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Insights into the structure and dynamics of K + ions at the muscovite–water interface from machine learning potential simulations
The surfaces of many minerals are covered by naturally occurring cations that become partially hydrated and can be replaced by hydronium or other cations when the surface is exposed to water or an aqueous solution. These ion exchange processes are relevant to various chemical and transport phenomena, yet elucidating their microscopic details is challenging for both experiments and simulations. Here, in this work, we make a first step in this direction by investigating the behavior of the native K + ions at the interface between neat water and the muscovite mica (001) surface with ab-initio -based machine learning molecular dynamics and enhanced sampling simulations. Our results show that the desorption of the surface K + ions in pure ion-free water has a significant free energy barrier irrespective of their local surface arrangement. In contrast, facile K + diffusion between mica’s ditrigonal cavities characterized by different Al/Si orderings is observed. This behavior suggests that the K + ions may favor a dynamic disordered surface arrangement rather than complete desorption when exposed to deionized water.
Advancing Solar Irradiance Measurement for Climate-Related Studies: Accurate Constraint on Direct Aerosol Radiative Effect (DARE)
Earth's climate is driven primarily by solar radiation. As summarized in various IPCC reports, the global average of radiative forcing for different agents and mechanisms, such as aerosols or CO2 doubling, is in the range of a few W/sq m. However, when solar irradiance is measured by broadband radiometers, such as the fleet of Eppley Precision Solar Pyranometers (PSP) and equivalent instrumentation employed worldwide, the measurement uncertainty is larger than 2% (e.g., WMO specification of pyranometer, 2008). Thus, out of the approx. 184 W/sq m (approx.263 W/sq m if cloud-free) surface solar insolation (Trenberth et al. 2009), the measurement uncertainty is greater than +/-3.6 W/sq m, overwhelming the climate change signals. To discern these signals, less than a 1 % measurement uncertainty is required and is currently achievable only by means of a newly developed methodology employing a modified PSP-like pyranometer and an updated calibration equation to account for its thermal effects (li and Tsay, 2010). In this talk, we will show that some auxiliary measurements, such as those from a collocated pyrgeometer or air temperature sensors, can help correct historical datasets. Additionally, we will also demonstrate that a pyrheliometer is not free of the thermal effect; therefore, comparing to a high cost yet still not thermal-effect-free "direct + diffuse" approach in measuring surface solar irradiance, our new method is more economical, and more likely to be suitable for correcting a wide variety of historical datasets. Modeling simulations will be presented that a corrected solar irradiance measurement has a significant impact on aerosol forcing, and thus plays an important role in climate studies.
Corrosion of Zinc Cold Spray Coatings in a Wet Sweet and Sour Gas Environment
Internal corrosion is a problem for steel pipelines transporting natural gas or CO 2 containing water and partial pressures of H 2 S higher than 0.3 kPa (0.05 psi). This work aims to mitigate internal corrosion in steel pipelines transporting natural gas containing H 2 S using cold spray coatings. Two types of the cold spray binary metallic coatings (zinc chromium [ZnCr]. zinc niobium [ZnNb]) were studied using electrochemical techniques: potentiodynamic polarization, linear polarization resistance, and electrochemical impedance spectroscopy. The corrosion resistance of cold spray coatings (ZnCr, ZnNb) was evaluated in an environment containing 4 bar CO 2 pressure, simulating the partial pressures found in gas transmission lines over a solution of 3.5 wt% NaCl heated to 40°C. A concentration of 0.003 M Na 2 S 2 O 3 ·5H 2 O, corresponding to H 2 S partial pressures around 0.079 bar (1.146 psi), was used to simulate sour conditions. Postcorrosion surface characterization was performed using a scanning electron microscope (SEM) equipped with an energy-dispersive x-ray spectroscope (EDS) and x-ray diffraction analysis. The data showed that the presence of 0.003 M Na 2 S 2 O 3 ·5H 2 O shifted the corrosion potential to more anodic values and decreased the corrosion current density. Both coatings showed similar behavior after 1 h of exposure in the CO 2 /H 2 S environment, indicating that similar electrochemical reactions were occurring on ZnNb and ZnCr. SEM images and EDS surface analyses for specimens showed a significant change in the surface chemical composition of carbon steel coated with ZnNb and ZnCr after 24 h of immersion. In the presence of thiosulfate (under sour conditions), the formation of corrosion product layers (ZnCO 3 and ZnS) on top of ZnNb and ZnCr coatings increased their corrosion resistance, which helped to reduce their corrosion by a factor of 2. Under a sweet environment, the corrosion rates for steel coated with cold spray coatings after 14 d of exposure are lower than that for galvanized steel by a factor of 5 due to the ZnCO 3 layer formed on top of the coatings. The ZnCO 3 layer formed on the steel surface acts as a physical barrier against corrosion by blocking the diffusion of corrosive species to the surface. No localized attack was observed. ZnCr Cold spray coating with defect showed promising corrosion protection against CO 2 corrosion (sweet corrosion) after 14 d of exposure to a CO 2 environment. Here, the scratch on the coating simulated damage created in service, and it was deep enough to expose the substrate material (steel). The formation of zinc oxide (ZnO) and zinc carbonate (ZnCO 3 ) on the scratch confirmed the cathodic protection of the steel by ZnCr and ZnNb coatings.
Experimental measurements of the ground cloud effluents and cloud growth for the May 20, 1975, Titan 3C launch at Air Force Eastern Test Range, Florida
The experiment included surface level and airborne in situ cloud measurements of the exhaust effluents from the Titan IIIC solid rocket boosters. Simultaneous visible spectrum photographic pictures of the ground cloud as well as infrared imaging of the cloud were obtained to study the cloud rise, growth, and direction of travel within the earth's surface mixing layer. The NASA multilayer diffusion model predictions of cloud growth, direction of travel, and expected surface level effluent concentrations were made prior to launch and after launch using measured meteorological conditions. Prelaunch predictions were used to position the effluent monitoring instruments, and the postlaunch predictions were compared with the measured data. Measurement results showed that surface level effluent values were low, often below the detection limits of the instrumentation. The maximum surface level hydrogen chloride concentration measured 50 parts per billion at about 8 km from the launch pad. The maximum observed in-cloud (airborne measurement) hydrogen chloride concentration was 7 per million.
Modeling the interaction Between Ethylene Diamine and Water Films on the Surface of a Carbon Nanotube
It has been observed that a carbon nanotube (CNT) AFM tip coated with ethylene diamine (EDA) penetrates the liquid water-air interface more easily than an uncoated nanotube tip. The EDA coating remains intact through repeated cycles of dipping and removal. In order to understand the physical basis for this observation, we use ab initio quantum chemistry calculations to study the EDA-CNT-water interaction and to parameterize a force field describing this system. Molecular dynamics (MD) simulations are carried out for EDA-water mixtures and an EDA-coated carbon nanotube immmed in water. These simulations are similar to our earlier MD study that characterized the CNT-water interface. The attractive CNT-EDA and CNT-water interactions arise primarily from van der Waals forces, and the EDA-EDA, EDA-water and water-water interactions are mainly due to hydrogen bond formation. The binding energ of single EDA molecule to the nanotube is nearly three times larger than the corresponding value found for water (4.3 versus 1.5 kcal mol, respectively). The EDA molecules readily stick to and diffuse along the CNT surface. As a resulf mixing of the EDA and water films does not occur on the timescale of the MD simulations. The EDA film reduces the hydrophobicity of the nanotube surface and acts like a prototypical surfactant in stabilizing the suspension of carbon nanotubes in water. For this presentation, we use the MD simulations to determine how the presence of the carbon nanotube surface perturbs the properties of EDA-water mixtures.
Understanding the Intrinsic Surface Reactivity of Single-Layer and Multilayer PdO(101) on Pd(100)
In this work, we investigated the intrinsic reactivity of CO on single and multilayer PdO(101) grown on Pd(100) using temperature programmed reaction spectroscopy (TPRS) and reflection absorption infrared spectroscopy (RAIRS) experiments as well as density functional theory (DFT) calculations. We find that CO binds more strongly on multilayer than single-layer PdO(101) (~119 vs. 43 kJ/mol), and that CO oxidizes negligibly on single-layer PdO(101) whereas nearly 90% of a saturated layer of CO oxidizes on multilayer PdO(101) during TPRS experiments. RAIRS further shows that CO molecules adsorb on both bridge and atop-Pd cus sites (coordinatively-unsaturated Pd sites) of single-layer PdO(101)/Pd(100), while CO binds exclusively on atop-Pd cus sites of multilayer PdO(101). The DFT calculations reproduce the much stronger binding of CO on multilayer PdO(101) as well as the observed binding site preferences, and reveal that the stronger binding is entirely responsible for the higher CO oxidation activity of multilayer PdO(101)/Pd(100). We show that the O-atom below the Pd cus site, present only on multi-layer PdO(101), modifies the electronic states of the Pd cus atom in a way that enhances the CO-Pd cus bonding. Lastly, we show that a precursor-mediated kinetic model, with energetics determined from the present study, predicts that the intrinsic CO oxidation rates achieved on both single and multilayer PdO(101)/Pd(100) can be expected to exceed the gaseous CO diffusion rate to the surface during steady-state CO oxidation at elevated pressures, even though the intrinsic reaction rates are 4-5 orders of magnitude lower on single layer than on multilayer PdO(101)/Pd(100).
Electron and proton damage coefficients in low-resistivity silicon
The electron and proton damage coefficients for low resistivity p-type boron-doped silicon were determined from minority-carrier lifetime measurements on bulk material and diffusion length measurements on solar cells. The bulk samples were irradiated with electrons at three energy levels (0.5, 1.5, and 2.5 MeV) using a Dynamitron. Lifetime measurements were made with a steady-state photoconductivity apparatus, and comparison measurements of diffusion length were obtained using the steady-state surface photovoltage method (Goodman, 1961). The diffusion-length damage coefficients increased with decreasing resistivity for boron-doped silicon; this dependence can be qualitatively accounted for using a two-level Hall-Shockley-Read model. The damage coefficients for solar cells were larger than for their bulk-material counterparts. The damage coefficient was apparently independent of the dislocation density in the 0.1 ohm-cm bulk samples and solar cells investigated.
Two-dimensional hygrothermal diffusions into a finite width composite laminate
Two dimensional hygroscopic diffusion into composite laminates with free edges was obtained through the use of a second order finite difference scheme. A computer program was developed for the transient nonlinear coupled hygrothermal diffusion into finite width laminates with varying surface conditions along two edges. The formulation permits the diffusion coefficient to be a function of temperature, moisture concentration, and fiber orientation. The moisture distributions thus obtained are necessary for analysis of the moisture induced interlaminar stresses in the vicinity of free edges. It is shown that large diffusion times tend to eliminate the significance of stacking sequence, but gradients within and between layers are significant for all diffusion times.
A Starfish Preplanetary Nebula: IRAS 19024+0044
Using the Hubble Space Telescope, we have imaged the OH/IR star IRAS 19024+0044 (I19024) at 0.6, 0.8, 1.1, and 1.6 micrometers, as part of our surveys of candidate preplanetary nebulae. The images show a multipolar nebula of size approximately equal to 3.'7 2.'3, with at least six elongated lobes emanating from the center of the nebula. Two of the lobes show limb-brightened tips having point-symmetric structure with respect to the expected location of the central star. The central region shows two dark bands southwest and northeast of a central shallow maximum that may be either two inclined dusty toroidal structures or the dense parts of a single wide, inhomogeneous, toroid. Avery faint, surface brightness-limited, diffuse halo surrounds the lobes. Long-slit/echelle optical spectroscopy obtained at the Mount Palomar and Keck observatories shows a spatially compact source of H(alpha) emission; the H(alpha) line shows a strong, narrow, central core with very broad (+/-1000 km/sec), weak wings, and a narrower blueshifted absorption feature signifying the presence of an approximately 100 km/sec(exp -1) outflow. The spectrum is characterized by a strong, relatively featureless, continuum and lacks the strong forbidden emission lines characteristic of planetary nebulae, confirming that IRAS 19024 is a preplanetary nebula; the spectral type for the central star, although uncertain, is most likely early G. Interferometric observations of the CO J = 1 -0 line emission with the Owens Valley Radio Interferometer show a marginally resolved molecular envelope (size 5.'5 x 4.'4) with an expansion velocity of 13 km/sec (exp -1), resulting from the asymptotic giant branch (AGB) progenitor's dense, slow wind. We derive a kinematic distance of 3.5 kpc to I19024, based on its radial velocity. The bolometric flux is 7:3 x 10(exp -9) erg s(exp -1) cm(exp -2), and the luminosity 2850 L. The relatively low luminosity of I19024, in comparison with stellar evolutionary models, indicates that the initial mass of its central star was approximately 1-1.5 solar mass. The lobes, which appear to be hollow structures with dense walls, have a total mass greater than or equal to about 0.02 solar mass. The lobes, which appear to be hollow structures with dense walls, have a total mass greater than or equal to about 0.02 solar mass. The dusty tori in the center have masses of a few times 10(exp -3) solar mass. The faint halo has a power-law radial surface brightness profile with an exponent of about -3 and most likely represents the remnant spherical circumstellar envelope formed as a result of constant mass loss during the AGB expansion age of less than or approximately equal to 2870 yr, giving a mass-loss rate of greater than or approximately equal to 10(exp -5) solar mass yr (exp -1), The far-infrared fluxes of I19024 indicate the presence of a large mass of cool dust in the nebula, from a simple model we infer the presence of 'cool' (109 K) and 'warm' (280 K) components of dust mass 5.7 x 10(exp -4) and 1.5 x 10(exp -7) solar mass. We discuss our results for I19024 in the light of past and current ideas for the dramatic transformation of the morphology and kinematics of mass-ejecta as AGB stars evolve into planetary nebulae.
Venus - Surface electromagnetic properties
Pioneer Venus high-angle radar imaging data are used here to correct values of the specular power reflection coefficient for the effects of diffusely scattering small-scale surface roughness. A value of 5.0 + or - 0.9 is found for the average dielectric permittivity of the rolling plains and lowlands, suggesting that most of the Venus surface is overlain by at most only a few cm of soil or dust. The unexpectedly high values of power reflection coefficient are confirmed by observations of correspondingly low values of radiothermal emission. Thus there can be little doubt that most of the highlands contain significant amounts of a conducting mineral near the surface.
Atomistic thermodynamics and kinetics of dicalcium silicate dissolution
Low-temperature cement manufacturing has garnered academic and industrial attention for its low environmental footprints. However, the sluggish hydration kinetics of the resultant cement affects their early-age strength development. This motivates fundamental studies to unravel the mechanistic picture of the dissolution process and discover science-informed pathways to accelerate hydration. Standard atomistic simulations seldomly exceed a microsecond making them impractical to study slow dissolution processes. We are using rare event sampling techniques, we provide the mechanistic picture of Ca 2+ ion dissolution from a kink site on the dicalcium silicate surface. The Ca 2+ ion dissolution is comprised of two sequential stages: breaking restraints from the kink sites to form a ledge adatom and detaching from the ledge/terrace adatom sites into the solution. The first and second stages feature free energy barriers of ~63 kJ/mol and ~ 29 kJ/mol respectively, making the first stage the rate-limiting step of the entire Ca 2+ dissolution kinetics. Using the reactive flux method, the rate and equilibrium constants for each reaction step are calculated, which yield the Ca 2+ ion activity of ~1.03 × 10 -5 . The diffusion calculations indicate that the surface effects lower the self-diffusion coefficient of Ca 2+ ions at the solid-water interface.
Choosing the Best Modeling Platform for Radiological Risk Assessment Models - 20468
Radiological risk assessments, in the form of performance or safety assessments, are often required under regulations or guidance for remediation of contaminated land, decommissioning of contaminated buildings or structures, and radioactive waste disposal. These risk assessments are usually supported by fate and transport models that address decay and ingrowth of radionuclides, as well as their movement through engineered systems and the natural environment. These models are often projected thousands, or more, years into the future, largely because the radioactive species change through decay and ingrowth, and hence the magnitude of the radioactive effect changes with time. There are many computer codes that are available to address this type of modeling. They range from addressing specific pathways or processes such as infiltration of water, groundwater, surface water, air, biota, diffusion and advection of water and gases, to those that try to couple all processes together to evaluate the impact of fate and transport through the entire system to places in space and time to which access is assumed. These different types of codes are sometimes separated with the monikers process-level and systems-level codes, although it is often not clear that this separation does justice to the capabilities of the many codes that are available to evaluate fate and transport of radionuclides. The focus of this paper is the latter group of modeling codes. Several systems level modeling codes exist and are used. There are differences between these codes in terms of utility, flexibility, complexity and cost. The purpose of this paper is to compare a few of these codes in the context of work currently being performed by the International Atomic Energy Agency (IAEA) Modeling and Data for Radiological Impact Assessments (MODARIA) II Working Group 1 (WG1). The MODARIA II WG1's main focus is how stakeholder engaged decision analysis can, or should, be applied to radiological contamination problems so that better, longstanding, sustainable, solutions are reached. However, the WG1 also recognizes the potential impact of the modeling tools that are chosen to address radiological risk, which is often a primary objective of decision making for radiological problems. Other objectives might also be important, such as constraining costs, obtaining financing, minimizing impact on ecosystems, saving cultural resources, saving jobs, farmland, environmental justice, etc., in a full decision analysis for a given radiological contamination problem, but none of these other objectives have the same types of complex modeling needs as minimize radiological dose. Consequently, a further focus of WG1 is to evaluate the potential impacts on decision making of the choice of fate and transport, and risk assessment, modeling codes that are used to support decision making. The WG1 will produce a report at the end of 2020 that will focus on an approach to effective decision making and stakeholder engagement. The report will also consider the role that performance assessment modeling should play in the decision-making process, including the impact of the choice of modeling tools or computer codes on risk-informed decision making. Several sites around the World have been made available by Member States for these model comparisons, and several modeling tools have been considered. However, the focus of this paper is on two of the sites, one in Belgium and one in Ukraine, and on three of the tools: NORMALYSA (NORM And Legacy Site Assessment); GoldSim{sup C}, and AMBER{sup C}. The final report from this working group will also cover other modeling tools, including RESRAD, and PC-Cream{sup R}. (authors)
Porous Enzymatic Membrane for Nanotextured Glucose Sweat Sensors with High Stability toward Reliable Noninvasive Health Monitoring
Development of reliable glucose sensors for noninvasive monitoring without interruption or limiting users' mobility is highly desirable, especially for diabetes diagnostics, which requires routine/long-term monitoring. However, their applications are largely limited by the relatively poor stability. In this paper, a porous membrane is synthesized for effective enzyme immobilization and it is robustly anchored to the modified nanotextured electrode solid contacts, so as to realize glucose sensors with significantly enhanced sensing stability and mechanical robustness. To the best of our knowledge, this is the first report of utilizing such nanoporous membranes for electrochemical sensor applications, which eliminates enzyme escape and provides a sufficient surface area for molecular/ion diffusion and interactions, thus ensuring the sustainable catalytic activities of the sensors and generating reliable measureable signals during noninvasive monitoring. The as-assembled nanostructured glucose sensors demonstrate reliable long-term stable monitoring with a minimal response drift for up to 20 h, which delivers a remarkable enhancement. Moreover, they can be integrated into a microfluidic sensing patch for noninvasive sweat glucose monitoring. The as-synthesized nanostructured glucose sensors with remarkable stability can inspire developments of various enzymatic biosensors for reliable noninvasive composition analysis and their ultimate applications in predictive clinical diagnostics, personalized health-care monitoring, and chronic diseases management.
Kinetically Dormant Ni‐Rich Layered Cathode During High‐Voltage Operation
Abstract The degradation of Ni‐rich cathodes during long‐term operation at high voltage has garnered significant attention from both academia and industry. Despite many post‐mortem qualitative structural analyses, precise quantification of their individual and coupling contributions to the overall capacity degradation remains challenging. Here, by leveraging multiscale synchrotron X‐ray probes, electron microscopy, and post‐galvanostatic intermittent titration technique, the thermodynamically irreversible and kinetically reversible capacity loss is successfully deconvoluted in a polycrystalline LiNi 0.83 Mn 0.1 Co 0.07 O 2 cathode during long‐term charge/discharge cycling in full cell configuration. Contradicting the dramatic capacity loss, the layered structure remains highly alive even after 1000 cycles at 4.6 V while undergoing a three‐order of magnitude reduction in the mass transfer kinetics, leading to almost fully recoverable capacity under kinetic‐free conditions. Such kinetic dormant behavior after cycling is not simply ascribed to poor chemical diffusion by reconstructed cathode surface but highly synchronizes with the lattice strain evolution stemming from the structural heterogeneity between deeply delithiated layered and degraded rock‐salt phases at high voltage. These findings deepen the degradation mechanism of high‐voltage cathodes to achieve long‐cycling and fast‐charging performance.
Thermodynamic Stability and Site‐Specific Distribution of Graphitic and Pyridinic Nitrogen in Graphene Moiré on Ru(0001)
Abstract Graphene‐like materials are of interest for large‐scale hydrogen storage applications due to their lightweight, durable, and scalable properties. Nitrogen‐doping minimizes kinetic limitations in diffusion and recombination on surfaces, however, the role of graphitic nitrogen (GN) and pyridinic nitrogen (PN) is not well understood. Nitrogen‐doped graphene is synthesized on Ru(0001) using chemical vapor deposition (CVD) of pyridine and ion irradiation. Scanning tunneling microscopy (STM), x‐ray photoelectron spectroscopy (XPS), and density functional theory (DFT) are used to identify the structure, location, and thermodynamic stability of nitrogen species within the graphene moiré. CVD of pyridine results in a low nitrogen concentration (<0.1at%), while the post‐growth nitrogen ion irradiation allows us to increase the concentration further. The concentration of GN and PN is controlled by varying the ion dose and annealing temperature. Comparison of measured and simulated STM images of GN and PN yield an excellent agreement, allowing us to confidently establish that GN is preferentially located near the center of the Atop region, while PN is located in the valley region of the graphene moiré. This report explicitly confirms the site assignments and provides a foundation for the site synthesis and analysis of structural and electronic properties that drive the reactivity of N‐doped graphene.
Microstructure and hardness evolution induced by annealing of ion irradiated LiTaO 3
We report the evolution of the microstructure and mechanical properties of low-energy heavy-ion-irradiated LiTaO 3 crystals annealed at various temperatures was investigated by transmission electron microscopy (TEM) observations and nanoindentation tests to extend the applications of irradiated LiTaO 3 crystals. Before annealing, randomly distributed voids formed in an approximately 200 nm thick region at the end of the ion irradiation range, which was attributed to preferential absorption of interstitials by the amorphous-crystalline interface. After annealing, a new directional diffusion path of defects was identified, resulting in a void string. Furthermore, void string diffusion to the free surface was also found during the annealing temperature increase process, which offers a potential application in designing custom sized-thickness exfoliation at the nanoscale. Meanwhile, two competing processes were identified during the annealing process: epitaxial recrystallization from the amorphous-crystalline interface and grain nucleation process in the amorphous region, which formed phases different from the matrix crystal structure, resulting in an interaction between them. Furthermore, the hardness of irradiated samples was also found to be affected by the annealing process; in particular, a hardness decrease induced by the interstitial Fe ions in the recrystallized region was also confirmed, which can improve the processability of samples for further application.
Concurrent measurement of strain and chemical reaction rates in a calcite grain pack undergoing pressure solution: Evidence for surface-reaction controlled dissolution
Pressure solution is inferred to be a significant contributor to sediment compaction and lithification, especially in carbonate sediments. For a sediment deforming primarily by pressure solution, the compaction rate should be directly related to the rate of calcite dissolution, transport along grain contacts, and calcite reprecipitation. Previous experimental work has shown that there is evidence that deformation in wet calcite grain packs is consistent with control by pressure solution, but considerable ambiguity remains regarding the rate limiting mechanism. We present the results of laboratory compaction experiments designed to directly measure calcite dissolution and precipitation rates (recrystallization rates) concurrently with strain rate to test whether measured rates are consistent with predicted rates both in absolute magnitude and time evolution. Recrystallization rates are measured using trace element chemistry (Sr/Ca, Mg/Ca) and isotopes (87Sr/86Sr) of fluids flowing slowly through a compacting grain pack as it is being triaxially compressed. Imaging techniques are used to characterize the grain contacts and strain effects in the post-experiment grain pack. Our data show that calcite recrystallization rates calculated from all three geochemical parameters are in approximate agreement and that the rates closely track strain rate. The geochemically inferred rates are close to predicted rates in absolute magnitude. Uncertainty in grain contact dimensions makes distinguishing between surface reaction control and diffusion control difficult. Measured reaction rates decrease faster than predicted from standard pressure solution creep flow laws. This inconsistency may indicate that calcite dissolution rates at grain contacts are more complex, and more time-dependent, than suggested by geometric models designed to predict grain contact stresses.