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Low-Level Cloud Variability over the Equatorial Cold Tongue in Observations and Models

A fourth paper now in press is, Low-level cloud variability over the equatorial cold tongue in observations and models, by D. K. Mansbach and J. R. Norris (2007, J. Climate). This study examined cloud and meteorological observations from satellite, surface, and reanalysis datasets and fount that monthly anomalies in low-level cloud amount and near-surface temperature advection are strongly negatively correlated on the southern side of the equatorial Pacific cold tongue. This inverse correlation occurs independently of relationships between cloud amount and sea surface temperature (SST) or lower tropospheric static stability (LTS) and the combination of advection plus SST or LTS explains significantly more interannual cloud variability in a multilinear regression than does SST or LTS alone. Warm anomalous advection occurs when the equatorial cold tongue is well defined and the southeastern Pacific trade winds bring relatively warm air over colder water. Ship meteorological reports and soundings show that the atmospheric surface layer becomes stratified under these conditions, thus inhibiting the upward mixing of moisture needed to sustain cloudiness against subsidence and entrainment drying. Cold anomalous advection primarily occurs when the equatorial cold tongue is weak or absent and the air-sea temperature difference is substantially negative. These conditions favor a more convective atmospheric boundary layer, greater cloud amount, and less frequent occurrence of clear sky. Examination of output from global climate models developed by the Geophysical Fluid Dynamics Laboratory (GFDL) and the National Center for Atmospheric Research (NCAR) indicates that both models generally fail to simulate the cloud-advection relationships observed on the northern and southern sides of the equatorial cold tongue. Although the GFDL atmosphere model does reproduce the expected signs of cloud-advection correlations when forced with prescribed historical SST variations, it does not consistently do so when coupled to an ocean model. The NCAR model has difficulty reproducing the observed correlations in both atmosphere-only and coupled versions. This suggests that boundary layer cloud parameterizations could be improved through better representation of the effects of advection over varying SST.

Mansbach, David K.↗

Molecular-Level Insight of the Effect of Hofmeister Anions on the Interfacial Surface Tension of a Model Protein

The effect of the Hofmeister anion series on the structure and stability of proteins is often discussed using simple systems such as a water-vapor interface with the assumption that the vapor region mimics the hydrophobic surface. Microscopic theories suggest that the Hofmeister anion series is highly correlated with the different contributions of the various ions to the surface tension of such a water-vapor interface. Proteins, however, have both hydrophobic and hydrophilic regions rather than just a pure hydrophobic one. Using a solvated parallel β -sheet layer consisting of both hydrophobic and positively charged hydrophilic surfaces as a more realistic model to represent a protein surface, we investigated the interaction of such a system with hydrophilic-like (SO42-) and hydrophobic-like (ClO4-) anions via Born-Oppenheimer Molecular Dynamics (BOMD) simulations. We found that both the SO42- and ClO4- anions prefer to reside on the hydrophilic rather than on the hydrophobic surface of the parallel β -sheet layer. In addition, our simulations suggest that the ClO4- ions not only penetrate towards the peptide groups through the hydrophilic residues, but also allow water molecules to penetrate as well to form water-peptide hydrogen bonds, while the SO42- ions stabilize the interface of the water-hydrophilic surface. Our results render a plausible explanation of why hydrophobic-like Hofmeister anions act as protein denaturants. This work was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle.

density functional theory↗

Recent advances in multispectral sensing of ocean surface temperature from space

Visual and infrared measurements from the five channel AVHRR on the NOAA-7 satellite are used operationally to derive sea surface temperatures. The multichannel data perform daytime and nighttime cloud detection tests, and the several atmospheric window channels in the thermal infrared correct for atmospheric attenuation. Monitoring of the sea surface temperature product with buoy data indicates stability in mean bias and rms difference with little variation by season or geographic area. Global mapping enables the derivation of monthly mean isotherms, monthly and annual changes, and anomaly patterns relative to climatology. Problems are associated with noise in the 3.7 micro m window channel, and with the injection of substantial volcanic aerosol into the stratosphere by the El Chichon eruption. Multichannel sea surface temperature charts are used to study phenomena such as equatorial long waves and the recent El Nino episode.

Mcclain, E. P.↗

Turbulent spectra, fluxes, stability and growth of the mixed layer in the boundary layer of Mars

Spectra of wind and temperature from high frequency measurements in the atmospheric surface layer of Mars are presented for the first time. Heat and momentum fluxes, and stability are calculated for early spring from estimates of the surface temperature and mean Viking Lander 2 temperature and wind at 44 degrees N, using similarity theory. This study provides the first estimates of (1) the height of the mixed layer, (2) spectra of wind and temperature, (3) the validity of similarity theories on Mars, and (4) bounds of effective measuring height and surface roughness. It confirms and extends the universiality of model wind spectra. Finally and more important, we provide the ability to estimate and determine the self-consistency of Martian atmospheric mixed layer fluxes, stability and heights on a diurnal and annual basis. This can be used to initialize and validate the various models, which previously could only be compared with each other or the efforts of Sutton, Leovy and Tillman: these were restricted in season and limited by the results from the surface temperature model available at that time. Analysis of additional data can better estimate z(sub 0) values directly from the measurements and provide the parameters necessary to calculate the vertical profiles of wind and temperature on a daily, seasonal and annual basis.

Tillman, James E.↗

Aerodynamic Effects and Modeling of Damage to Transport Aircraft

A wind tunnel investigation was conducted to measure the aerodynamic effects of damage to lifting and stability/control surfaces of a commercial transport aircraft configuration. The modeling of such effects is necessary for the development of flight control systems to recover aircraft from adverse, damage-related loss-of-control events, as well as for the estimation of aerodynamic characteristics from flight data under such conditions. Damage in the form of partial or total loss of area was applied to the wing, horizontal tail, and vertical tail. Aerodynamic stability and control implications of damage to each surface are presented, to aid in the identification of potential boundaries in recoverable stability or control degradation. The aerodynamic modeling issues raised by the wind tunnel results are discussed, particularly the additional modeling requirements necessitated by asymmetries due to damage, and the potential benefits of such expanded modeling.

Shah, Gautam H.↗

Abstract for CRADA between NETL and the University of Massachusetts Lowell (AGMT-1275)

The demand for printed electronics over conventional electronics is growing each year due to their low costs, low material waste during manufacturing, and compatibility with flexible substrates. The development of inks for printed electronics is a challenge because each printing technology requires different viscosities and curing behaviors to create devices with controlled structures at the micron scale, or smaller. Carbon is a great candidate for fabricating printed electronics devices because it is inexpensive and earth abundant, easily functionalized to impart miscibility with solvent systems, and has electrical properties that can be tuned from insulating to conducting. Despite these advantages, carbons are rarely used for printed electronics because there is a scarcity of inks available for non-contact printing technologies. To address these challenges, the National Energy Technology Laboratory (NETL) will collaborate with the University of Massachusetts Lowell (Participant) through its Printed Electronics Research Collaborative (PERC) to develop engineered carbons and ink formulations optimized specifically for printing radio- and microwave-frequency electronic devices using ink jet, aerosol jet, syringe dispensing, and other additive manufacturing techniques. NETL will process coal, petroleum, and other carbon feedstocks to make engineered carbons with the appropriate composition, microstructure, surface functionalization, and particle morphologies needed to stabilize ink suspensions and impart useful electronic properties to printed devices. The University of Massachusetts Lowell will utilize these engineered carbons to determine which solvent systems and ink additives are needed to achieve the appropriate viscosity, stability, and printability to make useful ink formulations. The University of Massachusetts Lowell will then utilize these inks to manufacture printed resistors and conductors using inkjet, aerosol jet, and syringe dispensing printing methods and will characterize device performance using four-point probe resistivity measurements, contact angle measurements to assess wettability, adhesion evaluation to various substrates, and focused ion beam and scanning electron microscopy for surface and density investigations of printed devices.

36 MATERIALS SCIENCE↗

Ageostrophic instabilities in a two fluid system with rotation

The stability of synoptic scale waves formed on a frontal surface is studied including nongeostrophic effects with the basic flow subjected to both vertical and horizontal shear. Spectral method is used to obtain the desired solutions. The stability characteristics of the developed unstable modes are presented as a function of shears of the basic flow. With the inclusion of barotropic shear the spectrum of instabilities increase. The lower speeded member of the mixed mode (gravitational-rotational) pair is influenced by the barotropic shear in the basic current and it appears at lower vertical shears. The structure of the height perturbations are utilized to distinguish the various unstable modes developed in the system together with their stability characteristics. This investigation has shown that the ageostrophic effects can be a significant factor in the development of synoptic scale waves on a frontal surface.

Ramanathan, N.↗

Development of manganese-rich cathodes as alternatives to nickel-rich chemistries

High-energy, inexpensive and safe electrochemistries have been the main goals of lithium-ion battery research for many years. Historically, manganese-based cathodes have long been studied for their attractive cost and safety characteristics [1]. However, due to issues related to both surface and bulk instabilities, manganese-rich electrodes have yet to find substantial success in the high-energy lithium-ion battery market. With current trends in cathode chemistries leaning heavily toward Ni-rich compositions, the factors of cost and safety are again at the forefront of research and development efforts. This paper reports the recent progress made at Argonne National Laboratory (USA) to stabilize manganese-rich cathode structures and surfaces with a specific focus on composite materials with intergrown layered and spinel components; it presents an overview of their electrochemical properties in terms of capacity, energy, and cycle-life in cells with metallic lithium, graphite, and Li 4 Ti 5 O 12 anodes. These layered-spinel cathodes show promise as alternatives to highly nickel-rich electrode compositions, which bodes well for continued advances.

25 ENERGY STORAGE↗

SNF Interim Storage Canister Corrosion and Surface Environment Investigations (FY2020 Status Report)

This progress report describes work performed during FY20 at Sandia National Laboratories (SNL) to assess the localized corrosion performance of container/cask materials used in the interim storage of spent nuclear fuel (SNF). Of particular concern is stress corrosion cracking (SCC), by which a through-wall crack could potentially form in a canister outer wall over time intervals that are shorter than possible dry storage times. Work in FY20 further defined our understanding of the potential chemical and physical environment present on canister surfaces, evaluated the relationship between the environment and the resultant corrosion that occurs, and initiated crack growth rate testing under relevant environmental conditions. In FY20, work to define dry storage canister surface environments included several tasks. First, collection of dust deposition specimens from independent spent fuel storage installation (ISFSI) site locations helped to establish a more complete understanding of the potential chemical environment formed on the canister. Second, the predicted evolution of canister surface relative humidity RH) values was estimated using ISFSI site weather data and the horizontal canister thermal model used by the SNL probabilistic SCC model. These calculations determined that for typical ISFSI weather conditions, seasalt deliquescence to produce MgCl2-rich brines could occur in less than 20 years at the coolest locations on the canister surface, and, even after nearly 300 years, conditions for NaCl deliquescence (75% RH) are not reached. This work illustrates the importance of understanding the stability of MgCl2-rich brines on the heated canister surface, and the potential impact of brine composition on corrosion processes, including pitting and stress corrosion cracking. In an additional study, the description of the canister surface environment was refined in order to define more realistic corrosion testing environments including diurnal cycles, soluble salt chemistries, and inert mineral particles. The potential impacts of these phenomena on canister corrosion are being evaluated experimentally. Finally, work over the past few years to evaluate the stability of magnesium chloride brines continued in FY20. MgCl2 degassing experiments were carried out, confirming that MgCl2 brines slowly degas HCl on heated surfaces, converting to less deliquescent magnesium hydroxychloride phases and potentially leading to brine dryout.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Applications and Results of MODIS Lunar Observations

Both Terra and Aqua MODIS have been making periodic lunar observations since their launch in December 1999 and May 2002, respectively. The primary objective of the MODIS lunar observations is to monitor on-orbit response changes for the reflective solar bands (RSB) and to track long-term radiometric calibration stability. The Moon is an extremely stable surface reflectance reference and, together with the lunar radiometric model developed recently by the US Geological Survey (USGS), the applications of lunar observations for Earth remote sensing missions have been greatly enhanced and expanded. In particular, calibration inter-comparisons among sensors on different platforms and operated in different time frames have been enabled in the VIS/NIR/SWIR spectral regions. In this paper, we discuss various applications of MODIS lunar observations, such as monitoring the RSB radiometric stability and calibration consistency between the two sensors, evaluating the calibration differences among detectors within the same spectral band, and tracking the on-orbit changes of band-to-band registration (BBR). Other applications designed for the thermal emissive bands (TEB) and special sensor characterization purposes are also illustrated. Results from multi-year Terra and Aqua MODIS lunar observations demonstrate clearly that the two sensors have been calibrated consistently to within 1% for most RSB compared to the 2% radiometric calibration requirement. In addition the spatial characterization results derived from lunar observations are in good agreement with those derived from the instrument's on-board calibrator. The applications and results of MODIS lunar observations presented in this paper provide useful references for other sensors that also make use of lunar surface observations.

Xiong, X.↗

Formation and Stability of Radiation Products in Europa's Icy Shell

Spectra of Europa reveal a surface dominated by water-ice along with hydrated materials and minor amounts of SO2, CO2, and H2O2. Jovian magnetospheric ions (protons, sulfur, and oxygen) and electrons produce significant chemical modifications of the surface on time scales of a few years at micrometer depths. Our laboratory studies examine the formation and stability of radiation products in H2O-rich ices relevant to Europa. Infrared (IR) spectra of ices before and after irradiation reveal the radiation destruction of molecules and the formation of products at 86 - 132 K. In addition, spectra of ices during warming track thermal evolution due to chemical changes and sublimation processes. IR-identified radiation products in 86 - 132 K irradiated H2O + SO2 ices are the bisulfate ion, HSO4(-), sulfate ion, SO4(2-) and the hydronium ion, H3O(+). Warming results in the formation of a residual spectrum similar to liquid sulfuric acid, H2SO4, for H2O:SO2 ratios of 30:1, whereas hydrated sulfuric acid, H2SO4 4 H2O, forms for ratios of 30:1. Radiation products identified for irradiated H2O + H2S ices at 86 K are H2S2 and SO2. When irradiated at 110 and 132 K, ices with H2O:H2S ratios if either 3:1 or 30:1 show the formation of H2SO4 4 H2O on warming to 175 K. We have also examined the radiation stability of H2SO4. Addition of CO2 to H2O + SO2 ices results in the formation of CO3 at 2046 cm (sup -1) (4.89 m). This is the strongest band from a carbon-containing product in the mid-IR spectral region, and it is also seen when either pure CO2 or H2O + CO2 ice is irradiated. Experiments with CH4 added to H2O + SO2 + CO2 ices addressed the question of methane's use as a marker of methanogens in an irradiated ice environment. New results on the near-IR spectrum of pure H2O2 will be included in this presentation. Interpretations of near-IR water bands, with H2O2 present, will be discussed. Irradiations of H2O2 and H2O + H2O2 mixtures, to examine the possibility of O2 and O3 formation, are currently under investigation and new results will be discussed.

Moore, M. H.↗

Functional stimuli-responsive polymers on micro- and nano-patterned interfaces

Micro- and nano-patterned surfaces offer precise control over morphology and chemical composition, enhancing the stability, durability, and functionality of coating materials. When combined with stimuli-responsive polymers, these surfaces gain dynamic adaptability, enabling reversible binding, reusable sensing, and selective molecular capture. Furthermore, while recent review articles have explored various aspects of stimuli-responsive materials, from hydrogel patterns for bioanalytical applications to shape-morphing hydrogels for soft robotics and sensors, a comprehensive review focused on the integration of smart polymers with micro- or nano-patterned interfaces remains absent. This review addresses key surface patterning techniques, including soft lithography, colloidal lithography, and polymer brush photolithography, as well as advances in surface-initiated polymerization methods, such as surface-initiated controlled radical polymerization (SI-CRP). In addition, we discuss recent progress in integrating stimuli-responsive polymers with patterned surfaces to create advanced, functional materials.

Colloidal lithography↗

Stability and Heat Transfer Characteristics of Condensing Films

The overall objective of this research is to investigate the fundamental physics of film condensation in reduced gravity. The condensation of vapor on a cool surface is important in many engineering problems,including spacecraft thermal control and also the behavior of condensate films that may form on the interior surfaces of spacecraft. To examine the effects of body force on condensing films, two different geometries have been tested in the laboratory: (1) a stabilizing gravitational body force (+1g, or condensing surface facing 'upwards') and (2) de-stabilizing gravitational body force (-1g, or 'downwards'). For each geometry, different fluid configurations are employed to help isolate the fluid mechanical and thermal mechanisms operative in condensing films. The fluid configurations are (a) a condensing film, and (b) a non-condensing film with film growth by mass addition by through the plate surface. Condensation experiments are conducted in a test cell containing a cooled copper or brass plate with an exposed diameter of 12.7 cm. The metal surface is polished to allow for double-pass shadowgraph imaging, and the test surface is instrumented with imbedded heat transfer gauges and thermocouples. Representative shadowgraph images of a condensing, unstable (-1g) n-pentane film are shown. The interfacial disturbances associated with the de-stabilizing body force leading to droplet formation and break-off can be clearly seen. The heat transfer coefficient associated with the condensing film is shown. The heat transfer coefficient is seen to initially decrease, consistent with the increased thermal resistance due to layer growth. For sufficiently long time, a steady value of heat transfer is observed, accompanied by continuous droplet formation and break-off. The non-condensing cell consists of a stack of thin stainless steel disks 10 cm in diameter mounted in a brass enclosure. The disks are perforated with a regular pattern of 361 holes each 0.25 mm in diameter. Non-condensing experiments in -1g have employed 50 cSt and 125 cSt silicone oil pumped through the perforated disks at a specified rate by a syringe micropump. The time to droplet break-off and the disturbance wavelengths appear to decrease with increasing pumping rate. The ability to reliably perform multi-point, ultrasonic measurements of the film thickness has been demonstrated. A linear array of eight transducers of 6 mm diameter (with a beam footprint of comparable size) are pulsed with a square-wave signal at a frequency of 5 MHz and a pulse duration of approximately 0.3 s. For thin films (60 m to 2-3 mm in thickness) the layer thickness is determined by frequency analysis, where the received ultrasound pulse is Fourier transformed and the spacing between the peaks in the frequency spectrum is analyzed. For thicker layers (up to at least 1 cm in thickness), time-domain analysis is performed of the received ultrasound pulses to generate directly the layer thickness. A time-trace of the film thickness at a point using a single transducer in the linear array is shown for the case of an unstable (-1g) n-pentane film. The oscillations in film thickness are evidently due to the passage and/or shedding of droplets from the cooled plate surface. The entire transducer array was used to measure the changes in film thickness resulting from the passage of gravity waves generated either by an oscillating wall or the impact of a single droplet on the free surface of a film. The enclosure in both cases was 14 cm square and the transducer spacing was 12 mm. Best results were obtained using as test fluid a mixture of 50% glycerol and 50% water with a fluid layer thickness of 3-5 mm. In both cases the measured wavelengths and wave propagation speeds using the ultrasound technique compared reasonably well with those observed by optical imaging. Additional information can be found in the original extended abstract.

Hermanson, J. C.↗

Room-temperature Synthesis of High-entropy Perovskite Oxide Nanoparticle Catalysts via Ultrasonication-based Method

Currently, a sonochemical-based technique for one-pot synthesis of entropy-stabilized perovskite oxide nanoparticle catalysts with high surface area is reported. The high-entropy perovskite oxides were synthesized as monodispersed, spherical nanoparticles with average crystallite size of ~5.9 nm. Taking advantage of the acoustic cavitation phenomenon in ultrasonication process, the nanoparticles of BaSr(ZrHfTi)O 3 , BaSrBi(ZrHfTiFe)O 3 and Ru/BaSrBi(ZrHfTiFe)O 3 were crystallized as single-phase perovskite structures through ultrasonication exposure without calcination. Of utmost importance, the entropically-driven stability of Ru/BaSrBi(ZrHfTiFe)O 3 with excellent dispersion of Ru in the perovskite phase, bestowed the nanoparticles of Ru/BaSrBi(ZrHfTiFe)O 3 with good catalytic activity for CO oxidation.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Parameter Estimation of Lateral Spacecraft Fuel Slosh

Predicting the effect of fuel slosh on the attitude control system of a spacecraft or launch vehicle is a very important and challenging task. Whether the spacecraft is spinning or moving laterally, the dynamic effect of the fuel slosh helps determine whether the spacecraft will remain on its intended trajectory. Three categories of slosh can be caused by launch vehicle or spacecraft maneuvers when the fuel is in the presence of an acceleration field. These are bulk-fluid motion, subsurface wave motion (currents), and free-surface slosh. Each of these slosh types has a periodic component defined by either a spinning or a lateral motion. For spinning spacecraft, all three types of slosh can greatly affect stability. Bulk-fluid motion and free-surface slosh can affect the lateral-slosh characteristics. For either condition, an unpredicted coupled resonance between the spacecraft and its onboard fuel could threaten a mission. This ongoing research effort seeks to improve the accuracy and efficiency of modeling techniques used to predict these types of fluid motions for lateral motion. Particular efforts focus on analyzing the effects of viscoelastic diaphragms on slosh dynamics.

Sudermann, James E.↗

Developing Robust Ceria-Supported Catalysts for Catalytic NO Reduction and CO/Hydrocarbon Oxidation

Synthesis of robust and hydrothermally stable PGM/ceria materials for NO, CO, and hydrocarbon abatement remains a formidable challenge, as ceria and PGMs are known to sinter severely >800 °C under hydrothermal conditions, leading to irreversible activity loss. In this work, we tackle this challenge by synthesizing well-defined catalysts with atomically dispersed rhodium supported on ceria with varying abundance of (100), (101), and (111) facets. Evaluation of these catalysts for NO reduction by CO as well as CO and propylene oxidation under model and industrially relevant conditions reveals pronounced reactivity and stability differences. Different modes of interaction of Rh ions with the ceria facets and their facile reducibility were shown to be the crucial parameters controlling reactivity, resulting in pronounced activity and stability variations. Facet-dependent poisoning of surfaces by nitrites was identified as the main reason for deactivation of the catalysts at low temperature, which is mitigated for (111) ceria facets. (111)-enriched ceria nanoparticles survive very harsh hydrothermal aging at 950 °C by maintaining and preserving (111) facets, unlike other ceria nanoparticles which sinter into poorly defined shapes. Thus, putting atomically dispersed PGM sites on (111) ceria facets lead to the catalytic material with the highest activity and stability for all studied reactions, providing the pathway to catalysts that can endure extremely harsh hydrothermal aging conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗