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At least 181 records · Page 10

Vertical profiles of trace gas and aerosol properties over the eastern North Atlantic: variations with season and synoptic condition

Abstract. Because of their extensive coverage, marine low clouds greatly impact the global climate. Presently, the response of marine low clouds to the changes in atmospheric aerosols remains a major source of uncertainty in climate simulations. One key contribution to this large uncertainty derives from the poor understanding of the properties and processes of marine aerosols under natural conditions and the perturbation by anthropogenic emissions. The eastern North Atlantic (ENA) is a region of persistent but diverse subtropical marine boundary layer (MBL) clouds, where cloud albedo and precipitation are highly susceptible to perturbations in aerosol properties. Here we examine the key processes that drive the cloud condensation nuclei (CCN) population in the MBL using comprehensive characterizations of aerosol and trace gas vertical profiles during the Aerosol and Cloud Experiments in the Eastern North Atlantic (ACE-ENA) field campaign. During ACE-ENA, a total of 39 research flights were conducted in the Azores: 20 during summer 2017 and 19 during winter 2018. During summer, long-range-transported aerosol layers were periodically observed in the lower free troposphere (FT), leading to elevated FT CCN concentrations (NCCN). Both biomass burning and pollution from North America contribute to submicron aerosol mass in these layers, with pollution likely the dominant contributor. In contrast, long-range transported continental emissions have a much weaker influence on the aerosol properties in the ENA during the winter season. While the entrainment of FT air is a major source of particle number in the MBL for both seasons, on average it does not serve as a direct source of CCN in the MBL because the average FT NCCN is the same or even lower than that in the MBL. The particle number flux due to FT entrainment is dominated by pre-CCN (particles that are too small to form cloud droplets under typical conditions, i.e., particles with sizes below the Hoppel minimum) due to the elevated Npre-CCN in the lower FT. Once these pre-CCN are entrained into the MBL, they can grow and reach CCN size range through condensational growth, representing an indirect and major source of MBL CCN in the ENA. The impact of synoptic conditions on the aerosol properties is examined. Under pre-front and post-front conditions, shallow convective activity often leads to a deep and decoupled boundary layer. Coalescence scavenging and evaporation of drizzle below clouds lead to reduced NCCN and larger accumulation-mode particle sizes in the upper cloud-containing decoupled layer, indicating that surface measurements overestimate the NCCN relevant to the formation of MBL clouds under decoupled conditions.

54 ENVIRONMENTAL SCIENCES↗

Available energy from diffusive and reversible phase space rearrangements

Rearranging the six-dimensional phase space of particles in plasma can release energy. The rearrangement may happen through the application of electric and magnetic fields, subject to various constraints. The maximum energy that can be released through a rearrangement of a distribution of particles can be called its available or free energy. Rearrangement subject to phase space volume conservation leads to the classic Gardner free energy. Less free energy is available when constraints are applied, such as respecting conserved quantities. Furthermore, less energy is available if particles can only be diffused in phase-space from regions of high phase-space density to regions of lower phase-space density. The least amount of free energy is available if particles can only be diffused in phase space, while conserved quantities still need to be respected.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Role of phonon softening induced by anisotropic fluctuations in the enhanced mobility at free glassy surfaces

The surface of a glassy material exhibits enhanced mobility compared to the bulk counterpart, however the underlying mechanism for this remains elusive. Herein, we present studies of the dynamical properties of a prototypical glass-forming metallic liquid Zr 50 Cu 50 as a function of the distance from both the free surface and pinned surface using molecular dynamics simulations. We found that the surface mobility increases gradually on approaching the free surface, with a concomitant increase of the non-Gaussianity. The phonon density of states at the free surface exhibits lower characteristic frequencies than in the bulk and pinned surface. These findings suggest phonon softening caused by anisotropic fluctuations at free surfaces as an alternative physical mechanism leading to the enhanced dynamics at free glassy surfaces from the perspective of collective excitations.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Transparent and Conductive Polyimide‐Ionene Hybrid Interlayers for High Performance and Cost‐Effective Semitransparent Organic Solar Cells

The contradiction between high transmittance and favorable conductivity poses a great challenge in developing effective cathode interlayer (CIL) materials with sufficient thickness tolerance, which hinders the further advancement of organic solar cells (OSCs). Herein, a completely new class of alcohol processable polyimide-ionene hybrids (PIIHs) is proposed by melding pyromellitic diimide (PMD) subunits into imidazolium-based ionenes backbone covalently. These PIIHs, named PMD-DI and PMD-PD, boast high transparency, suitable energy levels, and decent conductivity. A higher PMD content endows PMD-PD with improved work function tunability, electrical properties, and crystallinity, enabling PMD-PD as CIL material with excellent thickness-insensitive characteristics, while simultaneously improving device stability significantly. Furthermore, PMD-PD also exhibits good compatibility with various electrodes and active layers, offering solar cell efficiencies of up to 19.91% and 19.29% with Ag and Cu cathodes, respectively. More importantly, the application of PMD-PD can improve the performance of semi-transparent OSCs without losing transmittance, thereby drastically enhancing the light utilization efficiency to 4.04% with an ultrathin, low-cost Cu cathode, that competes with leading optical modulation-free semitransparent OSCs with expensive Ag cathodes. This work opens a pathway to realize transparent and conductive interlayers by strategic molecular design, leading to highly efficient, stable, and cost-effective OSCs suitable for diverse applications.

You, Zuhao↗

Molecular-level understanding of gibbsite particle aggregation in water

Using molecular dynamics simulations, we investigate the molecular scale origin of crystal face selectivity when one gibbsite particle attaches to another in water. A comparison of the free energy per unit surface area of particle–particle attachment indicates that particle attachment through edge surfaces, where the edge surfaces are either (1 0 0) or (1 1 0) crystal faces, is more energetically favorable compared to attachment between two basal surfaces (i.e., (0 0 1) crystal faces) or between the basal surface of one particle and the edge surface of another. This result suggests that gibbsite crystals with low basal/edge surface area ratio will preferentially attach through edge surfaces, potentially helping the crystals grow laterally. However, for larger gibbsite particles (high basal/edge surface area ratio) the total free energy, not normalized by surface area, of particle attachment through the basal surfaces is lower (more negative) than attachment through the edge surfaces, indicating that larger gibbsite particles will preferentially aggregate through basal surface attachments. The short-range electrostatic interactions including the interparticle hydrogen bonds from surface –OH groups drive particle attachment, and the dominant contribution to the free energy minimum is enthalpic rather than entropic. However, the enthalpy of basal-edge attachment is significantly offset by the entropy leading to a higher free energy (less negative) compared to that of basal-basal attachment. Study of the free energy for a few imperfect attachments of two particles indicates a higher free energy (i.e., less negative, less stable), compared to a perfect attachment

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Deciphering the effect of traps on electronic charge transport properties of methylammonium lead tribromide perovskite

Halide perovskites have undergone remarkable developments as highly efficient optoelectronic materials for a variety of applications. Several studies indicated the critical role of defects on the performance of perovskite devices. However, the parameters of defects and their interplay with free charge carriers remain unclear. In this study, we explored the dynamics of free holes in methylammonium lead tribromide (MAPbBr 3 ) single crystals using the time-of-flight (ToF) current spectroscopy. By combining ToF spectroscopy and Monte Carlo simulation, three energy states were detected in the bandgap of MAPbBr 3 . In addition, we found the trapping and detrapping rates of free holes ranging from a few microseconds to hundreds of microseconds. Contrary to previous studies, we revealed a strong detrapping activity of traps. We showed that these traps substantially affect the transport properties of MAPbBr 3 , including mobility and mobility-lifetime product. Our results provide an insight on charge transport properties of perovskite semiconductors.

36 MATERIALS SCIENCE↗

Electrochemical deposition of amorphous aluminum oxides on lead pipes to prevent lead leaching into the drinking water

Over 5000 public drinking water systems in the US are out of compliance with the Lead and Copper Rule. Lead leaching from lead pipes is limited by the solubility of a naturally occurring scale. Changes in water quality may cause this scale to become more soluble, releasing lead into the drinking water. We propose a novel electrochemical method to prevent lead leaching from lead pipes. In this method, an aluminum wire and an alkaline phosphate electrolyte are inserted into the pipes. The pipes are then anodized for 2 h by using an external power supply, resulting in the electrodeposition of an insoluble aluminum oxide layer on top of the preexisting scale. This technology was tested on lead pipes from the EBMUD water distribution systems located in Berkeley, CA, using recirculating synthetic and actual tap water for 120 days. The untreated pipes leached an average of 23 ppb and 38 ppb of lead respectively, when using free chlorine and monochloramine as disinfection residuals. In contrast, the treated pipes leached 3 ppb and 5 ppb respectively. These results suggest that the proposed treatment has the potential to prevent lead leaching regardless of the disinfection residual and thus should be further explored in a field trial.

36 MATERIALS SCIENCE↗

Pairing instability on a Luttinger surface: A non-Fermi liquid to superconductor transition and its Sachdev-Ye-Kitaev dual

Superconductivity results from an instability of the Fermi surface—contour of poles of the single-particle propagator—to an infinitesimally small attraction between electrons. Here, we instead discuss the analogous problem on a model Luttinger surface, or contour of zeros of the Green function. At zero temperature ($β → \infty$) and a critical interaction strength ($u_{c∞}$) characterized by the residue of self-energy pole, we find that the pair susceptibility diverges leading to a superconducting instability. We evaluate the pair fluctuation partition function and find that the spectral density in the normal state has an interaction-driven, power-law $\frac{1}{\sqrt{ω}}$ type, van-Hove singularity (vHS), indicating non-Fermi liquid (NFL) physics. Crucially, in the strong coupling limit ($βu \gg 1$), the leading-order fluctuation free-energy terms in the normal state of this NFL-SC transition resembles the equivalent [$\textit{O}(1)$] terms of the Sachdev-Ye-Kitaev (SYK) model. This free-energy contribution takes a simple form $–βF = βu_{c∞} – γ \text{ln}(βu_{c∞}$), where $\gamma$ is a constant equal to $\frac{1}{2}$. Weak impurity scattering ($τ \gg β^{–1}$) leaves the low-energy spectral density unaffected but leads to an interaction-driven enhancement of superconductivity. Our results in this work shed light on the role played by order-parameter fluctuations in providing the key missing link between Mott physics and strongly coupled toy models exhibiting gravity duals.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Approaching PetaVolts per Meter Plasmonics Using Structured Semiconductors

A newly uncovered class of plasmons in the strongly excited limit opens access to unprecedented Petavolts per meter electromagnetic fields with wide-ranging, transformative impact. Unlike conventional plasmons, such plasmons are constituted by non-perturbative, large-amplitude oscillations of the ultradense, delocalized free electron Fermi gas inherent in conductive media. Here structured semiconductors doped to have an appropriate conduction electron density are introduced to tune the properties of the Fermi gas for matched excitation of large-amplitude plasmons using readily available electron beams which enables immediate experimental validation. Specifically, an electrostatic, surface “crunch-in” plasmon is collisionlessly excited by the beam launched inside a tube. Strong excitation due to matching results in relativistic oscillations of the electron gas and unravels unique phenomena. Relativistically induced ballistic electron transport comes about due to relativistic multifold increase in the mean free path and also leads to unconventional heat deposition beyond Ohm’s law. This explains the absence of observed damage or solid-plasma formation in past experiments on conductive samples interacting with electron bunches shorter than 10-13 seconds. Furthermore, relativistic momentum leads to copious tunneling of electron gas across the surface, which then crunches inside the tube. Relativistic effects along with large, localized electron density variations underlying these modes necessitate kinetic approach to theoretical and computational modeling. Kinetic model presented here demonstrates experimental viability of observing tens of gigavolts per meter plasmonic fields excited by matching readily available electron beams to plasmons in semiconductors with 1018cm-3 free electron density, and paves the way for Petavolts per meter plasmonics.

42 ENGINEERING↗

Critical differences in 3D atomic structure of individual ligand-protected nanocrystals in solution

Precise three-dimensional (3D) atomic structure determination of individual nanocrystals is a prerequisite for understanding and predicting their physical properties. Nanocrystals from the same synthesis batch display what are often presumed to be small but possibly important differences in size, lattice distortions, and defects, which can only be understood by structural characterization with high spatial 3D resolution. We solved the structures of individual colloidal platinum nanocrystals by developing atomic-resolution 3D liquid-cell electron microscopy to reveal critical intrinsic heterogeneity of ligand-protected platinum nanocrystals in solution, including structural degeneracies, lattice parameter deviations, internal defects, and strain. These differences in structure lead to substantial contributions to free energies, consequential enough that they must be considered in any discussion of fundamental nanocrystal properties or applications.

Kim, Byung Hyo↗

First 3D vector tracking of helium recoils for fast neutron measurements at Super$\mathrm{KEKB}$

Here we present results from the first deployment of novel, high definition, compact gas Time Projection Chambers (TPCs) with pixel chip readout as part of the BEAST II beam background measurement project at SuperKEKB. The TPCs provide detailed 3D imaging of ionization from neutron-induced nuclear recoils in a helium and carbon dioxide target gas mixture at standard temperature and pressure. We present the TPC performance and the neutron backgrounds observed during the initial stage of collider commissioning. We find excellent electron background rejection, leading to background-free nuclear recoil measurements above 50 keV ee , despite the extreme high-background environment. We measure an angular resolution better than 20° for recoil tracks longer than 1.7 mm, corresponding to an average ionization energy of approximately 100 keV ee . We also obtain the full 3D vector direction of helium recoils by utilizing charge profile measurements along the recoil axis, with a correct head/tail assignment efficiency of approximately 80%. With this performance, we present comparisons between measured and simulated event rates, recoil energy spectra, and directional distributions originating from beam–gas and Touschek beam losses at SuperKEKB. We utilize head/tail recognition to distinguish neutron components traveling with positive radial velocity in the Belle II coordinate system from those traveling in the opposite direction. Finally, we present a novel method of discriminating beam–gas interactions from Touschek beam losses that can eliminate the need for dedicated accelerator runs for background measurements. This method is still statistics-limited. However, future studies should be able to verify this method, which in turn could lead to neutron background analysis runs symbiotic with normal Belle II operation. The capabilities demonstrated here also suggest that high definition recoil imaging in gas TPCs is applicable to low energy, low-background experiments, such as directional dark matter searches.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Ambipolar Electrochemistry of Pre‐Intercalated Ti 3 C 2 T x MXene in Ionic Liquid Electrolyte

Abstract Cation intercalation with or without redox remains the dominant charge storage mechanism for two‐dimensional (2D) Ti 3 C 2 T x MXene. Anion‐based charge storage remains unexplored due to intrinsic negative surface charge of MXenes preventing spontaneous intercalation of anions and irreversible oxidation of Ti at anodic potentials in aqueous electrolytes. In this work, we report on the ambipolar electrochemical behavior of the Ti 3 C 2 T x in ionic liquid electrolyte over a 2.5 V electrochemically stable window. The experiments are conducted on a thin Ti 3 C 2 T x film current collector coated with an electroactive layer of small flakes (∼150 nm) of Ti 3 C 2 T x pre‐intercalated with 1‐ethyl‐3‐methylimidazolium bis‐(trifluoromethylsulfonyl)‐imide (EMIM‐TFSI) ionic liquid. Couples of redox peaks with a very small potential separation during the voltage sweep are observed at high negative (−0.75 V vs. Ag wire) and high positive (+0.75 V vs. Ag wire) potentials. Our experimental electrochemical data combined with density functional theory (DFT) calculations suggest feasibility of pseudo‐intercalation of TFSI anions between Ti 3 C 2 T x flakes. This study provides a pathway for elucidating anion intercalation for different MXene chemistries in solvent‐free electrolytes, which can lead to development of MXene based energy storage devices with improved performance.

Electrochemistry↗

Creep Deformation and Damage Mechanisms in an Advanced High-Temperature Additively Manufactured Nickel-Base Superalloy

Abstract This research investigates the processing–structure–properties–performance relationship in a novel nickel-base superalloy, ABD ® -900AM, designed for extreme environments. Specifically tailored for additive manufacturing (AM), ABD ® -900AM maintains mechanical integrity at high temperatures and is comparable to other nickel-based superalloys with a 30–40% gamma-prime volume fraction. A comprehensive study was conducted using laser-beam powder bed fusion and electron-beam powder bed fusion methods. Factors such as heat treatment, porosity, build orientation, and hot isostatic pressing were evaluated to understand their effects on microstructure and mechanical performance. Microstructural characterization revealed significant differences in grain size and orientation across build processes and heat treatments. High-temperature mechanical testing indicated that grain size, heat treatment, and orientation significantly influence creep behavior. A super-solvus heat treatment led to recrystallization and grain growth, significantly improving creep properties compared to a near-solvus heat treatment. Various creep mechanisms were identified across different conditions, and creep rupture models were developed for each build process. Post-test microstructural analysis showed grain boundary damage, with differences in creep cavitation morphology under varying stress conditions. It was shown that MC carbides grow at the expense of gamma-prime near grain boundaries, leading to precipitate-free zones in specimens tested at higher temperatures. This study fills a significant gap in fundamental research by offering a deeper insight into the high-temperature mechanical behavior of additively manufactured nickel-base superalloys. It also explores critical research questions regarding the role of carbides and the significance of heat treatment. The insights gained enhance confidence in the industry adoption of ABD ® -900AM and similar alloys for high-temperature applications, bridging the knowledge gap and supporting the development of reliable AM processes for extreme environments.

Bridges, Alex (ORCID:000000030338759X)↗

Design of heterogeneous structured Al alloys with wide processing window for laser-powder bed fusion additive manufacturing

Required microstructural attributes of an alloy vary with structural applications. The microstructural fine-tuning capability of laser-powder bed fusion (L-PBF) additive manufacturing (AM) enables application specific manufacture of the components. Such manufacture with L-PBF AM requires alloys that exhibit wide processing window and are amenable to multiple deformation mechanisms. However, high hot cracking susceptibility of Al alloys poses a barrier to such printability-performance synergy. In this work we show that an integration of, a) grain refinement through heterogeneous nucleation, and b) eutectic solidification, leads to crack-free parts at wide range of process parameters, microstructural heterogeneity, and hierarchy in the Al-Ni-Ti-Zr alloy. Such an integration targets hot cracking at multiple stages of solidification in L-PBF as opposed to the contemporary alloy design strategies that target hot-cracking at only specific stages of solidification. The Al-Ni-Ti-Zr alloy exhibits excellent printability and a high as-built tensile performance. Due to the wide processing window and amenability to multiple deformation mechanisms, the alloy microstructure and subsequently the performance, can be fine-tuned. Here, such strategy opens the gateway for application-specific manufacture of Al alloys with L-PBF AM and establishes a fundamental shift in current methodologies for design of these alloys for L-PBF AM.

36 MATERIALS SCIENCE↗

Titrating Controlled Defects into Si-LTA Zeolite Crystals Using Multiple Organic Structure-Directing Agents

Controlling defects in zeolites is crucial for tuning their adsorption and catalytic properties. In this work, we have performed an integrated zeolite synthesis, spectroscopy, and density functional theory study to test the limit of F– as a charge-balancing agent that mitigates defects in siliceous zeolites. We focused on the synthesis of siliceous zeolite LTA at 150 °C with 1,2-dimethyl-3-(4-methylbenzyl) imidazolium as the primary organic structure-directing agent (OSDA) and tetramethyl ammonium (TMA) as the secondary OSDA. By varying the amount of TMA in the synthesis gel, positive charges were titrated into the resulting as-made Si-LTA. Surprisingly, we found that greater TMA concentration does not induce more F– to enter into the zeolite. 29Si solid-state MAS NMR, Raman spectroscopy, and density functional theory suggest that this system has surpassed its capacity for F– to balance OSDA charge, and additional positive charge is balanced by Si–O– framework defects. The number of defects in the as-made Si-LTA can be precisely titrated by the amount of TMA in the zeolite structures. For the Si-LTA synthesized without TMA, framework defects formed in the early stage of crystal growth were found to heal during later crystallization, leading to defect-free Si-LTA. However, for the Si-LTA synthesized with TMA, the defects formed in early stages do not heal. A DFT thermodynamic analysis explains that crowding of Si-LTA pores by TMA impedes defect healing; this prediction is corroborated by synthesis experiments at an elevated temperature (170 °C). These results indicate that F– can have a limited capacity to balance OSDA charge in zeolite synthesis, opening up a third route to zeolite synthesis intermediate between the fluoride and hydroxide routes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Insights into Copper Sulfide Formation from Cu and S K edge XAS and DFT studies

An understanding of the fundamentals of the reaction between CuO with trace amounts of H 2 S to form CuS products is critical for the optimal utilization of this process in sulfur removal applications. Unfortunately, CuS is a complex material, featuring various Cu 2-x S compounds (with 0 ≤ x ≤ 1), distorted crystal phases, and varying electronic structures and coordination environments of Cu and S ions. In this work, we combine ex situ and in situ X-ray absorption spectroscopy (XAS) at S and Cu K edges, fixed bed sorption experiments, DFT simulations, and other characterization techniques to speciate the CuS products formed at different temperatures (298–383 K) and from CuO sorbents with different crystallite sizes (2.8–40 nm). The results of our analysis identify the formation of a distorted CuS layer at the surface of CuO crystals with disulfide groups with shorter Cu–S bonds and higher delocalization of the positive charge of the Cu center into (S 1– )2. This distorted CuS layer dominates the XAS signal at lower temperatures (298–323 K) and at the initial stages of sulfidation at higher temperatures (353 and 383 K) where conversion is low (<40%). First-principles atomistic simulations confirm the thermodynamic favorability of the formation of surface (S 1– )2 on both CuO (111) and ($\bar{1}11$) surfaces, providing further support for our experimental observations. Furthermore, these simulations reveal that the presence of disulfide bonds stabilized surface hydroxyl groups, leading to lower Gibbs Free Energies of their surface migration.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ultralow Voltage GaN Vacuum Nanodiodes in Air

The III-nitride semiconductors have many attractive properties for field-emission vacuum electronics, including high thermal and chemical stability, low electron affinity, and high breakdown fields. In this work, we report top-down fabricated gallium nitride (GaN)-based nanoscale vacuum electron diodes operable in air, with record ultralow turn-on voltages down to ~0.24 V and stable high field-emission currents, tested up to several microamps for single-emitter devices. We leverage a scalable, top-down GaN nanofabrication method leading to damage-free and smooth surfaces. Gap-dependent and pressure-dependent studies provide new insights into the design of future, integrated nanogap vacuum electron devices. The results show promise for a new class of high-performance and robust, on-chip, III-nitride-based vacuum nanoelectronics operable in air or reduced vacuum.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Evaluation of the Causes of Wet-Season Dry Biases Over Amazonia in CAM5

This study investigates the causes of pronounced low precipitation bias over Amazonia in the Community Atmosphere Model version 5 (CAM5), a common feature in many global climate models. Our analysis is based on a suite of 3-day long hindcasts starting every day at 00Z from 1997 to 2012 and an AMIP simulation for the same period. The Amazonia dry bias appears by the second day in the hindcasts and is very robust for all the seasons with the largest bias magnitude during the wet season (December–February). The bias pattern and magnitude do not change much during different dynamical wind regimes on sub-seasonal time scales. We further classify the diurnal cycle of precipitation near the LBA sites from observations and hindcasts into three convective regimes: no precipitation, late afternoon deep convection, and nighttime deep convection. CAM5 can only simulate the late afternoon convective regime and completely fails to simulate the nighttime convection, which is mostly from propagating convective systems originating from remote locations. CAM5 mainly underestimates precipitation in the late afternoon and nighttime convective regimes, which occur during ~67% of wet season days and account for ~75% of accumulated precipitation amount in observations. The persistent warm temperature bias and slightly higher moisture below 850 mb likely trigger deep convection too frequently, resulting in an earlier but weaker rainfall peak in the diurnal cycle. Finally, shallow convection may not effectively transport moisture from boundary layer to the free atmosphere, which also leads to weaker deep convection events.

54 ENVIRONMENTAL SCIENCES↗