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At least 1,189 records · Page 66

Characterizing Ocean Acidification and Atmospheric Emission caused by Methane Released from Gas Hydrate Systems along the US Atlantic Margin (Final Report)

To assess the environmental impact of decomposing gas hydrates, this project characterized the atmospheric emission and ocean acidification associated with seafloor-released methane along the U.S. Atlantic Margin. This project leveraged the newly discovered seafloor seeps in this region, many of which are located near the landward limit of gas hydrate stability, to investigate the fate and environmental impact of methane once released from the seafloor. Several research directions were pursued during these investigations. First, high-spatial resolution surface surveys were conducted to characterize the degree to which sea-to-air emission of methane is correlated with acoustically detected seafloor bubble emissions. Second, the natural isotopic signatures of both radiocarbon and δ 13 C were measured throughout the water column to observe if seafloor-released methane was detected in surface waters or if it was replaced by a different source. Third, the extent of methane oxidation in the water column was constrained to assess the ability of this process to mitigate atmospheric methane emissions. Fourth, since aerobic methane oxidation ultimately converts methane to carbon dioxide, the extent of ocean acidification relating to this process was assessed. Ultimately, this project was conducted in four stages. Stage one involved preparations for the research expedition along the U.S. Atlantic Margin. This involved calibrating, modifying, and validating equipment needed for sample and data collection in this unique environment. Stage two involved executing the at-sea science. This research was conducted from 25 August to 5 September 2017 on the R/V Hugh R. Sharp. This expedition left from Lewes, Delaware and investigated the continental slope from approximately this latitude down to Cape Hatteras, North Carolina. Third, any samples unanalyzed on the research vessel were returned to the laboratory and measured. Fourth, the data were interpreted, and publications and presentations were prepared.

03 NATURAL GAS↗

Interfacial phonon scattering and transmission loss in > 1 µm thick silicon-on-insulator thin films

Scattering of phonons at boundaries of a crystal (grains, surfaces, or solid/solid interfaces) is characterized by the phonon wavelength, the angle of incidence, and the interface roughness, as historically evaluated using a specularity parameter p formulated by Ziman [Electrons and Phonons (Clarendon Press, Oxford, 1960)]. This parameter was initially defined to determine the probability of a phonon specularly reflecting or diffusely scattering from the rough surface of a material. The validity of Ziman's theory as extended to solid/solid interfaces has not been previously validated. Here, to better understand the interfacial scattering of phonons and to test the validity of Ziman's theory, we precisely measured the in-plane thermal conductivity of a series of Si films in silicon-on-insulator (SOI) wafers by time-domain thermoreflectance (TDTR) for a Si film thickness range of 1–10 μm and a temperature range of 100–300 K. The Si/SiO 2 interface roughness was determined to be 0.11±0.04nm using transmission electron microscopy (TEM). Furthermore, we compared our in-plane thermal conductivity measurements to theoretical calculations that combine first-principles phonon transport with Ziman's theory. Calculations using Ziman's specularity parameter significantly overestimate values from the TDTR measurements. We attribute this discrepancy to phonon transmission through the solid/solid interface into the substrate, which is not accounted for by Ziman's theory for surfaces. The phonons that are specularly transmitted into an amorphous layer will be sufficiently randomized by the time they come back to the crystalline Si layer, the effect of which is practically equivalent to a diffuse reflection at the interface. Finally, we derive a simple expression for the specularity parameter at solid/amorphous interfaces and achieve good agreement between calculations and measurement values.

36 MATERIALS SCIENCE↗

Surface heterogeneity propagation and homogenization for pouch cell-scale Li metal anodes

Li metal anode is a promising candidate for next-generation energy storage systems and is widely explored in Li-ion and solid-state batteries. Despite its potential, Li metal anodes face instabilities during long-term cycling, especially when paired with NMC or sulfur-based cathodes, where Li is cycled at high capacities of 6-8 mAh/cm2, equivalent to a thickness of 30-40 µm. During such extensive utilization, degradation mechanisms such as excessive solid electrolyte interphase (SEI), dendrites, and dead Li emerge, and ultimately lead to sudden failure and reduced cycle life. The origin of the degradation mechanisms stem from surface heterogeneities introduced during Li foil manufacturing and storage [1, 2]. As cycling progresses, the local heterogeneities propagate, resulting in uneven Li utilization and degradation-prone regions across the electrode [3], which consequently induce performance variations at the cell level. This heterogeneity propagation is particularly pronounced in large-format pouch cells in practical applications, where the surface effects are magnified. Without a clear understanding of the multi-scale heterogeneities and the development of surface homogenization methods, the performance consistency will be compromised, hindering the commercialization of Li metal batteries. In this presentation, we investigate the evolution of surface heterogeneity propagation on commercially available Li foils. We discover that inhomogeneous Li utilization appears as early as the first half-cycle of formation, manifesting as localized clusters and pits. In pouch cell configurations, these features exhibit areal density variations across the electrode on a scale of millimeters. To improve Li utilization homogeneity, a scalable mechanical brushing method is introduced to remove the chemically heterogeneous surface passivation layer. Furtherore, the influence of utilization homogeneity on cell-to-cell consistency is evaluated using 32 Li-NMC811 pouch cells divided into as-received and brushed Li groups. On the brushed Li, clusters and pits are no longer observable, and the cells exhibit significantly improved consistency in discharge capacity trajectories and cycle lifetime. Overall, this study highlights the role of Li surface utilization homogeneity on long-term cycling performance. Our research provides a pathway for improving large-area electrode uniformity and establishing evaluation methods for cell-to-cell consistency, both are key steps toward the commercialization of Li metal batteries and beyond. [1] Otto, Svenja-K., et al. "In-depth characterization of lithium-metal surfaces with XPS and ToF-SIMS: toward better understanding of the passivation layer." Chemistry of Materials 33.3 (2021): 859-867. [2] Hatzell, Kelsey, et al. "Aligning lithium metal battery research and development across academia and industry." Joule (2024). [3] Kim, Sangwook, et al. "Calendar life of lithium metal batteries: Accelerated aging and failure analysis." Energy Storage Materials 65 (2024): 103147.

25 - ENERGY STORAGE↗

Behavior of the Ru-bda water oxidation catalyst covalently anchored on glassy carbon electrodes

Electrochemical reduction of the dizaonium complex, [Ru II (bda)(NO)(N–N 2 ) 2 ] 3+ , 2 3+ (N–N 2 2+ is 4-(pyridin-4-yl) benzenediazonium and bda 2– is [2,2'-bipyridine]-6,6'-dicarboxylate), in acetone produces the covalent grafting of this molecular complex onto glassy carbon (GC) electrodes. Multiple cycling voltammetric experiments on the GC electrode generates hybrid materials labeled as GC-4, with the corresponding Ru-aqua complex anchored on the graphite surface. GC-4 has been characterized at pH = 7.0 by electrochemical techniques and X-ray absorption spectroscopy (XAS) and has been shown to act as an active catalyst for the oxidation of water to dioxygen. This new hybrid material has a lower catalytic performance than its counterpart in homogeneous phase and progressively decomposes to form RuO 2 at the electrode surface. The resulting metal oxide attached at the GC electrode surface, GC-RuO 2 , is a very fast and rugged heterogeneous water oxidation catalyst with TOF i s of 300 s –1 and TONs >45000. The observed performance is comparable to the best electrocatalysts reported so far, at neutral pH.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Galvanic corrosion of AZ31B joined to dual-phase steel with and without Zn layer by ultrasonic and friction stir welding

Galvanic corrosion of AZ31B joined with bare or Zn-coated DP590 steel by ultrasonic spot welding or linear friction stir welding was quantitatively studied by pre-defining anode and cathode in the lap joint samples. Corrosion volume and depth from Mg anode surfaces exposed to 0.1 M sodium chloride solution was analyzed as functions of cathode surface type and welding method. Characterization of as-welded joints was performed to identify any microstructural feature of the bonding zone that could impact galvanic corrosion behavior. COMSOL modeling with modified user subroutine was conducted to simulate the progression of Mg corrosion in the same joint and electrode configurations used for the corrosion experiments. The experimental results indicated that Zn-coated cathode surface can reduce Mg galvanic corrosion significantly as galvanic polarization and cathodic current on Zn-coated surface remained relatively low for Mg in the weld joints. COMSOL modeling described the growth of Mg galvanic corrosion in a reasonable manner but showed limitation by underestimating the corrosion volume as it did not capture self-corrosion.

36 MATERIALS SCIENCE↗

Dealloying, Microstructure and the Corrosion/Protection of Cast Magnesium Alloys

The purpose of this project was to develop a greater understanding of micro-galvanic corrosion effects in cast magnesium alloys using both experimental and computational methods. Experimental accomplishments have been made in the following areas of interest: characterization, aqueous free-corrosion, atmospheric corrosion, ionic liquid dissolution, rate kinetics of oxide dissolution, and coating investigation. Commercial alloys (AZ91D, AM60, and AZ31B), binary-phase alloys (αMg-2at.%Al, αMg-5at.%Al, and Mg-8at.%Al), and component phases (Mg, Al, β-Mg, β-1%Zn, MnAl3) were obtained and characterized using energy dispersive spectroscopy (EDS), X-ray diffraction (XRD), and scanning electron microscopy (SEM). Full immersion in aqueous chloride was used to characterize the corrosion behavior of alloys. Rotating disc electrodes (RDEs) were used to observe accelerated long-term corrosion behavior. Al surface redistribution for freely corroded samples was analyzed using SEM, EDS, and lithium underpotential deposition (Li UPD). Atmospheric corrosion was observed using contact angle evolution, overnight pH monitoring, and surface pH evolution studies. Ionic liquid corrosion characterization was performed using linear sweep voltammetry and potentiostatic dissolution in 150° choline chloride-urea (cc-urea). Two surface coatings were investigated: (1) Li-carbonate and (2) cc-urea. Li-carbonate coatings were characterized using X-ray photoelectron spectroscopy (XPS), SEM, and aqueous free corrosion potential monitoring. Hydrophobic cc-urea coatings were characterized using contact angle measurements and electrochemical impedance spectroscopy. Oxide dissolution rate kinetics were studied using inductively coupled plasma mass spectroscopy (ICP-MS). Computational accomplishments have been made through the development of Kinetic Monte Carlo (KMC) simulations which model time- and composition-dependent effects on the microstructure due to spatial redistribution of alloying elements during corrosion.

36 MATERIALS SCIENCE↗

Size-Dependent Coherent-Phonon Plasmon Modulation and Deformation Characterization in Gold Bipyramids and Nanojavelins

Localized surface plasmon resonances (LSPRs) arising from metallic nanoparticles offer an array of prospective applications that range from chemical sensing to biotherapies. Bipyramidal particles exhibit particularly narrow ensemble LSPR resonances that reflect small dispersity of size and shape but until recently were only synthetically accessible over a limited range of sizes with corresponding aspect ratios. Narrow size dispersion offers the opportunity to examine ensemble dynamical phenomena such as coherent phonons that induce periodic oscillations of the LSPR energy. Here, we characterize transient optical behavior of a large range of gold bipyramid sizes, as well as higher aspect ratio nanojavelin ensembles with specific attention to the lowest-order acoustic phonon mode of these nanoparticles. We report coherent phonon-driven oscillations of the LSPR position for particles with resonances spanning 670 to 1330 nm. Nanojavelins were shown to behave similarly to bipyramids but offer the prospect of separate control over LSPR energy and coherent phonon oscillation period. We develop a new methodology for quantitatively measuring mechanical expansion caused by photogenerated coherent phonons. Using this method, we find an elongation of approximately 1% per photon absorbed per unit cell and that particle expansion along the lowest frequency acoustic phonon mode is linearly proportional to excitation fluence for the fluence range studied. These characterizations provide insight regarding means to manipulate phonon period and transient mechanical deformation.

36 MATERIALS SCIENCE↗

Investigation of GaAs surface treatments for ZnSe growth by molecular beam epitaxy without a buffer layer

Atomically clean and smooth surfaces are critical prerequisite for the epitaxial regrowth of dissimilar semiconductors. Using ZnSe/GaAs as a model system, epitaxial regrowth without a buffer layer after thermal cleaning with various As-fluxes, atomic Ga flux, and atomic hydrogen treatments to the GaAs substrates and the surfaces were investigated in this work via in-situ Auger electron spectroscopy (AES). The ZnSe epilayers grown on the pre-treated GaAs surfaces without a buffer layer were characterized by X-ray diffraction (XRD), photoluminescence (PL) and atomic force microscopy (AFM) to evaluate the effectiveness of the surface treatment methods. It was found that a high quality ZnSe layer can be achieved by atomic hydrogen surface treatment at 300°C without requiring GaAs buffer layer growth, which reveals a path for epitaxy growth avoiding high temperature treatments.

42 ENGINEERING↗

Atmospheric Variability Drives Anomalies in the Bering Sea Air–Sea Heat Exchange

Abstract High latitudes, including the Bering Sea, are experiencing unprecedented rates of change. Long-term Bering Sea warming trends have been identified, and marine heatwaves (MHWs), event-scale elevated sea surface temperature (SST) extremes, have also increased in frequency and longevity in recent years. Recent work has shown that variability in air–sea coupling plays a dominant role in driving Bering Sea upper-ocean thermal variability and that surface forcing has driven an increase in the occurrence of positive ocean temperature anomalies since 2010. In this work, we characterize the drivers of the anomalous surface air–sea heat fluxes in the Bering Sea over the period 2010–22 using ERA5 fields. We show that the surface turbulent heat flux dominates the net surface heat flux variability from September to April and is primarily a result of near-surface air temperature and specific humidity anomalies. The airmass anomalies that account for the majority of the turbulent heat flux variability are a function of wind direction, with southerly (northerly) wind advecting anomalously warm (cool), moist (dry) air over the Bering Sea, resulting in positive (negative) surface turbulent flux anomalies. During the remaining months of the year, anomalies in the surface radiative fluxes account for the majority of the net surface heat flux variability and are a result of anomalous cloud coverage, anomalous lower-tropospheric virtual temperature, and sea ice coverage variability. Our results indicate that atmospheric variability drives much of the Bering Sea upper-ocean temperature variability through the mediation of the surface heat fluxes during the analysis period. Significance Statement A long-term ocean warming trend and a recent increase in marine heatwaves in the Bering Sea have been identified. Previous work showed that anomalies in the exchange of heat between the ocean and the atmosphere were the primary driver of Bering Sea temperature variability, but the processes responsible for the heat exchange anomalies were unknown. In this work, we show that the atmosphere is the primary driver of anomalies in the Bering Sea air–sea heat exchange and therefore plays an important role in altering the thermal state of the Bering Sea. Our results highlight the importance of understanding more about how the ocean and the atmosphere interact at high latitudes and how this relationship will be affected by future climate change.

Hayden, Emily E. [a College of Earth, Ocean, and A↗

Structural inversion asymmetry in epitaxial ultrathin films of Bi(111)/InSb(111)B

Bismuth (Bi) films hold potential for spintronic devices due to strong spin-orbit coupling. Understanding the growth, surface states, and interactions with the substrate is key to their functionalization. Large-area high-quality (111) Bi ultrathin films were grown on InSb (111)B substrates by molecular beam epitaxy (MBE). Strong film-substrate interactions epitaxially stabilize the (111) orientation and lead to nonequivalent interface potentials. Analysis of angle-resolved photoemission spectroscopy (ARPES) measurements, employed to characterize the evolution of the surface states with film thickness, indicate a crossing at the $\overline{M}$ point, suggesting a topologically trivial phase in the thin film. In conclusion, the results show the presence of interfacial bonds to the substrate breaks inversion symmetry, preventing the semimetal-to-semiconductor transition predicted for freestanding bismuth layers, highlighting the importance of controlled functionalization and surface passivation of two-dimensional materials.

Inbar, Hadass S. [Univ. of California, Santa Barba↗

Direct Observation of Plasma-Stimulated Activation of Surface Species Using Multimodal In Situ/Operando Spectroscopy Combining Polarization-Modulation Infrared Reflection-Absorption Spectroscopy, Optical Emission Spectroscopy, and Mass Spectrometry

Nonthermal plasmas (NTPs) produce reactive chemical environments, including electrons, ions, radicals, and vibrationally excited molecules, that can drive chemistry at temperatures at which such species are thermally inaccessible. There has been growing interest in the integration of conventional catalysis with reactive NTPs to promote novel chemical transformations. Unveiling the full potential of plasma-catalytic processes requires a comprehensive understanding of plasma-catalytic synergies, including characterization of plasma-catalytic surface interactions. In this work, we report on a newly designed multimodal spectroscopic instrument combining polarization-modulation infrared reflection-absorption spectroscopy (PM-IRAS), mass spectrometry, and optical emission spectroscopy (OES) for the investigation of plasma–surface interactions such as those found in plasma catalysis. In particular, this tool has been utilized to correlate plasma-phase chemistry with both surface chemistry and gas-phase products in situ (1) during the deposition of carbonaceous surface species via NTP-promoted nonoxidative coupling of methane and (2) during subsequent activation of surface deposits with an atmospheric pressure and temperature argon plasma jet on both nickel (Ni) and silicon dioxide (SiO 2 ) surfaces. For the first time, the activation of carbonaceous surface species by a NTP on Ni and SiO 2 surfaces to form hydrogen gas and C 2 hydrocarbons was directly observed, where both PM-IRAS and OES measurements suggest that they may form through different pathways. Furthermore, this unique tool for studying plasma–surface interactions could enable more rational design of plasma-stimulated catalytic processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Analysis and modification of defective surface aggregates on PCDTBT:PCBM solar cell blends using combined Kelvin probe, conductive and bimodal atomic force microscopy

Organic photovoltaic systems comprising donor polymers and acceptor fullerene derivatives are attractive for inexpensive energy harvesting. Extensive research on polymer solar cells has provided insight into the factors governing device-level efficiency and stability. However, the detailed investigation of nanoscale structures is still challenging. Here we demonstrate the analysis and modification of unidentified surface aggregates. The aggregates are characterized electrically by Kelvin probe force microscopy and conductive atomic force microscopy (C-AFM), whereby the correlation between local electrical potential and current confirms a defective charge transport. Bimodal AFM modification confirms that the aggregates exist on top of the solar cell structure, and is used to remove them and to reveal the underlying active layer. The systematic analysis of the surface aggregates suggests that the structure consists of PCBM molecules.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Deciphering the influence of high-flux helium plasma exposure on tungsten nanostructure growth using real-time, in situ spectroscopic ellipsometry

In situ analysis of surfaces during high-flux plasma exposure represents a long-standing challenge in the study of plasma–material interactions. While post-mortem microscopy can provide a detailed picture of structural and compositional changes, in situ techniques can capture the dynamic evolution of the surface. In this study, we demonstrate how spectroscopic ellipsometry can be applied to the real-time characterization of W nanostructure (also known as “fuzz”) growth during exposure to low temperature, high-flux He plasmas. Strikingly, over a wide range of sample temperatures and helium fluences, the measured ellipsometric parameters (Ψ,Δ) collapse onto a single curve that can be directly correlated with surface morphologies characterized by ex situ helium ion microscopy. The initial variation in the (Ψ,Δ) parameters appears to be governed by small changes in surface roughness (<50 nm) produced by helium bubble nucleation and growth, followed by the emergence of 50 nm diameter W tendrils. This basic behavior appears to be reproducible over a wide parameter space, indicating that the spectroscopic ellipsometry may be of general practical use as a diagnostic to study surface morphologies produced by high-flux He implantation in refractory metals. An advantage of the methods outlined here is that they are applicable at low incident ion energies, even below the sputtering threshold. As an example of this application, we apply in situ ellipsometry to examine how W fuzz growth is affected both by varying ion energy and the temperature of the surface.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Three-dimensional minority carrier lifetime mapping of thin film semiconductors for solar cell applications

This project addresses the difficulty of accurately measuring charge carrier dynamics in novel semiconductor materials for thin film photovoltaic cells. We have developed a two- photon lifetime tomography technique to separate bulk minority carrier lifetime from surface recombination effects and effects of recombination at sub-surface defects. This technique also enables us to characterize how local defects such as grain boundaries– buried below the surface of a sample–affect carrier lifetimes in the active layer, dynamics that have been previously inaccessible. We have applied this newly developed technique to illuminate how CdCl 2 treatment improves CdTe PV efficiency. From striking 3D lifetime tomography maps, a clear, sub- surface understanding emerges of the photophysical changes that occur in CdTe active medium following exposure to CdCl 2 , a standard step in the fabrication of high-efficiency CdTe-based solar cells. This work demonstrates a well-defined method to quantify grain-boundary, interface, and bulk recombination in CdTe and other optically-active polycrystalline semiconductor materials; information that can provide critical information to the development of next- generation photovoltaics and many other semiconductor technologies.

14 SOLAR ENERGY↗

Impedance spectroscopy study on graphene wrapped nanocrystalline V{sub 2}O{sub 5}

Nanocrystalline V{sub 2}O{sub 5} was synthesized by solvothermal technique, which has potential application as electrode material in supercapacitors. The graphene oxide (GO) was prepared by modified Hummer’s method. The V{sub 2}O{sub 5}/ reduced graphene oxide (RGO) composite was synthesized using surfactant free hydrothermal technique to enhance the functionality in terms of conductivity and surface area of V{sub 2}O{sub 5}. The structural characterization was accomplished through X-ray diffraction and Raman spectroscopy. Morphology was identified by SEM and surface area of VRGO was enhanced by 8 times in comparison with V{sub 2}O{sub 5} nano particles, as confirmed through BET surface area analysis. Electrical characterization was done through impedance spectroscopy and the results showed decrease in sample resistance after wrapping V{sub 2}O{sub 5} with RGO.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Probing ternary solvent effect in high V oc polymer solar cells using advanced AFM techniques

This work describes a simple method to develop a high V oc low band gap PSCs. In addition, two new atomic force microscopy (AFM)-based nanoscale characterization techniques to study the surface morphology and physical properties of the structured active layer are introduced. With the help of ternary solvent processing of the active layer and C 60 buffer layer, a bulk heterojunction PSC with V oc more than 0.9 V and conversion efficiency 7.5% is developed. In order to understand the fundamental properties of the materials ruling the performance of the PSCs tested, AFM-based nanoscale characterization techniques including Pulsed-Force-Mode AFM (PFM-AFM) and Mode-Synthesizing AFM (MSAFM) are introduced. Interestingly, MSAFM exhibits high sensitivity for direct visualization of the donor–acceptor phases in the active layer of the PSCs. Lastly, conductive-AFM (cAFM) studies reveal local variations in conductivity in the donor and acceptor phases as well as a significant increase in photocurrent in the PTB7:ICBA sample obtained with the ternary solvent processing.

25 ENERGY STORAGE↗

Temperature dependence of nickel ion release from nitinol medical devices

Abstract Nitinol exhibits unique (thermo)mechanical properties that make it central to the design of many medical devices. However, nitinol nominally contains 50 atomic percent nickel, which if released in sufficient quantities, can lead to adverse health effects. While nickel release from nitinol devices is typically characterized using in vitro immersion tests, these evaluations require lengthy time periods. We have explored elevated temperature as a potential method to expedite this testing. Nickel release was characterized in nitinol materials with surface oxide thickness ranging from 12 to 1564 nm at four different temperatures from 310 to 360 K. We found that for three of the materials with relatively thin oxide layers, ≤ 87 nm nickel release exhibited Arrhenius behavior over the entire temperature range with activation energies of 80 to 85 kJ/mol. Conversely, the fourth ''black–oxide'' material, with a much thicker, complex oxide layer, was not well characterized by an Arrhenius relationship. Power law release profiles were observed in all four materials; however, the exponent from the thin oxide materials was approximately 1/4 compared with 3/4 for the black–oxide material. To illustrate the potential benefit of using elevated temperature to abbreviate nickel release testing, we demonstrated that a > 50 day 310 K release profile could be accurately recovered by testing for less than 1 week at 340 K. However, because the materials explored in this study were limited, additional testing and mechanistic insight are needed to establish a protective temperature scaling that can be applied to all nitinol medical device components.

Saylor, David M.↗