrication with the DOE Battery Manufacturing Facility (BMF) at ORNL as next generation improvements to current methods, focusing on R2R calendering and slot die coating for lower cost, high volume approaches for multilayer green cell fabrication. Two paths were investigated in parallel in this project. The first path was to optimize R2R processing using traditional tape cast materials from the Redox production chain on the BMF’s heated calender for compressing and laminating multilayer materials. The second path was to use BMF’s pilot-scale slot-die coater for R2R manufacturing as an alternative to tape casting of some or all of the layers in the green cell. Processes have been developed and and process conditions have been identified. Additionally, basic process economics were estimated for comparison to Redox current manufacturing approaches for the applicable process modules. The SBV program results will enable Redox to advance lower cost R2R manufacturing processes to produce millions of green cells per year on a single production line. As a result of this work, one invention disclosure has been submitted. In addition, one paper is under preparation for submission to a peer-reviewed journal.

30 DIRECT ENERGY CONVERSION↗

Plasma Chemical Conversion and Resource Generation Beyond Low-Earth Orbit

As humanity gears up for its return to the moon after more than half a century, collaborative efforts between NASA, Artemis Accords Partners, and private industry are underway to establish the necessary infrastructure and technologies for lunar habitation and eventual Mars exploration. However, the traditional ISS resupply and waste management model is impractical and economically infeasible for prolonged missions to the Moon and Mars. Advanced chemical conversion technologies are needed to generate vital consumable products from local planetary resources (ISRU) and recycled gasses and waste within semi-closed loop life-support systems. Low-temperature plasma reactors are emerging power-to-gas technologies with the potential to facilitate various chemical synthesis processes with hardware commonality and redundancy. In plasma-based systems, electrical power is used to ionize a feedstock gas, creating a highly reactive environment that leverages electron excitation chemistry to break stable molecular bonds and form value added products. Unlike thermal chemical processes, plasma reactors operate at non-equilibrium conditions, allowing for lower-temperature operation and instantaneous start-up, making them adaptable to intermittent power availability. Moreover, their scalability permits deployment in both portable astronaut systems and large-scale industrial setups for colonies. One promising application of plasmas is for CO 2 conversion. Carbon dioxide comprises 96% of the Martian atmosphere and is a byproduct of human respiration, which typically must be scrubbed and vented from space habitats. A plasma source integrated with membrane separation technology could generate a stream of oxygen for life support and rocket propellant. CO 2 splitting may also be beneficial as a precursor to manufacture carbon-based products and fuels in situ, like methane, methanol, and polyethylene. Plasma-assisted CO 2 conversion is a simpler case to study without the concern of selectivity and is the first step toward complex chemical synthesis. This work presents preliminary experimental case study from a plasma reactor for CO 2 conversion and casts a vision for the potential of plasma technologies in a sub-architecture for resource production to enable the next generation of human spaceflight activities.

Plasma↗

Roll-to-Roll Advanced Materials Manufacturing DOE Laboratory Collaboration - FY2018 Final Report

High-value R2R processing is used to support a wide range of products in applications which span many industrial business sectors. The overall R2R process technology can be considered as “mature” as the process methodology and has been in use for decades. This continuous processing technique traditionally involves deposition of material(s) onto moving webs or carriers or other continuous R2R, belt-fed, or conveyor-based processes that enable successive steps to build a final version which serves to support the deposited materials. Current process technologies, which typify “roll to roll”, include tape casting, silk-screen printing, reel-to-reel vacuum deposition/coating and R2R lithography. Products supported by R2R manufacturing include micro-electronics, electro-chromic window films, PVs, fuel cells for energy conversion, battery electrodes for energy storage, and barrier materials. Due to innovation in materials and process equipment, high-quality yet very low-cost multi-layer technologies can be manufactured on a very cost-competitive basis. To move energy-related products from high-cost niche applications to the commercial sector, a means must be available to enable manufacture of these products in a cost-competitive manner that is affordable by the general consumer. Fortunately, products such as fuel cells, thin- and mid-film PVs, batteries, electrochromic and piezoelectric films, water separation membranes, and other energy saving technologies readily lend themselves to manufacture using R2R approaches.Within the DOE EERE AMO, it was recognized that establishment of a program supported at the DOE National Laboratories, along with their immense design of materials and equipment modelling capabilities enabled with use of high-performance computing, could take advantage of available R2R infrastructure to manufacture new technologies. In FY 2016, a R2R Consortium was established and provided with initial “seed” funding to take an approach that was envisioned to be supportable by advanced manufacturing R2R processes. This collaborative approach was designed to foster identification and development of materials and processes related to R2R for clean-energy product development. Using computational and experimental capabilities by acknowledged subject matter experts within the supported National Laboratory system, this collaborative project would leverage the capabilities and expertise at each of four laboratories to further the development of an enabling high-volume cost-competitive platform technology. The collaboration team that is comprised of ORNL, ANL, NREL and LBNL, coordinating with EPB and other selected industry partners, was formed in April 2016 to initially address enhancing battery electrode performance and R2R manufacturing challenges. The research efforts were to predict and measure changes and results in electrode morphology and performance based on process condition changes; to evaluate mixed, active, particle size deposition and drying for novel electrode materials; to model various process condition changes and the resulting morphology and electrode performance; and to develop and validate NDE techniques for in-line measurement of battery electrode material properties. These efforts carried through FY 2017 and completed at the end of FY 2018.The approach was to look at compositions of materials with different particle sizes to make electrode samples using a R2R manufacturing process. The shape, size, and morphology of the materials, the chemistry of the formulation, the nature of slurries, their coating rate, the rate of drying all play a role in determining the final coating architecture, quality, and performance. A commercial cathode material was selected to make a series of cathodes and anodes by single pass, dual pass and slot die methods. Analysis of all the compiled results for this battery electrode development were that the best performing cathodes included: dual-pass electrode with large particles near the foil, mixed small and large particles, and small particles only. Whereas, the best performing anodes were with a mix of small and large graphite particles. An additional core project was added in FY 2017 to conduct studies of fuel cell materials that can be produced using R2R processes. The goal of this project is to explore, understand and optimize material and process parameters to support increased throughput, increased quality, and reduced cost for high volume production of gas-diffusion electrodes (GDEs) for PEMFCs. Project work in FY 2018 were to use a R2R process to fabricate electrodes without ionomer overlayer that can produce the equivalent mass activity as spray-coated electrodes with an ionomer overlayer. Oxygen-limiting current measurements were utilized to optimize oxygen mass transport. Alcohol-rich solvents were investigated, and results were that the alcohol and water ratio can be tuned to control ionomer distribution. Water-rich solvents produce a more dispersed ink which results in better high-current density performance.

36 MATERIALS SCIENCE↗

Automated Rapid Prototyping of 3D Ceramic Parts

An automated system of manufacturing equipment produces three-dimensional (3D) ceramic parts specified by computational models of the parts. The system implements an advanced, automated version of a generic rapid-prototyping process in which the fabrication of an object having a possibly complex 3D shape includes stacking of thin sheets, the outlines of which closely approximate the horizontal cross sections of the object at their respective heights. In this process, the thin sheets are made of a ceramic precursor material, and the stack is subsequently heated to transform it into a unitary ceramic object. In addition to the computer used to generate the computational model of the part to be fabricated, the equipment used in this process includes: 1) A commercially available laminated-object-manufacturing machine that was originally designed for building woodlike 3D objects from paper and was modified to accept sheets of ceramic precursor material, and 2) A machine designed specifically to feed single sheets of ceramic precursor material to the laminated-object-manufacturing machine. Like other rapid-prototyping processes that utilize stacking of thin sheets, this process begins with generation of the computational model of the part to be fabricated, followed by computational sectioning of the part into layers of predetermined thickness that collectively define the shape of the part. Information about each layer is transmitted to rapid-prototyping equipment, where the part is built layer by layer. What distinguishes this process from other rapid-prototyping processes that utilize stacking of thin sheets are the details of the machines and the actions that they perform. In this process, flexible sheets of ceramic precursor material (called "green" ceramic sheets) suitable for lamination are produced by tape casting. The binder used in the tape casting is specially formulated to enable lamination of layers with little or no applied heat or pressure. The tape is cut into individual sheets, which are stacked in the sheet-feeding machine until used. The sheet-feeding machine can hold enough sheets for about 8 hours of continuous operation.

McMillin, Scott G.↗

The Interaction Between an Insoluble Particle and an Advancing Solid/Liquid Interface: Micro-Gravity Experiments and Theoretical Developments

The interaction of an insoluble particle with an advancing solid/liquid interface (SLI) has been a subject of investigation for the past four decades. While the original interest stemmed from geology applications (e.g., frost heaving in soil), researchers soon realized that the complex science associated with such an interaction is relevant to many other scientific fields encompassing metal matrix composites (MMCs), high temperature superconductors, inclusion management in steel, growth of monotectics, and preservation of biological cells. During solidification of a liquid containing an insoluble particle, three distinct interaction phenomena have been experimentally observed: instantaneous engulfment of the particle, continuous pushing, and particle pushing followed by engulfment. It was also observed that for given experimental conditions and particle size there is a critical solidification velocity, V(sub cr), above which a particle is engulfed. During solidification of MMCs pushing leads to particle agglomeration at the grain boundaries and this has detrimental effects on mechanical properties of the casting. Consequently, the process must be designed for instantaneous engulfment to occur. This implies the development of accurate theoretical models to predict V(sub cr), and perform benchmark experiments to test the validity of such models. Although considerable progress has been made in understanding the pushing/engulfment phenomenon (PEP), its quantification in terms of the material and processing parameters remains a focus of research. Since natural convection currents occurring during terrestrial solidification experiments complicate the study of PEP, execution of experiments on the International Space Station (ISS) has been approved and funded by NASA. Extensive terrestrial (1g) experiments and preliminary micro-gravity (mu g) experiments on two space shuttle missions have been conducted in preparation for future experiments on the ISS. The investigated systems included metal-ceramic particles (pure aluminum - zirconia particles) and transparent organic - non-reactive particles (succinonitrile - polystyrene and biphenyl - glass). This paper will discuss the experimental results obtained in both lg and pg conditions and the influence of the natural convection on V(sub cr). A summary of past mathematical models and our recent theoretical developments will also be presented to explain the experimentally observed particle/SLI interaction.

Catalina, Adrian V.↗

Roll-to-Roll Advanced Materials Manufacturing DOE Laboratory Collaboration (FY2020 Final Report)

R2R processing is used to manufacture a wide range of products for various applications which span many industrial business sectors. The overall R2R methodology has been in use for decades and this continuous technique traditionally involves deposition of material(s) onto moving webs, carriers or other continuous belt-fed or conveyor-based processes that enable successive steps to build a final version which serves to support the deposited materials. Established methods that typify R2R processing include tape casting, silk-screen printing, reel-to-reel vacuum deposition/coating, and R2R lithography. Products supported by R2R manufacturing include micro-electronics, electro-chromic window films, PVs, fuel cells for energy conversion, battery electrodes for energy storage, and barrier and membrane materials. Due to innovation in materials and process equipment, high-quality yet very low-cost multilayer technologies have the potential to be manufactured on a very cost-competitive basis. To move energy-related products from high-cost niche applications to the commercial sector, the means must be available to enable manufacture of these products in a cost-competitive manner that is affordable. Fortunately, products such as fuel cells, thin- and mid-film PVs, batteries, electrochromic and piezoelectric films, water separation membranes, and other energy saving technologies readily lend themselves to manufacture using R2R approaches. However, more early-stage research is needed to solve the challenge of linking the materials (particles, polymers, solvents, additives) used in ink and slurry formulations and the coating and drying processes to the ultimate performance of the final R2R product, especially for a process that uses multiple layers of deposition to achieve the end product. To solve the problems associated with these challenges, the R2R Collaboration is executing a research program with outcomes that will ultimately link modeling, processing, metrology and defect detection tools, thereby directly relating the properties of constituent particles and processing conditions to the performance of final devices. This collaborative approach was designed to foster identification and development of materials and processes related to R2R for clean-energy materials development. Using computational and experimental capabilities by acknowledged subject matter experts within the supported National Laboratory system, this project leverages the capabilities and expertise at each of five National Laboratories to further the development of multilayer technologies that will enable high-volume, cost-competitive platforms. A typical R2R process has three steps: (1) mixing of particles and various constituents in a slurry, (2) coating of the ink/slurry mixture on a substrate, and (3) drying/curing and processing of the coating. Final performance of devices made via R2R processes is dependent on the active materials (e.g., electrochemical particles in battery or fuel cell electrodes) and the device structure that stems from the governing component interactions within the various steps. However, a fundamental understanding of the underlying mechanisms and phenomena is still lacking, which is why industrial-scale R2R process development and manufacturing is still largely empirical in nature. The FY 2019 through FY 2021 program addresses aspects of the following two targets from the AMO Multi-Year Program Plan: (1) Target 8.1 Develop technologies to reduce the cost per manufactured throughput of continuous R2R manufacturing processes. (A) Increasing throughput of R2R processes by 5 times for batteries (to 50 square feet per minute (50 ft 2 /min)) and capacitors and 10 times for printed electronics and the manufacture of other substrates and MEs used in support of these products. (B) Developing resolution capabilities to enable registration and alignment that will detect, align, and co-deposit multiple layers of coatings and print < 1-micron (1 µm) features using continuous process scalable for commercial production. (C) Developing scalable and reliable R2R processes for solution deposition of ultra-thin (<10 nm) films for active and passive materials. (D) Develop in-line multilayer coating technology on thin films with yields greater than 95%. (2) Target 8.2 Develop in-line instrumentation tools that will evaluate the quality of single and multilayer materials in-process. (A) Developing in-line QC technologies and methodologies for real-time identification of defects and expected product properties “in-use/application” during continuous processing at all size-scales with a focus on the “micro” and “nano” scale traces, lines, and devices, i.e., <1 μm at 300 ft./min for R2R processing in air and <10 nm at 20 ft./min for vacuum (B) Developing technologies to increase the measurement frequency of surface rheology without significant cost increases with a goal of a 10-nanometer in-line profilometry at a production rate of 100,000 square millimeters per minute (100,000 mm 2 /min).

42 ENGINEERING↗

Additive Manufacturing of Advanced High Temperature Masking Fixtures for EBPVD TBC Coating

The purpose of this Manufacturing Demonstration Facility (MDF) technical collaboration project between Praxair Surface Technologies, Inc. (PST) and Oak Ridge National Laboratory (ORNL) was to develop an additive manufacturing process to fabricate next generation high temperature masking fixtures for coating of turbine airfoils with ceramic Thermal Barrier Coatings (TBC) by the Electron Beam Physical Vapor Deposition (EBPVD) process. Typical masking fixtures are sophisticated designs and require complex part manipulation in order to achieve the desired coating distribution. Fixtures are typically fabricated from high temperature nickel (Ni) based superalloys. The fixtures are fabricated from conventional processes by welding of thin sheet material into a complex geometry, to decrease the weight load for the manipulator and to reduce the thermal mass of the fixture. Recent attempts have been made in order to fabricate the fixtures through casting, but thin walled sections are difficult to cast and have high scrap rates. This project focused on understanding the potential for fabricating high temperature Ni based superalloy fixtures through additive manufacturing. Two different deposition processes; electron beam melting (EBM) and laser powder bed fusion were evaluated to determine the ideal processing route of these materials. Two different high temperature materials were evaluated. The high temperature materials evaluated were Inconel 718 and another Ni base alloy, designated throughout the remainder of this document as Alloy X, as the alloy composition is sensitive. Inconel 718 is a more widely utilized material for additive manufacturing although it is not currently the material utilized for current fixtures. Alloy X is the alloy currently used for the fixtures, but is not a commercially available alloy for additive manufacturing. Praxair determined it was possible to build the fixture using laser powder bed technology from Inconel 718. ORNL fabricated the fixture geometry using the EBM technology in order to compare deposition features such as surface roughness, geometric accuracy, deposition rate, surface and subsurface porosity, and material quality. It was determined that the laser powder bed technology was ideal for the geometry and requirements of the fixture set by Praxair, and Praxair moved forward with the purchase of a laser powder bed system. The subsequent portion of the project focused on determining the ideal processing parameters for alloy X for the laser powder bed system using ORNL’s Renishaw laser powder bed system. Praxair supplied gas atomized powders of alloy X material with properties specified by ORNL. ORNL printed text cube arrays in order to determine the ideal combination of laser powder and laser travel speed in order to maximize material density, improve surface quality, and maintain geometric accuracy. Additional powder supplied by Praxair was used to fabricate a full-scale fixture component.

42 ENGINEERING↗

Evaluation of Low Cost, User-Centered Alerting Devices for the Mitigation of Flight Crew Spatial Disorientation

The National Aeronautics and Space Administration (NASA) is conducting research into technologies which have the potential to reduce flight crew Spatial Disorientation (SD). While flight deck technology has advanced rapidly over the past fifty (50) years, the reported occurrences of flight crew SD have not decreased. The Cost-Effective Devices for Alerting Research (CEDAR) effort has focused on the identification and development of low cost, user-centered alerting solutions for the purpose of mitigating the occurrence of flight crew SD. This effort seeks to evaluate both existing technologies as well as new and emerging technologies which have a viable path to implementation in commercial aviation within the next five (5) years. This research is intended to develop a proof-of-concept for real-time SD mitigation which could eventually be utilized to improve safety in future air transport operations. NASA has partnered with the United States Naval Aeromedical Research Unit in Dayton, OH (NAMRU-D) to conduct flight crew SD research utilizing their Disorientation Research Device (DRD), dubbed “The Kraken”. This high-tech simulator features never-before-seen capabilities for side-by-side commercial aviation flight crew SD research, and is capable of re-creating the forces necessary to induce SD illusions in a safe and repeatable manner. Prototype SD mitigation solutions were incorporated into this simulator for scenario-based testing and evaluation using airline pilots within a contextually representative operational environment. SD mitigation technology prototypes designed to provide haptic feedback for both alerting and guidance, as well as innovative visual and aural alerting displays were evaluated. In December 2014, as a result of analyzing eighteen (18) loss-of-control events, the Commercial Aviation Safety Team (CAST) recommended research into flight deck technologies that have potential to mitigate the problems and contributing factors that lead to flight crew loss of airplane state awareness (ASA) and conditions likely to produce SD. The aviation community (government, industry and academia) have been charged with conducting research into cost-effective, user-centered flight deck alerting systems to alert flight crews; especially for the two conditions that produced SD (sub-threshold rolls and the somatogravic illusion). Somatogravic illusions are defined as illusions in which “there is a false perception of attitude on exposure to a force vector that differs in direction and/or magnitude from the normal gravitational force”. The sub-threshold roll illusion (aka the “leans” illusion) is a false sensation of roll attitude. A prolonged roll of less than two degrees becomes physiologically imperceptible to the pilot, and can lead to an incorrect perception of aircraft orientation. The sub-threshold roll illusion forms the entry point for the “graveyard spiral”, a maneuver in which the pilot’s corrective action (based on their false perception of aircraft orientation) causes the aircraft to spiral down into the ground. In both of these SD illusions, it is when the pilot attempts to correct the aircraft’s attitude (based on a false perception of its state) that problems arise, sometimes with lethal consequences.

Ronald J Daiker↗

Carbon Fiber Prepreg Recycling- Automated Perform Manufacturing Equipment (Final Technical Report)

Discontinuous fiber composites have a compelling business case as related to light metals such as aluminum and magnesium machined or die cast components. DFC’s have been in commercial production using carbon fiber/epoxy prepreg for both commercial aircraft and for military applications for a number of years and their usage is expanding into automotive and consumer goods components. Reasons for this include significantly lower cost as compared to continuous fiber composites easier design and understanding of the material by metal traditionalists, higher degree of part complexity with relatively simple and low cost molds when compared to high-pressure die casting, and potential for near zero waste. IACMI’s 10-year goals of reduction in carbon fiber reinforced plastics manufacturing cost by 25%, reduction in their embodied energy by 50%, and recyclability of 95% can all be advanced through robust recycling. With recycling We have shown that a 15% contribution in manufacturing cost reduction is feasible, that a significant reduction in embodied energy (over 90% for the recycled fraction) is achievable, and that when combined with primary pyrolysis recycling, the 95% target can be met. Large-scale application of advanced composites began with the aerospace industry, and CRTC’s location in Washington State provided access to a waste stream of nearly 900 tonnes/year that was going to landfill. As the aerospace industry has automated parts production, their material forms have become significantly easier to recycle, and some evidence of this exists for the future automotive and wind turbine components as well. CRTC decided to focus on re-purposing the carbon fiber/epoxy aerospace scrap streams through materials reformatting and reuse, and not on primary recycling (pyrolysis mainly) as this technology is commercially available. The main reasons for this were that it offers a route to effective use of the most widely available and consistent feedstock called edge-trim, as well as allows creation of complex and low-cost parts using rapid and cost-effective compression molding technologies. The reasons also include leading the way for potential automotive pre-preg recycling as the combination of roughly 85% virgin pre-preg and 15% recycled pre-preg directly supports IACMI’s goals and enables significant part cost reduction and a path to zero-waste composite manufacturing at the OEMs or Tier 1’s. The purpose of the project was to develop equipment and technology to transform continuous fiber pre-preg in roll forms into smaller chip-format DFC feedstock, and to determine impacts on moldability and performance based on lessons learned along the path. The availability of scrap from pre-preg manufacturers was a significant value to the program even though the aerospace pre-preg is designed to be autoclave molded thus has handling, tackiness, and processing factors that are not ideal for DFCs. The scope of the project was to develop a Phase 1 system that could identify and resolve some of the major hurdles, determine where to focus effort on building a commercial-scale Phase 2 system, and develop technology for handling a wide variety of incoming scrap materials to produce the most usable product. A chopping system was developed and reduced to practice via an experimental approach that enabled all forms of scrap coming from the pre-preg manufacturers and some forms of the scrap coming from OEM production lines to be very effectively re-purposed. The systems that were developed were not considered to be production robust but rather identified and resolved some of the major technical hurdles, and demonstrated the path towards effective full-scale commercialization.

36 MATERIALS SCIENCE↗

Volumetric Additive Manufacturing of Dormant Catalytic Chemistries to Generate Silicone Micro‐ and Millifluidic Devices and Instant Molds

Tomographic volumetric additive manufacturing (T‐VAM) rapidly prints solid objects within minutes, accessing photochemistries that are traditionally challenging for layer‐based additive manufacturing methods. This includes high‐viscosity materials, air‐free chemistries, and solid‐state systems. Catalytic chemistries are appealing as a pathway to engineering advanced materials, including tough thermosets, silicone elastomers, and complex block copolymers. However, photoactivated dormant catalytic chemistries, where the catalyst irreversibly activates upon exposure to light, are incompatible with typical tomographic VAM approaches. To address this limitation, a zero‐dose optimization strategy is devised to preserve dormant catalysts in desired regions by keeping them unexposed to light. VAM printed micro‐ and millifluidic devices and instant molds are successfully produced within minutes in silicones polymerized using photoactivated dormant platinum photohydrosilylation catalysts. The printed channels are programmed to be 500 and 2500 µm for the micro‐ and millifluidic devices, and print fidelity is assessed by X‐ray computed tomography. This work demonstrates the potential of zero‐dose optimization to expand the range of chemistries accessible for VAM, enabling the rapid fabrication of complex devices.

Additive Manufacturing↗

A High-Efficiency, Low Cost, High-Temperature Nanocomposite Soft Magnetic Materials for Vehicle Power Electronics.

The charge components for each gas atomization experiment (GA-1-230, GA-1-232, and GA-1-238) was provided by Aegis and consisted of elemental materials, while MPC provided the master alloy arc melted button castings that were added to yield a charge composition of (Co35Fe65)88Zr7B4Cu. The atmosphere in the melting chamber and connected atomization system was evacuated with a mechanical pump prior to backfilling with ultrahigh purity (UHP grade) Ar. The melt was contained in a bottom tapped zirconia crucible with an alumina stopper rod to seal the exit while heating to a pouring temperature of 1550 – 1575oC. When the desired superheat was reached, the stopper rod was lifted and melt flowed through a yttria stabilized zirconia (YSZ) pour tube with a 3.2 mm orifice and was atomized with Ar from a 45-22-052-409 gas atomization nozzle (or atomization die), having a jet apex angle of 45 degrees with 22 cylindrical gas jets (each with diameter of 1.32 mm or 0.052 inches) arrayed around the axis of a 10.4 mm central bore. The Ar atomization gas supply regulator pressure was set to produce nozzle manifold pressures for the series of runs at a pressure of 450 psi. Secondary gas halos of Ar and He also were added to the interior of the spray chamber at various downstream locations for additional cooling of the atomized droplets and to prevent coalescence of the resulting powder. Powder size analysis and size classification were performed with a full set of ASTM sieves, starting with the 106 µm screen and proceeding down through the 20 µm screen. A Microtrac particle size analyzer was used to verify the size classification results of the particulate resulting from the runs. The resulting powder size distribution results are provided with this report labeled with their respective run numbers (GA-1-230, GA-1-232, and GA-1-238). It should be noted that the size distribution results of the first atomization run were quite acceptable and the same parameters were used for the second and third runs to test the reproducibility for technology transfer purposes.

33 ADVANCED PROPULSION SYSTEMS↗

Wireless Self-Acquistion of 12-Lead ECG via Android Smart Phone

Researchers at NASA s Johnson Space Center and at Orbital Research, Inc. (a NASA SBIR grant recipient) have recently developed a dry-electrode harness that allows for self-acquisition of resting 12-lead ECGs by minimally trained laypersons. When used in conjunction with commercial wireless (e.g., Bluetooth(TM) or 802.11-enabled) 12-lead ECG devices and custom smart phone-based software, the collected 12-lead ECG data can also immediately be forwarded from any geographic location within cellular range to the user s physician(s) of choice. The system can also be used to immediately forward to central receiving stations 12-lead ECG data collected during space flight or during activities in any remote terrestrial location supported by an internet or cellular phone infrastructure. The main novel aspects of the system are first, the dry-electrode 12-lead ECG harness itself, and second, an accompanying Android(TM) smart phone-based wireless 12-lead ECG capability. The ECG harness nominally employs dry electrodes manufactured by Orbital Research, Inc, recently cleared through the Food and Drug Administration (FDA). However, other dry electrodes that are not yet FDA cleared, for example those recently developed by Nanosonic, Inc as part of another NASA SBIR grant, can also be used. The various advantageous features of the harness include: 1) laypersons can be quickly instructed on its correct use, remotely if necessary; 2) all tangled "leadwire spaghetti" is eliminated, as is the common clinical problem of "leadwire reversal"; 3) all adhesives and disposables are also eliminated, the harness being fully reusable; if multiple individuals intend to use use the same harness, then standard antimicrobial wipes can be employed to sterilize the dry electrodes (and harness surface if needed) between users; 5) padded cushions at the lateral sides of the torso function to press the left arm (LA) and right arm (RA) dry electrodes mounted on the cushions against sideward or downward-rested arms of the subject; 6) sufficient distal placement of the arm electrodes achieves good electrode abutment to the arms without the need for adhesives, straps, bands, bracelets, or gloves; 7) padding over the sternum avoids "tenting" in the V1 through V3 (and, when present, the V3R) electrode positions; 8) easy-to-don, one-piece design with an adjustable, front-side single point of connection and an adjustable shoulder strap; and 9) Lund or "modified Lund" placement of the dry electrodes, the results of which more effectively reproduce results from "standard" 12-lead ECG placements than do results from Mason-Likar placements. The main limitation of the harness is that "one size does not fit all", meaning that an appropriately sized harness (small, medium, large, etc) must be chosen on the basis of an individual's size. To facilitate the use of the harness with inexpensive, commodity-grade cell phones and tablet devices, 12-lead ECG software is also being developed to accompany the harness for wireless use with Android. For this part of the project, NASA has teamed with TopCoder, Inc and the Harvard-affiliated NASA Tournament Lab in sponsoring java-based software programming contests through TopCoder. While ECG signals from the harness can already be wirelessly received and thoroughly processed (locally or remotely) by commercial-grade conventional (as well as advanced) 12-lead ECG software running on Microsoft Windows(TM), the Android-based software, once completed, will "cast a wider net" by allowing for a greater percentage of cell phone owners to participate in inexpensive, store-and-forward recordings of 12-lead ECGs worldwide, including for example Android cell phone users in many remote, third-world locations. At the time of writing, the Android 12-lead ECG software platform consists of a basic but expanding graphical user interface and accompanying software that: 1) wirelessly receives the 12-lead ECG data stream from a Bluetooth-based, FDA-cleared 12-leaCG device attached to the harness; 2) locally stores the same data in binary format to the SD card on the Android cell phone; and 3) makes the data stream in available in real time, for now to TopCoder's java programming contestants.

Schlegel, Todd T.↗