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All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

New High-Entropy Perovskite Oxides with Increased Reducibility and Stability for Thermochemical Hydrogen Generation

This project aims to design, synthesize, and test a transformative class of High-Entropy Perovskite Oxides (HEPOs) as redox oxides to enable thermochemical hydrogen generation with improved stability, kinetics, and efficiency. These developed HEPOs are expected to demonstrate improved kinetics with oxygen surface exchange coefficient ( k > 7.5×10 -4 cm/s) in Budget Period (BP) 1, retain its structural stability in a broad range of oxygen non-stoichiometry (Δδ > 0.15) at a low operating reduction temperature of T red < 1400°C in BP 2, and deliver a H 2 yield of over 400 µmol per gram of oxide and high stability with less than 20% degradation after at least 50 cycles in BP 3. This project is feasible due to the unique thermodynamic properties (simultaneously increased reducibility and phase stability) and kinetic characters (stability against particle coarsening and potentially enhanced oxygen transport and surface reaction kinetics) of such HEPOs, and it is enabled by a unique active learning computational design approach. Computational studies have been conducted to investigate the oxygen vacancy formation in complex perovskite systems. * Accurate prediction of V O .. concentration with disordered A-site cations in Fe-based high-entropy perovskite oxides * Combined MC/DFT computation elucidates the mechanism of Co preference on the redox due to the strain introduced by local distortion. In this project, we explored a large number (~150) of perovskite compositions, which are listed in Tables 2 – 4). * All perovskite specimens have been synthesized through a high-throughput high-energy ball milling process, followed by the conventional sintering process. * XRD, SEM/EDS and TGA were performed to confirm the crystal structure, phase homogeneity and oxygen non-stoichiometry for compositionally complex perovskite oxides (CCPOs). * 110 compositions show single-phase from XRD * Unusual aliovalent doping effects in medium-entropy perovskite compositions. * V-shape relation between Δδ vs. x (La 1-x Sr x )(Mn 1/3 Fe 1/3 Ti 1/3 )O 3 * The highest reported hydrogen production for the CCPOs made in this project ( T re = 1350 ºC 30 min, T Ox = 1100 ºC 30 min) * B-site mixing (La 0.8 Sr 0.2 )(Mn 0.2 Fe 0.2 Co 0.4 Al 0.2 )O 3 : 89.97 ± 2.73 mmol H2 /mol oxide (395 ± 10 μmol/g oxide ) (i) No phase transformation during reactions when Co molar ratio is less than 61% (ii) Balance between intrinsic kinetics (oxygen surface exchange) and thermodynamics (oxygen non-stoichiometry) (iii) Preference of Co identified by in-situ XPS * A-site mixing (La 1/6 Pr 1/6 Nd 1/6 Gd 1/6 Ba 1/6 Sr1/6)MnO 3 : 98.48 mmol H2 /mol oxid e (~415 μmol/g oxide )

08 HYDROGEN↗
DOE OSTI2025

Hot Hydrogen Exposure of U x Zr 1-x C y Nuclear Fuel: The Effect of Additional Carbon

Nuclear thermal propulsion (NTP) using hydrogen as propellant in a solid-state fission reactor to reach temperatures of up to 3000K can achieve significantly higher specific impulse than chemical propulsion. A promising fuel that is again considered for NTP is U x Zr 1-x C y . To reduce the overall mass loss as well as the uranium fuel loss, a range of experiments using additional carbon in hot hydrogen (2600 K, 6 SLPM flow rate) were performed for up to 5-6 h. Both a CH 4 addition (0.1 and 0.2 vol%) in the hydrogen stream and the use of sacrificial graphite pieces upstream of the samples were tested, with sample compositions from 5 at% UC to 30 at% UC. The results showed a strong reduction of mass loss, up to a factor of 3, as well as a reduction of surface uranium losses in the presence of additional carbon in the atmosphere. Even with additional carbon in the atmosphere, material with 30 at% UC was not stable, but material with 20 at% UC was stable for up to 6h. The sample surfaces showed texturing after processing, possibly by grain growth on the surface. This led to a separation into grains with high uranium content close to the (100)-orientation, and with low uranium content in grains close to the (111)-orientation.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2017

Boride Based Electrode Materials with Enhanced Stability Under Extreme Conditions for MHD Direct Power Extraction. Final Scientific Report

Coal power currently makes up almost 40% of global electricity production. This method of extracting energy from coal can be added to any coal plant, improving its energy output. Not only would this prepare us to keep up with the ever-increasing energy demands but it could also allow us to significantly cut the greenhouse gas emissions for the coal power industry. Hafnium diboride (HfB 2 ), Zirconium diboride (ZrB 2 ), and their solid solution mixtures were studied, primarily for electrode coating applications in coal-fired magnetohydrodynamic (MHD) direct power extraction plants. MHD works by directly extracting current from superheated plasma flame (2725 °C) seeded with potassium salts. Obviously, the electrodes near this flame are subject to extreme temperatures and corrosive environments. The coating material needs to protect the electrodes from salt corrosion, oxidation, and melting, while still providing electrical conductivity. Transition metal diborides have many of the desired properties but need improvement for oxidation resistance above 1200 °C. Two main methods of oxidation resistance improvements were investigated during this research. The first was through electrochemical anodization, a process where a thin protective oxide layer is grown on the surface to prevent further detrimental oxidation at high temperatures. Several solutions, voltages, and methods were used to find an oxide layer that would protect at high temperatures. The second method was to use various additives and mixture ratios to improve densification and oxidation resistance. Ratios of HfB 2 and ZrB 2 tested were 1:4, 1:1, 4:1 and 1:1 with additives of Ta, Hf, and Zr metals, bringing the boron to metal ratio down to 1.86. Additionally, 1.8 mol% Gd 2 O 3 and LaB 6 were added to the 1:1 ratio HfB 2 -ZrB 2 . Hydrogen evolution reaction kinetics were also investigated to shed some light on the ability of these materials to resist corrosion. Aqueous corrosion tests were also performed in several solutions of different pH. The 1:1 ratio solution added with LaB 6 gave the best overall results both in high temperature and room temperature aqueous experiments. Further work will be needed to evaluate the efficacy of these materials for such applications.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2020

Higher-order phonon scattering: advancing the quantum theory of phonon linewidth, thermal conductivity and thermal radiative properties

Phonon scattering plays a central role in the quantum theory of phonon linewidth, which in turn governs important properties including infrared spectra, Raman spectra, lattice thermal conductivity, thermal radiative properties, and also signifi- cantly affects other important processes such as hot electron relaxation. Since Maradudin and Fein’s classic work in 1962, three-phonon scattering had been considered as the dominant intrinsic phonon scattering mechanism and has seen tremendous advances. However, the role of the higher-order four-phonon scattering had been persistently unclear and so was ignored. The tremendous complexity of the formalism and computational challenges stood in the way, prohibiting the direct and quantitative treatment of four-phonon scattering. In 2016, a rigorous four-phonon scattering formalism was developed, and the prediction was realized using empirical potentials. In 2017, the method was extended using first-principles calculated force constants, and the thermal conductivities of boron arsenides (BAs), Si and diamond were predicted. The predictions for BAs were later confirmed by several independent experiments. Four-phonon scattering has since been investigated in a range of materials and established as an important intrinsic scattering mechanism for thermal transport and radiative properties. Specifically, four-phonon scattering is important when the fourth-order scattering potential or phase space becomes relatively large. The former scenario includes: (i) nearly all materials when the temperature is high; (ii) strongly anharmonic (low thermal conductivity) materials, including most rocksalt compounds, halides, hydrides, chalcogenides and oxides. The latter scenario includes: (iii) materials with large acoustic–optical phonon band gaps, such as XY compounds with a large atomic mass ratio between X and Y; (iv) two- dimensional materials with reflection symmetry, such as single-layer graphene, single-layer boron nitride and carbon nanotubes; and (v) phonons with a large density of states, such as optical phonons, which are important for Raman, infrared and thermal radiative properties. Four-phonon scattering is expected to gain broad interest in various technologically important materials for thermoelectrics, thermal barrier coatings, thermal energy storage, phase change, nuclear power, ultra-high temperature ceramics, infrared spectra, Raman spectra, radiative transport, hot electron relaxation and radiative cooling. Four-phonon scattering has been, and will continue to be, established as an important intrinsic phonon scattering mechanism beyond three-phonon scattering. The prediction of four-phonon scattering will transition from a breakthrough to a new routine in the next decade.

Feng, Tianli↗
DOE OSTI2017

Performance of a Steel/Oxide Composite Waste Form for Combined Waste Steams from Advanced Electrochemical Processes

The results of electrochemical corrosion tests and modeling activities performed collaboratively by researchers at the University of Illinois at Chicago and Argonne National Laboratory as part of workpackage NU-13-IL-UIC-0203-02 are summarized herein. The overall objective of the project was to develop and demonstrate testing and modeling approaches that could be used to evaluate the use of composite alloy/ceramic materials as high-level durable waste forms. Several prototypical composite waste form materials were made from stainless steels representing fuel cladding, reagent metals representing metallic fuel waste streams, and reagent oxides representing oxide fuel waste streams to study the microstructures and corrosion behaviors of the oxide and alloy phases. Microelectrodes fabricated from small specimens of the composite materials were used in a series of electrochemical tests to assess the corrosion behaviors of the constituent phases and phase boundaries in an aggressive acid brine solution at various imposed surface potentials. The microstructures were characterized in detail before and after the electrochemical tests to relate the electrochemical responses to changes in both the electrode surface and the solution composition. The results of microscopic, electrochemical, and solution analyses were used to develop equivalent circuit and physical models representing the measured corrosion behaviors of the different materials pertinent to long-term corrosion behavior. This report provides details regarding (1) the production of the composite materials, (2) the protocol for the electrochemical measurements and interpretations of the responses of multi-phase alloy and oxide composites, (3) relating corrosion behaviors to microstructures of multi-phase alloys based on 316L stainless steel and HT9 (410 stainless steel was used as a substitute) with added Mo, Ni, and/or Mn, and (4) modeling the corrosion behaviors and rates of several alloy/oxide composite materials made with added lanthanide and uranium oxides. These analyses show the corrosion behaviors of the alloy/ceramic composite materials are very similar to the corrosion behaviors of multi-phase alloy waste forms, and that the presence of oxide inclusions does not impact the corrosion behaviors of the alloy phases. Mixing with metallic waste streams is beneficial to lanthanide and uranium oxides in that they react with Zr in the fuel waste to form highly durable zirconates. The measured corrosion behaviors suggest properly formulated composite materials would be suitable waste forms for combined metallic and oxide waste streams generated during electrometallurgical reprocessing of spent nuclear fuel. Electrochemical methods are suitable for evaluating the durability and modeling long-term behavior of composite waste forms: the degradation model developed for metallic waste forms can be applied to the alloy phases formed in the composite and an affinity-based mineral dissolution model can be applied to the ceramic phases.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2023

Phase evolution during conventional and reactive flash sintering of (Mg,Ni,Co,Cu,Zn)O via in situ X-ray diffraction

Reactive flash sintering (RFS) enables the simultaneous synthesis and sintering of ceramics and has been shown to affect the reaction pathway of different materials. Herein, in situ synchrotron X-ray diffraction (XRD) is used to investigate the (Mg,Ni,Co,Cu,Zn)O entropy-stabilized oxide formation during: (i) conventional heating and (ii) RFS under current rate-controlled mode. The same reaction pathway is verified in both instances: the starting rock-salt (RS), spinel (Co 3 O 4 ), tenorite (CuO), and wurtzite (ZnO) phases transform into a single RS phase with a (1 1 1) to (2 0 0) intensity ratio of 0.67, consistent with a random distribution of the cations into the structure. Pt lattice peak shift from the XRD patterns is used as standard to monitor the sample surface temperature, revealing a strong endothermic reaction during the RS single-phase formation (Pt peaks shift toward higher angles while increasing sample temperature/current density). Furthermore, in RFS, the single-phase RS structure is formed in just 60 s at a furnace temperature of 600°C and a current rate of 220 mA mm -2 /min. Therefore, RFS greatly accelerates the synthesis of (Mg,Ni,Co,Cu,Zn)O, however, it does not play a role in the reaction pathway for this material formation.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Reactive flash sintering and characterization of bulk high entropy nitrides

Over the past decade, numerous high-entropy ceramics have been synthesized, often displaying attractive properties. However, the study on facile preparation of bulk high entropy nitrides (HEN) are limited, despite its broad potential applications. This research demonstrates for the first time rapid fabrication (within ∼6 min) of bulk high-entropy nitrides, especially (Al 0.17 Nb 0.17 Ta 0.17 Ti 0.32 Zr 0.17 )N, from binary nitride powder mixtures using a highly efficient reactive flash sintering (RFS) technique. X-ray diffraction (XRD) shows the HENs from RFS are near single-phase solid solutions with a rock salt crystal structure, while in situ synchrotron study carried out during RFS captured in real time the formation of HEN, which was preserved upon cooling, suggesting thermodynamic stability of the HEN phase, even up to extreme pressure (∼35.6 GPa). Microscopic analyses using SEM, STEM, and EDS reveal decent uniformity for HEN with no obvious segregation of elements, even to submicron scale. Some properties of the obtained bulk HENs are consistent with expectations. For example, their hardness and bulk modulus are close to estimates based on rule-of-mixture (ROM) values from the constituent binary nitrides. Meanwhile, some other measured properties seem to show surprises. For example, the fracture toughness for the HENs (e.g., 7.81 ± 1.40 MPa•m 1/2 or higher) turns out to be more than double of the expected ROM estimates. The significantly improved fracture toughness is attributed to the observed nano-layered structure of the HENs, despite the HEN’s cubic crystal structure and high hardness. In addition, the oxidation resistance shows improvement up till ∼800°C, possibly due to Ta doping that suppress oxygen vacancy formation in the oxide shell, while the 5-metal HEN of (Al 0.17 Nb 0.17 Ta 0.17 Ti 0.32 Zr 0.17 )N displays superconductivity (T c of ∼5–7 K from magnetism and resistivity measurements, slightly lower than ROM estimate), despite insulating property of starting AlN. Furthermore, future study combining experimental investigation using larger samples to confirm the observed increase in fracture toughness and oxidation resistance, theoretical modeling at different length scale, and more detailed structural/chemical characterization, especially at the atomic scale, are all needed to fully understand the inter-relationships between composition, processing, structure, and novel properties for these HENs and the development of related new materials for different applications.

Flash sintering↗
DOE OSTI2023

Boosting the performance of reversible solid oxide electrochemical cells with a novel hybrid oxygen electrode, Pr 1.39 Ba 0.14 Sr 0.53 Co 1.48 Fe 0.76 O 6- δ -Ba 0.66 Sr 0.34 CoO 3- δ

Solid oxide electrochemical cells (SOECs) stand out as a highly promising clean energy technology that offers several benefits, showing significant potential to play a pivotal role in the transition towards a sustainable and low-carbon energy future. SOECs can efficiently convert the chemical energy stored in fuels to electricity in fuel cell mode, and produce various chemicals from abundant feedstocks (e.g., CO 2 , H 2 O) and intermittent solar/wind-based renewable electricity. Despite extensive efforts that have been devoted to designing novel materials and optimizing SOEC manufacturing processes, aiming to achieve enhanced energy efficiency, the current SOECs still suffer from poor performance, which is mainly due to the sluggish oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) kinetics. To address this challenge, in this work, we have successfully designed an in situ formed hybrid oxygen electrode material (Pr 1.39 Ba 0.14 Sr 0.53 Co 1.48 Fe 0.76 O 6- δ -Ba 0.66 Sr 0.34 CoO 3- δ ), which significantly improves the surface oxygen exchange coefficient and bulk oxygen-ion diffusion coefficient, enhancing the OER and ORR electrocatalytic activities. Further, the SOECs equipped with this newly developed oxygen electrode achieved exceptional performance for power generation using both hydrogen and propane as the fuels. At 750 °C, a peak power density of 2.4 W cm -2 was obtained with H 2 as the fuel. Additionally, the SOECs attain unprecedented performance in steam electrolysis mode. A current density of 4.4 A cm -2 was achieved at 1.3 V and 750 °C, which represents the highest performance among all yttria-stabilized zirconia (YSZ) electrolyte-based SOECs. The SOECs also deliver remarkable stability during the accelerated stability testing, highlighting the great potential of Pr 1.39 Ba 0.14 Sr 0.53 Co 1.48 Fe 0.76 O 6- δ -Ba 0.66 Sr 0.34 CoO 3- δ as a high-performance oxygen electrode for next generation SOECs.

08 HYDROGEN↗
DOE OSTI2020

Bi aliovalent substitution in Li 7 La 3 Zr 2 O 12 garnets: Structural and ionic conductivity effects

We report on the synthesis of cubic-phase garnet-type solid-state electrolytes based on Bi-doped Li 7 La 3 Zr 2 O 12 (LLZO). Bi aliovalent substitution of Zr in LLZO utilizing the Pechini processing method is employed to synthesize Li 7-x La 3 Zr 2-x Bi x O 12 compounds. A strong dependence of the ionic conductivity on Bi content is observed, and under our synthesis and sintering conditions, a >100-fold increase over the un-doped sample is observed for x=0.75. Cubic-phase Li 6 La 3 Zr 1 BiO 12 compounds are generated upon annealing in air in the temperature range 650 °C-900 °C. In contrast, in the absence of Bi, the cubic garnet phase of Li 7 La 3 Zr 2 O 12 is not formed below 700 °C and a transformation to the tetragonal phase is observed at similar to 900 °C for this un-doped compound. The role of Bi in lowering the formation temperature of the garnet cubic phase and in the ionic conductivity improvements is investigated in this work. We ascribe the effect of Bi-doping on ionic conductivity increments to changes in Li + -site occupancy and lattice parameters and the reduction in the formation temperature for the cubic-phase formation to rate enhancements of the solid-state reaction. To identify the site occupancy of Bi in the garnet structure, we employ synchrotron extended x-ray absorption fine structure spectroscopy. Our results indicate that Bi additions occupy the Zr-type sites exclusively, to within the accuracy of the measurements.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Layer-by-layer deposition of ultra-thin hybrid/microporous membrane for CO 2 separation

Based on two issued US patent, US7947579B2 and US8187678B2 that were invented by our team member at the University of New Mexico and Sandia National Labs, using atomic layer deposition technique (ALD) and molecular self-assembly or templating technique, An ultra-thin CO 2 membrane with CO 2 permeance up to 1580 GPU and CO 2 /N 2 up to 62 has been achieved in phase I project, promising for cost-effective CO 2 separations. As the first step of the project, a robust membrane fabrication protocol was established. To address the defects in the membrane structure, ALD treatment on AO support, multiple dip-coating processes and slow calcination steps were adopted. Consequently, defects were no longer evident in the nanoporous support, which ensures a reliable procedure for lab-scale membrane fabrications as well as the high-fidelity experimental findings. The same procedures may also be helpful for future scaling-up protocols. The layer-by-layer membrane fabrication was started by using a bridged disilane BTEE as the ALD precursor, wherein the organic groups at the bridging site were expected to be aligned layer-by-layer to form Angstrom-channels for CO 2 transport. Using 2-level factorial experimental design, we have found that ALD reaction time and ALD temperature were important factors impacting the CO 2 permeance and selectivity. Longer reaction time and higher ALD temperature were found to be advantageous for better CO 2 permeance and selectivity, which is in agreement with our model that better-aligned CO 2 -channels formed by the layer-by-layer stacking of the organic ligands can be achieved by a slower “stacking” process (longer reaction time) and stronger self-alignment tendency (higher ALD temperature). This observation will be an important guidance for our future membrane designs. The CO 2 -channel templated by –(CH 2 ) 2 - in BTEE was found to be too tight to facilitate fast CO 2 transport, but larger channel diameter is in contradiction with higher CO 2 selectivity. Therefore, the size-exclusion mechanism by itself is not sufficient for effective CO 2 separation. For this reason, the chemistry of the CO 2 -channel has to be carefully tuned. An amine bridged-disilane BTMA was therefore used as ALD precursor for larger CO 2 channel and high CO 2 -affinity chemistry. For BMTA membrane with amine chemistry measured at 100C, the CO 2 permeance was 1030 GPU for 100-cycle-ALD sample with CO 2 /N 2 selectivity of 17, and 302 GPU for 200-cycle-ALD sample with CO 2 /N 2 selectivity of 44. The increase of CO 2 permeance and the CO 2 /N 2 selectivity at elevated temperature is an evidence showing that there is a preferential chemical interaction between CO 2 and –NH functional groups in the membrane, which facilitates selective transport of CO 2 through the membrane. Therefore, using larger organic ligands as the CO 2 -channel template and the introduction of –NH chemistry to the membrane structure were proved to be an effective strategy in achieving better CO 2 permeance and selectivity. Guided by the same strategy, BTMA membrane was irradiated with UV to remove the bridging ligands for larger CO-channel, followed by Zn 2+ and Ni 2+ chemistry modification. Results showed that Zn 2+ or Ni 2+ chemistries will both enhance the selective CO 2 transport thereby the CO 2 /N 2 selectivity, and increasing separation temperature will further improve the CO2 permeance and selectivity. For BTMA membrane with Ni 2+ chemistry measured at 100C, CO 2 permeance of 1580 GPU and CO 2 /N 2 of 62 were achieved, promising for scaled-up industrial applications. Further, same membrane was tested at simulated flue gas condition (with SO 2 at 60C), the CO 2 permeance was 920 GPU and the CO 2 /N 2 selectivity was 52, suggesting the membrane still worked well under simulated flue gas conditions, primarily due to the stable ceramic framework of this membrane.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Minimizing Cr-Evaporation from Balance of Plant Components by Utilizing Cost-Effective Alumina-Forming Austenitic Steels

A solid oxide fuel cell (SOFC) is a clean and efficient energy conversion device. The development of intermediate-temperature SOFCs has made it preferable to use metallic interconnects (MICs) to greatly reduce the cost and significantly increase the efficiency compared to ceramic interconnect materials. However, gaseous chromium species will evaporate from the chromium-containing layer formed on the surface of commonly used MICs and balance of plant (BoP) components. Volatile chromium species have been shown to form solid deposits which poison the cathodes of SOFCs, causing drastic cell performance degradation and thereby limiting commercialization. In order to alleviate the Cr poisoning and achieve long-term high performance of SOFC stacks, various Al2O3-forming austenitic (AFA) stainless steels applied at different temperatures are evaluated in this project. Based on our Phase I results (500 h operation), it is shown that on the AFAs, an alumina-based protective layer forms under high temperature that is invulnerable to water vapor effects and suppresses the diffusion of chromium and manganese which can prevent the generation of spinels on the alloy surface. Therefore, 310S, OC4 and OC5 at 800 °C and 625, OC11 and OC11LZ at 900 °C are selected to be tested in the Phase II long-term operation. From the results, we find that besides the lower Cr evaporation rates and better oxidation resistance of AFAs than benchmark alloys after short-term (500 h) operation, AFAs also possess the sturdy and compact alumina layer after a long-term operation (5000 h). A protective oxide layer is of great importance for the long-term high-temperature operation of structural materials. The high-temperature oxidation behavior of AFAs and commercial 310S and 625 alloys in Air + 10% H 2 O at 800 °C and 900 °C is systematically investigated. Severe breakaway oxidation and minor spallation are observed for the 310S and 625 after the long-term operation, while the AFAs show high oxidation resistance. It is found that the formation of a continuous alumina layer could greatly prevent the volatilization of chromium vapors. In addition, the corresponding evolving models are discussed. Chromium evaporation from BoP components in high-temperature environment could severely deteriorate the electrochemical performance of SOFC. Several methods were applied to evaluate the Cr evaporation rates of BoP after 500 h exposure at 800 °C to 900 °C in air with 10% H 2 O. An optimal method was designed to exclude the effect of silicon (Si) deposits from quartz tube and sodium (Na) deposits from the sodium carbonate on the oxidation process and the chemical interaction between Cr gaseous species and alumina tube which could provide further quantitative correlation of the evaporated Cr species quantities and degradation rates of SOFC. Based on the great performance of AFAs after long-term operation, AFAs are assembled with Anode-supported cells (ASC) to investigate the the Cr deposition of anode-supported cell under a constant current density of 0.5 A cm -2 at 800 °C with AFA alloys compared with commercial alloys. In addition, the anodic and cathodic processes are deconvoluted by distribution of relaxation times (DRT) method which are comprehensively discussed. It is found out that the voltage exhibited a slight decrease of 5.09 % and 1.54 % in the presence of OC11 and OC11LZA alloy, respectively. However, a considerable decrease of 22.14 % and 12.06 % was determined in the presence of 310S and 625 alloy, respectively. AFAs possessing the low-cost, low Cr evaporation rates and the high oxidation resistance will make it of great potential to replace the existing BoP components.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Integrated protonic ceramic electrochemical cell for sustainable energy economy using water-energy nexus framework

Reliance on fossil fuels will continue for the next decades even though there are global pushes away from it to mitigate the overarching climate challenge, most especially by its highest consumers and availability. While there is a hastening global shift away from fossil fuel, integrating its assets into this technology helps limit the risk and future losses of stranded assets and reduce the cost of investment in the new technologies. Moreover, the generation of electricity from intermittent renewable sources like solar and wind has witnessed a significant surge in recent years, leading to a pressing demand for practical energy storage systems. Electrical energy storage is anticipated to play a pivotal role in the future global energy system, facilitating load-leveling operations to support the greater integration of renewable and distributed generation. Reversible electrochemical cells (RECs) offer a promising option for addressing the fossil fuel assets integration and energy storage challenges through the interconversion between electrical and chemical energy and concurrent utilizing carbon emission. In their electrolysis mode, the RECs convert electricity into durable, storable, and portable valuable chemical fuels such as syngas and methane. Conversely, the produced chemical fuels can be used as reactants in the fuel cell mode to generate electricity on demand with minimal (hydrocarbons) or zero when H2 or NH3 is used emissions. However, a challenging goal for this type of technology remains to achieve optimal operation and high roundtrip efficiencies, which has hindered the deployment of previous electrochemical cells. This dissertation demonstrates how reversible protonic ceramic electrochemical cells (RePCECs) can be integrated with fossil fuel power plants and renewable energy sources as a potential energy storage system. In this work, integrated RePCEC systems are designed and examined using computational modeling at scales to determine appropriate system configurations and operating conditions that achieve high roundtrip efficiencies. Cell level design of the PCEC is the first approach, several cells are assembled for the stack level model that is integrated into combined cycle powerplant and solar photovoltaic for the system level model. After critical literature review, this answered the operational and integration research questions proposed to address these challenges. The designed systems perform two functions, utilizing captured CO2 and storing renewable energy through co-electrolysis of steam and CO2. The co-electrolysis reaction involves endothermic water electrolysis and exothermic methanation reaction. To enhance high roundtrip efficiency, there is a need for thermal balance and management in the electrolysis mode. This involves operating the RePCEC stack under conditions that favor methane production to balance out heat needed by water electrolysis, it crucial for the RePCEC system operation. Methanation is enhanced by low temperatures. Leveraging on fabricated BCZYYb-electrolyte RePCEC, the cell model designed revealed that the optimum temperature for methane production is 450℃ at atmospheric pressure. Thus, to achieve optimum system performance, operating in the temperature range 450-525℃ is recommended at the given configuration, combining between the optimum temperature for methane production and temperature for the optimum stack roundtrip efficiency. Configuration with carbon capture system and purge stream is the optimum configuration from the seven conceptualized and evaluated. The modeling outcomes include a thermodynamic examination of integrated RePCEC systems, calibration of cell and stack level models, and steady-state simulation and integration into a 600MW combined cycle power plant retrofitted with two two-stage membrane-based carbon capture system and a wastewater treatment and recovery unit. At 100% powerplant loading, the stack and system roundtrip efficiencies are 72% and 51.37% respectively. Adding a purge stream for produced hydrogen at the system downstream improves the efficiencies to 74 and 55.48% respectively. At atmospheric pressure and 525℃, the system model suggests that a stack roundtrip of 82% is achievable, and overall system efficiency increases by reducing the energy consumption by the balance of plant components for steam generation and storage. Economic analysis of the process gives levelized cost of methane as $2.24/MMBtu lower than the conventional production route that range between $3.46/MMBtu and $9.85/MMBtu. The lifecycle analysis shows that the global warming potential for the production of methane and hydrogen from the RePCEC system is 3.83 kg CO2 eq which is lower than 9.35 kg CO2 eq emission during steam methane reforming for hydrogen production. This answered both the environmental and economic concerns in the raised research question. The proposed RePCEC configuration and analysis carried out in this dissertation to address the surge in renewable energy and challenges with PCEC technology hold significant potential in achieving large-scale energy storage while simultaneously reducing carbon emissions. These advancements, coupled with suitable governmental policies and incentive programs, have the potential to economically disrupt the natural gas industries by using RePCEC systems for methane production, thereby making them more favorable for eventual implementation and commercialization.

25 ENERGY STORAGE↗
DOE OSTI2021

Minimizing Cr-Evaporation from Balance Of Plant Components By Utilizing Cost-Effective Alumina-Forming Austenitic Steels

A solid oxide fuel cell (SOFC) is a clean and efficient energy conversion device. The development of intermediate-temperature SOFCs has made it preferable to use metallic interconnects (MICs) to greatly reduce the cost and significantly increase the efficiency compared to ceramic interconnect materials. However, gaseous chromium species will evaporate from the chromium-containing layer formed on the surface of commonly used MICs and balance of plant (BoP) components. Volatile chromium species have been shown to form solid deposits which poison the cathodes of SOFCs, causing drastic cell performance degradation and thereby limiting commercialization. In order to alleviate the Cr poisoning and achieve long-term high performance of SOFC stacks, various Al 2 O 3 -forming austenitic (AFA) stainless steels applied at different temperatures are evaluated in this project. Based on our Phase I results (500 h operation), it is shown that on the AFAs, an alumina-based protective layer forms under high temperature that is invulnerable to water vapor effects and suppresses the diffusion of chromium and manganese which can prevent the generation of spinels on the alloy surface. Therefore, 310S, OC4 and OC5 at 800 °C and 625, OC11 and OC11LZ at 900 °C are selected to be tested in the Phase II long-term operation. From the results, we find that besides the lower Cr evaporation rates and better oxidation resistance of AFAs than benchmark alloys after short-term (500 h) operation, AFAs also possess the sturdy and compact alumina layer after a long-term operation (5000 h). A protective oxide layer is of great importance for the long-term high-temperature operation of structural materials. The high-temperature oxidation behavior of AFAs and commercial 310S and 625 alloys in Air + 10% H 2 O at 800 °C and 900 °C is systematically investigated. Severe breakaway oxidation and minor spallation are observed for the 310S and 625 after the long-term operation, while the AFAs show high oxidation resistance. It is found that the formation of a continuous alumina layer could greatly prevent the volatilization of chromium vapors. In addition, the corresponding evolving models are discussed. Chromium evaporation from BoP components in high-temperature environment could severely deteriorate the electrochemical performance of SOFC. Several methods were applied to evaluate the Cr evaporation rates of BoP after 500 h exposure at 800 °C to 900 °C in air with 10% H 2 O. An optimal method was designed to exclude the effect of silicon (Si) deposits from quartz tube and sodium (Na) deposits from the sodium carbonate on the oxidation process and the chemical interaction between Cr gaseous species and alumina tube which could provide further quantitative correlation of the evaporated Cr species quantities and degradation rates of SOFC. Based on the great performance of AFAs after long-term operation, AFAs are assembled with Anode-supported cells (ASC) to investigate the the Cr deposition of anode-supported cell under a constant current density of 0.5 A cm -2 at 800 °C with AFA alloys compared with commercial alloys. In addition, the anodic and cathodic processes are deconvoluted by distribution of relaxation times (DRT) method which are comprehensively discussed. It is found out that the voltage exhibited a slight decrease of 5.09 % and 1.54 % in the presence of OC11 and OC11LZA alloy, respectively. However, a considerable decrease of 22.14 % and 12.06 % was determined in the presence of 310S and 625 alloy, respectively. AFAs possessing the low-cost, low Cr evaporation rates and the high oxidation resistance will make it of great potential to replace the existing BoP components.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2019

Tailored Perovskite Waste Forms for Plutonium Trapping

Perovskite ceramics have been extensively studied as host matrixes for radionuclide entrapment for nuclear waste disposal. As an expansion of these investigations, cerium, neodymium, and plutonium were incorporated into a perovskite phase, ACu 3 FeTi 3 O 12 (A = Nd, Ce, Pu), using sol–gel methods under oxidizing and reducing atmospheres. The targeted materials contained varying levels of Ce 3+ and Nd 3+ on the A site, yielding potential compositions of Nd 1–x Ce x Cu 3 FeTi 3 O 12 (x = 0, 0.1, 0.2, 0.3, 0.4, 0.8). However, interrogation of these materials shows that the maximum Ce 3+ loading is achieved near x ≈ 0.2. A single composition with plutonium was targeted, Nd 0.9 Pu 0.1 Cu 3 FeTi 3 O 12 , in order to properly model more realistic loading levels for a repository-destined material. These compounds were characterized using powder X-ray diffraction with Rietveld refinements of the structures and by a variety of spectroscopic techniques. Finally, the data suggest that, in order to achieve Pu 3+ substitution onto the A sites in the Nd 0.9 Pu 0.1 Cu 3 FeTi 3 O 12 , a reducing atmosphere must be employed. Otherwise, the redox activity of plutonium results in substitution onto multiple sites in the material as well as the formation of secondary phases such as TiO 2 .

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2016

Chemical Composition Measurements of LAWA44 Glass Samples

DOE is building the Hanford Tank Waste Treatment and Immobilization Plant (WTP) at the Hanford Site in Washington to remediate 55 million gallons of radioactive waste that is temporarily stored in 177 underground tanks. Both low-activity and high-level wastes will then be vitrified into borosilicate glass using Joule-heated ceramic melters. Efforts are being made to increase the loading of Hanford tank wastes in the glass. One area of work is enhancing waste glass composition/property models and broadening the compositional regions over which those models are applicable. In this report, the Savannah River National Laboratory provides chemical analysis results for several samples of a simulated low-activity waste glass, LAWA44, provided by the Pacific Northwest National Laboratory as part of an ongoing development task. The measured chemical composition data are reported and compared with the targeted values for each component for each glass. A detailed review showed no indications of errors in the preparation or measurement of the study glasses. All of the measured sums of oxides for the study glasses fell within the interval of 97.9 to 102.6 wt %, indicating acceptable recovery of the glass components. Comparisons of the targeted and measured chemical compositions showed that the measured values for the glasses met the targeted concentrations within 10% for those components present at more than 5 wt %. It was noted that the measured B 2 O 3 concentrations are somewhat above the targeted values for the study glasses. No obvious trends were observed with regard to the multiple melting steps used to prepare the study glasses, indicating that any potential effects of volatility were below measurable thresholds.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2020

Thermally Driven Interfacial Degradation between Li 7 La 3 Zr 2 O 12 Electrolyte and LiNi 0.6 Mn 0.2 Co 0.2 O 2 Cathode

Solid-state batteries offer higher energy density and enhanced safety compared to the present lithium-ion batteries using liquid electrolytes. A challenge to implement them is the high resistances, especially at the solid electrolyte interface with the cathode. Sintering at elevated temperature is needed in order to get good contact between the ceramic solid electrolyte and oxide cathodes and thus to reduce contact resistances. Many solid electrolyte and cathode materials react to form secondary phases. It is necessary to find out which phases arise as a result of interface sintering and evaluate their effect on electrochemical properties. Herein, we assessed the interfacial reactions between LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622) and Li 7 La 3 Zr 2 O 12 (LLZO) as a function of temperature in air. We prepared model systems by depositing thin-film NMC622 cathode layers on LLZO pellets. The thin-film cathode approach enabled us to use interface-sensitive techniques such as X-ray absorption spectroscopy in the near-edge as well as the extended regimes and identify the onset of detrimental reactions. We found that the Ni and Co chemical environments change already at moderate temperatures, on-setting from 500 °C and becoming especially prominent at 700 °C. By analyzing spectroscopy results along with X-ray diffraction, we identified Li 2 CO 3 , La 2 Zr 2 O 7 , and La(Ni,Co)O 3 as the secondary phases that formed at 700 °C. The interfacial resistance for Li transfer, measured by electrochemical impedance spectroscopy, increases significantly upon the onset and evolution of the detected interface chemistry. Our findings suggest that limiting the bonding temperature and avoiding CO 2 in the sintering environment can help to remedy the interfacial degradation.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Advanced monitoring of soil-vegetation co-dynamics reveals the successive controls of snowmelt on soil moisture and on plant seasonal dynamics in a mountainous watershed

Evaluating the interactions between above- and below-ground processes is important to understand and quantify how ecosystems respond differently to atmospheric forcings and/or perturbations and how this depends on their intrinsic characteristics and heterogeneity. Improving such understanding is particularly needed in snow-impacted mountainous systems where the complexity in water and carbon storage and release arises from strong heterogeneity in meteorological forcing and terrain, vegetation and soil characteristics. This study investigates spatial and temporal interactions between terrain, soil moisture, and plant seasonal dynamics at the intra- and inter-annual scale along a 160 m long mountainous, non-forested hillslope-to-floodplain system in the upper East River Watershed in the upper Colorado River Basin. To this end, repeated UAV-based multi-spectral aerial imaging, ground-based soil electrical resistivity imaging, and soil moisture sensors were used to quantify the interactions between above and below-ground compartments. Results reveal significant soil-plant co-dynamics. The spatial variation and dynamics of soil water content and electrical conductivity, driven by topographic and soil intrinsic characteristics, correspond to distinct plant types, with highest plant productivity in convergent areas. Plant productivity in heavy snow years benefited from more water infiltration as well as a shallow groundwater table depth. In comparison, low snowpack years with an early first bare-ground date, which are linked to an early increase in plant greenness, imply a short period of saturated conditions that leads to lower average and maximum greenness values during the growing season. Overall, these results emphasize the strong impact of snowpack dynamics, and terrain and subsurface characteristics on the heterogeneity in plant type and seasonal dynamics.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Tribological Behavior of Structural Materials in High Temperature Helium Gas-Cooled Reactor Environments

The High-Temperature Gas-cooled Reactor (HTGR) is a Generation IV concept designed to produce electricity and hydrogen at high efficiencies via high operating temperatures (700 °C or higher). Helium, the primary coolant for HTGRs, contains impurities (e.g., CO, H2O and CH4) that can induce corrosion reactions at high temperatures such as oxidation and (de)carburization, which in turn can affect the tribological behavior of components. Incoloy® 800HT (Ni-Fe-Cr austenitic solid-solution alloy) and Inconel® 617 (Ni-Cr-Co-Mo solid-solution alloy) are two high-temperature superalloys currently selected as candidate structural materials for the HTGR. The objective of this study is to evaluate the high-temperature tribological performance of these two candidate alloys after conditioning them in HTGR environments. Four regimes of corrosion were considered: a non-conditioned regime (Regime I), an oxidizing regime (Regime II), a carburizing and oxidizing regime (Regime III), and a carburizing regime (Regime IV). To simulate oxidation in HTGR, samples were conditioned for 22 days at elevated temperatures in a once-through helium loop with 4 ppmv H2O. Carburization of the samples was achieved by the commercial process, Kolsterising®. In addition, two surface treatments – shot peening and aluminization – were considered as potential routes of improving the alloys’ wear resistance. Surface-treated samples were tested both before and after conditioning in Regime II. Tribological testing of the samples was performed via a pin-on-disk tribometer at elevated temperatures in ambient environment – 650 and 750°C for 800HT; 850 and 900°C for 617 – with applied loads of 1N, 2N and 5N. The wear behavior of the alloys was assessed via wear volume and friction coefficient measurements, supported by morphological, structural and compositional analyses of the wear tracks. Conditioning the samples in Regime II led to the formation of a chromium oxide on both alloys. This protective scale increased the wear resistance compared to that of as-received samples (Regime I) due to the formation of a compacted ‘glaze’ oxide layer during sliding, rendering the wear track nearly undistinguishable from the unworn background and resulting in wear volumes below the detection limits of the measurement technique. The variability of the friction coefficients of the conditioned samples was also considerably reduced compared to that of the as-received samples due to the glaze layer. Additionally, the initial friction coefficients of the samples conditioned in Regime II were reduced by 45% and 54% compared to those of as-received samples for alloys 800HT and 617, respectively. Carburizing the samples (Regime IV) hardened the surfaces of both alloys and promoted the formation of an iron oxide on 800HT during tribological testing, thereby increasing the wear resistance and decreasing the initial friction coefficient by a factor of two compared to those of as-received 800HT. Alloy 617 exhibited an enhanced wear resistance but similar initial friction coefficient compared to those of as-received samples due to the increased surface hardness. The Mn-Cr oxide developed during Regime III conditioning of 800HT did not develop a glaze layer during tribotesting, even at lower loads. Thus, it was not as protective as the oxide produced during conditioning of Regime II samples, leading to lower wear resistance of 800HT in Regime III compared to that measured in the Regime II condition. 800HT benefited from the aluminization surface treatment, particularly before conditioning in Regime II, due to the promotion of a wear-resistant aluminum oxide layer during testing and the increase in surface hardness due to the presence of a FeAl intermetallic phase. The presence of this phase caused an order-of-magnitude reduction in wear volumes compared to those of as-received 800HT. Aluminization of 617 decreased its wear resistance, particularly after conditioning in Regime II, due to significant wear of the aluminum oxide via a ceramic wear mechanism. This aluminum oxide was removed during sliding, causing the wear volumes to increase by a factor of five compared to those of 617 conditioned in Regime II. Shot-peened 800HT exhibited a tribological behavior similar to that of as-received 800HT, despite an enhancement in the rate of chromium oxide formation. Shot-peened 800HT conditioned in Regime II showed lower wear resistance compared to that of 800HT conditioned in Regime II due to the poor adhesion between the oxide and the underlying metal, preventing the formation of the glaze layer during sliding. Shot peening of 617 increased its wear resistance at higher load, reducing worn volumes by 60% compared to that measured with as-received 617. Tribotesting of shot-peened 617 in Regime II revealed that the glaze-oxide layer was formed at every load, resulting in negligible wear, similar to what was observed from testing 617 after conditioning in Regime II. Overall, alloy 617 exhibited tribologically superior behavior compared to that of alloy 800HT, as demonstrated by its lower friction coefficients and its order-of-magnitude lower wear volumes when measurable.

36 MATERIALS SCIENCE↗