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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 109 records · Page 6

Friction and wear results from sputter-deposited chrome oxide with and without nichrome metallic binders and interlayers

Friction and wear tests were conducted on optimized sputtered Cr2O3 and Cr2O3 with metallic binder coatings. The coatings were applied on the bearing surface of journal foil air bearings and were tested against chrome-carbide-coated journal surfaces. The objective of the study was to develop a coating system which would withstand 9000 start-stops and high-speed rubs (maximum acceleration, 100 gs) in temperatures ranging from room temperature to 650 C. The Cr2O3 coating completed the test sequence and the coating consisting of Cr2O3 with metallic binders completed 3000 start-stops. The coefficient of friction of the coatings at 650 C was found to be about half that at room temperature. It was concluded, therefore, that the coatings should perform much better in a high temperature environment alone. The decrease in friction at high temperature is attributed to oxidation and interactions of the coatings and substrates at the interface temperature.

Bhushan, B.↗

Epitaxial Ferroelectric Hf 0.5 Zr 0.5 O 2 with Metallic Pyrochlore Oxide Electrodes

The synthesis of fully epitaxial ferroelectric Hf 0.5 Zr 0.5 O 2 (HZO) thin films through the use of a conducting pyrochlore oxide electrode that acts as a structural and chemical template is reported. Such pyrochlores, exemplified by Pb 2 Ir 2 O 7 (PIO) and Bi 2 Ru 2 O 7 (BRO), exhibit metallic conductivity with room-temperature resistivity of <1 mΩ cm and are closely lattice matched to yttria-stabilized zirconia substrates as well as the HZO layers grown on top of them. Evidence for epitaxy and domain formation is established with X-ray diffraction and scanning transmission electron microscopy, which show that the c-axis of the HZO film is normal to the substrate surface. The emergence of the non-polar-monoclinic phase from the polar-orthorhombic phase is observed when the HZO film thickness is ≥≈30 nm. Furthermore, thermodynamic analyses reveal the role of epitaxial strain and surface energy in stabilizing the polar phase as well as its coexistence with the non-polar-monoclinic phase as a function of film thickness.

36 MATERIALS SCIENCE↗

Boosting the interfacial superionic conduction of halide solid electrolytes for all-solid-state batteries

Designing highly conductive and (electro)chemical stable inorganic solid electrolytes using cost-effective materials is crucial for developing all-solid-state batteries. Here, we report halide nanocomposite solid electrolytes (HNSEs) ZrO 2 (-ACl)-A 2 ZrCl 6 (A = Li or Na) that demonstrate improved ionic conductivities at 30 °C, from 0.40 to 1.3 mS cm -1 and from 0.011 to 0.11 mS cm -1 for Li + and Na + , respectively, compared to A 2 ZrCl 6 , and improved compatibility with sulfide solid electrolytes. The mechanochemical method employing Li 2 O for the HNSEs synthesis enables the formation of nanostructured networks that promote interfacial superionic conduction. Via density functional theory calculations combined with synchrotron X-ray and 6 Li nuclear magnetic resonance measurements and analyses, we demonstrate that interfacial oxygen-substituted compounds are responsible for the boosted interfacial conduction mechanism. Compared to state-of-the-art Li 2 ZrCl 6 , the fluorinated ZrO 2 -2Li 2 ZrCl 5 F HNSE shows improved high-voltage stability and interfacial compatibility with Li 6 PS 5 Cl and layered lithium transition metal oxide-based positive electrodes without detrimentally affecting Li + conductivity. We also report the assembly and testing of a Li-In||LiNi 0.88 Co 0.11 Mn 0.01 O 2 all-solid-state lab-scale cell operating at 30 °C and 70 MPa and capable of delivering a specific discharge of 115 mAh g -1 after almost 2000 cycles at 400 mA g -1 .

36 MATERIALS SCIENCE↗

Supported Oxygen Evolution Catalysts by Design: Toward Lower Precious Metal Loading and Improved Conductivity in Proton Exchange Membrane Water Electrolyzers

Reducing the precious metal content of water oxidation catalysts for proton-exchange-membrane water electrolyzers remains a critical barrier to their large-scale deployment. Herein, we present an engineered architecture for supported iridium catalysts, which enables decreased precious metal content and improved activity and conductivity. The improvement in performance at lower precious metal loading is realized by the deposition of a conformal layer of platinum nanoparticles on titanium dioxide (TiO 2 ) using a facile photoreduction method to prepare conductive layer coated supports (CCSs). Platinum nanoparticles are homogeneously dispersed on TiO 2 , and the conductivity of the subsequent catalysts with 39 wt % precious group metal loadings is significantly higher than the commercial 75 wt % loaded IrO 2 -TiO 2 catalysts. The conformal conductive layer also maintains an enhanced conductivity and electrochemical activity upon thermal annealing when compared to catalysts without the conductive layer and nonconformal heterogeneous conductive layer. The iridium mass activity from half-cell studies shows a 141% improvement for CCS supported catalysts at 42% lower loadings compared to the commercial catalysts. The conductive layer also improves the single cell electrolyzer performance at a similar catalyst loading in comparison to a commercial state-of-the-art catalyst. Here, we correlate the physical properties of the engineered catalysts with their electrochemical performance in electrolyzers to understand structure-activity relationships, and we anticipate further performance improvements upon synthesis and materials optimizations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Impacts of PTL coating gaps on cell performance for PEM water electrolyzer

The anode porous transport layer (PTL) is a critical component of polymer electrolyte membrane (PEM) water electrolyzers, providing electrical conduction and water/oxygen transport to the anode catalyst layer. Platinum group metal (PGM) coatings are applied to titanium PTLs to prevent oxidation and preserve conductivity. To implement PEM water electrolysis on a large scale, it is essential to minimize the cost of mass-manufactured cell components while ensuring that defects in materials and components do not adversely affect the performance of the cell. In this study, we created gaps in the Pt coatings that are typically applied to PTLs to understand their effects on cell performance and inform on fabrication tolerances. The PTL coatings were fabricated by sputter deposition of Pt, intentionally leaving uncoated regions in either large patches or thin strips. For either geometry, the cell performance decreased with the increasing fraction of the uncoated regions. However, PTLs containing multiple thin uncoated strips caused a less severe performance effect than PTLs with continuous uncoated regions of the same relative total area. Through analysis of cell performance, impedance, and 3D charge transport modelling, here we demonstrate that both the anode catalyst layer and membrane play a role in distributing current to mitigate the impact of coating defects at a short length scale. These results allow to draw conclusions about the tolerance requirements with regards to PTL coating uniformity in terms of both the size and total area of defects.

08 HYDROGEN↗

Advanced Multi-Component Defect Cluster Oxide Doped Zirconia-Yttria Thermal Barrier Coatings

The advantages of using ceramic thermal barrier coatings in gas turbine engine hot sections include increased fuel efficiency and improved engine reliability. However, current thermal barrier coatings will not have the low thermal conductivity and necessary sintering resistance under higher operating temperatures and thermal gradients required by future advanced ultra efficient and low emission aircraft engines. In this paper, a novel oxide defect cluster design approach is described for achieving low thermal conductivity and excellent thermal stability of the thermal barrier coating systems. This approach utilizes multi-component rare earth and other metal cluster oxide dopants that are incorporated in the zirconia-yttna based systems, thus significantly reducing coating thermal conductivity and sintering resistance by effectively promoting the formation of thermodynamically stable, essentially immobile defect clusters and/or nanoscale phases. The performance of selected plasma-sprayed cluster oxide thermal barrier coating systems has been evaluated. The advanced multi-component thermal barrier coating systems were found to have significantly lower initial and long-term thermal conductivities, and better high temperature stability. The effect of oxide cluster dopants on coating thermal conductivity, sintering resistance, oxide grain growth behavior and durability will be discussed.

Zhu, Dongming↗

Advanced Multi-Component Defect Cluster Oxide Doped Zirconia-Yttria Thermal Barrier Coatings

The advantages of using ceramic thermal barrier coatings in gas turbine engine hot sections include increased fuel efficiency and improved engine reliability. However, current thermal barrier coatings will not have the low thermal conductivity and necessary sintering resistance under higher operating temperatures and thermal gradients required by future advanced ultra-efficient and low-emission aircraft engines. In this paper, a novel oxide defect cluster design approach is described for achieving low thermal conductivity and excellent thermal stability of the thermal barrier coating systems. This approach utilizes multi-component rare earth and other metal cluster oxide dopants that are incorporated in the zirconia-yttria based systems, thus significantly reducing coating thermal conductivity and sintering resistance by effectively promoting the formation of thermodynamically stable, essentially immobile defect clusters and/or nanoscale phases. The performance of selected plasma-sprayed cluster oxide thermal barrier coating systems has been evaluated. The advanced multi-component thermal barrier coating systems were found to have significantly lower initial and long-term thermal conductivities, and better high temperature stability. The effect of oxide cluster dopants on coating thermal conductivity, sintering resistance, oxide grain growth behavior and durability will be discussed.

Zhu, Dongming↗

First Principle based Thermal Conductivity Modeling of Metal Alloys with Applications on Uranium Alloys

Thermal conductivity is an important materials property related to heat transport, which is essential to many applications, ranging from thermoelectrics to nuclear reactor materials. High- quality thermal conductivity data is critical to these materials and their associated technologies, including the nuclear fuel materials like traditional oxide fuels and metallic uranium (U) fuels, e.g. U-Zr and U-Mo alloys. And thermal conductivity modeling is widely used to interpolate or extrapolate experimental data, to obtain high-quality thermal conductivity data over wide temperature and composition range, and to understand the impacts of different factors including defects and microstructures. However, a general thermal conductivity model for metal alloys which can work regrading different phase components is still missing. Also, for U alloys, a thermal conductivity model working with different phases is needed. Therefore, in this work, we developed thermal conductivity models for metal alloys, based on ab-initio calculations, semi-classical physics rules, and limited experimental data. The goals of these models are to help obtain high- quality thermal conductivity data within a little experimental input as possible, have models that are extendable to varying microstructures, including different types of irradiation effects, and provide mechanistic understanding of heat transfer in the modeled alloys. In this work, our model solves several challenges in the development. The DFT-BTE approach is applied to decrease the reliance on experimental data and make the model extendable to composition changes and defects. A practical and efficient way to combine the DFT inputs with physics rules is pointed out in this work too. A staged approach, which starts from simple cases of elemental metals, then extends to solid solutions, different compound phases, and multi-phase mixtures, is presented to work with the metal alloys in different phase components. Our models are demonstrated respectively on aU for elemental metal model, on U-Zr and U-Mo alloys in aU temperature range for multi-phase mixture model, on high-temperature U-Zr, U-Nb, and U-Mo alloys in the body-centered cubic phase for concentrated solid solution model, and on irradiated U-Mo alloys for irradiated metal alloy model. All models show great agreement with experimental data. In these demonstrations, our model shows its advantages compared to previous empirical fitting model. Our model requires fewer experimental data, due to the inputs from DFT. The quantitative insights into the different physical factors are provided in our model, as it incorporates the electron and phonon scattering mechanisms. Our model also can be extended to incorporate the contributions of point defects, grain boundaries, and noble gas bubbles, to integrate their effects on heat transfer. This model can serve as both a foundation for understanding the more complex thermal conductivity of realistic U alloy fuels and a useful tool to guide further modeling of thermal conductivity to aid materials and device design.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Bi-directional tuning of thermal transport in SrCoO x with electrochemically induced phase transitions

Unlike the wide-ranging dynamic control of electrical conductivity, there does not exist an analogous ability to tune thermal conductivity by means of electric potential. The traditional picture assumes that atoms inserted into a material’s lattice act purely as a source of scattering for thermal carriers, which can only reduce thermal conductivity. In contrast, here we show that the electrochemical control of oxygen and proton concentration in an oxide provides a new ability to bi-directionally control thermal conductivity. On electrochemically oxygenating the brownmillerite SrCoO 2.5 to the perovskite SrCoO 3–δ , the thermal conductivity increases by a factor of 2.5, whereas protonating it to form hydrogenated SrCoO 2.5 effectively reduces the thermal conductivity by a factor of four. This bi-directional tuning of thermal conductivity across a nearly 10 ± 4-fold range at room temperature is achieved by using ionic liquid gating to trigger the ‘tri-state’ phase transitions in a single device. We elucidated the effects of these anionic and cationic species, and the resultant changes in lattice constants and lattice symmetry on thermal conductivity by combining chemical and structural information from X-ray absorption spectroscopy with thermoreflectance thermal conductivity measurements and ab initio calculations. This ability to control multiple ion types, multiple phase transitions and electronic conductivity that spans metallic through to insulating behaviour in oxides by electrical means provides a new framework for tuning thermal transport over a wide range.

36 MATERIALS SCIENCE↗

Corrosion behavior of a series of combinatorial physical vapor deposition coatings on SiC in a simulated boiling water reactor environment

Here, the simulated boiling water condition corrosion properties of multilayer and combinatorial physical vapor deposition metal coatings (Zr, Cr, and/or Ti) deposited on a SiC f -SiC composite were investigated. Various compositions within the ternary system were corroded to the most suitable composition preventing underlying SiC f -SiC from further attack. Mass measurements and visual observations were conducted to identify which coatings formed protective oxides and which coatings spalled. Transmission electron microscopy was conducted to observe the microstructure of the physical vapor deposition metal layer before and after corrosion as well as identify the oxide which were forming.

36 MATERIALS SCIENCE↗

Recent Progress in Transparent Conductive Materials for Photovoltaics

Transparent conducting materials (TCMs) are essential components for a variety of optoelectronic devices, such as photovoltaics, displays and touch screens. In recent years, extensive efforts have been made to develop TCMs with both high electrical conductivity and optical transmittance. Based on material types, they can be mainly categorized into the following classes: metal oxides, metal nanowire networks, carbon-material-based TCMs (graphene and carbon nanotube networks) and conjugated conductive polymers (PEDOT:PSS). This review will discuss the fundamental electrical and optical properties, typical fabrication methods and the applications in solar cells for each class of TCMs and highlight the current challenges and potential future research directions.

14 SOLAR ENERGY↗

Ab Initio Evaluation of Plutonium Dioxide $S(α,β)$ and Thermal Neutron Cross Sections

Plutonium Dioxide (PuO 2 ) is an advanced fuel-cycle nuclear fuel material for thermal and fast reactors, with a melting point at 3261.8 K and thermal conductivity above 3 Wm -1 K -1 for temperatures below 1500 K. Plutonium from spent UO 2 is reprocessed to form chemically stable mixed oxide (MOX) fuel. In contrast to metallic fuels, the low PuO 2 conductivity results in high thermal gradients between fuel center and surface, resulting in structural annealing and efficient fission product migration over burnup. Crystal binding affects the doppler broadening of epithermal resonances for nuclear fuels and scattering behavior of thermal neutrons. Currently, there is no ENDF/B Thermal Scattering Law, i.e., $S(α,β)$, evaluation for PuO 2 , only free atom cross sections for Plutonium and Oxygen, respectively, which neglect lattice contributions to total cross section. Herein, ab initio lattice dynamics (AILD) techniques are employed to calculate the phonon density of states (DOS) using spin-orbit-coupling density functional theory (DFT) to predict the PuO2 paramagnetic ground-state structure. These results highlight the evaluation of $S(α,β)$ for Plutonium and Oxygen, respectively in PuO 2 and consequential generation of thermal neutron scattering cross sections for high fidelity criticality safety analysis and reactor calculations.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

A Free-Standing Boron-Doped Diamond Grid Electrode for Fundamental Spectroelectrochemistry

Spectroelectrochemistry (SEC) is a powerful technique that enables a variety of redox properties to be studied, including formal potential (E o ), thermodynamic values (ΔG, ΔH, ΔS), diffusion coefficient (D), electron transfer stoichiometry (n), and others. SEC requires an electrode which light can pass through while maintaining sufficient electrical conductivity. This has been traditionally composed of metal or metal oxide films atop transparent substrates like glass, quartz, or metallic mesh. Robust electrode materials like boron-doped diamond (BDD) could help expand the environments in which SEC can be performed, but most designs are limited to thin films (~100–200 nm) on transparent substrates less resilient than free-standing BDD. Here, this work presents a free-standing BDD grid electrode (G-BDD) for fundamental SEC measurements, using the well-characterized Fe(CN) 6 3–/4– redox couple as proof-of-concept. With a combination of cyclic voltammetry (CV), thin-layer SEC, and chronoabsorptometry, several of the redox properties mentioned above were calculated and compared. For E o' , n, and D, similar results were obtained when comparing the CV [E o' = +0.279 (±0.002) V vs Ag/AgCl; n = 0.97; D = 4.1 × 10 –6 cm 2 ·s –1 ] and SEC [E o' = +0.278 (±0.001) V vs Ag/AgCl; n = 0.91; D = 5.2 × 10 –6 cm 2 ·s –1 ] techniques. Both values align with what has been previously reported. To calculate D from the SEC data, modification of the classical equation used in chronoabsorptometry was required to accommodate the G-BDD electrode geometry. Overall, this work expands on the applicability of SEC techniques and BDD as a versatile electrode material.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Doping Bottleneck in Hematite: Multipole Clustering by Small Polarons

We report highly effective doping in transition metal oxides is critical to fundamentally overcome low carrier conductivity due to small polaron formation and reach their ideal efficiency for energy conversion applications. However, the optimal doping concentration in polaronic oxides such as hematite has been extremely low, for example, less than a percent, which hinders the benefits of doping for practical applications. In this work, we investigate the underlying mechanism of low optimal doping concentration with group IV (Ti, Zr, and Hf) and XIV (Si, Ge, Sn, and Pb) dopants from first-principles calculations. We find that novel dopant-polaron clustering occurs even at very low dopant concentrations and resembles electric multipoles. These multipoles can be very stable at room temperature and are difficult to fully ionize compared to separate dopants, and thus they are detrimental to carrier concentration improvement. This allows us to uncover mysteries of the doping bottleneck in hematite and provide guidance for optimizing doping and carrier conductivity in polaronic oxides toward highly efficient energy conversion applications.

36 MATERIALS SCIENCE↗

Twin-Domain Formation in Epitaxial Triangular Lattice Delafossites

Twin domains are often found as structural defects in symmetry mismatched epitaxial thin films. The delafossite ABO 2 , which has a rhombohedral structure, is a good example that often forms twin domains. Although bulk metallic delafossites are known to be the most conducting oxides, high conductivity is yet to be realized in thin film forms. Suppressed conductivity found in thin films is mainly caused by the formation of twin domains, and their boundaries can be a source of scattering centers for charge carriers. To overcome this challenge, the underlying mechanism for their formation must be understood so that such defects can be controlled and eliminated. Here, we report the origin of structural twins formed in a CuCrO 2 delafossite thin film on a substrate with hexagonal or triangular symmetries. A robust heteroepitaxial relationship is found for the delafossite film with the substrate, and the surface termination turns out to be critical to determine and control the domain structure of epitaxial delafossites. Based on such discoveries, we also demonstrate twin-free epitaxial thin films grown on high-miscut substrates. Finally, this finding provides an important synthesis strategy for growing single-domain delafossite thin films and can be applied to other delafossites for the epitaxial synthesis of high-quality thin films.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Broad Electronic Modulation of Two-Dimensional Metal–Organic Frameworks over Four Distinct Redox States

Two-dimensional (2D) inorganic materials have emerged as exciting platforms for (opto)electronic, thermoelectric, magnetic, and energy storage applications. However, electronic redox tuning of these materials can be difficult. Instead, 2D metal–organic frameworks (MOFs) offer the possibility of electronic tuning through stoichiometric redox changes, with several examples featuring one to two redox events per formula unit. Here, we demonstrate that this principle can be extended over a far greater span with the isolation of four discrete redox states in the 2D MOFs Li x Fe 3 (THT) 2 (x = 0–3, THT = triphenylenehexathiol). This redox modulation results in 10,000-fold greater conductivity, p- to n-type carrier switching, and modulation of antiferromagnetic coupling. Physical characterization suggests that changes in carrier density drive these trends with relatively constant charge transport activation energies and mobilities. Furthermore, this series illustrates that 2D MOFs are uniquely redox flexible, making them an ideal materials platform for tunable and switchable applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Quantum prediction of ultra-low thermal conductivity in lithium intercalation materials

Lithium-intercalated layered transition-metal oxides, Li x TMO 2, brought about a paradigm change in rechargeable batteries in recent decades and show promise for use in memristors, a type of device for future neural computing and on-chip storage. Thermal transport properties, although being a crucial element in limiting the charging/discharging rate, package density, energy efficiency, and safety of batteries as well as the controllability and energy consumption of memristors, are poorly managed or even understood yet. Here, for the first time, we employ quantum calculations including high-order lattice anharmonicity and find that the thermal conductivity κ of Li x TMO 2 materials is significantly lower than hitherto believed. More specifically, the theoretical upper limit of κ of LiCoO 2 is 6 W/m-K, 2–6 times lower than the prior theoretical predictions. Delithiation further reduces κ by 40–70% for LiCoO 2 and LiNbO 2 . Grain boundaries, strain, and porosity are yet additional causes of thermal-conductivity reduction, while Li-ion diffusion and electrical transport are found to have only a minor effect on phonon thermal transport. The results elucidate several long-standing issues regarding the thermal transport in lithium-intercalated materials and provide guidance toward designing high-energy-density batteries and controllable memristors.

25 ENERGY STORAGE↗

GaAs Schottky barrier photo-responsive device and method of fabrication

A gallium arsenide photo-responsive device is provided with an intermediate, transparent layer of a refractory metal or alkaline earth metal forming a tenacious bond between a non-hydroscopic oxide layer and a noble metal Schottky barrier layer. The device has a gallium arsenide substrate with a predetermined type conductivity and a gallium arsenide epitaxial layer with the same type conductivity but a lower charge carrier concentration grown on the substrate. The oxide layer is formed to cover the epitaxial layer, and the transparent metal layer followed by the noble metal layer are deposited upon the oxide layer. An interdigitated ohmic contact is then formed upon the noble metal layer.

Alcorn, G. E.↗