“Supersaturated” Self-Assembled Charge-Selective Interfacial Layers for Organic Solar Cells
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bio-inspired↗
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Results for “SUPERSATURATION”
Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.
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Haze–cloud correlations mediated by supersaturation fluctuations
Atmospheric aerosol particles that contain water-soluble components can absorb water vapor in humid environments and form either haze particles or cloud droplets, depending on supersaturation conditions. Laboratory and in situ measurements have shown that haze particles and cloud droplets often coexist and compete for available water vapor in shallow clouds and fogs, especially under polluted conditions. It is expected that more aerosol particles can form more haze particles and cloud droplets, so that the haze and cloud number concentrations are positively correlated. However, recent large-eddy simulations show that haze and cloud number concentration can be negatively correlated under extremely polluted conditions. Haze–cloud interactions across different environmental settings remain poorly understood. In this study, experiments in a convection cloud chamber with the same aerosol injection rate show that, as supersaturation forcing increases (i.e., changing from polluted to clean conditions), the covariance between haze and cloud droplet number concentration changes from negative to positive and finally to zero. Large-eddy simulations (LES) of the cloud chamber with a fixed supersaturation forcing but varying aerosol injection rates show a similar result for the haze–cloud correlation: near zero in clean, mean-supersaturation-dominated activation conditions; positive in moderate, supersaturation-fluctuation-influenced activation conditions; and negative in polluted, supersaturation-fluctuation-dominated activation conditions. A theoretical covariance framework was developed to interpret this behavior based on the relative magnitude and signs of the correlations between supersaturation and the populations of haze and cloud droplets. Significantly, experiments, LES, and theory all yield the same three-regime behavior for the sign of the haze–cloud covariance. Furthermore, our results show that the haze–cloud covariance remains robust and easily measurable, thereby providing a useful metric for regime identification in the atmosphere, improving regime-aware parameterizations, and informing aerosol interventions such as fog dispersion, rainfall enhancement, and albedo modification.
54 ENVIRONMENTAL SCIENCES↗
Cluster Nucleation and Growth from a Highly Supersaturated Adatom Phase: Silver on Magnetite
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catalysis (heterogeneous), hydrogen and fuel cells↗
Microscopic Evidence for Liquid-Liquid Separation in Supersaturated CaCO[subscript 3] Solutions
Abstract not provided
Wallace, Adam F.↗
Quasi‐Steady State Supersaturation: Do High Values Derived From ESCAPE Represent Real High Supersaturations and the Potential for Condensational Invigoration?
Deep convective clouds were intensively sampled during the Experiment of Sea Breeze Convection, Aerosols, Precipitation, and Environment (ESCAPE) with coordinated flights of the NRC Convair-580 and SPEC Learjet. A total of 219 updraft core segments were sampled over coastal Texas and Louisiana under diverse meteorological conditions. Median updraft properties included widths of ∼1 km, velocities of 4.8 m s −1 , droplet number concentrations of ∼400 cm −3 , and liquid water contents of 0.9 g m −3 . The limitations of using the quasi-steady state approximation to derive supersaturations were explored. Supersaturation (S QSS ) estimated from in situ observations under a quasi-steady state assumption averaged 0.4% but occasionally exceeded 2%, with values >1% (high supersaturations) identified as statistical outliers. Two case studies illustrated the conditions linked to high supersaturations. In a storm over the Gulf, median core S QSS reached 2.46% in the developing stage compared to 2.17% in the mature stage under similar thermodynamic conditions. In a storm over coastal Louisiana, S QSS peaked near 11% within a 13.7-m s −1 updraft, accompanied by predominantly supercooled liquid droplets at −13°C and exceptionally low diameter concentrations of 0.29 mm cm −3 . Bootstrap analysis of all sampled cores showed that high supersaturations are most probable in cold and mixed-phase regimes with moderate to strong updrafts and are strongly influenced by vertical velocity and droplet number concentrations. In conclusion, while extreme supersaturations (∼10%) were rare, their occurrence underscores the need for targeted multiplatform observations to resolve their spatiotemporal variability and assess their potential role in deep convective invigoration.
54 ENVIRONMENTAL SCIENCES↗
Supersaturated calcium carbonate solutions are classical
We will present a description of nucleation phenomena in the condensed phase that takes into account non-ideal solution effects associated with cluster-cluster interaction. To do this we employ aggregation-volume bias Monte Carlo simulation, making the estimation of free-energy of large pre-critical clusters of sizes 10-20 tractable. We will compare and contrast empirical potential and electronic structure (e.g. Density functional theory) based descriptions of molecular interaction associated with the nucleation of CaCO 3 , highlighting free-energy trends and qualitative differences in populations of pre-critical clusters as a function of supersaturation. The influence of how the precise local interaction influences the non-ideal solution behavior on the nucleation and growth processes will be highlighted. This research was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences.
Henzler, Katja (ORCID:0000000335905005)↗
Dynamical conditions of ice supersaturation and ice nucleation in convective systems: A comparative analysis between in situ aircraft observations and WRF simulations: Ice Supersaturation in Convective System
Occurrence frequency and dynamical conditions of ice supersaturation (ISS, where relative humidity with respect to ice (RHi) > 100%) are examined in the upper troposphere around convective activity. Comparisons are conducted between in situ airborne observations and the Weather Research and Forecasting model simulations using four double-moment microphysical schemes at temperatures ≤-40°C. All four schemes capture both clear-sky and in-cloud ISS conditions. However, the clear-sky (in-cloud) ISS conditions are completely (significantly) limited to the RHi thresholds of the Cooper parameterization. In all of the simulations, ISS occurrence frequencies are higher by ~3–4 orders of magnitude at higher updraft speeds (>1 m s -1 ) than those at the lower updraft speeds when ice water content (IWC) > 0.01 g m -3 , while observations show smaller differences up to ~1–2 orders of magnitude. The simulated ISS also occurs less frequently at weaker updrafts and downdrafts than observed. These results indicate that the simulations have a greater dependence on stronger updrafts to maintain/generate ISS at higher IWC. At lower IWC (≤0.01 g m -3 ), simulations unexpectedly show lower ISS frequencies at stronger updrafts. Overall, the Thompson aerosol-aware scheme has the closest magnitudes and frequencies of ISS >20% to the observations, and the modified Morrison has the closest correlations between ISS frequencies and vertical velocity at higher IWC and number density. The Cooper parameterization often generates excessive ice crystals and therefore suppresses the frequency and magnitude of ISS, indicating that it should be initiated at higher ISS (e.g., ≥25%).
54 ENVIRONMENTAL SCIENCES↗
Atomistic modeling of long-term evolution of twist boundaries under vacancy supersaturation
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nuclear (including radiation effects), defects, me↗
Lagrangian and Eulerian Supersaturation Statistics in Turbulent Cloudy Rayleigh–Bénard Convection: Applications for LES Subgrid Modeling
Abstract Turbulent fluctuations of scalar and velocity fields are critical for cloud microphysical processes, e.g., droplet activation and size distribution evolution, and can therefore influence cloud radiative forcing and precipitation formation. Lagrangian and Eulerian water vapor, temperature, and supersaturation statistics are investigated in direct numerical simulations (DNS) of turbulent Rayleigh–Bénard convection in the Pi Convection Cloud Chamber to provide a foundation for parameterizing subgrid-scale fluctuations in atmospheric models. A subgrid model for water vapor and temperature variances and covariance and supersaturation variance is proposed, valid for both clear and cloudy conditions. Evaluation of phase change contributions through an a priori test using DNS data shows good performance of the model. Supersaturation is a nonlinear function of temperature and water vapor, and relative external fluxes of water vapor and heat (e.g., during entrainment-mixing and phase change) influence turbulent supersaturation fluctuations. Although supersaturation has autocorrelation and structure functions similar to the independent scalars (temperature and water vapor), the autocorrelation time scale of supersaturation differs. Relative scalar fluxes in DNS without cloud make supersaturation PDFs less skewed than the adiabatic case, where they are highly negatively skewed. However, droplet condensation changes the PDF shape response: it becomes positively skewed for the adiabatic case and negatively skewed when the sidewall relative fluxes are large. Condensation also increases correlations between water vapor and temperature in the presence of relative scalar fluxes but decreases correlations for the adiabatic case. These changes in correlation suppress supersaturation variability for the nonadiabatic cases and increase it for the adiabatic case. Implications of this work for subgrid microphysics modeling using a Lagrangian stochastic scheme are also discussed.
54 ENVIRONMENTAL SCIENCES↗
Estimation of Deposition Behavior of Supersaturated Silicic Acid around Geological Disposal Facility - 19137
For safety evaluation about the geological disposal system, the leakage of radionuclides with groundwater flow is estimated by considering the groundwater flow through the manmade and natural barriers. In such an estimate, we should also consider the influence of cement materials used for the construction of the disposal facility system. Cement material including high alkalinity alters groundwater condition up to 13 in pH and dissolves numerous silicate materials, which release silicic acid to groundwater. Since this groundwater mixes with natural groundwater downstream, supersaturated silicic acid will be produced with the decrease of pH to 8 around the repository system. Thus, in this study, the behavior of supersaturated silicic acid in a flow system was examined by using the column packed with amorphous silica particles under the condition of constant hydraulic head. The packed length is 20 mm or 40 mm, and the supersaturated silicic acid solution was continuously injected into the column. Here, the supersaturated silicic acid was adjusted by mixing with distilled water of pH 8 just before the solution was injected into the column. In the results, the supersaturated silicic acid quickly deposited in the packed column, and colloidal silicic acid was not detected at the outlet of the column. The deposition amount of supersaturated silicic acid in the column decreased with time, and became larger in the longer column. Besides, the flow rate decreased with the deposition of supersaturated silicic acid. Thus, this study monitored the decrease rate of permeability with the supply amount of silicic acid. In the results, the change rate did not depend on packed length. This suggested that even with a short packed length, by considering the amount of precipitation of supersaturated silicic acid, it is possible to estimate the change in permeability similarly to the case of a long packed length. Such a decrease effect in permeability may contribute to retarding the migration of radionuclides around the repository. (authors)
12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
Direct observation of metal nanoparticles as heterogeneous nuclei for the condensation of supersaturated organic vapors: Nucleation of size-selected aluminum nanoparticles in acetonitrile and n-hexane vapors
This work reports the direct observation and separation of size-selected aluminum nanoparticles acting as heterogeneous nuclei for the condensation of supersaturated vapors of both polar and nonpolar molecules. In the experiment, we study the condensation of supersaturated acetonitrile and n-hexane vapors on charged and neutral Al nanoparticles by activation of the metal nanoparticles to act as heterogeneous nuclei for the condensation of the organic vapor. Aluminum seed nanoparticles with diameters of 1 and 2 nm are capable of acting as heterogeneous nuclei for the condensation of supersaturated acetonitrile and hexane vapors. The comparison between the Kelvin and Fletcher diameters indicates that for the heterogeneous nucleation of both acetonitrile and hexane vapors, particles are activated at significantly smaller sizes than predicted by the Kelvin equation. The activation of the Al nanoparticles occurs at nearly 40% and 65% of the onset of homogeneous nucleation of acetonitrile and hexane supersaturated vapors, respectively. The lower activation of the charged Al nanoparticles in acetonitrile vapor is due to the charge-dipole interaction which results in rapid condensation of the highly polar acetonitrile molecules on the charged Al nanoparticles. The charge-dipole interaction decreases with increasing the size of the Al nanoparticles and therefore at low supersaturations, most of the heterogeneous nucleation events are occurring on neutral nanoparticles. No sign effect has been observed for the condensation of the organic vapors on the positively and negatively charged Al nanoparticles. The present approach of generating metal nanoparticles by pulsed laser vaporization within a supersaturated organic vapor allows for efficient separation between nucleation and growth of the metal nanoparticles and, consequently controls the average particle size, particle density, and particle size distribution within the liquid droplets of the condensing vapor. Strong correlation is found between the seed nanoparticle's size and the degree of the supersaturation of the condensing vapor. This result and the agreement among the calculated Kelvin diameters and the size of the nucleating Al nanoparticles determined by transmission electron microscopy provide strong proof for the development of a new approach for the separation and characterization of heterogeneous nuclei formed in organic vapors. These processes can take place in the atmosphere by a combination of several organic species including polar compounds which could be very efficient in activating charged nanoparticles and cluster ions of atmospheric relevance.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
A new approach to estimate supersaturation fluctuations in stratocumulus cloud using ground-based remote-sensing measurements
Abstract. Supersaturation, crucial for cloud droplet activation and condensational growth, varies in clouds at different spatial and temporal scales. In-cloud supersaturation is poorly known and rarely measured directly. On the scale of a few tens of meters, supersaturation in clouds has been estimated from in situ measurements assuming quasi-steady-state supersaturation. Here, we provide a new method to estimate supersaturation using ground-based remote-sensing measurements, and results are compared with those estimated from aircraft in situ measurements in a marine stratocumulus cloud during the Aerosol and Cloud Experiment (ACE-ENA) field campaign. Our method agrees reasonably well with in situ estimations, and it has three advantages: (1) it does not rely on the quasi-steady-state assumption, which is questionable in clean or turbulent clouds, (2) it can provide a supersaturation profile, rather than just point values from in situ measurements, and (3) it enables building statistics of supersaturation in stratocumulus clouds for various meteorological conditions from multi-year ground-based measurements. The uncertainties, limitations, and possible applications of our method are discussed.
54 ENVIRONMENTAL SCIENCES↗
Supersaturation, buoyancy, and deep convection dynamics
Motivated by recent discussions concerning differences of convective dynamics in polluted and pristine environments, the so-called convective invigoration in particular, this paper provides an analysis of factors affecting convective updraft buoyancy, such as the in-cloud supersaturation, condensate and precipitation loading, and entrainment. We use the deep convective period from simulations of daytime convection development over land discussed in our previous publications. An entraining parcel framework is used in the theoretical analysis. We show that for the specific case considered here, finite (positive) supersaturation noticeably reduces pseudo-adiabatic parcel buoyancy and cumulative convective available potential energy (cCAPE) in the lower troposphere. This comes from keeping a small fraction of the water vapor in a supersaturated state and thus reducing the latent heating. Such a lower-tropospheric impact is comparable to the effects of condensate loading and entrainment in the idealized parcel framework. For the entire tropospheric depth, loading and entrainment have a much more significant impact on the total CAPE. For the cloud model results, we compare ensemble simulations applying either a bulk microphysics scheme with saturation adjustment or a more comprehensive double-moment scheme with supersaturation prediction. We compare deep convective updraft velocities, buoyancies, and supersaturations from all ensembles. In agreement with the parcel analysis, the saturation-adjustment scheme provides noticeably stronger updrafts in the lower troposphere. For the simulations predicting supersaturation, there are small differences between pristine and polluted conditions below the freezing level that are difficult to explain by standard analysis of the in-cloud buoyancy components. By applying the piggybacking technique, we show that the lower-tropospheric buoyancy differences between pristine and polluted simulations come from a combination of temperature (i.e., latent heating) and condensate loading differences that work together to make polluted buoyancies and updraft velocities slightly larger when compared to their pristine analogues. Overall, the effects are rather small and contradict previous claims of a significant invigoration of deep convection in polluted environments.
54 ENVIRONMENTAL SCIENCES↗
Dissolution of Danazol Amorphous Solid Dispersions: Supersaturation and Phase Behavior as a Function of Drug Loading and Polymer Type
Amorphous solid dispersions (ASDs) are of great interest as enabling formulations because of their ability to increase the bioavailability of poorly soluble drugs. However, the dissolution of these formulations under nonsink dissolution conditions results in highly supersaturated drug solutions that can undergo different types of phase transitions. As such, the purpose of this study was to characterize the phase behavior of solutions resulting from the dissolution of model ASDs as well as the degree of supersaturation attained. Danazol was chosen as a poorly water-soluble model drug, and three polymers were used to form the dispersions: polyvinylpyrrolidone (PVP), hydroxypropylmethyl cellulose (HPMC), and hydroxypropylmethyl cellulose acetate succinate (HPMCAS). Dissolution studies were carried out under nonsink conditions, and solution phase behavior was characterized using several orthogonal techniques. It was found that liquid–liquid phase separation (LLPS) occurred following dissolution and prior to crystallization for most of the dispersions. Using flux measurements, it was further observed that the maximum attainable supersaturation following dissolution was equivalent to the amorphous solubility. The dissolution of the ASDs led to sustained supersaturation, the duration of which varied depending on the drug loading and the type of polymer used in the formulation. The overall supersaturation profile observed thus depended on a complex interplay between dissolution rate, polymer type, drug loading, and the kinetics of crystallization.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Supersaturating silicon with transition metals by ion implantation and pulsed laser melting
We investigate the possibility of creating an intermediate band semiconductor by supersaturating Si with a range of transition metals (Au, Co, Cr, Cu, Fe, Pd, Pt, W, and Zn) using ion implantation followed by pulsed laser melting (PLM). Structural characterization shows evidence of either surface segregation or cellular breakdown in all transition metals investigated, preventing the formation of high supersaturations. However, concentration-depth profiling reveals that regions of Si supersaturated with Au and Zn are formed below the regions of cellular breakdown. Fits to the concentration-depth profile are used to estimate the diffusive speeds, v{sub D,} of Au and Zn, and put lower bounds on v{sub D} of the other metals ranging from 10{sup 2} to 10{sup 4} m/s. Knowledge of v{sub D} is used to tailor the irradiation conditions and synthesize single-crystal Si supersaturated with 10{sup 19} Au/cm{sup 3} without cellular breakdown. Values of v{sub D} are compared to those for other elements in Si. Two independent thermophysical properties, the solute diffusivity at the melting temperature, D{sub s}(T{sub m}), and the equilibrium partition coefficient, k{sub e}, are shown to simultaneously affect v{sub D}. We demonstrate a correlation between v{sub D} and the ratio D{sub s}(T{sub m})/k{sub e}{sup 0.67}, which is exhibited for Group III, IV, and V solutes but not for the transition metals investigated. Nevertheless, comparison with experimental results suggests that D{sub s}(T{sub m})/k{sub e}{sup 0.67} might serve as a metric for evaluating the potential to supersaturate Si with transition metals by PLM.
36 MATERIALS SCIENCE↗
Droplet Growth or Evaporation Does Not Buffer the Variability in Supersaturation in Clean Clouds
Abstract Water vapor supersaturation in clouds is a random variable that drives activation and growth of cloud droplets. The Pi Convection–Cloud Chamber generates a turbulent cloud with a microphysical steady state that can be varied from clean to polluted by adjusting the aerosol injection rate. The supersaturation distribution and its moments, e.g., mean and variance, are investigated for varying cloud microphysical conditions. High-speed and collocated Eulerian measurements of temperature and water vapor concentration are combined to obtain the temporally resolved supersaturation distribution. This allows quantification of the contributions of variances and covariances between water vapor and temperature. Results are consistent with expectations for a convection chamber, with strong correlation between water vapor and temperature; departures from ideal behavior can be explained as resulting from dry regions on the warm boundary, analogous to entrainment. The saturation ratio distribution is measured under conditions that show monotonic increase of liquid water content and decrease of mean droplet diameter with increasing aerosol injection rate. The change in liquid water content is proportional to the change in water vapor concentration between no-cloud and cloudy conditions. Variability in the supersaturation remains even after cloud droplets are formed, and no significant buffering is observed. Results are interpreted in terms of a cloud microphysical Damköhler number (Da), under conditions corresponding to , i.e., the slow-microphysics regime. This implies that clouds with very clean regions, such that is satisfied, will experience supersaturation fluctuations without them being buffered by cloud droplet growth. Significance Statement The saturation ratio (humidity) in clouds controls the growth rate and formation of cloud droplets. When air in a turbulent cloud mixes, the humidity varies in space and time throughout the cloud. This is important because it means cloud droplets experience different growth histories, thereby resulting in broader size distributions. It is often assumed that growth and evaporation of cloud droplets buffers out some of the humidity variations. Measuring these variations has been difficult, especially in the field. The purpose of this study is to measure the saturation ratio distribution in clouds with a range of conditions. We measure the in-cloud saturation ratio using a convection cloud chamber with clean to polluted cloud properties. We found in clouds with low concentrations of droplets that the variations in the saturation ratio are not suppressed.
54 ENVIRONMENTAL SCIENCES↗
Deposition Behavior of Supersaturated Silicic Acid onto Illite as an Altered Backfilling Material - 18114
The pH gradient, which is generated by cement-based materials, causes the deposition of silicic acid in the backfilled tunnels in the repository. This deposition behavior blocks the flow-path, whence it also acts effectively for the retardation of radionuclides besides the similar effect with swelling property. Such deposition effect is expected to be maintained in the backfilling material even after illitization has progressed. The aim of this study is to evaluate the deposition rate constant, k [m/s], of supersaturated silicic acid on illite under some different conditions, considering its temperature dependence. In the experiments, deposition behavior was observed during 6 hours. After adding illite powder into the supersaturated silicic acid solution (pH>10), the pH was set to 8 in order to adjust the solution supersaturated. As a result of these experiments, the values of k were several 10-10 m/s in the temperature range of 288 K to 323 K. Several previous studies with some experiments and numerical simulations showed that the values of k for various minerals, e.g. Ca-type bentonite and amorphous silica, were in the range of 10-11 to 10-10 m/s, and that those values are large enough to clog micro flow-paths. These means that illite shows the clogging effect caused by the deposition of supersaturated silicic acid as in other silicate minerals. In addition, the deposition amount of supersaturated silicic acid increased as the temperature was raised. Therefore, the deposition reaction could progress rapidly under the condition of relatively high temperature caused by the geothermal heat and the waste heat in the repository. (authors)
12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗