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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 181 records · Page 10
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Growth of PdCoO 2 films with controlled termination by molecular-beam epitaxy and determination of their electronic structure by angle-resolved photoemission spectroscopy

Utilizing the powerful combination of molecular-beam epitaxy (MBE) and angle-resolved photoemission spectroscopy (ARPES), we produce and study the effect of different terminating layers on the electronic structure of the metallic delafossite PdCoO 2 . Attempts to introduce unpaired electrons and synthesize new antiferromagnetic metals akin to the isostructural compound PdCrO 2 have been made by replacing cobalt with iron in PdCoO 2 films grown by MBE. Using ARPES, we observe similar bulk bands in these PdCoO 2 films with Pd-, CoO 2 -, and FeO 2 -termination. Nevertheless, Pd- and CoO 2 -terminated films show a reduced intensity of surface states. Additionally, we are able to epitaxially stabilize PdFe x Co 1– x O 2 films that show an anomaly in the derivative of the electrical resistance with respect to temperature at 20 K, but do not display pronounced magnetic order.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Rapid Screening of Liquid Metal Wetting for a Materials Compatibility Library

Wetting behavior of molten metals on solid substrates is a critical phenomenon influencing numerous industrial applications, including welding, anti-corrosion coatings, and metal additive manufacturing (AM). In particular, molten metal jetting (MMJ), an emerging AM technology, requires that the molten metal remain pinned at the nozzle exit. Thus, each new metal requires a specific nozzle material to ensure consistent droplet ejection and deposition, making it important to rapidly identify the appropriate wetting combinations. However, traditional measurements of wetting angles require expensive equipment and only allow one combination of materials to be investigated at a time which can be time consuming. This work introduces a rapid screening method based on sessile droplet experiments to evaluate wetting profiles across multiple metal–substrate combinations simultaneously. This study investigates the wetting interactions of molten Al alloy (Al4008), Cu, and Sn on various ceramic and metal substrates to identify optimal material combinations for MMJ nozzle designs. Results demonstrate that Al4008 achieves wetting on ceramic substrates such as AlN, TiO 2 , and SiC, with varying mechanisms including chemical reactions and weak surface interactions. Additionally, theoretical predictions regarding miscibility gaps and melting point differences were verified for Cu and Sn on refractory metals like Mo and W. Findings from this study contribute to the establishment of a materials compatibility library, enabling the selection of wetting/non-wetting combinations for stable MMJ operation. This resource not only advances MMJ technologies but also provides valuable insights for broader applications such as welding, coating, and printed electronics.

Materials science↗
DOE OSTI2022

Toward a more realistic representation of surface albedo in NASA CERES-derived surface radiative fluxes

Accurate multidecadal radiative flux records are vital to understand Arctic amplification and constrain climate model uncertainties. Uncertainty in the NASA Clouds and the Earth’s Radiant Energy System (CERES)-derived irradiances is larger over sea ice than any other surface type and comes from several sources. The year-long Multidisciplinary drifting Observatory for the Study of Arctic Climate (MOSAiC) expedition in the central Arctic provides a rare opportunity to explore uncertainty in CERES-derived radiative fluxes. First, a systematic and statistically robust assessment of surface shortwave and longwave fluxes was conducted using in situ measurements from MOSAiC flux stations. The CERES Synoptic 1degree (SYN1deg) product overestimates the downwelling shortwave flux by +11.40 Wm –2 and underestimates the upwelling shortwave flux by –15.70 Wm –2 and downwelling longwave fluxes by –12.58 Wm –2 at the surface during summer. In addition, large differences are found in the upwelling longwave flux when the surface approaches the melting point (approximately 0°C). The biases in downwelling shortwave and longwave fluxes suggest that the atmosphere represented in CERES is too optically thin. The large negative bias in upwelling shortwave flux can be attributed in large part to lower surface albedo (–0.15) in satellite footprint relative to surface sensors. Additionally, the results show that the spectral surface albedo used in SYN1deg overestimates albedo in visible and mid-infrared bands. A series of radiative transfer model perturbation experiments are performed to quantify the factors contributing to the differences. The CERES-MOSAiC broadband albedo differences (approximately 20 Wm –2 ) explain a larger portion of the upwelling shortwave flux difference than the spectral albedo shape differences (approximately 3 Wm –2 ). In addition, the differences between perturbation experiments using hourly and monthly MOSAiC surface albedo suggest that approximately 25% of the sea ice surface albedo variability is explained by factors not correlated with daily sea ice concentration variability. Biases in net shortwave and longwave flux can be reduced to less than half by adjusting both albedo and cloud inputs toward observed values. The results indicate that improvements in the surface albedo and cloud data would substantially reduce the uncertainty in the Arctic surface radiation budget derived from CERES data products.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Molecular Functionalization of Semiconductor Surfaces

The presence of molecules on semiconductor surfaces can have a profound impact on their properties and applications in solar energy conversion. In this chapter we discuss the methods used to effect functionalization of semiconductor surfaces with molecular dipoles and catalysts. A major focus is the energetic impacts such molecules have to the fields at the semiconductor|contact interface. These field modulations are strongly dependent on the nature of the surface-bound molecule including its dipole moment and orientation as well as the distance of the dipole from the semiconductor surface. The contacting phase also has a strong impact on the energetics, since ions in the liquid electrolytes relevant to inorganic photochemistry partially screen dipolar effects at the surface. In addition to detailed description of these fundamentals, we present the history of this field as well as state-of-the-art chemistries that leverage the preceding decades of knowledge to impart the molecular interfacial layer with dynamic properties such as light absorption and catalysis. The challenges of establishing stable molecular attachment schemes at semiconductor|electrolyte interfaces are interwoven throughout the chapter. We conclude with a prognosis and future outlook that we hope will be a useful guide to those interested in developing the next generation of molecular chemistries at photoelectrode interfaces.

CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS,I↗
DOE OSTI2026

Modulating Mid-Gap Electronic States Through Site-Selective Modification in B-Pbx/B'-CuyV2O5/CdS Heterostructures for Photocatalytic Hydrogen Evolution

We interfaced ..beta..-Pbx/..beta..'-CuyV2O5 compounds, with varying stoichiometries of precisely positioned Pb-ions (x) and Cu-ions (y) in interstitial sites along a tunnel-structured ?-V2O5 framework, with cysteine-capped CdS (cysCdS) quantum dots (QDs) to yield heterostructured photocatalysts. ..beta..-Pbx/..beta..'-CuyV2O5 compounds exhibit midgap electronic states with orbital contributions from both Cu 3d and stereochemically active Pb 6s states that show distinctive light-initiated reactivity with photoexcited QDs. ..beta..-Pbx/..beta..'-CuyV2O5/CdS heterostructures were prepared by linker-assisted assembly (LAA). Scanning and transmission electron microscopy, energy-dispersive X-ray spectroscopy, and Raman spectroscopy revealed that cysCdS QDs were deposited onto surfaces of ..beta..-Pbx/..beta..'-CuyV2O5 via LAA. HAXPES revealed that the site-selective positioning of Pb-ions and Cu-ions promoted close energetic alignment of the midgap states of ..beta..-Pbx/..beta..'-CuyV2O5 compounds with the valence-band maximum of cysCdS QDs. Transient absorption spectroscopy revealed that photogenerated holes were transferred from CdS QDs to midgap states of ..beta..-Pbx/..beta..'-CuyV2O5 compounds on time scales <50 ps. Finally, photoelectrochemical and photochemical experiments revealed that ..beta..-Pbx/..beta..'-CuyV2O5/CdS heterostructures promoted the photocatalytic reduction of H+ to H2. In photoelectrochemical experiments, under oxidative conditions, for all ..beta..-Pbx/..beta..'-CuyV2O5/CdS heterostructures, H2 was evolved at a Pt counter electrode while a sacrificial donor was oxidized at the heterostructure-functionalized working electrode. In contrast, under reductive conditions, for ..beta..-Pb0.152V2O5/CdS and ..beta..-Pbx/..beta..'-CuyV2O5/CdS heterostructures, H2 was evolved at the working electrode. In photochemical experiments, dispersed ..beta..-Pbx/..beta..'-CuyV2O5/CdS heterostructures promoted the reduction of H+ to H2 under white-light illumination; ..beta..'-Cu0.55V2O5/CdS and ..beta..-Pbx/..beta..'-CuyV2O5/CdS heterostructures, for which midgap states have Cu 3d orbital character, generated 2-fold more H2 than ..beta..-Pb0.152V2O5/CdS heterostructures. Cu-ion insertion thus appends additional acceptor surface states that improve ligand-mediated hole transfer from photoexcited QDs, but such states are intrinsically limited in mediating hole transport to the substrate as a result of the low mobility of holes in narrow Cu 3d-states. Our results reveal that the density and orbital character of midgap states of ..beta..-Pbx/..beta..'-CuyV2O5 compounds, tunable through recently developed site-selective ion insertion strategies, determine efficiencies of charge-transfer and charge-transport mechanisms that underpin photocatalysis.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Understanding Photovoltage Deficits in Electrochemically Grown Tin Sulfide (SnS) Thin-Film Photovoltaic Devices

Tin­(II) sulfide (SnS) is an earth-abundant semiconductor with a direct optical bandgap of ca. 1.1 eV, which makes it a promising absorber material for thin-film photovoltaic (PV) devices. However, existing devices have significant photovoltage deficits, which may be related to the anisotropic structure of the layered Herzenbergite SnS crystal structure. Here, we explore electrochemical deposition as a near room temperature path to oriented SnS crystal films on Mo and FTO substrates and employ vibrating Kelvin probe surface photovoltage (SPV) spectroscopy and J–V measurements to identify conversion losses in them. According to grazing-incidence X-ray diffraction and SEM, the SnS films consist of crystalline microplates with preferred orientation in the [111] and [001] directions. The bare SnS films produce only small and irreversible surface photovoltage signals, due charge trapping and recombination at the SnS surfaces, but addition of a CdS buffer layer lowers the charge recombination rate by 2 orders of magnitude and increases both the photovoltage and its reversibility due to the formation of a p-SnS/n-CdS junction. According to SPV, the FTO/SnS back interface (but not the Mo/SnS interface) forms a detrimental p–n junction that hinders hole transfer. Additional shunting through the relatively open microcrystal SnS layers and a lower conductivity of the FTO substrate explain the low power conversion efficiencies of the final devices (0.18 and 0.10% for the Mo and FTO substrates). Altogether, this work establishes a low-temperature path for the fabrication of crystalline SnS film-based solar cells and identifies the bottlenecks that limit high photoconversion efficiency.

deposition↗
DOE OSTI2020

Structural integrity of additively manufactured stainless steel with cold sprayed barrier coating under combined cyclic loading

Integration of metal additive manufacturing (AM) and cold spray (CS) technologies provide an unprecedented opportunity to manufacture coated material systems with complex geometrical features. The application of these material systems in functionally critical components requires adequate structural integrity, particularly in the presence of cyclic loading. This article researches the multiaxial fatigue (axial-torsional cyclic loading) behavior of a coated material system consisting of 15Cr-5Ni precipitation-hardening stainless steel (15-5 PH SS) substrate additively manufactured by direct metal laser sintering with a layer of chromium carbide nickel (CrC-Ni) barrier coating deposited by CS. The influence of AM and CS-induced residual stresses on fatigue performance of test specimens was thoroughly studied. Additionally, the effect of surface roughness and processes induced defects were considered to explain the crack growth mechanism. Stresses assessed by synchrotron X-ray diffraction indicated a substantial accumulation of residual stresses, particularly in the outer surface of the as-fabricated 155 PH SS specimens. The state of residual stress was changed notably following the deposition of CrC-Ni coating in the axial, hoop, and radial directions of the fatigue test specimen. Also, CS deposition of CrC-Ni coating caused significant improvement in the surface quality of the additively manufactured components. Fatigue test results indicated, CS deposition of CrC-Ni substantially enhances the fatigue life of the AM-produced 15-5 PH SS substrate in all loading conditions, particularly in the high cycle fatigue regime. The improvement in the fatigue life of the specimens with coating was associated with a reduction in equivalent residual stress at the substrate surface and improvement in the specimens' surface condition (i.e., reduced surface roughness). The fractographic analysis of the specimen indicated the cracks tend to initiate in the surface of both as-fabricated and cold-sprayed specimens. However, the mechanism of crack growth changed notably following the deposition of CrC-Ni coating. The cracks tended to propagate in the planes parallel or with a small deviation from the build layers of the AM-produced specimens. On the other hand, deposition of CrC-Ni coating increased the deviation of crack growth plane from the build layers of the substrate.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Evaluating the stability and activity of dilute Cu-based alloys for electrochemical CO 2 reduction

Cu-based catalysts currently offer the most promising route to actively and selectively produce value-added chemicals via electrochemical reduction of CO 2 (eCO 2 R); yet further improvements are required for their wide-scale deployment in carbon mitigation efforts. Here, we systematically investigate a family of dilute Cu-based alloys to explore their viability as active and selective catalysts for eCO 2 R through a combined theoretical–experimental approach. Using a quantum–classical modeling approach that accounts for dynamic solvation effects, we assess the stability and activity of model single-atom catalysts under eCO 2 R conditions. Our calculations identify that the presence of eCO2R intermediates, such as CO*, H*, and OH*, may dynamically influence the local catalyst surface composition. Additionally, we identify through binding energy descriptors of the CO*, CHO*, and OCCO* dimer intermediates that certain elements, such as group 13 elements (B, Al, and Ga), enhance the selectivity of C 2+ species relative to pure Cu by facilitating CO dimerization. The theoretical work is corroborated by preliminary testing of eCO 2 R activity and selectivity of candidate dilute Cu-based alloy catalyst films prepared by electron beam evaporation in a zero-gap gas diffusion electrode-based reactor. Of all studied alloys, dilute CuAl was found to be the most active and selective toward C 2+ products like ethylene, consistent with the theoretical predictions. Finally, we attribute the improved performance of dilute CuAl alloys to more favorable dimerization reaction energetics of bound CO species relative to that on pure Cu. In a broader context, the results presented here demonstrate the power of our simulation framework in terms of rational catalyst design.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2026

Operational stability of mixed Sn–Pb perovskite solar cells: Mechanisms, mitigation strategies, and perspectives

Mixed Sn–Pb perovskites provide the 1.2–1.3 eV narrow-bandgap absorber needed for high efficiency of all perovskite tandems, but their deployment is limited by operational instability under light. This review synthesizes mechanistic origins and recent mitigation strategies for mixed Sn–Pb perovskite solar cells. The oxidation of Sn 2+ to Sn 4+ , often driven by iodine formation under light and bias, is the primary failure pathway; it creates Sn vacancies, self-doping, and nonradiative loss. Surface/grain-boundary defects, halide migration, reactive oxygen species, and interfacial redox at charge-transport layers, along with hole accumulation from poor band alignment, further accelerate Sn–Pb perovskite degradation. Here we survey recent stability advances across additive chemistry, surface and grain-boundary passivation, buried-interface redesign with modified or alternative hole transport layers, and solvent systems that preserve Sn 2+ and correct Sn–Pb speciation for scalable coating. Together, these recent advances have enabled devices to retain 80%–90% output for hundreds to over a thousand hours. Lastly, we provide our perspectives on further improving the operational stability of Sn–Pb perovskite and solar cells.

14 SOLAR ENERGY↗
DOE OSTI2020

Intensive agricultural management‐induced subsurface accumulation of labile phosphorus in Midwestern agricultural soils dominated by tile lines

Abstract In addition to surface runoff, subsurface P loss through tile lines in agricultural lands has received attention over the last decade. It is not clearly understood how this strong ligand, phosphate, is distributed in subsoils (≤180 cm), contributing to subsurface P loss. We hypothesized that subsurface accumulation of labile P as a result of long‐term intensive agricultural management contributes to subsurface P loss. The depth sequence distribution of P and its speciation and reactivity were investigated in tile‐line‐dominated Midwestern agricultural fields via chemical extraction and digestion, batch desorption experiments, and X‐ray absorption near‐edge structure spectroscopy. The results suggest that labile P in subsoils exceeds the eutrophication‐inducing level (>0.01 mg L –1 ). Because of intensive agricultural management, total P was ∼400 mg kg –1 in surface soils and ∼200‐300 mg kg –1 in subsoils. The depth sequence distribution of P indicated the translocation of P to subsoils. Although phosphate and phytic acid adsorbed by Al or Fe (oxyhydro)oxides and calcite were found in surface soils, phosphate adsorbed to calcite, hydroxyapatite, or both were the dominant P species in subsoils. Phosphate was highest in surface soils and decreased sharply with increasing depth. Slightly alkaline soil in subsoils suppressed the release of P but the process was continuous after 30 d. Subsurface P loss was influenced by the dissolution and desorption process of inorganic P phases and preferentially transported P from surface soils. Subsurface P loss should be considered in strategies to reduce agricultural P loss in the Gulf of Mexico.

Xu, Suwei↗
DOE OSTI2022

Effect of Topology on Transient Dynamic and Shock Response of Polymeric Lattice Structures

Architected cellular materials, such as lattice structures, offer potential for tunable mechanical properties for dynamic applications of energy absorption and impact mitigation. In this work, the static and dynamic behavior of polymeric lattice structures was investigated through experiments on octet-truss, Kelvin, and cubic topologies with relative densities around 8%. Here, dynamic testing was conducted via direct impact experiments (25–70 m/s) with high-speed imaging coupled with digital image correlation and a polycarbonate Hopkinson pressure bar. Mechanical properties such as elastic wave speed, deformation modes, failure properties, particle velocities, and stress histories were extracted from experimental results. At low impact velocities, a transient dynamic response was observed which was composed of a compaction front initiating at the impact surface and additional deformation bands whose characteristics matched low strain-rate behavior. For higher impact velocities, shock analysis was carried out using compaction wave velocity and Eulerian Rankine–Hugoniot jump conditions with parameters determined from full-field measurements.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Assessing the fidelity of shallow-water carbonates as records of the Ni isotope composition of surface seawater

Nickel is a bioessential metal that is used in enzymes important to the C, N, and O cycles, and changes in its marine abundance and bioavailability may have affected the evolutionary trajectory of early life. Changes over time in the Ni isotope composition (δ 60 Ni) of surface seawater, which reflects biological demand for Ni, could allow for the reconstruction of the dynamics of Ni demand over Earth’s history, but this approach would require geologic records of surface seawater. Here, we investigate the fidelity of shallow-water carbonates as a record of the Ni isotope composition of surface seawater by determining how Ni is first partitioned into natural carbonates and then how post-depositional processes influence the Ni signal. Our samples come from the Great Bahama Bank, which is a well-studied, modern carbonate platform often used to study ancient platforms. We found that Ni is fractionated from seawater upon incorporation into carbonates capturing shallow (<18 cm), recent deposition (0.1 ‰–0.4 ‰ lighter than seawater). Variation among these [Ni] and δ 60 Ni values may be controlled by variation in mineral proportions. Meteoric diagenesis shifts δ 60 Ni to lower values, which we attribute to isotopically light meteoric fluids. In contrast, carbonates that experienced sediment-buffered marine diagenesis with respect to Ca isotopes and Sr/Ca ratios do not appear to differ in δ 60 Ni values from sediments generally representative of their initial deposition. The sensitivity of δ 60 Ni to diagenetic reset in these samples appears comparable to the sensitivities of Ca isotopes and Sr/Ca ratios, to first order. Thus, in general, carbonates that experienced sediment-buffered marine diagenesis with respect to these elements may hold the most promise as a record of the δ 60 Ni of coeval surface seawater. Additionally, we use our results to infer that the fraction of Ni removed from seawater into carbonates is less than 10 % of the total Ni output from the global oceans and incorporation of this Ni sink into global biogeochemical models will only have a minor impact on the modeled modern Ni budget.

Great Bahama Bank carbonates↗
DOE OSTI2024

Porosity in Sr 1-x Ca x FeO 3-δ oxygen carriers: The role of surface area and pretreatment on storage activity

Perovskite oxides have generated interest as robust, low-temperature oxygen carrier materials for a variety of clean energy applications, including chemical looping gasification and air separations. Methods to improve O 2 desorption kinetics are vital to allow these carriers to compete economically with traditional metal oxide carriers or cryogenic separations. In this report we investigated the cumulative roles that surface area, pretreatment, and elemental composition have on the oxygen storage properties of a state-of-the-art carrier system, Sr 1-x Ca x FeO 3-δ (x = 0.20, 0.25, 0.30) synthesized using multiple methods. Porous materials synthesized by the Pechini, or citrate, method had their surface area controlled using the synthesis temperature. The high surface area of the Sr 0.7 Ca 0.3 FeO 3-δ materials is most beneficial at low operating temperatures, such as 350 and 400 °C, as their reduction rates are twice as fast as those obtained with their bulk counterparts. These effects are observed at higher operating temperatures and within a single composition, but temperature tunability using variable Ca 2+ substitution in the Sr 1-x Ca x FeO 3-δ overshadows the improvements gained from higher surface areas. Additionally, we establish that pretreatment in N2 at an elevated temperature is necessary to enhance kinetics further. For maximum efficiency, pretreatment at the synthesis temperature is suggested for the Pechini method-synthesized systems, whereas 800 °C is adequate for bulk materials.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Hairy nanoparticles by atom transfer radical polymerization in miniemulsion

Polymer nanoparticles with various architectures and functionalities are promising materials in numerous fields. Miniemulsion polymerization is one of the suitable pathways to prepare polymer nanoparticles since each droplet could act as a “nanoreactor”. A “smart” atom transfer radical polymerization (ATRP) catalytic system comprising Cu-TPMA/DS – (TPMA = tris(2-pyridylmethyl)amine, DS – = dodecyl sulfate anion) ion pair catalyst was efficiently applied in miniemulsion ATRP at low catalyst concentrations. Herein, hairy nanoparticles consisting of hydrophobic poly(n-butyl methacrylate) (P(BMA/EGDMA), EGDMA = ethylene glycol dimethacrylate) network “core” and hydrophilic oligo(ethylene oxide) methyl ether methacrylate (OEOMA) chains as “hair” were prepared by miniemulsion ATRP and a successive chain extension by aqueous ATRP from the particle surface. The addition of an inimer, 2-(α-bromoisobutyryloxy)ethyl methacrylate (HEMA-iBBr) to the P(BMA/EGDMA) network introduced more ATRP initiation sites for ATRP of OEOMA, enabling adjustment of the particle size from >400 nm to <150 nm. The miniemulsion system remained stable after the one pot synthesis of P(BMA/EGDMA)-g-POEOMA and P(BMA/EGDMA/HEMA-iBBr)-g-POEOMA, and the resulting polymer nanoparticles were re-dispersed in water for further modification. A zwitterionic monomer, [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide (SBMA), was grafted from P(BMA/EGDMA/HEMA-iBBr)-g-POEOMA. The resulting hairy nanoparticles provide an avenue for the design and preparation of novel nanostructured materials.

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

Wear penalty for steel rubbing against hard coatings in reactive lubricants due to tribochemical interactions

Hard coatings and surface adsorptive/reactive lubricants are two common strategies for improving wear protection, but what if they are used together? In this study, steel-steel and steel-coating sliding was investigated in boundary lubrication of polar and non-polar oils containing a ZDDP or an ionic liquid. Two hard coatings, diamond-like-carbon (DLC) and chromium nitride (CrN), were used. Furthermore, for a steel-steel contact, wear was effectively reduced by using a more surface reactive lubricant, as expected. However, the steel ball wear was increased against a hard coating and further worsened with a more polar oil and/or a more surface reactive additive. The wear mechanism is proposed as a combined effect of physicochemical interactions with the lubricant, mechanical polishing by the counterface, and material adhesion.

36 MATERIALS SCIENCE↗
DOE OSTI2023

A semi-continuous process for co-production of CO 2 -free hydrogen and carbon nanotubes via methane pyrolysis

Heterogeneous catalytic pyrolysis of hydrocarbons to produce CO 2 -free hydrogen and high-quality solid carbon have historically been stymied by issues related to catalyst deactivation by carbon formed during pyrolysis on the catalyst surface. In addition, a system that demonstrates sustained performance in terms of high conversion, high H 2 yield, and high quality of produced carbon has remained elusive. Here, we propose and demonstrate a semi-continuous methane pyrolysis process to H 2 and carbon nanotubes (CNTs) consisting of repeated pyrolysis and in situ (i.e., within the reactor) CNT dislodging by vigorous steam/argon fluidization. With this process, we demonstrate 10 process cycles with high H 2 yield from CH 4 and CNT dislodging in a fluidized-bed reactor with an Fe/q-Al 2 O 3 catalyst synthesized by an easily scalable incipient wetness impregnation process. We also identify and present opportunities for future catalyst and process development.

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

Are Contact Angle Measurements Useful for Oxide-Coated Liquid Metals?

This work establishes that static contact angles for gallium-based liquid metals have no utility despite the continued and common use of such angles in the literature. In the presence of oxygen, these metals rapidly form a thin (~1–3 nm) surface oxide “skin” that adheres to many surfaces and mechanically impedes its flow. This property is problematic for contact angle measurements, which presume the ability of liquids to flow freely to adopt shapes that minimize the interfacial energy. We show here that advancing angles for a metal are always high (>140°)—even on substrates to which it adheres—because the solid native oxide must rupture in tension to advance the contact line. The advancing angle for the metal depends subtly on the substrate surface chemistry but does not vary strongly with hydrophobicity of the substrate. During receding measurements, the metal droplet initially sags as the liquid withdraws from the “sac” formed by the skin and thus the contact area with the substrate initially increases despite its volumetric recession. Furthermore, the oxide pins at the perimeter of the deflated “sac” on all the surfaces are tested, except for certain rough surfaces. With additional withdrawal of the liquid metal, the pinned angle gets smaller until eventually the oxide “sac” collapses. Thus, static contact angles can be manipulated mechanically from 0° to >140° due to hysteresis and are therefore uninformative. We also provide recommendations and best practices for wetting experiments, which may find use in applications that use these alloys such as soft electronics, composites, and microfluidics.

36 MATERIALS SCIENCE↗