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Determination of He and D permeability of neutron-irradiated SiC tubes to examine the potential for release due to micro-cracking

Driven by the need to enlarge the safety margins of light water reactors in both design-basis and beyond-design-basis accident scenarios, the research and development of accident-tolerant fuel (ATF) has become an importance topic in the nuclear engineering and materials community. Continuous SiC fiber-reinforced SiC matrix ceramic composites are under consideration as a replacement for traditional zirconium alloy cladding owing to their high-temperature stability, chemical inertness, and exceptional irradiation resistance. Among the key technical feasibility issues, potential failure of the fission product containment due to probabilistic penetrating cracking has been identified as one of the two most critical feasibility issues, together with the radiolysisassisted hydrothermal corrosion of SiC. The experimental capability to evaluate the hermeticity of SiC-based claddings is an urgent need. In this report, we present the development of a comprehensive permeation testing station established in the Low Activation Materials Development and Analysis laboratory at Oak Ridge National Laboratory. Preliminary results for the hermeticity evaluation of un-irradiated monolithic SiC tubes, uncoated and coated SiC/SiC composite tubes, and neutron-irradiated monolithic SiC tubes at room temperature are exhibited. The results indicate that this new permeation testing station is capable of evaluating the hermeticity of SiC-based tubes by determining the helium and deuterium permeation flux as a function of gas pressure at a high resolution of 8.07 x 10 -12 atm-cc/s for helium and 2.83 x 10 -12 atm-cc/s for deuterium, respectively. The detection limit of this system is sufficient to evaluate the maximum allowable helium leakage rate of lab-scale tubular samples, which is linearly extrapolated from the evaluation standard used for a commercial as-manufactured light water reactor fuel rod at room temperature. The un-irradiated monolithic SiC tube is hermetic, as is manifested by the un-detectable deuterium permeation flux at various feeding gas pressures. A large helium leakage rate was detected for the uncoated SiC/SiC composite tube exposed to atmosphere, indicating it is inherently not hermetic. The hermeticity of coated SiC/SiC composite tubes is strongly dependent on the coating materials and the preparation of the substrate SiC/SiC composite samples. To simulate the practical application environment, monolithic CVD SiC tubes were exposed to neutron irradiation at the High Flux Isotope Reactor under high heat flux from the internal surface to the external surface. Although finite element analysis and resonant ultrasound spectroscopy measurement indicated that the combined neutron irradiation and high heat flux gave rise to a high probability of cracking within the sample, the hermeticity evaluation of the tested sample still exhibited gas tightness, emphasizing that SiC cracking is inherently a statistical phenomenon. The developed permeation testing station is capable of measuring the gas permeation flux in the range of interest with full confidence based on the presented results. It is considered a critical pre- /post-irradiation examination technique to characterize SiC-based cladding materials in asreceived and irradiated states to aid the research and development of ATF.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Preliminary Assessment of Two Alternative Core Design Concepts for the Special Purpose Reactor

The Special Purpose Reactor (SPR) is a small 5 MWt, heat pipe-cooled, fast reactor based on the Los Alamos National Laboratory (LANL) Mega-Power concept. The LANL concept features a stainless steel monolithic core structure with drilled channels for UO2 pellet stacks and evaporator sections of the heat pipes. Two alternative active core designs are presented here that replace the monolithic core structure with simpler and easier to manufacture fuel elements. The two new core designs are simply referred to as Design A and Design B. In addition to ease of manufacturability, the fuel elements for both Design A and Design B can be individually fabricated, assembled, inspected, tested, and qualified prior to their installation into the reactor core leading to greater reactor system reliability and safety. Design A fuel elements will require the development of a new hexagonally-shaped UO2 fuel pellet. The Design A configuration will consist of an array of hexagonally-shaped fuel elements with each fuel element having a central heat pipe. This hexagonal fuel element configuration results in four radial gaps or thermal resistances per element. Neither the fuel element development, nor the radial gap issue are deemed to be serious and should not impact an aggressive reactor deployment schedule. Design B uses embedded arrays of heat pipes and fuel pins in a double-wall tank filled with liquid metal sodium. Sodium is used to thermally bond the heat pipes to the fuel pins, but its usage may create reactor transportation and regulatory challenges. An independent panel of U.S. manufacturing experts has preliminarily assessed the three SPR core designs and views Design A as simplest to manufacture. Herein are the results of a preliminary neutronic, thermal, mechanical, material, and manufacturing assessment of both Design A and Design B along with comparisons to the LANL concept (monolithic core structure). Despite the active core differences, all three reactor concepts behave similarly and retain the same ex-core features and characteristics. While INL has developed Designs A and B, LANL is evaluating a Hot Isostatic Pressed reactor configuration to overcome the drawbacks of the monolithic core design.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Preliminary Assessment of Two Alternative Core Design Concepts for the Special Purpose Reactor

The Special Purpose Reactor (SPR) is a small 5 MWt, heat pipe-cooled, fast reactor based on the Los Alamos National Laboratory (LANL) Mega-Power concept. The LANL concept features a stainless steel monolithic core structure with drilled channels for UO 2 pellet stacks and evaporator sections of the heat pipes. Two alternative active core designs are presented here that replace the monolithic core structure with simpler and easier to manufacture fuel elements. The two new core designs are simply referred to as Design A and Design B. In addition to ease of manufacturability, the fuel elements for both Design A and Design B can be individually fabricated, assembled, inspected, tested, and qualified prior to their installation into the reactor core leading to greater reactor system reliability and safety. Design A fuel elements will require the development of a new hexagonally-shaped UO 2 fuel pellet. The Design A configuration will consist of an array of hexagonally-shaped fuel elements with each fuel element having a central heat pipe. This hexagonal fuel element configuration results in four radial gaps or thermal resistances per element. Neither the fuel element development, nor the radial gap issue are deemed to be serious and should not impact an aggressive reactor deployment schedule. Design B uses embedded arrays of heat pipes and fuel pins in a double-wall tank filled with liquid metal sodium. Sodium is used to thermally bond the heat pipes to the fuel pins, but its usage may create reactor transportation and regulatory challenges. An independent panel of U.S. manufacturing experts has preliminarily assessed the three SPR core designs and views Design A as simplest to manufacture. Herein are the results of a preliminary neutronic, thermal, mechanical, material, and manufacturing assessment of both Design A and Design B along with comparisons to the LANL concept (monolithic core structure). Despite the active core differences, all three reactor concepts behave similarly and retain the same ex-core features and characteristics. While INL has developed Designs A and B, LANL is evaluating a Hot Isostatic Pressed reactor configuration to overcome the drawbacks of the monolithic core design.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Rapid Development of Hybrid Perovskites and Novel Tandem Architectures

Multijunction solar cells based on epitaxially grown III-V materials hold the record for solar energy power conversion efficiency (PCE). However, due to the high cost of fabricating these devices, they are typically only used for concentrator cells and space applications. The overarching goal of this project was to develop low-cost printable hybrid perovskite (HP) materials appropriate and optimized for tandem solar cells with high power conversion efficiency under “1 Sun” illumination. Key results and findings over the course of the project we: Developed higher-performance high-bandgap (1.75 eV) perovskite materials and devices. In particular, we explored tens-of-thousands of compositions for high bandgap perovskites, achieving quasi-Fermi level splitting of 1.35 eV for a 1.75 eV bandgap material. We achieved World-record open circuit voltages from single junction p-i-n devices, 1.24 V from 1.75 eV bandgap material, which is what is preferable for tandems with a PCE of 14.3% using a guanidinium/formanadinium/ cesium alloyed lead iodobromide. We also developed a series of World-record efficiency devices at higher band-gaps based on 2D/3D perovskites using PEA. Developed higher-performance low-bandgap (1.35 eV) perovskite materials and devices. In particular, we developed a 1.35 eV bandgap perovskite of composition MAPb0.5Sn0.5(I0.8Br0.2)3 and showed its superiority to MAPb0.75Sn0.25I3. High efficiency solar cells were fabricated using PEDOT:PSS and doped-ICBA as HTL and ETL, respectively. Short circuit currents of 25.7 mA/cm2 and PCEs of 17.1% were obtained. Developed mechanically stacked 4-terminal CIGS-Perovskite tandems with PCE of 18.8% and monolithic 2-terminal CIGS-Perovskite tandems with PCE of 8.5%. The low efficiency of the monolithic device is a result of the high surface roughness of the solution processed CIGS bottom cells. This is not an intrinsic problem for CIGS-perovskite tandems, but does mean that smooth evaporated or sputtered CIGS films likely need to be used, unless a polishing step is employed. Developed monolithic 2-terminal Perovskite-Perovskite tandems with a stabilized PCE of 18.5%. This was the World-record perovskite-perovskite monolithic tandems for over a year in 2017-2018. Revealed that light is not an essential component of the so-called “light-induced” phase segregation. By using charge injection in the dark and electroluminescence, we showed that the presence of electrons in the conduction band and hole in the valence band is sufficient to drive the nearly ubiquitously observed phase segregation in high bandgap perovskites. Developed a new method to simultaneously measure absolute intensity photoluminescence and photoconductivity and use them to obtain simultaneous in-situ measurement of quasi-Fermi level splitting and diffusion length. This is important since it provides a proxy for device Voc and device Jsc. In addition, 67 papers were published with support from this award that detail many more advances in the field, including numerous publications in high impact journals such as Nature Photonics, Advanced Materials, ACS Energy Letters, and Energy and Environmental Science.

14 SOLAR ENERGY↗

Metal Oxide Nano-Array Catalysts for Low Temperature Diesel Oxidation. Final Report

In this project, a series of metal oxide nanostructure arrays (nano-arrays) with or without metal decoration, have been successful integrated onto monolithic honeycombs with well-defined size, shape, and chemical compositions, forming a new type of monolithic catalysts. These catalysts have displayed good durability and catalytic performance toward various gas phase catalytic reactions, while showing good potential of reducing the material usage. Specifically in situ grown onto monolithic honeycomb substrates, the metal oxide nanostructure arrays (nano-arrays) (e.g., CeO 2 , Co 3 O 4 , (Cu, Mn)O 2 , (La, Sr)MnO 3 , TiO 2 , etc.), with or without Pt-group metal (PGM) decoration, have displayed good durability and catalytic performance toward catalytic oxidation of hydrocarbons and CO, while showing good potential of reducing the material (noble metal and metal oxides) usage. As unique supports, the nano-array ‘forest-like’ structure configuration proves to improve the dispersion and immobilization of metal nanocatalysts under various aging and reactive conditions, besides the lower pressure drop and improved adherence to the monolith substrates over wash-coated catalysts. On the other hand, electronic interactions between metals and nano-array support are found to be adjustable toward favoring catalytic oxidation while improving the catalyst robustness. Furthermore, chemical leaching treatment in these metal oxide based catalysts could help tune their chemical and structural characteristics, boosting low temperature oxidation reactivity while maintaining robustness. Both CeO 2 and TiO 2 nano-array supported PGM catalysts have shown promising low temperature reactivity with 90% conversion at temperatures approaching 150oC toward CO, HC, and NO x oxidation under both probe and simulated exhaust conditions.

36 MATERIALS SCIENCE↗

Inexpensive and durable aerogel-based VIP cores

The goal of this project was development of low-cost aerogels to be used as cores of Vacuum Insulated Panels (VIP). The specific aims were: 1. Aerogels to be based on phenolic chemistry to minimize flammability. 2. Aerogels to be in monolithic form and to have mechanical properties sufficient to allow their use as cores of VIPs without collapsing after evacuation. 3. Aerogels to have a cost per kg lower than the cost of fumed silica, one of the most common VIP cores. The achievements are: 1. Phenolic aerogels have been fabricated in monolithic form with thermal conductivity of 0.023 W/m·K, density ~ 0.25 g/cm 3 and a modulus of compression > 10 MPa. The aerogels can withstand the stresses of VIP evacuation without any appreciable deformation. 2. Drying of aerogels was carried in the initial stages of the project via sublimation of frozen solvents, following the procedure described in M. F. Bertino and T. Selden, “Fabrication of Aerogels and Aerogel Composites by Ambient Pressure Sublimation of Frozen Solvents”, PCT/US20/39485. Monoliths as large as 30 x 30 x 2 cm can be fabricated with the proprietary ambient fabrication technique which are free of cracks and warping. 3. Cost analysis was carried out and refined multiple times, cost drivers were identified, and the fabrication procedure was streamlined. Our cost model yields an aerogel cost of $\$$5.78/kg, which compares well with the price of fumed silica ($\$$6.2/kg FOB New York as of March 2023). 4. The monoliths can be cut into custom shapes and used as VIP cores. Cores fabricated with our technique have a thermal conductivity λ = 0.011 W/m·K at a pressure >10 mbar. 5. A variant of the technology yielded fireproof materials, described in M. F. Bertino, T. Moon, G. Waller, J. Ko and D. Clifford, “Fireproof thermal insulation”, Provisional Patent Application 63/415,386. 6. A spin-off company was created (ThermaGel Innovations, Inc.) which licensed technologies developed under this award. PI Bertino is a board member of the newco which is now raising capital to build a pilot plant.

36 MATERIALS SCIENCE↗

Co-synthesis of Hydrogen and High-Value Carbon Products from Methane Pyrolysis

The ARPA-E Methane Pyrolysis Project successfully developed a scalable technology for hydrogen production with low-CO x emission through methane pyrolysis, co-producing high-value carbon nanotubes (CNTs). The project focused on optimizing reactor design, enhancing catalyst performance, and assessing techno-economic feasibility to create a commercially viable and environmentally sustainable process. The fluidized bed reactor achieved over 90% methane (CH 4 ) conversion by using a 5% CO 2 co-feed, which stabilizes carbon yields and minimizes catalyst deactivation. This setup allowed for continuous operation across ten cycles, each consisting of a 14-minute pyrolysis phase followed by a 10-minute dislodging phase to remove a fraction of the accumulated carbon, resulting in stable performance and high-quality CNT production. In parallel, monolith reactors coated with Fe demonstrated a sustained methane conversion of 73% while producing CNTs with high crystallinity. Although promising for continuous operation, monolith reactors face challenges in coating durability and scalability, highlighting areas for further optimization in commercial applications. Catalyst formulation played a key role in enhancing process efficiency. The core catalyst used was 5%Fe/Al 2 O 3 (wt%), optimized through wet impregnation, which improved CNT morphology, yielding longer and more uniform CNTs. The catalyst's performance was further enhanced by adding promoters: 2.5 wt% Ni increased methane conversion close to the thermodynamic limit, while 2.5 wt% Mn improved CNT alignment and crystallinity, and 1.5 wt% NaCl boosted CNT morphology but slightly lowered methane conversion. These adjustments allowed the reactor to maintain high methane conversion while producing high-quality CNTs, enabling stable performance over multiple cycles. To address carbon buildup and ensure uninterrupted operation, a pneumatic conveying tube was implemented for effective carbon dislodging in the fluidized bed configuration. CO 2 and H 2 O co-feeds were also introduced to enhance carbon removal, with CO 2 boosting CNT yield by approximately 15%. This setup enabled stable reactor operation across multiple cycles, preventing clogging and minimizing catalyst wear, making the process suitable for industrial scaling. Techno-economic analysis (TEA) projected hydrogen production costs between $\$$1.00 and $\$$1.64 per kilogram, with CNT values assumed at $\$$375/ton and $\$$100/ton. The life cycle assessment showed that CO 2 emissions could be as low as 0.64 kg CO 2 e/kg H 2 at 95% methane conversion assuming an electricity input of 50 kg CO 2 e/MWh. Even at 50% methane conversion, emissions remained below 1 kg CO 2 e/kg H 2 , demonstrating the process's low-emission potential and making it a viable alternative to traditional steam methane reforming. Overall, the results from this project demonstrate the feasibility of a pyrolysis process where carbon is continuously removed from the catalyst surface and hydrogen is continuously produced until a catalyst regeneration step is required to fully clean the catalyst surface and renew catalyst performance. Major open challenges are related to avoiding the loss of catalyst material in the dislodged carbon during fluidized bed conditions, since our best result demonstrated a carbon purity of ~70 wt. % (rest being iron and alumina). A monolith reactor was used to favor dislodgement of carbon compared to fluidized bed conditions but our results do not demonstrate an advantage of the monolith configuration. Catalyst performance was similar to fluidized bed conditions with slower deactivation rates overall, but we could not observe carbon dislodging in any of the tens of experiments that were run at Stanford. Our results show that the most relevant areas of improvement are related to the fundamental understanding of the iron-carbon interface for dislodging, and the development of catalyst that can produce CNTs via a base-growth mechanism such that catalyst is not lost in the dislodgement steps. The final report documents all findings and methodologies in detail, providing a valuable resource for the scientific community. By building on these results, researchers can further advance methane pyrolysis technology, moving toward a more sustainable, scalable pathway for hydrogen production. This work lays the foundation for future research and commercial efforts to reduce emissions in hydrogen production while generating valuable carbon products.

08 HYDROGEN↗

Proliferated Resilient Economical Half-Meter Aperture Space Telescopes (PREEMPT)

The PREEMPT LDRD was motivated by a major national need for better space-based imaging systems that are both high performing and affordable for the US Government. Current optical payloads for intelligence, surveillance and reconnaissance (ISR) and space domain awareness (SDA) missions can cost hundreds of millions of dollars and take years to develop, which makes it difficult to build the large constellations required for persistent, world-wide coverage. To address this, the team aimed to advance a different kind of large-aperture (>25 cm) telescope, called a monolithic telescope, in which key optical surfaces are built into a single piece of fused silica. This design greatly reduces payload and spacecraft complexity, the need for precision focus actuators, improves mechanical and thermal robustness, and lowers cost when compared with traditional Cassegrain telescopes that rely on many precisely aligned components. The project focused on five primary thrusts. The first thrust was to advance the concept of a V10, 25 cm, monolithic telescope forward from optical design to flight-ready stage. This was accomplished in partnership with Optimax, who delivered the first test unit in the early stages of the LDRD. The team developed several technologies necessary for this optic to be integrated into a flight demonstration. These include carbon fiber housings, highly detailed structural and thermal models and stress-reducing elastic averaging Hirth groove designs. These technologies resulted in a successful maturation of the optic, which is now slated to fly in late 2026/early 2027 for a demonstration mission. The second thrust was to advance the manufacturability of these optics. In collaboration with NIF’s optical manufacturing shop, we reduced polishing time from 480 hours to 65 hours through the implementation of optimized processes and new tools. The NIF team utilized a conceptual V8 (18 cm) optic to demonstrate this optimization, though it can be applied to the rest of the monolithic optic portfolio. Third, the team developed the first conceptual V20 (50 cm) payload, which is slated to be the next generation of LLNL optical payload systems. A set of structural, dynamic and thermal simulations were performed to identify potential challenges in the future development of this payload. Early-stage simulations suggest the payload is feasible, though thermal management will be the key focus area to maintain optimal performance. Fourth, a non-linear model of Viton was developed, to further enhance the reliability of our structural and dynamic models for future payloads. Viton acts as the primary interface material between the optic and its housing. Lastly, the team focused on successfully displaying the feasibility of using additively manufactured metal composites for optical space payloads. The team successfully demonstrated layer by layer deposition of Al-SiC composites, which have highly tunable structural and coefficient of thermal expansion (CTE) properties. These are crucial for optical payloads because CTE mismatch is one of the causes for degraded optical performance for telescopes in orbit. Overall, the work showed that monolithic telescopes could become a practical, lower-cost path to high-resolution space imaging for both national security and scientific missions.

42 ENGINEERING↗

GaAs-based optoelectronic neurons

An integrated, optoelectronic, variable thresholding neuron implemented monolithically in GaAs integrated circuit and exhibiting high differential optical gain and low power consumption is presented. Two alternative embodiments each comprise an LED monolithically integrated with a detector and two transistors. One of the transistors is responsive to a bias voltage applied to its gate for varying the threshold of the neuron. One embodiment is implemented as an LED monolithically integrated with a double heterojunction bipolar phototransistor (detector) and two metal semiconductor field effect transistors (MESFET's) on a single GaAs substrate and another embodiment is implemented as an LED monolithically integrated with three MESFET's (one of which is an optical FET detector) on a single GaAs substrate. The first noted embodiment exhibits a differential optical gain of 6 and an optical switching energy of 10 pJ. The second embodiment has a differential optical gain of 80 and an optical switching energy of 38 pJ. Power consumption is 2.4 and 1.8 mW, respectively. Input 'light' power needed to turn on the LED is 2 micro-W and 54 nW, respectively. In both embodiments the detector is in series with a biasing MESFET and saturates the other MESFET upon detecting light above a threshold level. The saturated MESFET turns on the LED. Voltage applied to the biasing MESFET gate controls the threshold.

Lin, Steven H.↗

Kinetics of Cyclic Oxidation and Cracking and Finite Element Analysis of MA956 and Sapphire/MA956 Composite System

Sapphire fiber-reinforced MA956 composites hold promise for significant weight savings and increased high-temperature structural capability, as compared to unreinforced MA956. As part of an overall assessment of the high-temperature characteristics of this material system, cyclic oxidation behavior was studied at 1093 C and 1204 C. Initially, both sets of coupons exhibited parabolic oxidation kinetics. Later, monolithic MA956 exhibited spallation and a linear weight loss, whereas the composite showed a linear weight gain without spallation. Weight loss of the monolithic MA956 resulted from the linking of a multiplicity of randomly oriented and closely spaced surface cracks that facilitated ready spallation. By contrast, cracking of the composite's oxide layer was nonintersecting and aligned nominally parallel with the orientation of the subsurface reinforcing fibers. Oxidative lifetime of monolithic MA956 was projected from the observed oxidation kinetics. Linear elastic, finite element continuum, and micromechanics analyses were performed on coupons of the monolithic and composite materials. Results of the analyses qualitatively agreed well with the observed oxide cracking and spallation behavior of both the MA956 and the Sapphire/MA956 composite coupons.

Lee, Kang N.↗

Thermophotovoltaic Cell Technology Transferred to the Department of Energy Laboratory and a Commercial Manufacturer

Researchers in the NASA Lewis Research Center's Photovoltaic Branch have developed novel photovoltaic device, called a Monolithically Interconnected Module (MIM), for use in thermophotovoltaic (TPV) power systems. TPV power systems function by heating an emitter to produce light. This light is then converted into electricity by a photovoltaic device or a solar cell. Possible heat sources for the system include concentrated solar energy, the combustion of various fuels, and nuclear decay. NASA has an interest in TPV systems for deep space (nuclear-powered) and near-Sun (solar-powered) missions. There also are many commercial and military applications for TPV, given its potential for high efficiency, low noise, and reliable power. The Monolithically Interconnected Module consists of many small solar cells that are series-interconnected on a common substrate. The cells are fabricated from indium gallium arsenide (InGaAs), which can convert the near-infrared portion of the emitter output spectrum into electricity. The InGaAs devices are deposited on an indium phosphide (InP) substrate that provides electrical isolation. On the bottom the InP substrate is an infrared reflector that returns all the photons that are not converted by the InGaAs device back to the emitter where they are absorbed. This process helps maintain the emitter temperature and dramatically improves the system efficiency. Monolithically Interconnected Module InGaAs thermophotovoltaic cell developed by Lewis. Compared with conventional TPV cells, this TPV device has higher output voltages and lower resistive losses, higher output power density, simplified thermal management, improved reliability, and higher efficiency. The Monolithically Interconnected Module was initially developed under an internally funded effort (Director's Discretionary Fund). Development is now being funded by another government agency, and prototype devices are being produced by a commercial solar cell manufacturer.

Wilt, David M.↗

Catalytic Ignition and Upstream Reaction Propagation in a Platinum Tube

A challenge for catalytic combustion in monolithic reactors at elevated temperatures is the start-up or "light-off" from a cold initial condition. In this work, we demonstrate a concept called "back-end catalytic ignition that potentially can be utilized in the light-off of catalytic monoliths. An external downstream flame or Joule heating raises the temperature of a small portion of the catalyst near the outlet initiating a localized catalytic reaction that propagates upstream heating the entire channel. This work uses a transient numerical model to demonstrate "back-end" ignition within a single channel which can characterize the overall performance of a monolith. The paper presents comparisons to an experiment using a single non-adiabatic channel but the concept can be extended to the adiabatic monolith case. In the model, the time scales associated with solid heat-up are typically several orders of magnitude larger than the gas-phase and chemical kinetic time-scales. Therefore, the model assumes a quasi-steady gas-phase with respect to a transient solid. The gas phase is one-dimensional. Appropriate correlations, however, account for heat and mass transfer in a direction perpendicular to the flow. The thermally-thin solid includes axial conduction. The gas phase, however, does not include axial conduction due to the high Peclet number flows. The model includes both detailed gas-phase and catalytic surface reactions. The experiment utilizes a pure platinum circular channel oriented horizontally though which a CO/O2 mixture (equivalence ratios ranging from 0.6 to 0.9) flows at 2 m/s.

Struk, P. M.↗

Reversible Ammonia Sorption for the Primary Life Support System (PLSS)

Results are presented on the development of regenerable trace-contaminant (TC) sorbent for use in Extravehicular Activities (EVAs), and more specifically in the Primary Life Support System (PLSS). Since ammonia is the most important TC to be captured, data presented in this paper are limited to ammonia sorption, with results relevant to other TCs to be reported at a later time. The currently available TC-control technology involves the use of a packed bed of acid-impregnated granular charcoal. The sorbent is non-regenerable, and its use is associated with appreciable pressure drop, i.e. power consumption. The objective of this work is to demonstrate the feasibility of using vacuum-regenerable sorbents for PLSS application. In this study, several carbon sorbent monoliths were fabricated and tested. Multiple adsorption/vacuum-regeneration cycles were demonstrated at room temperature, as well as carbon surface conditioning that enhances ammonia sorption without impairing sorbent regeneration. Depending on sorbent monolith geometry, the reduction in pressure drop with respect to granular sorbent was found to be between 50% and two orders of magnitude. Resistive heating of the carbon sorbent monolith was demonstrated by applying voltage to the opposite ends of the monolith.

Wojtowicz, Marek A.↗

Ultrasensitive microanalytical diagnostic methods for rickettsial pathogens

A strategic CRADA was established between Sandia National Laboratories (SNL) and the University of Texas Medical Branch (UTMB) at Galveston to address pressing needs for US protection against biological weapons of mass destruction (WMD) and emerging infectious diseases. The combination of unique expertise and facilities at UTMB and SNL enabled interdisciplinary research efforts in the development of rapid and accurate diagnostic methods for early detection of trace priority pathogen levels. Outstanding postdoctoral students were also trained at both institutions to help enable the next generation of scientists to tackle the challenging interdisciplinary problems in the area of biodefense and emerging infectious diseases. Novel approaches to diagnostics were developed and the both the speed of assays as well as the detection sensitivity were improved by over an order of magnitude compared to traditional methods. This is a significant step toward more timely and specific detection of dangerous infections. We developed in situ polymerized porous polymer monoliths that can be used as (1) size exclusion elements for capture and processing of rickettsial infected cells from a sample, (2) photopatternable framework for grafting high densities of functionalized antibodies/fluorescent particles using novel monolith chemistry. Grafting affinity reagents specific to rickettsial particles enables rapid, ultra-sensitive assays by overcoming transport limitations of traditional planar assay approaches. We have selectively trapped particles and bacteria at the cell trap and have also detected picomolar mouse IL-6 captured with only 20 minutes total incubation times using the densely patterned monolith framework. As predicted, the monolith exhibits >10x improvements in both capture speed and capture density compared to traditional planar approaches. The most significant advancements as part of this CRADA is the optimization of techniques allowing the detection of <10 rickettsial cells in a whole blood sample. This detection limit is over 2 orders of magnitude more sensitive that previously reported methods and overcomes a key hurdle in ability to sense dangerous infections before they are too late to treat and contain. We also showed that in the new format, cross-reactivity with interfering species is reduced thereby increasing the specificity of such tests. Promising options to treat whole blood and avoid clogging and non-specific fouling of sensors were also developed.

45 MILITARY TECHNOLOGY, WEAPONRY, AND NATIONAL DEF↗

Airfoil having internally cooled wall with liner and shell

An airfoil includes an airfoil section that has an airfoil wall that surrounds a cavity. The airfoil wall includes a first wall section comprised of a monolithic ceramic shell, a second wall section comprised of a CMC liner that is bonded along an interface to an interior side of the monolithic ceramic shell, and a ceramic barrier coating that is bonded to an exterior side of the monolithic ceramic shell. The airfoil wall includes at least one of: inter-section cooling channels that extend along the interface and are bounded by the monolithic ceramic shell and the CMC liner, or intra-section cooling channels that extend within the CMC liner.

Croteau, Paul F.↗

Ceramic airfoil trailing end configuration

An airfoil includes an airfoil body that has a trailing edge region. The trailing edge region includes first and second monolithic ceramic exterior walls, a flow discharge passage between the first and second monolithic ceramic exterior walls, a ceramic matrix composite (CMC) liner at least a portion of which is disposed in the flow discharge passage between the first and second monolithic ceramic exterior walls, and an array of pedestals disposed in the flow discharge passage. Each of the flow guides bridges the CMC liner and at least one of the first and second monolithic ceramic exterior walls.

Kennedy, Matthew B.↗

Ceria-based nanoflake arrays integrated on 3D cordierite honeycombs for efficient low-temperature diesel oxidation catalyst

A new, surfactant-free hydrothermal method has been developed for the growth of CeO 2 -based nanoflake arrays onto three-dimensional-channeled cordierite honeycomb substrates. Herein, a leaching-crystallization mechanism was proposed where the hydrothermal reaction, only involving cerium nitrate and water, leached the cordierite surface slightly and induced the formation of CeO 2 nanoparticles subsequently. Further continued reaction reincorporated Al and Si atoms leached from cordierite into CeO 2 , finally recrystallizing Ce-Al-Si composite nanoflake structures. Here, by using atomic layer deposition process, well-dispersed, size-controlled Pt nanoparticles were uniformly decorated on the CeO 2 -based nanoflakes to form the Pt/ CeO 2 nano-array-based monolithic catalyst. Despite 5-50 times reduction in the active material usage compared with the traditional wash-coated catalyst, the Pt/CeO 2 nano-array monolithic catalyst exhibited good catalytic oxidation activities over various individual gases, such as propylene, propane, CO, and NO oxidation, with 90% conversion efficiencies at temperatures below 200 °C. Under the simulated exhaust condition of low-temperature diesel combustion (LTC-D) developed by US DRIVE, the monolithic catalyst with low Pt loading (˜1 g/l) exhibits 90% conversion of catalytic oxidation over CO and hydrocarbonsat temperatures as low as ˜180 °C, much superior to the performance of traditional washcoated catalysts.

36 MATERIALS SCIENCE↗

Scalable continuous flow synthesis of ZnO nanorod arrays in 3-D ceramic honeycomb substrates for low-temperature desulfurization

Scalable and cost-effective synthesis and assembly of technologically important nanostructures in three-dimensional (3D) substrates hold keys to bridge the demonstrated nanotechnologies in academia with industrially relevant scalable manufacturing. In this paper, using ZnO nanorod arrays as an example, a hydrothermal-based continuous flow synthesis (CFS) method is successfully used to integrate the nano-arrays in multi-channeled monolithic cordierite. Compared to the batch process, CFS enhances the average growth rate of nano-arrays by 125%, with the average length increasing from 2 μm to 4.5 μm within the same growth time of 4 hours. The precursor utilization efficiency of CFS is enhanced by 9 times compared to that of batch process by preserving the majority of precursors in recyclable solution. Computational fluid dynamic simulation suggests a steady-state solution flow and mass transport inside the channels of honeycomb substrates, giving rise to steady and consecutive growth of ZnO nano-arrays with an average length of 10 μm in 12 h. The monolithic ZnO nano-array-integrated cordierite obtained through CFS shows enhanced low-temperature (200 °C) desulfurization capacity and recyclability in comparison to ZnO powder wash-coated cordierite. This can be attributed to exposed ZnO {101¯0} planes, better dispersion and stronger interactions between sorbent and reactant in the ZnO nanorod arrays, as well as the sintering-resistance of nano-array configurations during sulfidation–regeneration cycles. Finally, with the demonstrated scalable synthesis and desulfurization performance of ZnO nano-arrays, a promising, industrially relevant integration strategy is provided to fabricate metal oxide nano-array-based monolithic devices for various environmental and energy applications.

36 MATERIALS SCIENCE↗