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At least 793 records · Page 44

Understanding Mechanisms of Selective Crystal Nucleation and Growth Using In Situ Electron Microscopy

Separation processes are essential for purifying and isolating critical materials, but are challenging due to the natural tendency of systems to mix. This project explores far-from-equilibrium separation methods using external electric and magnetic fields to drive selective nucleation and crystal growth. Using in situ electrochemical transmission electron microscopy (TEM), we observed ion transport and crystallization behavior under applied electric fields. We found that ions migrate toward the working electrode, where nucleation preferentially occurs. These findings advance our understanding of non-equilibrium separation mechanisms and support the development of efficient, sustainable methods for extracting critical materials from unconventional domestic sources.

36 MATERIALS SCIENCE↗

Dataset for "Development of heterogeneous ice nucleation rate coefficient parameterizations from ambient measurements"

Ice nucleating particles (INPs) are a rare subset of particles that can have an outsized impact relative to their prevalence. To simulate INP variability, models require parameterizations for the most important sources of INPs. Most parameterizations in the literature were developed from laboratory experiments that used proxies for ambient particles. Whether these laboratory models effectively represent ambient aerosol is still not well understood and parameterizations developed from field measurements may be more atmospherically relevant. Expanding on previous work in which we used an ice chamber and an single particle mass spectrometer (SPMS) to characterize INP composition, we use the combined measurements to calculate heterogeneous ice nucleation rate coefficients for ambient particles. We find good agreement between our results for dust and sea spray aerosol with previous results. We also determine the relative contribution of each measurement to the total measurement uncertainty using a Monte Carlo approach and find that the biggest source of uncertainty is the sampling efficiency of the SPMS.

Cornwell, Gavin C↗

In Situ Characterization of the Effect of Twin-Microstructure Interactions on {$1 0 \bar{1} 2$} Tension and {$1 0\bar {1} 1$} Contraction Twin Nucleation, Growth and Damage in Magnesium

Through in situ electron backscatter diffraction (EBSD) experiments, this paper uncovers dominant damage mechanisms in traditional magnesium alloys exhibiting deformation twinning. The findings emphasize the level of deleterious strain incompatibility induced by twin interaction with other deformation modes and microstructural defects. A double fiber obtained by plane-strain extrusion as a starting texture of AM30 magnesium alloy offered the opportunity to track deformation by EBSD in neighboring grains where some undergo profuse {$1 0\bar {1} 2$} twinning and others do not. For a tensile loading applied along extrusion transverse (ET) direction, those experiencing profuse twinning reveal a major effect of grain boundaries on non-Schmid behavior affecting twin variant selection and growth. Similarly, a neighboring grain, with its $\langle$c$\rangle$-axis oriented nearly perpendicular to tensile loading, showed an abnormally early nucleation of {$1 0\bar {1} 1$} contraction twins (2% strain) while the same {$1 0\bar {1} 1$} twin mode triggering under $\langle$c$\rangle$-axis uniaxial compression have higher value of critical resolved shear stress exceeding the values for pyramidal $\langle$c + a$\rangle$ dislocations. The difference in nucleation behavior of contraction vs. compression {$1 0\bar {1} 1$} twins is attributed to the hydrostatic stresses that promote the required atomic shuffles at the core of twinning disconnections.

36 MATERIALS SCIENCE↗

Ground-based observation of clusters and nucleation-mode particles in the Amazon

We investigated atmospheric new particle formation (NPF) in the Amazon rainforest using direct measurement methods. To our knowledge this is the first direct observation of NPF events in the Amazon region. However, previous observations elsewhere in Brazil showed the occurrence of nucleation-mode particles. Here, our measurements covered two field sites and both the wet and dry season. We measured the variability of air ion concentrations (0.8–12nm) with an ion spectrometer between September 2011 and January 2014 at a rainforest site (T0t). Between February and October 2014, the same measurements were performed at a grassland pasture site (T3) as part of the GoAmazon 2014/5 experiment, with two intensive operating periods (IOP1 and IOP2 during the wet and the dry season, respectively). The GoAmazon 2014/5 experiment was designed to study the influence of anthropogenic emissions on the changing climate in the Amazon region. The experiment included basic aerosol and trace gas measurements at the ground, remote sensing instrumentation, and two aircraft-based measurements.The results presented in this work are from measurements performed at ground level at both sites. The site inside the rainforest (T0t) is located 60km NNW of Manaus and influenced by pollution about once per week. The pasture (T3) site is located 70km downwind from Manaus and influenced by the Manaus pollution plume typically once per day or every second day, especially in the afternoon. No NPF events were observed inside the rainforest (site T0t) at ground level during the measurement period. However, rain-induced ion and particle bursts (hereafter, rain events) occurred frequently (643 of 1031 days) at both sites during the wet and dry season, being most frequent during the wet season. During the rain events, the ion concentrations in three size ranges (0.8–2, 2–4, and 4–12nm) increased up to about 10 4 –10 5 cm -3 . This effect was most pronounced in the intermediate and large size ranges, for which the background ion concentrations were about 10–15cm -3 compared with 700 cm -3 for the cluster ion background. We observed eight NPF events at the pasture site during the wet season. We calculated the growth rates and formation rates of neutral particles and ions for the size ranges 2–3 and 3–7 nm using the ion spectrometer data. The observed median growth rates were 0.8 and 1.6nmh -1 for 2–3nm sized ions and particles, respectively, with larger growth rates (13.3 and 7.9 nmh -1 ) in the 3–7 nm size range. The measured nucleation rates were of the order of 0.2 cm -3 s -1 for particles and 4–9×10 -3 cm -3 s -1 for ions. There was no clear difference in the sulfuric acid concentrations between the NPF event days and nonevent days (~9×10 5 cm -3 ). The two major differences between the NPF days and nonevent days were a factor of 1.8 lower condensation sink on NPF event days (1.8×10 -3 s -1 ) compared to nonevents (3.2 × 10 -3 s -1 ) and different air mass origins. In conclusion, to our knowledge, this is the first time that results from ground-based sub-3nm aerosol particle measurements have been obtained from the Amazon rainforest.

54 ENVIRONMENTAL SCIENCES↗

The influence of multiple groups of biological ice nucleating particles on microphysical properties of mixed-phase clouds observed during MC3E

Abstract. A new empirical parameterization (EP) for multiple groups of primary biological aerosol particles (PBAPs) is implemented in the aerosol–cloud model (AC) to investigate their roles as ice nucleating particles (INPs). The EP describes the heterogeneous ice nucleation by (1) fungal spores, (2) bacteria, (3) pollen, (4) detritus of plants, animals, and viruses, and (5) algae. Each group includes fragments from the originally emitted particles. A high-resolution simulation of a midlatitude mesoscale squall line by AC is validated against airborne and ground observations. Sensitivity tests are carried out by varying the initial vertical profiles of the loadings of individual PBAP groups. The resulting changes in warm and ice cloud microphysical parameters are investigated. The changes in warm microphysical parameters, including liquid water content and cloud droplet number concentration, are minimal (<10 %). Overall, PBAPs have little effect on the ice number concentration (<6 %) in the convective region. In the stratiform region, increasing the initial PBAP loadings by a factor of 1000 resulted in less than 40 % change in ice number concentrations. The total ice concentration is mostly controlled by various mechanisms of secondary ice production (SIP). However, when SIP is intentionally shut down in sensitivity tests, increasing the PBAP loading by a factor of 100 has an effect of less than 3 % on the ice phase. Further sensitivity tests revealed that PBAPs have little effect on surface precipitation and on the shortwave and longwave flux (<4 %) for a 100-fold perturbation in PBAPs.

54 ENVIRONMENTAL SCIENCES↗

A numerical framework for simulating the atmospheric variability of supermicron marine biogenic ice nucleating particles

Abstract. We present a framework for estimating concentrations of episodically elevated high-temperature marine ice nucleating particles (INPs) in the sea surface microlayer and their subsequent emission into the atmospheric boundary layer. These episodic INPs have been observed in multiple ship-based and coastal field campaigns, but the processes controlling their ocean concentrations and transfer to the atmosphere are not yet fully understood. We use a combination of empirical constraints and simulation outputs from an Earth system model to explore different hypotheses for explaining the variability of INP concentrations, and the occurrence of episodic INPs, in the marine atmosphere. In our calculations, we examine the following two proposed oceanic sources of high-temperature INPs: heterotrophic bacteria and marine biopolymer aggregates (MBPAs). Furthermore, we assume that the emission of these INPs is determined by the production of supermicron sea spray aerosol formed from jet drops, with an entrainment probability that is described by Poisson statistics. The concentration of jet drops is derived from the number concentration of supermicron sea spray aerosol calculated from model runs. We then derive the resulting number concentrations of marine high-temperature INPs (at 253 K) in the atmospheric boundary layer and compare their variability to atmospheric observations of INP variability. Specifically, we compare against concentrations of episodically occurring high-temperature INPs observed during field campaigns in the Southern Ocean, the Equatorial Pacific, and the North Atlantic. In this case study, we evaluate our framework at 253 K because reliable observational data at this temperature are available across three different ocean regions, but suitable data are sparse at higher temperatures. We find that heterotrophic bacteria and MBPAs acting as INPs provide only a partial explanation for the observed high INP concentrations. We note, however, that there are still substantial knowledge gaps, particularly concerning the identity of the oceanic INPs contributing most frequently to episodic high-temperature INPs, their specific ice nucleation activity, and the enrichment of their concentrations during the sea–air transfer process. Therefore, targeted measurements investigating the composition of these marine INPs and drivers for their emissions are needed, ideally in combination with modeling studies focused on the potential cloud impacts of these high-temperature INPs.

54 ENVIRONMENTAL SCIENCES↗

Importance of ice nucleation and precipitation on climate with the Parameterization of Unified Microphysics Across Scales version 1 (PUMASv1)

Cloud microphysics is critical for weather and climate prediction. In this work, we document updates and corrections to the cloud microphysical scheme used in the Community Earth System Model (CESM) and other models. These updates include a new nomenclature for the scheme, now called Parameterization of Unified Microphysics Across Scales (PUMAS), and the ability to run the scheme on graphics processing units (GPUs). The main science changes include refactoring an ice number limiter and associated changes to ice nucleation, adding vapor deposition onto snow, and introducing an implicit numerical treatment for sedimentation. We also detail the improvements in computational performance that can be achieved with GPU acceleration. We then show the impact of these scheme changes on the (a) mean state climate, (b) cloud feedback response to warming, and (c) aerosol forcing. We find that corrections are needed to the immersion freezing parameterization and that ice nucleation has important impacts on climate. We also find that the revised scheme produces less cloud liquid and ice but that this can be adjusted by changing the loss process for cloud liquid (autoconversion). Furthermore, there are few discernible effects of the PUMAS changes on cloud feedbacks but some reductions in the magnitude of aerosol–cloud interactions (ACIs). Small cloud feedback changes appear to be related to the implicit sedimentation scheme, with a number of factors affecting ACIs.

54 ENVIRONMENTAL SCIENCES↗

Size_resolved_ice_nucleating_particle_INP_concentrations_from_the_INPOP_campaign

Ground-based immersion mode ice nucleation measurements were conducted on samples collected at the US DOE ARM AMF3 in Oliktok Point, AK from 1 Mar to 31 May 2017. Samples were collected using a Davis Rotating-drum Unit for Monitoring (DRUM; DRUMAir, LLC) cascading impactor in 4 stages (i.e., size bins). Instrument information on the model used, the DA400, can be found at the DRUMAir website (http://www.drumair.com/). Stages A, B, C, and D, had particle size cuts at 2.96, 1.21, 0.34, and 0.15 &micro;m in particle diameter. Strips of sample substrate (PFA, perfluoroalkoxy; McMaster) were adhered to each disc in each stage and coated with petrolatum to enable particles to stick on impact. The discs move slowly over time, such that aerosol loading is streaked onto the PFA. Every 24 hours, a blank is created on the PFA to separate daily samples. The pump typically pulled 25 lpm at the inlet with all the discs in place in each stage. Daily samples were collected for each of the four stages, equaling 36,000 total L of air per sample. Discs rotated for approximately 24 days before the sampling per strip was complete and changed to a new disc. Discs were stored frozen after collection. Following collection and transport from AMF3 to PI Creamean's laboratory in Boulder, CO, strips were removed from the discs and cut up to separate daily samples. Each daily portion of the strip was stored in separate sterile bags and stored in a standard commercial freezer until analysis (approximately 4 &ndash; 5 months after collection). Drop freezing assays (DFAs) were conducted on one daily sample per week of the study for all four stages, with daily samples analyzed from 22 - 29 May 2017. Immediately after removal from the freezer, 2 mL of ultrapure water was added with a single-use sterile syringe directly to the bags, then mixed using a vortex mixer for 2 hours at 500 rpm to resuspend particles from the PFA into the ultrapure water. Following sample preparation, another single-use syringe was used to create 100 aliquots on a 3-inch diameter copper plate, then covered with a transparent plastic dome. The drops were approximately the same volume (2.5 &micro;L each), though careful inspection. The plate was cooled at approximately 3 &ndash; 10 K min-1 from room temperature until all drops froze on the plate. Temperature was measured by an Omega thermocouple probes and meter. Drop freezing was visually detected, but recorded through monitoring software to provide the time frozen, channel of the meter used, temperature, and cooling rate for each drop. Not all 100 drops were always detected; the total number of rows in each data file equals the number of drops recorded, which typically was > 80 %. Each sample was tested three times (i.e., a new set of 100 drops was created for each test). Data provided are files containing these parameters. From the freezing temperatures recorded, the fraction frozen can be calculated as can the estimated INP concentration per L of air using the equation from Vali (1971): [INPs] = &minus;(ln(f)/Valiquot)*(Vsuspension/Vair) where f is the proportion of droplets not frozen, Valiquot is the volume of each aliquot (i.e., 2.5e-6 L), Vsuspension is the volume of the suspension (i.e., 0.002 L), and Vair is the volume of air per sample (i.e., 36000 L). Vali, G.: Quantitative Evaluation of Experimental Results an the Heterogeneous Freezing Nucleation of Supercooled Liquids, Journal of the Atmospheric Sciences, 28, 402-409, 1971.

4-stage DRUM aerosol collector (DA400),Aerosol imp↗

Ice nucleating particle concentrations measured by the CSU-CFDC during the AGINSGP field experiment

Real-time, immersion mode ambient ice nucleating particle (INP) concentrations were measured at ARM&rsquo;s Southern Great Plains (SGP) site during the AGINSGP field experiment using a continuous flow diffusion chamber (CFDC) from Colorado State University (CSU). The CSU-CFDC is an ice-thermal gradient diffusion chamber that optically detects the freezing of single aerosol particles (Rogers 1988; Rogers et al. 2001; and Eidhammer et al. 2010). The instrument was located in the guest instrument facility (GIF) and measured INP concentrations from April 8th to April 29th. Air was drawn into the GIF through custom aluminum stack inlets (6&rdquo; inner diameter) attached vertically to the outer GIF wall and the GIF outside platform. A blower pulled air through the stacks at a velocity of 1 m/s. Aerosol instruments subsampled via wall ports, through either 3/8&rdquo; or 1/4" copper lines, depending on sample flow of the instrument. Rogers, D. C., Development of a continuous flow thermal gradient diffusion chamber for ice nucleation studies, Atmospheric Research, 22(2), 149-181, doi:10.1016/0169-8095(88)90005-1, 1988. Rogers, D. C., P. J. DeMott, S. M. Kreidenweis and Y. Chen, A continuous flow diffusion chamber for airborne measurements of ice nuclei, J. Atmos. Oceanic Technol., 18, 725-741, doi:10.1175/1520-0426(2001)018<0725:ACFDCF>2.0.CO;2, 2001. Eidhammer, T., DeMott, P. J., Prenni, A. J., Petters, M. D., Twohy, C. H., Rogers, D. C., Stith, J., Heymsfield, A., Wang, Z., Haimov, S., French, J., Pratt, K., Prather, K., Murphy, S., Seinfeld, J., Subramanian, R., and Kreidenweis, S. M., Ice initiation by aerosol particles: Measured and predicted ice nuclei concentrations versus measured ice crystal concentrations in an orographic wave cloud, J. Atmos. Sci., 67, 2417-2436, doi:10.1175/2010JAS3266.1, 2010

54 ENVIRONMENTAL SCIENCES↗

The influence of defects and impurities on the nucleation and growth of oriented films by evaporation

The influence of substrate imperfections on the nucleation and growth of fcc metals on alkali halides is discussed. Films deposited on well characterized substrated under well defined vacuum evaporation conditions are investigated. The experimental results of this work are correlated with similar work by other investigators. Models which have been proposed by various authors to explain experimental results are critically examined and areas of difficulty are pointed out. The influence of defects on nucleation rate and the orientation of the film is emphasized. Specific examples of impurity effects, irradiation effects and the influence of amorphous layers are discussed in detail. Evidence is shown that the formation of multiply twinned particles is a result of coalescence and growth. The only consistent model for the orienting influence of impurities is shown to be a chemical reaction effect. It is demonstrated that an alkali metal impurity is very likely responsible for the orienting influence of both water vapor exposure and irradiation. A negative result is found for the reported possibility of an orienting influence being transmitted through an amorphous layer.

Green, A. K.↗

Heat transfer with nucleate boiling of liquids under weak mass force field conditions

The motion is examined of a vapor bubble growing and rising from a flat horizontal heater in the ideal fluid approximation and taking drag into account. Estimates are given of bubble lifetime, bubble radius at detachment, bubble detachment frequency, and time for the bubble to attain a constant rate of rise. The relations obtained for the microcharacteristics of the boiling process are used to determine the coefficients of heat transfer in developed nucleate boiling. A new form of the equations for describing heat transfer in nucleate boiling in dimensionless parameters is proposed.

Kirichenko, Y. A.↗

Summary of in situ epitaxial nucleation and growth measurements

In situ nucleation and growth measurements of Ag and Au on single-crystal PbSe thin films were made using a transmission electron microscope. Properties studied were polymorphism, crystalline perfection, and the stoichiometric composition of the initial and the autoepitaxially thickened PbSe substrates. The quantitative nucleation and cluster growth measurements were limited to low-saturation conditions. The epitaxial orientations are discussed, and evidence is presented as to the stage of deposition at which the epitaxial order for Ag is introduced. Strong substrate/overgrowth interaction manifested itself by alloying and interdiffusion.

Poppa, H.↗

Nuclei growth kinetics during the nucleation of gold on UHV-cleaved mica substrates

Measurements of crystalline sizes during nucleation of gold on mica surfaces cleaved in ultra-high vacuum (UHV) reveal the presence of symmetric, sharply peaked distributions which flatten and broaden with increasing nucleation time. When the number density of nuclei increases, the growth rate is suppressed. The time taken to reach a given size increases with increasing temperature when the nuclei are growing as isolated particles. When the nuclei are spaced so far that their diffusion fields overlap, then the time taken to reach a given size decreases with increasing temperature.

Elliot, A. G.↗

Crack nucleation in Fe-3% Si in a hydrogen environment

An investigation has been made of the grain-size and strain-rate dependence of the crack nucleation process in iron-3% silicon polycrystals tested in a low-pressure hydrogen environment. The results are compared with similar observations made in an air environment and are discussed in terms of the role of hydrogen on the process of crack nucleation in iron.

Kamdar, M. H.↗

Oxide nucleation on thin films of copper during in situ oxidation in an electron microscope

Single-crystal copper thin films were oxidized at an isothermal temperature of 425 C and at an oxygen partial pressure of 0.005 torr. Specimens were prepared by epitaxial vapor deposition onto polished faces of rocksalt and were mounted in a hot stage inside the ultrahigh-vacuum chamber of a high-resolution electron microscope. An induction period of roughly 30 min was established which was independent of the film thickness but depended strongly on the oxygen partial pressure and to exposure to oxygen prior to oxidation. Neither stacking faults nor dislocations were found to be associated with the Cu2O nucleation sites. The experimental data, including results from oxygen dissolution experiments and from repetitive oxidation-reduction-oxidation sequences, fit well into the framework of an oxidation process involving the formation of a surface charge layer, oxygen saturation of the metal with formation of a supersaturated zone near the surface, and nucleation followed by surface diffusion of oxygen and bulk diffusion of copper for lateral and vertical oxide growth, respectively.

Heinemann, K.↗

Aerosol and nucleation research in support of NASA cloud physics experiments in space

Tasks performed in the development of an ice nucleus generator which, within the facility concept of the ACPL, would provide a test aerosol suitable for a large number and variety of potential experiments are described. The impact of Atmospheric Cloud Physics Laboratory scientific functional requirements on ice nuclei generation and characterization subsystems was established. Potential aerosol generating systems were evaluated with special emphasis on reliability, repeatability and general suitability for application in Spacelab. Possible contamination problems associated with aerosol generation techniques were examined. The ice nucleating abilities of candidate test aerosols were examined and the possible impact of impurities on the nucleating abilities of those aerosols were assessed as well as the relative merits of various methods of aerosol size and number density measurements.

Vali, G.↗

Crystal nucleation in glass-forming alloy and pure metal melts under containerless and vibrationless conditions

Crystal nucleation behavior in metallic alloys known to form glasses in melt quenching was characterized and from this characterization the possibility that massive amounts of certain alloys could be slow cooled to the glass state was assessed. Crystal nucleation behavior of pure liquid metals was examined experimentally, under containerless conditions, and theoretically.

Turnbull, D.↗

Sudden grain nucleation and growth in supernova and nova ejecta

The thermal conditions leading to the rapid nucleation and growth of dust in astronomical explosions are examined. The contribution to nucleation physics lies only in the clarification of the ambient conditions where it apparently occurs. In both nova and interior shells of supernovae, dust precipitates in gas densities of the order of 10 to the -14th g/cu cm a few months after the explosion. The ambient conditions differ widely, however. Supernova condensation occurs in a thermal equilibrium, with photons, ions, electrons, and grains having equal temperatures. In novae huge disequilibria exist, with photon and electron temperatures near 50,000 K, photon energy density near 750 K, and forming refractory grains near 1800 K. In neither type of explosion can the condensed matter easily maintain chemical equilibrium with the total system. Interesting isotopic anomalies are trapped in both types of refractory condensate in the interstellar medium. The nova provides the best astronomical laboratory for observing the condensation.

Clayton, D. D.↗