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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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All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Trion Formation Resolves Observed Peak Shifts in the Optical Spectra of Transition-Metal Dichalcogenides

Monolayer transition-metal dichalcogenides (ML-TMDs) have the potential to unlock novel photonic and chemical technologies if their optoelectronic properties can be understood and controlled. Yet, recent work has offered contradictory explanations for how TMD absorption spectra change with carrier concentration, fluence, and time. Here, we test our hypothesis that the large broadening and shifting of the strong band-edge features observed in optical spectra arise from the formation of negative trions. We do this by fitting an ab initio based, many-body model to our experimental electrochemical data. Our approach provides an excellent, global description of the potential-dependent linear absorption data. We further leverage our model to demonstrate that trion formation explains the nonmonotonic potential dependence of the transient absorption spectra, including through photoinduced derivative line shapes for the trion peak. Our results motivate the continued development of theoretical methods to describe cutting-edge experiments in a physically transparent way.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Synthesis, transport properties and electronic structure of p-type Cu 1+x Mn 2–x InTe 4 ( x = 0, 0.2, 0.3)

The synthesis, electronic structure and temperature dependent transport properties of polycrystalline Cu 1+x Mn 2–x InTe 4 (x = 0, 0.2, 0.3) are reported for the first time. These quaternary chalcogenides were synthesized by direct reaction of the elements, followed by solid state annealing and hot press densification. The thermal conductivity is low for all specimens and intrinsic to the material system. Furthermore, the off-stoichiometry specimens illustrate the sensitivity of the transport properties to stoichiometry, with a greater than two-orders-of magnitude increase in carrier concentration with increased Cu content. First principles calculations of the electronic structure are also reported, and are in agreement with the experimental data. Here, this fundamental investigation shows the potential towards further optimization of the electrical properties that, in addition to the intrinsically low thermal conductivity, provides a basis for further research into the viability of this material system for potential energy-related applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Quantifying Species Populations in Multivalent Borohydride Electrolytes

Multivalent batteries represent an important beyond Li-ion energy storage concept. The prospect of calcium batteries, in particular, has emerged recently due to novel electrolyte demonstrations, especially that of a ground-breaking combination of the borohydride salt Ca(BH 4 ) 2 dissolved in tetrahydrofuran. Recent analysis of magnesium and calcium versions of this electrolyte led to the identification of divergent speciation pathways for Mg 2+ and Ca 2+ despite identical anions and solvents, owing to differences in cation size and attendant flexibility of coordination. To test these proposed speciation equilibria and develop a more quantitative understanding thereof, we have applied pulsed-field-gradient nuclear magnetic resonance and dielectric relaxation spectroscopy to study these electrolytes. Additionally, concentration-dependent variation in anion diffusivities and solution dipole relaxations, interpreted with the aid of molecular dynamics simulations, confirms these divergent Mg 2+ and Ca 2+ speciation pathways. These results provide a more quantitative description of the electroactive species populations. We find that these species are present in relatively small quantities, even in the highly active Ca(BH 4 ) 2 /tetrahydrofuran electrolyte. This finding helps interpret previous characterizations of metal deposition efficiency and morphology control and thus provides important fundamental insight into the dynamic properties of multivalent electrolytes for next-generation batteries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Real-Space Local Dynamics of Molten Inorganic Salts Using Van Hove Correlation Function

Molten inorganic salts are attracting resurgent attention because of their unique physicochemical properties, making them promising media for next-generation concentrating solar power systems and molten salt reactors. The dynamics of these highly disordered ionic media is largely studied by theoretical simulations, while the robust experimental techniques capable of observing local dynamics are not well-developed. To provide fundamental insights into the atomic-scale transport properties of molten salts, we report the real-space dynamics of molten magnesium chloride at high temperatures employing the Van Hove correlation function obtained by inelastic neutron scattering. Overall, our results directly depict the distance-dependent dynamics of a molten salt on the picosecond time scale. This study demonstrates the capability of the developed approach to describe the locally correlated- and self-dynamics in molten salts, significantly improving our understanding of the interplay between microscopic structural parameters and their dynamics that ultimately control physical properties of condensed matter in extreme environments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Ironing out the transition metal contribution to the magnetism of the n = 3 members of the homologous series Pr n +1 M n Ge 3 n +1 (M = Fe, Co): Pr 4 Fe 3 Ge 10 vs. Pr 4 Co 3 Ge 10

The Ln n+1 M n X 3n+1 (Ln = lanthanide, M = transition metal, and X = tetrel) homologous series provides a platform to study collective phenomena in quantum materials. Here, in this work, we compare the crystal growth, structure, and magnetic properties of the n = 3 members of the Pr n+1 M n Ge 3n+1 (M = Fe, Co) analogues, Pr 4 Fe 3 Ge 10 (a = 4.3207 (10) Å, b = 35.523 (8) Å, c = 4.2982 (15) Å, and V = 659.7 (3) Å 3 ) and Pr 4 Co 3 Ge 10 (a = 4.3091 (12) Å, b = 35.750 (9) Å, c = 4.2807 (11) Å, and V = 659.4 (3) Å 3 ). We determined that the ideal flux growth conditions for each compound are highly dependent on the concentration of Sn flux and quench temperature. Pr 4 Fe 3 Ge 10 orders ferromagnetically at 10 K along the c-direction while Pr 4 Co 3 Ge 10 orders antiferromagnetically at 16 K along the b-direction. For both compounds, we observed a magnetic moment higher than that expected for only Pr 3+ ions (3.58 µ B /Pr), implying that the transition metal ions contribute to magnetic ordering (3.91, 3.48, and 3.69 µ B /Pr for Pr 4 Fe 3 Ge 10 , and 3.76, 4.04, and 3.83 µ B /Pr for Pr 4 Co 3 Ge 10 measured along the a-, b-, and c-directions, respectively). Moreover, the zero-field Mössbauer spectrum obtained at 4.2 K for Pr 4 Fe 3 Ge 10 demonstrates that the iron sites participate in magnetic ordering.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Ba 1−x Sr x FeO 3−δ as an improved oxygen storage material for chemical looping air separation: a computational and experimental study

Chemical looping air separation (CLAS) is a promising technology to generate oxygen-rich gas streams to enable efficient carbon dioxide capture during fossil fuel combustion or gasification. CLAS relies on the capture and release of oxygen from the atmosphere using the redox properties of an oxygen-selective solid oxide carrier. This study investigates the redox characteristics of Ba 1−x Sr x FeO 3−δ (0.0 ≤ x ≤ 0.417, 0.0 ≤ δ ≤ 0.5) using a combination of density functional theory (DFT) calculations and experimental verification using X-ray diffraction, thermogravimetric analysis, and oxygen-temperature-programmed desorption. The DFT computed energies of the Ba 1−x Sr x FeO 3−δ perovskites reveal a composition-dependent transition from hexagonal to cubic phases as the Sr-concentration or oxygen vacancy concentration increases. Oxygen vacancy formation energies of the cubic perovskites are found to be lower than those of their hexagonal counterparts. A low oxygen diffusion barrier of ∼1 eV combined with the thermodynamic preference of Ba 1−x Sr x FeO 3−δ compositions that form in a cubic phase suggests them as promising candidates for oxygen storage applications. The experimental results corroborate this finding by identifying Ba 0.75 Sr 0.25 FeO 3−δ in the cubic phase as an optimal composition offering low-temperature oxygen storage capacities comparable to that of the state-of-the-art Sr 0.75 Ca 0.25 FeO 3−δ perovskite oxygen storage material at 325 °C and 350 °C.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Unexpected dependence of the anomalous Hall angle on the Hall conductivity in amorphous transition metal thin films

The anomalous Hall effect (AHE), and magnetic and electronic transport properties were investigated in a series of amorphous transition metal thin films— Fe x S i –x , Fe x Ge 1-x , Co x Ge 1–x , Co x Si 1–x , and Fe 1–y Co y Si. The experimental results are compared with density functional theory calculations of the density of Berry curvature and intrinsic anomalous Hall conductivity. In all samples, the longitudinal conductivity (σ xx ), magnetization (M), and Hall resistivity (ρ xy ) increase with increasing transition metal concentration; due to the structural disorder σ xx is lower in all samples than a typical crystalline metal. In the systems with Fe as the transition metal (including Fe 1–y Co y Si), the magnetization and AHE are large and in some cases greater than the crystalline analog. In all samples, the AHE is dominated by the intrinsic mechanism, arising from a nonzero, locally derived Berry curvature. The anomalous Hall angle (AHA) (= σ xy /σ xx ) is as large as 5% at low temperature. These results are compared with the AHAs reported in a broad range of crystalline and amorphous materials. Previous work has shown that in a typical crystalline ferromagnet the Hall conductivity (σ xy ) and σ xx are correlated and are usually either both large or both small, resulting in an AHA that decreases with increasing σ xy . By contrast, the AHA increases linearly with increasing σ xy in the amorphous systems. This trend is attributed to a generally low σ xx , while σ xy varies and can be large. In the amorphous systems, σ xx and σ xy are not coupled, and there may thus exist the potential to further increase the AHA by increasing σ xy .

36 MATERIALS SCIENCE↗
DOE OSTI2024

Coatings for CSP Lifetime

The feasibility and performance of tower-technology-based concentrated solar power (CSP) is highly dependent on the efficiency of the energy transformation from sun to heat at the receiver. The higher the solar absorptivity of the receiver coating, the higher the efficiency of the plant as a whole. BrightSource Energy (BSE) has developed a series of High-Performance Coating (HPC) systems in order to achieve high absorptivity over the plant lifetime (25-35 years). This requires stable coatings that are easily applicable on the large receiver surface and will maintain their optical properties under intense solar flux and thousands of heating and cooling cycles in desert conditions. Different coating formulations are required according to the differing plant conditions: receiver materials, operating conditions (temperatures, daily cycles, etc.), and environmental conditions. BSE also developed a coating for the next generation of CSP receivers, such as those being under DOE’s CSP Gen3 program, which will be operated with high temperature heat transfer fluids at temperatures of up to 800°C, which is significantly hotter than the operating temperature of current systems. Once the coating is formulated, the next challenge is evaluating its lifetime properties. BSE has found several independent failure modes that impact HPC absorptivity degradation: • Decrease in HPC optical properties due to oxidation in the receiver tubes surface below the HPC; • HPC film deterioration due to cycling of temperatures and humidity due to daily operation startup and shutdown as well as changing ambient conditions; • Mechanical degradation due to erosion by sand and wind. Existing test methods examine various aspects independently, but do not provide a combined accelerated lifetime result. Creating such a combined test suite, with a way to interpret the results to predict the coating’s projected lifetime, was the ultimate goal of this project. The project was divided into three major workstreams: lab testing (individual failure mode tests and combined failure mode tests); developing a theoretical model for aging; and validation of the test apparatus via on-sun testing in near real-world conditions at CIEMAT-PSA. Developing a test apparatus that accurately controlled the temperature while also introducing the desired solar flux proved more challenging than expected. While in the end we did succeed in creating a test apparatus that can control temperature, solar flux, and humidity, the results did not appear to accelerate the lifetime of the samples as desired. We suspect that to properly accelerate the samples we must also subject the samples to increased amounts of oxygen. Similarly, while we successfully created a combined model that is publicly available, we were unable to validate it sufficiently to feel comfortable recommending it as a general guideline.

14 SOLAR ENERGY↗
DOE OSTI2023

Performance of Structural Alloys in Bio-oil Production, Upgrading, and Storage Systems

Selection of corrosion-resistant, cost-effective structural materials for the process and containment vessels required for the production, upgrading, and storage of biomass-derived oils has been the subject of study in our laboratory for many years. The wide variety of biomass resources and the many liquefaction techniques and processing conditions result in products with a broad range of properties and compositions. Here, this paper will address the materials issues in three distinct areas. In production, materials are exposed to temperatures that range from 350 to 550 °C depending upon the process. Generally, austenitic stainless steels have performed reasonably well, although thicker oxide scales and intergranular attack have sometimes been observed. For storage and transport of the bio-oil products, temperatures experienced by the containment materials are not expected to exceed 50 °C. Our studies have shown that most raw bio-oils contain significant concentrations of organic acids, and low-molecular-weight organic acids were quite corrosive to carbon and low alloy steels. For some applications, subsequent processing is required, which includes hydrotreating or co-processing with a petroleum-derived liquid. These processes utilize a catalyst that requires periodic retreatment with a sulfidizing gas, and the exposure to this gas at elevated temperatures can cause appreciable corrosion to the more common austenitic stainless steels. The materials considered most cost-effective and sufficiently corrosion-resistant for each of these environments were identified.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Pinning Characteristics of Zr and Hf- Added REBCO Coated Conductors Made by Advanced MOCVD in Low-to-High Magnetic Fields

BaMO 3 (M=Zr, Hf) pinning centers introduced in REBa 2 Cu 3 O 7-x (REBCO and RE = rare earth) coated conductors yield superior performance in high magnetic fields. We present the critical current density J c over a temperature range of 4.2-77 K and magnetic fields of 0-14 T (B || c-axis), of 5-15 mol.% Zr- and Hf-added REBCO 4+ μm thick film tapes fabricated by advanced metal organic chemical vapor deposition (A-MOCVD). The morphology of self-assembled BMO nanorods aligned along c-axis is found to be dependent on the Zr/Hf content. We also observe a correlation between the density of RE 2 O 3 in-plane nano-precipitates and the continuity and concentration of BMO nanorods in films of different Ba content. It is found that the (Ba+M)/Cu (M=Zr, Hf) content in REBa 2 Cu 3 O 7-x affects the shape of pinning force density curves over a wide magnetic field range and temperatures below 20 K. Another remarkable observation is the similarity in the critical current properties of Hf and Zr -added REBCO films as function of (Ba+M)/Cu content at intermediate to high range of (Ba+M)/Cu content. As a result, a quantitative analysis of pinning efficiency and correlation with the microstructure of Zr and Hf- added REBCO coated conductors is discussed.

2G high-temperature superconductor (2G-HTS)↗
DOE OSTI2023

Photoaging of phenolic secondary organic aerosol in the aqueous phase: evolution of chemical and optical properties and effects of oxidants

Abstract. While gas-phase reactions are well established to have significant impacts on the mass concentration, chemical composition, and optical properties of secondary organic aerosol (SOA), the aqueous-phase aging of SOA remains poorly understood. In this study, we performed a series of long-duration photochemical aging experiments to investigate the evolution of the composition and light absorption of the aqueous SOA (aqSOA) from guaiacyl acetone (GA), a semivolatile phenolic carbonyl that is common in biomass burning smoke. The aqSOA was produced from reactions of GA with hydroxyl radical (•OH-aqSOA) or a triplet excited state of organic carbon (3C∗-aqSOA) and was then photoaged in water under conditions that simulate sunlight exposure in northern California for up to 48 h. The effects of increasing aqueous-phase •OH or 3C∗ concentration on the photoaging of the aqSOA were also studied. High-resolution aerosol mass spectrometry (HR-AMS) and UV–Vis spectroscopy were utilized to characterize the composition and the light absorptivity of the aqSOA and to track their changes during aging. Compared to •OH-aqSOA, the 3C∗-aqSOA is produced more rapidly and shows less oxidation, a greater abundance of oligomers, and higher light absorption. Prolonged photoaging promotes fragmentation and the formation of more volatile and less light-absorbing products. More than half of the initial aqSOA mass is lost, and substantial photobleaching occurs after 10.5 h of prolonged aging under simulated sunlight illumination for 3C∗-aqSOA and 48 h for •OH-aqSOA. By performing positive matrix factorization (PMF) analysis of the combined HR-AMS and UV–Vis spectral data, we resolved three generations of aqSOA with distinctly different chemical and optical properties. The first-generation aqSOA shows significant oligomer formation and enhanced light absorption at 340–400 nm. The second-generation aqSOA is enriched in functionalized GA species and has the highest mass absorption coefficients in 300–500 nm, while the third-generation aqSOA contains more fragmented products and is the least light absorbing. These results suggest that intermediately aged phenolic aqSOA is more light absorbing than other generations, and that the light absorptivity of phenolic aqSOA results from a competition between brown carbon (BrC) formation and photobleaching, which is dependent on aging time. Although photoaging generally increases the oxidation of aqSOA, a slightly decreased O/C of the •OH-aqSOA is observed after 48 h of prolonged photoaging with additional •OH exposure. This is likely due to greater fragmentation and evaporation of highly oxidized compounds. Increased oxidant concentration accelerates the transformation of aqSOA and promotes the decay of BrC chromophores, leading to faster mass reduction and photobleaching. In addition, compared with •OH, photoaging by 3C∗ produces more low-volatility functionalized products, which counterbalances part of the aqSOA mass loss due to fragmentation and evaporation.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

Accurate and Efficient Prediction of p K w in Aqueous Electrolytes Using Local Electrostatic Potentials

The K w =10 -pK w in aqueous electrolytes exhibit significant variations as a function of ion concentration. This behavior is not well-described by the Pitzer model, particularly at high concentrations. Here, we provide a molecular interpretation of the concentration dependent trends in p K w and develop a new method that accurately predicts the dissociation constant based upon the local electrostatic potential of the water oxygen that is determined by its nearest neighbors. The method is computationally efficient, relying only upon sampling of the local configurations (via molecular dynamics) and a small set of experimentally measured p K w . It is extensible to a range of salt compositions and the molecular understanding of the local potentials provides new routes toward the development of electrolytes with tailored physicochemical properties like p K w .

anions↗
DOE OSTI2020

Cellular and extracellular C contributions to respiration after wetting dry soil

Wetting of dry soil triggers a pulse of microbial respiration that has been attributed to two broad mechanisms: (1) recycling of microbial cellular carbon (C), and (2) consumption of extracellular organic C made available to microbes by wetting. We evaluated these two mechanisms by measuring cumulative CO 2 release, changes in the size and chemical composition of microbial biomass, and water-extractable organic carbon (WEOC) concentrations following artificial wetting of soil sampled from two depths at each of seven sites across California spanning a range of geologic parent materials. In samples collected from surface soil (0–10 cm depth), we found that cumulative CO 2 release after wetting in the laboratory was most strongly correlated with microbial biomass. In these samples, the relative abundance of trehalose—a putative microbial osmolyte—decreased from 25% (SD = 12) to 16% (SD = 7) of the chloroform-labile fraction of the microbial biomass after wetting. This suggested a role for osmolyte consumption in generating the respiration pulse. In subsoil (40–50 cm depth, or sampled at contact with rock), however, the cumulative CO2 release after wetting was unrelated to microbial biomass and more strongly related to WEOC. The concentrations of selected microbial biomass constituents (e.g. trehalose and amino acids) in WEOC were negligible (< 1%), suggesting that cell lysis was not important in generating WEOC in this study. The amount of WEOC relative to total organic C was greatest in subsoil, and negatively related to ammonium oxalate-extractable Fe (Pearson’s R = 0.42, p < 0.01), suggesting a role for soil mineralogical properties in controlling WEOC release. Together, these findings suggest that microbial cellular C and extracellular C jointly contribute to the respiration pulse, and that their relative contribution depends on depth.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Thermophysical properties and reversible phase transitions in yttrium hydride

In this study, the thermophysical properties of yttrium hydrides were investigated as a function of temperature (room temperature [RT] to 700°C) and hydrogen concentration (H/Y ratio ranges from 1.52 to 1.93). The results indicate that at the temperatures below 300°C, the hydrogen content did not have a significant influence on the thermal expansion, while the specific heat capacity, the thermal diffusivity, and the calculated thermal conductivity were slightly higher for the larger H/Y ratio. Between 300°C and 700°C, a reversible second-order endothermic transition in all measured thermal properties was observed. It was also found that the onset temperatures of the observed transition varied, with the composition having inverse dependence on the hydrogen content. The phase transition from ( α - Y + δ -YH x ) mixed phase to the δ -YH x single phase was excluded from the main contributors to the observed transition. An attempt was made to explain the behavior of the thermophysical properties at higher temperatures by considering the order–disorder transition as a result of hydrogen redistribution.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Investigation of γ - ( U , Z r ) structural properties and its interfacial properties with liquid sodium using ab initio molecular dynamics

In this study, the elastic properties, structural parameters, sound velocity, and Debye temperature of γ–(U,Zr) were computed using ab initio molecular dynamics (AIMD) at temperatures between 1000 K and 1400 K and for Zr content between 0 at. % and 100 at. %. UZr is used as a metallic fuel for Sodium Fast Reactors (SFRs). The study of the mechanical and thermal behavior of these alloys leads to a better data-informed fuel design. The bulk modulus, shear modulus, Young's modulus, and Poisson's ratio were calculated from the elastic constants and their dependence on Zr content and temperature was investigated, comparing the results with previous computational work and the available experimental data in the literature. Interfacial properties between UZr (up to 32 at. % which typically exists in nuclear fuel) and liquid sodium are also of interest due to the presence of a sodium bond between the fuel and the cladding in metallic nuclear fuel. The interfacial energy between γ–(U,Zr) and liquid sodium, the surface tension of liquid sodium, and the work of adhesion were computed at different temperatures and Zr concentrations. It was demonstrated that γ–(U,Zr) is completely wetted by liquid sodium at all the investigated temperatures and Zr concentrations. Finally, this work provides the basis for the determination of interfacial resistances in SFRs and their implementation into heat transfer fuel performance simulations, which will be the subject of future work.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2026

A fresh perspective on the role of band bending, and related contributors, in light-driven production of electricity and chemicals

It is widely known that semiconductor-based solar energy conversion could power our planet. This is in part because high-quality semiconductor structures are unrivalled in their ability to separate photogenerated electrons and holes. One effective approach to achieving this photoinduced charge separation relies on a phenomenon known as “band bending”. But details to justify why band bending results in photoinduced charge separation are more complex than often appreciated. This underappreciation is an impediment to the rational, hypothesis-driven design of next-generation approaches to solar energy conversion. Herein we show, by means of derivations rooted in physical chemistry, that several phenomena – not just band bending – can facilitate photoinduced charge separation, and that each is influenced by nonequilibrium species concentration and a parameter, such as diffusion coefficient or rate coefficient, that introduces dynamics. To help visualize the impact of each phenomenon, we introduce plots that depict their contributions as free energy, force, flux, force constant, and rate. We reveal that spatial dopant distributions that define band bending are predictors of initial photogenerated species transport rates. But charge separation alone does not guarantee high-efficiency operation. A photogenerated change in energy that is freely available to do useful work is also essential, and is strongly dependent on semiconductor optical properties and reaction kinetics. Notably, this information reveals that specificity of interfacial chemical reactions – even when they are not preceded by charge separation elsewhere – can result in efficient solar energy conversion. We expect that this tutorial will guide researchers in their pursuit to uncover new mechanisms for light to perform useful work.

14 SOLAR ENERGY↗
DOE OSTI2020

Physical and Thermomechanical Properties of Yttrium Hydride from Large Scale Bulk Metal Hydriding Furnace

Given the superior thermal stability and highly attainable hydrogen density, yttrium hydride is an excellent high-temperature moderator material in advanced thermal neutron spectrum reactors that require small core volumes. Yttrium hydride has been selected as the moderator material for the Transformational Challenge Reactor, which was launched at Oak Ridge National Laboratory (ORNL) in 2019. However, fabrication of large-scale crack-free yttrium hydride is challenging and very limited efforts have been committed to the characterization of bulk yttrium hydride in response to the need to establish a complete database of the thermomechanical properties of YHx. In this report, the challenges associated with fabricating large-scale crack-free yttrium hydride are discussed herein. In response to those challenges, a hydriding system was designed and constructed at ORNL and was used to successfully fabricate crack-free yttrium hydride in complex geometries at large scales. This was accomplished by precisely controlling the hydrogen’s partial pressure and the retort temperature, which was informed by the well-established thermodynamic properties of the binary H-Y system. Hydrogen content in as-fabricated hydride was determined by the weight change method and vacuum hot extraction technique, complemented by the X-ray diffraction (XRD). In addition, significant efforts are being dedicated to establishing a complete database of the thermomechanical properties of as-fabricated yttrium hydride. In FY2020, we investigated the thermophysical properties of yttrium hydrides as a function of temperature (room temperature to 700°C) and hydrogen concentration (H/Y ratio ranges from 1.52 to 1.93). The results indicate that at the temperatures below 300 °C, the hydrogen content did not have a significant influence on the thermal expansion, while the specific heat capacity, the thermal diffusivity, and the calculated thermal conductivity were slightly higher for the higher H/Y ratio. Between 300°C and 700 °C, a reversible second-order endothermic transition in all measured thermal properties was observed. It was also found that the onset temperatures of the observed transition varied, with the composition having inverse dependence on the hydrogen content. An attempt was made to explain the behavior of the thermophysical properties at higher temperatures by considering the order– disorder transition as a result of hydrogen redistribution. In addition, nanoindentation was employed to determine the elastic modulus and hardness and to capture the crystal orientation dependence of these parameters. Vickers hardness was also reported. The final section of the report introduces ongoing neutron irradiation campaign of yttrium hydride.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2022

Watching Polarons Move in the Energy and Frequency Domains Using Color Impedance Spectroscopy

The hybrid electronic–ionic transport property of π-conjugated polymers enables new (opto)electrochemical device constructs for energy conversion and storage and biosensing applications. One major challenge is separating the energy and frequency dependence of Faradaic events–those involving charge transfer and the redox processes of the conjugated backbone–from the non-Faradaic components, such as ionic motion. Herein, we combine optical spectroscopy with electrochemical impedance spectroscopy (EIS) to resolve the frequency response of ionic–electronic coupling as a function of electrochemical doping potential. First, using EIS, we identify two different frequency regimes resulting in potential-dependent capacitive elements on the order of ~10 μF/cm 2 in a high-frequency regime and ~50–150 μF/cm 2 in a low-frequency regime. Given the larger magnitude and greater potential dependence, we posit that polaronic motion is more likely to occur at low frequencies (<1 kHz) and overlaps with ionic motion. The use of color impedance spectroscopy (CIS) enables observation of polaronic motion with frequency modulation. We observe that higher doping potentials show a greater motion of polarons above the DC-bias baseline concentration for onset in electrochemical doping, but all potentials considered demonstrate a critical frequency at which the polaronic motion is “frozen” (~40 Hz). Furthermore, this critical information obtained from CIS in highly dielectric environments offers a unique figure of merit for future studies on electronic–ionic coupling by which to compare across polymer/electrolyte interfaces, including the role of a charge-supporting electrolyte, a solvent, and alternative Faradaic processes (e.g., electrocatalysis).

36 MATERIALS SCIENCE↗