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At least 163 records · Page 9

Determining Multi-Component Phase Diagrams with Desired Characteristics Using Active Learning

Herein, we demonstrate how to predict and experimentally validate phase diagrams for multi-component systems from a high-dimensional virtual space of all possible phase diagrams involving several elements based on small existing experimental data. The experimental data for bulk phases for known systems represents a sampling from this space, and screening the space allows multi-component phase diagrams with given design criteria to be built. This approach uses machine learning methods to predict phase diagrams and Bayesian experimental design to minimize experiments for refinement and validation, all within an active learning loop. The approach is proven by predicting and synthesizing the ferroelectric ceramic system (1-ω)(Ba 0.61 Ca 0.28 Sr 0.11 TiO 3 )-ω(BaTi 0.888 Zr 0.0616 Sn 0.0028 Hf 0.0476 O 3 ) with a relatively high transition temperature and triple point, as well as the NiTi-based pseudo-binary phase diagram (1-ω)(Ti 0.309 Ni 0.485 Hf 0.20 Zr 0.006 )-ω(Ti 0.309 Ni 0.485 Hf 0.07 Zr 0.068 Nb 0.068 ) designed for high transition temperature (ω ≤ 1). Each phase diagram is validated and optimized through only three new experiments. The complexity of these compounds is beyond the reach of today’s computational methods.

36 MATERIALS SCIENCE↗

Heat Diffusion in High-Cp Nb3Sn Composite Superconducting Wires

A major focus of Nb3Sn accelerator magnets is on significantly reducing or eliminating their training. Demonstration of an approach to increase the Cp of Nb3Sn magnets using new materials and technologies is very important both for particle accelerators and light sources. It would improve thermal stability and lead to much shorter magnet training, with substantial savings in machines’ commissioning costs. Both Hypertech and Bruker-OST have attempted to introduce high-Cp elements in their wire design. This paper includes a description of these advanced wires, the finite element model of their heat diffusion properties as compared with the standard wires, and whenever available, a comparison between the minimum quench energy (MQE) calculated by the model and actual MQE measurements on wires.

43 PARTICLE ACCELERATORS↗

Innovative accident tolerant fuel concept enabled through direct manufacturing technology

Nuclear energy is one of the largest sources of carbon-free electricity in the world. Some countries are looking at new ways to support and revitalize the nuclear sector since the Fukushima disaster. The accident tolerant fuel program is geared toward improving the safety of nuclear energy by investigating materials that can replace or modify the current uranium-dioxide nuclear fuel and zirconium-based cladding. This research program is being supported by all major nuclear countries since 2011. The practical limitations on allowable uranium enrichment has taken the focus away from the most promising fuels with high radioactivity retention such as tristructural isotropic particle fuel. To overcome such enrichment limitation, a new fuel concept is proposed using advanced ceramic direct manufacturing with laser-induced chemical vapor deposition. The fuel-as-fiber concept is an accident-tolerant fuel design that features high thermal conductivity, strong capability of radioactivity retention and most importantly requires reasonable enrichment levels with uranium nitride as the fuel. In this work, the initial fabrication of uranium-based fuel with laser-induced chemical vapor deposition technology is demonstrated. Then an advanced multi-physics guided modeling approach based on finite element analysis codes and informed by the manufacturing capabilities is developed to accelerate the advancement of fuel-as-fiber concept for use in current light-water reactor technology. The detailed thermomechanical analysis showed promising results for viability of the innovative fuel-as-fiber concept. The predicted stresses in the fuel structural materials were similar to the case of tristructural isotropic particle fuel experience base that has shown excellent reliability in retention of fuel radioactivity at high temperatures.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Effects of edge-seal design on the mechanical and thermal performance of vacuum-insulated glazing

Although vacuum-insulated glazing (VIG) has been proposed as a promising solution towards developing energy-efficient buildings, VIGs have not become popular in the market due to several technical challenges including the complexity of the fabrication process. In particular, the edge-seal is a key component that significantly affects the thermal insulation and mechanical performance, and the development of edge-seal with adequate thermal insulation, mechanical strength, and reasonable processing cost is essential to overcome such technical issues in VIG. For this purpose, effects of edge-seal design parameters on the VIG performance should be identified. In this research, we analyzed the edge-seal for thermal transport as well as structural stresses to study the effects, and then identified and evaluated the material mixes for the edge-seal requirements. Here, the finite element simulations showed the significance of VIG corner calculation on overall thermal transmittance and the importance of seal conductivity below 1 W/m.K. The experiments with the flexible seals with different ratios of fine glass powder demonstrated that the measured shear strength values for the seal with less than 30% glass powder were more than 10 times larger than the calculated shear stress values. Based on these simulation and experimental results, a flexible sealant was developed using a proprietary mix of ceramic materials that meets the requirements of the designed VIG edge-seal, including structural as well as thermal stress resistance and a low conductivity. Moreover, the sealant is self-curing under atmospheric conditions, and thus it does not require costly inline process of laser curing or oven baking.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Low Cost Glass-Ceramic Matrix Composite Heat Exchanger

As part of ARPA-E’s High Intensity Thermal Exchange through Materials and Manufacturing Processes (HITEMMP) program, this project sought to develop novel heat exchanger (HX) capabilities to enable efficient and power dense power generation cycles. This class of HX comes under the category of ceramic/composite materials with the higher temperature goal in the program of ≥1100 °C inlet temperature operation. The enabling capability of this effort is the use of glass-ceramic matrix composite (GCMC) material which provides the high temperature durability of a ceramic, the flaw tolerance of a composite, a significantly faster and lower cost manufacturing process than conventional matrix CMCs and very low porosity levels < 0.5%. For thin-walled HX structures and the need to minimize leakage, the low porosity differentiator is particularly important. RTRC has prior experience with this material system and in the current project advanced the component design and manufacturing methods into new territory to produce features required for effective heat exchange under high pressures. In this approach, silicon carbide fiber is fabricated into a fiber preform using various textile processes. Graphite tooling is used both during the build-up of the fiber preform (interior tooling) and after the fiber preform has been completed (exterior tooling). This tooling assembly is heated to high temperature in an environment that has been evacuated and backfilled with inert gas. A reservoir of specialty glass is present and once the desired temperature has been reached to achieve the desired glass viscosity, an actuator distributes the glass throughout the fiber preform using passageways which are part of the tooling design in a process known as glass transfer molding. After the tooling has been removed, the composite is heat treated to convert the amorphous glass to a crystalline ceramic, providing improved properties. The project was divided into three phases focusing on the following: 1) 10 kW HX design and coupon-level tube sheet fabrication, 2) 10 kW HX fabrication, 3) 50 kW HX fabrication. During Budget Period 1 (BP1), additional risks were encountered and the need for additional funds was agreed upon by ARPA-E program leadership. Due to a variety of factors, the contract modification required nominally 18 months to execute at which time the HITEMMP program was effectively concluding. Because of this and the time that would be required to perform BP2 tasks, it was decided to conclude the project at the end of BP1. During the design of the 10 kW HX, manufacturing constraints were learned and incorporated, leading to a revised configuration for the fiber preform and HX. Heat exchange and pressure drop predictions also played a role in modifying the original design concept to be a higher aspect ratio shell-and-tube HX, simplifying the manufacturing process and improving the heat exchanger performance. Good gravimetric and volumetric thermal power densities of 11.2 kW/kg and 10,200 kW/m3 for the entire HX were projected that involved thermo-structural Finite Element Analysis to determine the structural mass needed for the high operation pressures of 250 bar cold inlet and 80 bar hot inlet. Fiber preforms using textile processes were produced for multiple headered tube sheets. Additional challenges were encountered during the glass transfer molding step for which solutions were identified, but programmatics did not allow them to be implemented in BP1. While complete HX test articles were not fabricated, the benefits of this GCMC material for a variety of high temperature applications remain.

30 DIRECT ENERGY CONVERSION↗

Printed copper-nanoplate conductor for electro-magnetic interference

As one of the conductive ink materials with high electric conductivity, elemental copper (Cu) based nanocrystals promise for printable electronics. Here, single crystalline Cu nanoplates were synthesized using a facile hydrothermal method. Size engineering of Cu nanoplates can be rationalized by using the LaMer model and the versatile Cu conductive ink materials are suitable for different printing technologies. The printed Cu traces show high electric conductivity of 6 MS m -1 , exhibiting electro-magnetic interference shielding efficiency value of 75 dB at an average thicknesses of 11 μ m. Together with flexible alumina ceramic aerogel substrates, it kept 87% conductivity at the environmental temperature of 400 °C, demonstrating the potential of Cu conductive ink for high-temperature printable electronics applications.

Materials Science↗

Ductile-Phase Toughened Tungsten for Plasma Facing Materials (Final Report)

Tungsten (W) and W-alloys are the leading candidates for plasma-facing components in nuclear fusion reactors because of their high melting point, high temperature strength, good thermal conductivity and low sputtering yield, however, they are too brittle to serve a structural function. A variety of processing approaches were employed to fabricate ductile-phase-toughened (DPT) tungsten (W) composites, that includes consolidating elemental W powder with Cu- or WC-coated W-wires via spark plasma sintering (SPS). Laminated W-composites with Cu-foils were also fabricated by hot-pressing or brazing. Mechanical testing and analytical modeling were used to guide composite development. The fracture toughness of thin W plate or laminated W-composites was measured in three-point bending (3PB) at room temperature (RT). Crack arrest and crack bridging were observed for the laminated composites, and fracture resistance curves were successfully calculated. An analytical model of crack bridging was developed using the specimen geometry, matrix properties, and the stress-displacement function of a ductile reinforcement (“bridging law”) to calculate the fracture resistance curve (R-curve) and load-displacement curve (P-D curve) for any test specimen geometry. The code was also implemented to estimate the bridging law of an arbitrary composite using R-curve data. In another approach, commercially available liquid-phase sintered W alloys with four different compositions were characterized in terms of microstructure, tensile and fracture toughness at different specimen, size, geometry and testing temperatures. The room temperature (RT) average maximum load fracture toughness values (KIc or KJm ≈ 38 to 107 MPa√m) of WHA, containing only 3 to 10 wt.% of a NiFe-based ductile phase (DP), are ≈ 5 to 13 times higher than for monolithic W (≈ 8 MPa√m). Most RT tests show extensive stable ductile tearing (DT) at all W contents, including 97W (KJm ≈ 69 MPa√m), for small baseline bend bars (B=1.65mm, W=2B). Exceptions to DT, include RT elastic fracture at 97W observed in 3x larger specimens than the baseline specimens. However, the WHA KIc was still almost 5 times higher than that for monolithic W. The other exception to RT ductile tearing was for some of the 6 to 8x larger 95W alloy specimens that contained large ceramic initiating inclusions at the precrack front, along with lower DP%, with a KIc ≈ 59 MPa√m, compare to their stable DT KJm ≈ 82 MPa√m. Small specimen tests down to -196°C, to partially emulate irradiation hardening, also transition to elastic fracture at a temperature (-150 for 90W to -25ºC for 97W) that depends on the W content. However, even at -196°C, the KIc at 97W is ≈ 3 times that of monolithic W at RT. In contrast to classical ductile phase toughening by macrocrack bridging, WHA toughening mainly involves new mechanisms associated with arrest, blunting and bridging of numerous process zone microcracks. Later, these WHAs were used to fabricate W-WHA hybrid composites by coating elemental W powder on WHA using SPS. Three-point bend bars were fabricated and fracture toughness was tested at room temperature. Crack initiated and propagated from W-part to the WHA part for the well-bonded (interface) W-WHA composites for 90 and 92.5WHAs, however, crack arrested and diverted at/or through the interface for loosely bonded W-95/97WHAs with increasing load.

36 MATERIALS SCIENCE↗

Nonthermal plasma synthesis of silicon carbonitride

Abstract The use of a low‐temperature plasma for the synthesis of amorphous silicon carbonitride (SiCN) nanoparticles enables the realization of sintered bulk samples with high thermal stability. Amorphous SiCN nanoparticles are produced from a mixture of silane, methane, and ammonia utilizing a mid‐pressure, radio‐frequency, continuous flow reactor. Particle characterization shows that the nanoparticles are largely amorphous with some crystalline silicon and silicon carbide domains <10 nm in size. Compositional tuning, controlled by varying the precursor flow rates, coupled with the uniform mixing of elements at the nanoscale, results in samples that resist crystallization even when sintered at temperatures as high as 2000°C. This study suggests that the low‐temperature plasma synthesis of nanoparticles has great potential to produce bulk structural materials for application in harsh environments.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Current activated reactive ultrafast joining (CARUJ) of silicon carbide

In this work we propose and demonstrate a novel approach for rapid fabrication of ceramic-ceramic joint assemblies, using sintered Silicon Carbide (SiC) as an initial example. Current Activated Reactive Ultrafast Joining (CARUJ) utilizes resistive heating of carbon-based materials to apply localized heat at or around the joint zone at heating rates of 101– 103 °C/min. CARUJ is used to fabricate SiC-SiC joints with a Si-SiC interface using minimal pressure (1–2 MPa) at time scales considerably shorter (several minutes opposed to hours) than conventional approaches for similar systems. The reaction of an interfacial precursor based on elemental silicon and carbon leads to in-situ SiC formation to produce a continuous and dense bond in a single step. Measured average joint strengths of roughly 15 MPa are achieved when tested in single lap offset (SLO) compressive shear. Optional additions of refractory metals such as molybdenum can be utilized to introduce secondary inclusions such as MoSi 2 within the joint interface. We further demonstrate SiC-SiC joining using Active Brazing Alloys (ABA) and proof of concept joining of tubular geometries. The localized and rapid heat application realizes a versatile material joining technique that could be extended for joining components at the plant site.

36 MATERIALS SCIENCE↗

Tuning Surface Stoichiometry of SOFC Electrodes at the Molecular and Nano-scale for Enhanced Performance and Durability

This project achieved the following objectives. Different cation segregation behaviors of different common SOFC cathodes, including La 0.6 Sr 0.4 Co0.2Fe 0.8 O 3-δ (LSCF), Sr 0.5 Sm 0.5 O 3-δ (SSC), and PrBa 0.5 Sr 0.5 Co 1.5 Fe 0.5 O5 +δ (PBSCF), were determined. We showed how oxygen partial pressure and gas impurities impact the stability of SOFC cathodes. We developed atomic layer deposition (ALD) coating techniques for electrodes and showed that by introducing different elements and different ALD oxidizers, electrode surface chemistry can be altered, resulting in enhanced oxygen reduction kinetics. In addition, we developed solution infiltration technique to enhance performance and durability of electrodes. Different infiltrates as well as different thermal treatment processes were screened to identify the optimal surface modification process that yields both low impedance and high durability. The modified cathode shows excellent stability and has a low area specific resistance (ASR) of only 0.2 Ωcm 2 at 600 °C after over 2000 hours of operation. Further, we developed ceramic anodes, SrFe(Co,Mo)O 3 (SFCM) and SrFe(Ni,Mo)O 3 (SFNM), and enhanced anode oxidation kinetics by solution infiltration or in situ catalyst exsolution from the ceramic anode surface. The modified anodes showed improved performance in full SOFCs, and the optimized anode modification shows high stability for over 400 hours at 550 °C. Moreover, the modified anode also demonstrates high durability in methane. This work provides fundamental understanding of electrode surface chemistry and demonstrates a simple, facile, cost-effective approach to enhance catalytic activity and durability of SOFC electrodes.

20 FOSSIL-FUELED POWER PLANTS↗

CRITICAL MINERAL RESOURCE ASSESSMENT OF COALS FROM THE POWDER RIVER BASIN, WYOMING, USA

Coal and associated sediments are potential sources of Rare Earth Elements (REE) and other critical minerals necessary for many consumer and defense-related products and development of energy technologies. For this study, 15 samples were sourced from Dry Fork Mine within the Powder River Basin near Gillette, Wyoming, to determine REE content along with select transition metals (t-metals) of interest in non-combusted coals and associated sediments. An excavator collected samples along a mine highwall, within benched intervals representing a foot to a few feet of coal strata. Homogenized sample subsets were crushed in an aluminum-ceramic vial, then passed through a 106-micron sieve. Sieved samples were pyrolyzed by a LECO TGA-108, which concurrently measured sample moisture, volatile, and ash content. Residual ash was then fused into a glass bead with lithium metaborate at a 6:1 Li-metaborate to sample ratio and then dissolved in 20% nitric acid. The nitric acid solutions containing digested beads were then diluted and passed through a 0.45 micron syringe filter. Filtered samples were analyzed by ICP-MS for REE and select t-metals. Reagent blanks were analyzed to assess for any potential contamination. Total REE plus Y (REE+Y) concentrations across the 15 samples range from 52 ppm to 1015 ppm with an average of 477 ppm on a dry ash basis. When normalized to upper continental crust (UCC; Taylor and McLennan, 1985) values, 13 of the 15 samples show average enrichment factors (EF) for REE+Y greater than 1. EF values indicate M-type enrichment (Sm through Er), as opposed to distinct preferential enrichment of light or heavy REE. T-metals with the highest average concentrations are V, Cu, Ni, and Zr at 215, 243, 123, and 118 ppm, respectively. Multiple t-metals had EF>1; however, Cu, Ge, and Sb have the highest average EF relative to UCC for t-metals, at 9.7, 8.0, and 17.0, respectively.

Copeland, Grant↗

Design, Synthesis, and Characterization of Polymer Precursors to Li x PON and Li x SiPON Glasses: Materials That Enable All-Solid-State Batteries (ASBs)

LiPON-like glasses that form lithium dendrite impenetrable interfaces between lithium battery components are enabling materials that may replace liquid electrolytes permitting production of all-solid-state batteries (ASBs). Unfortunately, to date, such materials are introduced only via gas-phase deposition. Furthermore, we demonstrate the design and synthesis of easily scaled, lowtemperature, low-cost, solution-processable inorganic polymers containing LiPON/LiSiPON elements. OPCl 3 and hexachlorophosphazene [Cl 2 P=N] 3 provide starting points for elaboration using MNH 2 (M = Li/Na) or (Me 3 Si)NH followed by reaction with controlled amounts of LiNH 2 to produce oligomers/polymers with molecular weights (MWs) ≈1–2 kDa characterized by multinuclear NMR, gel permeation chromatography (GPC), thermogravimetric analysis (TGA), Fourier-transform infrared (FTIR), X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and matrix-assisted laser desorption/ ionization (MALDI)-time-of-flight (ToF) offering stabilities to 150–200 °C and ceramic yields (800 °C) of 50–60%. 7 Li NMR suggests that precursor-bound Li + dissociates easily, beneficial for electrochemical applications. XPS shows higher N/P ratios (1–3) than via gas-phase methods (<1) correlating N/P ratios, 7 Li shifts, and Li + conductivities. Li 2 SiPHN offers the highest ambient conductivity of 3 × 10 –1 mS cm –1 at 400 °C/2 h/N 2 .

36 MATERIALS SCIENCE↗

Thickness dependence of piezo-bimorph adaptive mirror bending

A new generation of adaptive x-ray optics (AXO) is being installed on high-coherent-flux x-ray beamlines worldwide to correct and control the optical wavefront with sub-nm precision. These ultra-smooth mirrors achieve high reflectivities at glancing angles of incidence and can be hundreds of mm long. One type of adaptive x-ray mirror relies on piezoelectric ceramic strips which are segmented into channels and actuated to induce local, longitudinal bending, generating one-dimensional shape changes in the mirror substrate. A recently described mirror model uses a three-layer geometry with parallel actuators on the front and back surfaces of a thicker mirror substrate. By analogy to a solved problem in the thermal actuation of a tri-metal strip, we show that the achievable bending radius varies approximately as the square of the substrate thickness. We provide an analytic solution and simulate bending using a finite-element model.

47 OTHER INSTRUMENTATION↗

94ND10 Intergranular Phase Analysis and Fabrication

The composition and phase fraction of the intergranular phase of 94ND10 ceramic is determined and fabricated ex situ. The fraction of each phase is 85.96 vol% Al 2 O 3 bulk phase, 9.46 vol% Mg-rich intergranular phase, 4.36 vol% Ca/Si-rich intergranular phase, and 0.22 vol% voids. The Ca/Si-rich phase consists of 0.628 at% Mg, 12.59 at% Si, 10.24 at% Ca, 17.23 at% Al, and balance O. The Mgrich phase consists of 14.17 at% Mg, 0.066 at% Si, 0.047 at% Ca, 28.69 at% Al, and balance O. XRD of the ex situ intergranular material made by mixed oxides consisting of the above phase and element fractions yielded 92 vol% MgAl 2 O 4 phase and 8 vol% CaAl 2 Si 2 O 8 phase. The formation of MgAl 2 O 4 phase is consistent with prior XRD of 94ND10, while the CaAl 2 Si 2 O 8 phase may exist in 94ND10 but at a concentration not readily detected with XRD. The MgAl 2 O 4 and CaAl 2 Si 2 O 8 phases determined from XRD are expected to have the elemental compositions for the Mg-rich and Ca/Si-rich phases above by cation substitutions (e.g., some Mg substituted for by Ca in the Mg-rich phase) and impurity phases not detectable with XRD.

36 MATERIALS SCIENCE↗

The Thermodynamics of Crystallization and Phase-Separation in Melt-Derived Nuclear Waste Forms

This project aimed to gain detailed and fundamental understanding of the stability of glass waste forms to be used for safe and reliable encapsulation of nuclear waste. The focus was to understand thermodynamic and structural properties involved in crystallization and phase separation in melt-derived waste form glasses and glass-ceramics by studying a baseline glass composition with varying additives. This was achieved by combining neutron total scattering, advanced calorimetric measurements, and extensive modeling study. This project harnessed diverse and complementary approaches and expertise from four collaborating interdisciplinary institutions (two universities, one national laboratory, and one UK university partner). Samples were prepared at the national laboratory and exchanged with the two university institutions. The thermodynamic data obtained by various advanced calorimetry techniques were linked to the underlying short-range structure of waste forms measured by state-of-the-art neutron total scattering experiments. An important element of this project was extensive modeling to interpret and fundamentally understand the experimental results.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Evaluation of Additively Manufactured Monolithic SiC and SiC Ceramic Matrix Composites for Concentrating Solar Receiver Applications

Supported by an award from the Solar Technology Office, US Department of Energy, GE Aerospace Research in collaboration with Heliogen Holdings Inc, is engaged in the development of ultra-High Operating Temperature SiC-matrix Solar Thermal Air Receiver (HOTSSTAR). We report the results of our study of the effective heat transfer characteristic of several candidate structure motifs, or feature geometries, made of SiC via additive manufacturing in a simulative laboratory test. The SiC structure motifs studied include different permutations of three-dimensional periodic lattices and defined shapes. The solar-thermal simulating laboratory test setup is constructed using a 4kW CO2 laser system with beam shaping optics to apply radiative heating power on one face of 2”-diameter cylindrical feature specimens representing the structure motifs of interest for receiver element design. Using the test setup, simulative test conditions representative of a concentrated solar flux of up to ~2000 suns could be achieved in the lab tests under varying air flow through the test structure. A numerical analysis scheme is developed to extract an effective or compound heat transfer coefficient representative of the test structure under steady-state heat flow conditions.

14 SOLAR ENERGY↗

Development of a Robust Reference Electrode in Aggressive Chemical and Radiation Environments in the Hanford Waste Tanks

The Hanford site stores more than 200 million liters of radioactive and chemically hazardous wastes from the production of weapons materials. The wastes are stored in 177 underground carbon-steel storage tanks, separated between 149 single shell tanks (SSTs) and 28 double shell tanks (DSTs). The DSTs provide critical retrieval and interim storage before the waste is vitrified in the Waste Treatment and Isolation Plant (WTP). The tanks will need to remain in-service far beyond the initial 40-year design life, and effective corrosion control practices must remain in force to extend the tanks’ lifespans. This effort includes direct measurements of corrosion rate (e.g., ultrasonic measurements and corrosion coupons) and electrochemical processes (e.g., linear polarization measurements and open circuit potential measurements). The Hanford site began monitoring the corrosion potential in select DSTs in 2008. Of the 45 reference electrodes that have been installed, 29 have failed and 6 others provided unreliable results. DOE-EM is supporting a 3-year program to develop a chemical and radiation resistant reference electrode for application in the Hanford tanks. The first year of the program focused on understanding the failure mechanism for the reference electrodes and identification of candidate construction materials that would mitigate degradation of the electrodes in the waste environment. During the second year of the program, the objectives were to: 1) test candidate materials under simulated waste conditions, 2) design components that will extend the service life of the electrode, 3) fabricate materials for prototype reference electrodes, and 4) assemble prototype reference electrodes for accelerated testing. The reference electrode is constructed of four principal parts: 1) junction, 2) casing, 3) inner chamber backfill materials, and 4) the sensing wire. Principally, improvements of the junction, casing, and inner chamber backfill materials are being pursued. The junction material at the interface between the waste and the inner chamber of the reference electrode was identified as a critical component in the failure of the reference electrodes. Nine candidate replacement junction materials were tested under simulated waste conditions to evaluate permeation rate. These materials included a variety of polymeric and ceramic materials, some of which were 3-D printed. Thus far, porous polyvinylidene fluoride materials have performed satisfactorily and are being considered for prototype development. The commercial electrode casing materials in general have performed well. Additionally, 3-D printing of chemically and mechanically stable materials is being investigated as a means for further improvement in fabrication consistency. SRNL has also investigated altering the reference electrode design to extend the service life. The new design of the interior of the reference electrode casing creates a longer, more tortuous path between the junction material and the electrode sensing wire. A finite element model was used to optimize the design without adversely impacting the circuit resistance of the electrode during the measurements, thus preserving the measurement accuracy while enhancing the service life. The inner chamber back fill materials are also critical to the performance of the reference electrode. Materials that are resistant to intruding tank waste and provide a conductive path to the sensing wire were investigated. Gel and powder materials that are interspersed with a conductive chloride bearing material were tested for their influence on diffusion and electrode resistance. All the investigated materials and components will be assembled, with collaboration from commercial vendors, to fabricate the initial prototypes. Accelerated testing of the prototypes will be initiated in Year 2 of the program and will be completed in Year 3. A recommendation on the materials of construction and the design of the new robust reference electrode will be presented to the Hanford tank farm facility.

Sykes, Kiana [Savannah River National Laboratory (↗

Proton surface exchange kinetics of perovskite triple conducting thin films for protonic ceramic electrolysis cells: BaPr 0.9 Y 0.1 O 3–δ (BPY) vs. Ba 1–x Co 0.4 Fe 0.4 Zr 0.1 Y 0.1 O 3–δ (BCFZY)

Protonic ceramic electrolysis cells (PCECs) are an attractive green H 2 production technology, given their intermediate-temperature operating range and ability to produce dry H 2 . However, PCECs will benefit from development of more efficient and durable “triple conducting” anodes where steam is split, H incorporated, and oxygen evolved. In this work, we evaluated the kinetics of the steam-splitting/H incorporation reaction on BaPr 0.9 Y 0.1 O 3–δ (BPY) in comparison to the benchmark Ba 1–x Co 0.4 Fe 0.4 Z r0.1 Y 0.1 O 3–δ (BCFZY) composition, replacing most of the transition metal elements (Co, Fe, Zr) with the lanthanide Pr. We prepared geometrically well-defined perovskite BPY and BCFZY thin films by pulsed laser deposition and performed simultaneous optical transmission relaxation and electrical conductivity relaxation measurements at 400–500 °C in 0.21 atm O 2 during switching of the steam partial pressure to isolate and compare their proton surface exchange coefficients (k). The k values of BPY were comparable to those of BCFZY and more stable over time. According to angle-resolved XPS and STEM-EDS mapping of FIB cross-sections, the surface of BPY exhibited Ba enrichment, Pr deficiency, and Si contamination. In contrast, BCFZY exhibited Ba deficiency throughout, no obvious surface segregation, and less Si contamination. The Ba segregation on the BPY film appears to have promoted steam splitting/H incorporation kinetics even though the more basic surface reacted with the acidic environmental SiO x H y . Faster kinetics observed on stoichiometric BCFZY vs. Ba-deficient BCFZY confirmed the benefit of a high A-site Ba concentration. This result contrasts with most work on perovskites applied in solid oxide electrolysis cell anodes, in which A-site segregation is considered deleterious for surface reaction kinetics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗