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Closed-loop process produces semiconductor-grade silicon. Metallurgical-grade silicon converted to ultrapure silicon by reacting with hydrogen and silicon tetrahalide to form trihalosilane, purifying this intermediate and again decomposing to high purity silicon in third stage. Heterogeneously and homogeneously nucleated polycrystalline silicon used in semiconductor device applications and in silicon photovoltaic solar cell fabrication.
A new classification scheme of the IRAS LRS carbon stars is presented. It comprises the separation of 718 probable carbon stars into 12 distinct self-similar spectral groupings. Continuum temperatures are assigned and range from 470 to 5000 K. Three distinct dust species are identifiable: SiC, alpha:C-H, and MgS. In addition to the narrow 11 + micron emission feature that is commonly attributed to SiC, a broad 11 + micron emission feature, that is correlated with the 8.5 and 7.7 micron features, is found and attributed to alpha:C-H. SiC and alpha:C-H band strengths are found to correlate with the temperature progression among the Classes. We find a spectral sequence of Classes that reflects the carbon star evolutionary sequence of spectral types, or alternatively developmental sequences of grain condensation in carbon-rich circumstellar shells. If decreasing temperature corresponds to increasing evolution, then decreasing temperature corresponds to increasing C/O resulting in increasing amounts of carbon rich dust, namely alpha:C-H. If decreasing the temperature corresponds to a grain condensation sequence, then heterogeneous, or induced nucleation scenarios are supported. SiC grains precede alpha:C-H and form the nuclei for the condensation of the latter material. At still lower temperatures, MgS appears to be quite prevalent. No 11.3 micron PAH features are identified in any of the 718 carbon stars. However, one of the coldest objects, IRAS 15048-5702, and a few others, displays an 11.9 micron emission feature characteristic of laboratory samples of coronene. That feature corresponds to the C-H out of plane deformation mode of aromatic hydrocarbon. This band indicates the presence of unsaturated, sp(sup 3), hydrocarbon bonds that may subsequently evolve into saturated bonds, sp(sup 2), if, and when, the star enters the planetary nebulae phase of stellar evolution. The effusion of hydrogen from the hydrocarbon grain results in the evolution in wavelength of this 11.9 micron emission feature to the 11.3 micron feature.
A new classification scheme of the IRAS LRS carbon stars is presented. It comprises the separation of 718 probable carbon stars into 12 distinct self-similar spectral groupings. Continuum temperatures are assigned and range from 470 to 5000 K. Three distinct dust species are identifiable: SiC, alpha:C-H, and MgS. In addition to the narrow 11 + micron emission feature that is commonly attributed to SiC, a broad 11 + micron emission feature, that is correlated with the 8.5 and 7.7 micron features, is found and attributed to alpha:C-H. SiC and alpha:C-H band strengths are found to correlate with the temperature progression among the Classes. We find a spectral sequence of Classes that reflects the carbon star evolutionary sequence of spectral types, or alternatively developmental sequences of grain condensation in carbon-rich circumstellar shells. If decreasing temperature corresponds to increasing evolution, then decreasing temperature corresponds to increasing CIO resulting in increasing amounts of carbon rich dust, namely alpha:C-H. If decreasing the temperature corresponds to a grain condensation sequence, then heterogeneous, or induced nucleation scenarios are supported. SiC grains precede alpha:C-H and form the nuclei for the condensation of the latter material. At still lower temperatures, MgS appears to be quite prevalent. No 11.3 micron PAH features are identified in any of the 718 carbon stars. However, one of the coldest objects, IRAS 15048-5702, and a few others, displays an 11.9 micron emission feature characteristic of laboratory samples of coronene. That feature corresponds to the C-H out of plane deformation mode of aromatic hydrocarbon. This band indicates the presence of unsaturated, sp(sup 3), hydrocarbon bonds that may subsequently evolve into saturated bonds, sp(sup 2), if, and when, the star enters the planetary nebulae phase of stellar evolution. The effusion of hydrogen from the hydrocarbon grain results in the evolution in wavelength of this 11.9 micron emission feature to the 11.3 micron feature.
A one-dimensional, time-dependent model is used to study the chemical, microphysical, and radiative properties of volcanic aerosols produced by the Mount Pinatubo eruption on June 15, 1991. Our model treats gas-phase sulfur photochemistry, gas-to-particle conversion of sulfur, and the microphysics of sulfate aerosols and ash particles under stratospheric conditions. The dilution and diffusion of the volcanic eruption clouds are also accounted for in these conditions. Heteromolecular homogeneous and heterogeneous binary H2SO4/H2O nucleation, acid and water condensational growth, coagulation, and gravitational sedimentation are treated in detail in the model. Simulations suggested that after several weeks, the volcanic cloud was composed mainly of sulfuric acid/water droplets produced in situ from the SO2 emissions. The large amounts of SO2 (around 20 Mt) injected into the stratosphere by the Pinatubo eruption initiated homogeneous nucleation which generated a high concentration of small H2SO4/H2O droplets. These newly formed particles grew rapidly by condensation and coagulation in the first few months and then reach their stabilized sizes with effective radii in a range between 0.3 and 0.5 micron approximately one-half year after the eruption. The predicted volcanic cloud parameters reasonably agree with measurements in term of the vertical distribution and lifetime of the volcanic aerosols, their basic microphysical structures (e.g., size distribution, concentration, mass ratio, and surface area) and radiative properties. The persistent volcanic aerosols can produce significant anomalies in the radiation field, which have important climatic consequences. The large enhancement in aerosol surface area can result in measurable global stratospheric ozone depletion.
Recent high-altitude aircraft measurements with in situ imaging instruments indicated the presence of relatively large (approx.100 microns length), thin (aspect ratios of approx.6:1 or larger) hexagonal plate ice crystals near the tropical tropopause in very low concentrations (<0.01/L). These crystals were not produced by deep convection or aggregation. We use simple growth-sedimentation calculations as well as detailed cloud simulations to evaluate the conditions required to grow the large crystals. Uncertainties in crystal aspect ratio leave a range of possibilities, which could be constrained by knowledge of the water vapor concentration in the air where the crystal growth occurred. Unfortunately, water vapor measurements made in the cloud formation region near the tropopause with different instruments ranged from <2 ppmv to approx.3.5 ppmv. The higher water vapor concentrations correspond to very large ice supersaturations (relative humidities with respect to ice of about 200%). If the aspect ratios of the hexagonal plate crystals are as small as the image analysis suggests (6:1, see companion paper (Lawson et al., 2008)) then growth of the large crystals before they sediment out of the supersaturated layer would only be possible if the water vapor concentration were on the high end of the range indicated by the different measurements (>3 ppmv). On the other hand, if the crystal aspect ratios are quite a bit larger (approx.10:1), then H2O concentrations toward the low end of the measurement range (approx.2-2.5 ppmv) would suffice to grow the large crystals. Gravity-wave driven temperature and vertical wind perturbations only slightly modify the H2O concentrations needed to grow the crystals. We find that it would not be possible to grow the large crystals with water concentrations less than 2 ppmv, even with assumptions of a very high aspect ratio of 15 and steady upward motion of 2 cm/s to loft the crystals in the tropopause region. These calculations would seem to imply that the measurements indicating water vapor concentrations less than 2ppmv are implausible, but we cannot rule out the possibility that higher humidity prevailed upstream of the aircraft measurements and the air was dehydrated by the cloud formation. Simulations of the cloud formation with a detailed model indicate that homogeneous freezing should generate ice concentrations larger than the observed concentrations (20/L), and even concentrations as low as 20/L should have depleted the vapor in excess of saturation and prevented growth of large crystals. It seems likely that the large crystals resulted from ice nucleation on effective heterogeneous nuclei at low ice supersaturations. Improvements in our understanding of detailed cloud microphysical processes require resolution of the water vapor measurement discrepancies in these very cold, dry regions of the atmosphere.
The undercooling behavior of large spheroids of Pd40Ni40P40 was investigated. By surface etching, supporting the specimens on a fused silica substrate, and successive heating and cooling, crystallization can be eliminated, presumable due to the removal of surface heterogeneities. By this method samples up to 3.2g with a 0.53 mm minor diameter, were made entirely glassy, except for some superficial crystals comprising less than 0.5% of the volume. These experiments show that a cooling rate of approximately 1 K/sec is adequate to avoid copious homogeneous nucleation in the alloy, and that by eliminating or reducing the effectiveness of heterogeneous nucleation sites, it is possible to form bulk samples of this metallic glass with virtually unlimited dimensions.
Current models estimate global aviation contributes approximately 5% to the total anthropogenic climate forcing, with aerosol-cloud interactions having the greatest effect. However, radiative forcing estimates from aviation aerosol-cloud interactions remain undetermined. There is an expected significant increase in aircraft emissions with aviation demand expected to rise by over 4% per year. Soot may play an important role in the ice nucleation of aircraft-induced cirrus formation due to a high emission rate, but the ice nucleating properties are poorly constrained. Understanding the microphysical processes leading to atmospheric ice crystal formation is crucial for the reliable parameterization of aerosol-cloud interactions in climate models due to their impact on precipitation and cloud radiative properties. Ice nucleation of aircraft-emitted soot is potentially affected by particle morphology with condensation of supercooled water occurring in pores followed by ice nucleation. However, soot has heterogeneous properties and undergoes atmospheric aging and oxidation that could change surface properties and contribute to complex ice nucleation processes. Further, this review synthesizes current knowledge of ice nucleation catalyzed by aviation in the cirrus regime and its effects on global radiative forcing. Further research is required to determine the ice nucleation and microphysical processes of cirrus cloud formation from aviation emissions in both controlled laboratory and field investigations to inform models for more accurate climate predictions and to provide efficient mitigation strategies.
The present theoretical analysis of particle formation mechanisms at conditions relevant to the troposphere and stratosphere of Neptune indicates that the hydrocarbon-nucleation process in the lower stratosphere is very inefficient, because saturation ratios much greater than unity are required in the cases of aerosol formation by homogeneous, heterogeneous, and ion-induced nucleation. The latter two of these, however, should be possible on Neptune for most of the complex hydrocarbon species in question. The relative effectiveness of heterogeneous and ion-induced nucleation depends on the physical and thermodynamic properties of the species in question, condensable-species abundance, supersaturation temperatures, and the number and type of available condensation ions or nuclei.
Containerless processing using electromagnetic levitation (EML) is a powerful technique in the investigation of reactive molten metal systems. On ground, the power required to overcome the weight of the sample is sufficient to cause significant heating and induce substantial melt convection. In microgravity, the heating and positioning fields may be decoupled and the field strength may be varied to achieve the desired level of convection within the limits set by the geometry of the levitation coil and the sample size. From high-speed digital images of the double recalescence behavior of Fe-Cr-Ni alloys in ground-based testing and in reduced-gravity aboard the NASA KC-135 parabolic aircraft, we have shown that phase selection can be predicted based on a growth competition model. An important parameter in this model is the delay time between primary nucleation and subsequent nucleation of the stable solid within the liquid/metastable solid array. This delay time is a strong function of composition and a weak function of the undercooling of the melt below the metastable liquidus. From the results obtained during the first Microgravity Sciences Laboratory (MSL-1) mission, we also know that convection may significantly influence the delay time, especially at low undercoolings. Currently, it is unclear what mechanism controls the formation of a heterogeneous site that allows nucleation of the austenitic phase on the pre-existing ferrite skeleton. By examining the behavior of the delay time under different convective conditions, we hypothesize that we can differentiate between several of these mechanisms to gain an understanding of how to control microstructural. evolution. We will anchor these predictions by examining samples quenched at different times following primary recalescence in microgravity. A second important parameter in the growth competition model is the identification of the growth rate of the stable phase into the semi-solid array that formed during primary recalescence. Current dendritic growth theory is inadequate in predicting solidification behavior under these conditions as metallographic analyses show that stable phase growth proceeds along the interface between the metastable solid and residual liquid. Since growth velocity is independent of the initial undercooling relative to the metastable liquidus, we hypothesize that purely thermal effects can be separated from other important growth model parameters by careful selection of the liquid composition in a ternary system.
Aerosols modify cloud microphysical and radiative properties and thus impact the shortwave (SW) and longwave cloud forcing (LWCF). This study first reports the finding of contrasting aerosol effects on LWCF in South East Asia and Amazon in the Community Atmosphere Model version 5.3 (CAM5.3), which corresponds to the sum of LW indirect and semi-direct effects investigated in Ghan et al., (2012). A series of numerical experiments is conducted to decompose the complex aerosol effects on LWCF. Our analysis indicates that the cooling (negative aerosol effects on LWCF) in Amazon is due mainly to the aerosol effects on warm clouds and the inhibition of vertical motion by the aerosol-induced radiative cooling. In contrast, the warming (positive aerosol effects on LWCF) in South East Asia is due mainly to the aerosol effect on homogeneous freezing, thus reducing the ice particle size and prolonging the existence of ice cloud. Our results emphasize that a comprehensive analysis of integrated aerosol effects on both warm and ice clouds is necessary for better understanding the aerosol effects on LWCF.
Opportunities and problems associated with conducting containerless glass experiments in a microgravity environment are examined. Particular aspects of gel-derived glasses for space processing research are discussed, along with current space-related research activities in areas of amorphous phase separation, crystallization, and heterogeneous and homogeneous crystal nucleation.
An ideal backmixed reactor model (CSTR) and a fluidized bed bubbling reactor model (FBBR) were developed for silane pyrolysis. Silane decomposition is assumed to occur via two pathways: homogeneous decomposition and heterogeneous chemical vapor deposition (CVD). Both models account for homogeneous and heterogeneous silane decomposition, homogeneous nucleation, coagulation and growth by diffusion of fines, scavenging of fines by large particles, elutriation of fines and CVD growth of large seed particles. At present the models do not account for attrition. The preliminary comparison of the model predictions with experimental results shows reasonable agreement. The CSTR model with no adjustable parameter yields a lower bound on fines formed and upper estimate on production rates. The FBBR model overpredicts the formation of fines but could be matched to experimental data by adjusting the unkown jet emulsion exchange efficients. The models clearly indicate that in order to suppress the formation of fines (smoke) good gas-solid contacting in the grid region must be achieved and the formation of the bubbles suppressed.
This work presents the development of a two-moment cloud microphysics scheme within the version 5 of the NASA Goddard Earth Observing System (GEOS-5). The scheme includes the implementation of a comprehensive stratiform microphysics module, a new cloud coverage scheme that allows ice supersaturation and a new microphysics module embedded within the moist convection parameterization of GEOS-5. Comprehensive physically-based descriptions of ice nucleation, including homogeneous and heterogeneous freezing, and liquid droplet activation are implemented to describe the formation of cloud particles in stratiform clouds and convective cumulus. The effect of preexisting ice crystals on the formation of cirrus clouds is also accounted for. A new parameterization of the subgrid scale vertical velocity distribution accounting for turbulence and gravity wave motion is developed. The implementation of the new microphysics significantly improves the representation of liquid water and ice in GEOS-5. Evaluation of the model shows agreement of the simulated droplet and ice crystal effective and volumetric radius with satellite retrievals and in situ observations. The simulated global distribution of supersaturation is also in agreement with observations. It was found that when using the new microphysics the fraction of condensate that remains as liquid follows a sigmoidal increase with temperature which differs from the linear increase assumed in most models and is in better agreement with available observations. The performance of the new microphysics in reproducing the observed total cloud fraction, longwave and shortwave cloud forcing, and total precipitation is similar to the operational version of GEOS-5 and in agreement with satellite retrievals. However the new microphysics tends to underestimate the coverage of persistent low level stratocumulus. Sensitivity studies showed that the simulated cloud properties are robust to moderate variation in cloud microphysical parameters. However significant sensitivity in ice cloud properties was found to variation in the dispersion of the ice crystal size distribution and the critical size for ice autoconversion. The implementation of the new microphysics leads to a more realistic representation of cloud processes in GEOS-5 and allows the linkage of cloud properties to aerosol emissions.
The relative importance of heterogeneous and homogeneous ice nucleation for cirrus formation remains an active area of debate in the cloud physics community. From a theoretical perspective, a number of modeling studies have investigated the sensitivity of ice number concentration to the nucleation mechanism and the abundance of ice nuclei. However, these studies typically only addressed ice concentration immediately after ice nucleation. Recent modeling work has shown that the high ice concentrations produced by homogeneous freezing may not persist very long, which is consistent with the low frequency of occurrence of high ice concentrations indicated by cirrus measurements. Here, I use idealized simulations to investigate the impact of ice nucleation mechanism and ice nuclei abundance on the full lifecycle of cirrus clouds. The primary modeling framework used includes different modes of ice nucleation, deposition growth/sublimation, aggregation, sedimentation, and radiation. A limited number of cloud-resolving simulations that treat radiation/dynamics interactions will also been presented. I will show that for typical synoptic situations with mesoscale waves present, the time-averaged cirrus ice crystal size distributions and bulk cloud properties are less sensitive to ice nucleation processes than might be expected from the earlier simple ice nucleation calculations. I will evaluate the magnitude of the ice nuclei impact on cirrus for a range of temperatures and mesoscale wave specifications, and I will discuss the implications for cirrus aerosol indirect effects in general.
In this talk, I will begin by discussing the physical processes that govern the competition between heterogeneous and homogeneous ice nucleation in upper tropospheric cirrus clouds. Next, I will review the current knowledge of low-temperature ice nucleation from laboratory experiments and field measurements. I will then discuss the uncertainties and deficiencies in representations of cirrus processes in global models used to estimate the climate impacts of changes in cirrus clouds. Lastly, I will review the critical field measurements needed to advance our understanding of cirrus and their susceptibility to changes in aerosol properties.
Particle size distributions are used to calculate nucleation rates during new particle formation (NPF). However, the low time resolution and poor sensitivity of instruments deployed to observe particle size distributions can lead to inaccurate estimates of nucleation rates. We calculated nucleation rates in Pittsburgh, PA from particle size distributions measured with the new high time resolution Condensation Particle Counters For Atmospheric Rapid Measurements (CPC FARM) and from gas precursor concentrations measured with a chemical ionization mass spectrometer. The CPC FARM nucleation rates were calculated by examining the appearance rate of particles in the smallest size bin at 1.6 nm. The nucleation rate of 1.6 nm determined every second resulted in positive and negative rates, indicating the influence of inhomogeneous mixing and advection of precursor gases and clusters. These effects are not currently considered when estimating nucleation rates from measurements. The nucleation rates from the CPC FARM were compared to the nucleation rates determined from a transient acid‐base reaction model using measured sulfuric acid concentration, strong base concentrations, and CPC detection efficiencies. The transient form of the model allowed the advection of heterogeneously mixed precursors to influence the nucleation rate. Good agreement between particle and gas‐based nucleation rates is observed during sulfuric acid‐driven NPF events. This study demonstrates that high time resolution measurements of short‐lived and rapidly formed particles are needed to accurately capture nucleation rates, which are likely influenced by advection of nucleation precursors and clusters in heterogeneous environments such as urban areas.
Polyethylene-grafted nanoparticles (NPs) are organized into a variety of assemblies in a polydisperse polyethylene melt by tailoring the graft density and molecular weights of the graft chains. Under these conditions we systematically vary NP assemble state and study is consequences on crystal nucleation and growth rates. We find that the nucleation rate is suppressed below that of the unfilled polymer for good NP spatial dispersion. However, poorer dispersion, which leads to the formation of NP assemblies, can accelerate nucleation likely by providing multiple heterogenous sites due to topographical features. We find that a key parameter, the chain overcrowding in the brush, can predict these nucleation trends – in this language, the most enhanced nucleation rate is found when the grafts are the most overcrowded, and hence the least interpenetrated with the matrix chains. This result is consistent with one other literature result which utilized short crystallizable polyethylene glycol grafts in short PEO matrices. The growth kinetics were retarded for all nanocomposites, their temperature dependences were essentially equal to that for the pure polymer (in the absence of NPs) – the NPs thus do not affect secondary nucleation, indicating that the transport of the matrix to the growth front is the rate determining step. Thus, evidently the increase in matrix viscosity, or reduction in growth rates, is directly determined by the agglomeration state of the NPs. These results are consistent with past works with bare silica NPs in PEO, and with silica NPs grafted with amorphous chains in a PEO matrix, suggesting that growth kinetics in these systems apparently follow “universal” behavior. Additionally, there are initial hints that the ratio of the effective surface area of the NP clusters per unit matrix volume provides a unified description of the NP induced confinement that slows growth kinetics. Furthermore, our work thus shows that there is an evolving understanding of the role of NPs on crystallization kinetics, in particular crystal growth where trends appear to be independent of the grafts ability to crystallize.
Additives, such as ions, small molecules, and macromolecules, have been found to regulate the formation of CaCO 3 and control its morphologies and properties. However, a single additive usually affects dominantly one process in CaCO 3 's formation and is seldom found to significantly affect multiple CaCO 3 formation processes. In this work, we used in situ grazing incidence X-ray techniques to observe the heterogeneous formation of CaCO 3 and found that a series of formation processes (i.e., nucleation, growth, and Ostwald ripening) were modulated by sulfate. In the nucleation process, increased interfacial free energy and bulk free energy cooperatively increased the nucleation barrier and decreased nucleation rates. In the growth process, sulfate reduced the electrostatic repulsion between CaCO 3 precursors and nuclei, promoting CaCO 3 growth. This influence on the growth counteracted the inhibition effect in the nucleation process, causing a nearly 100% increase in the volume of heterogeneously formed CaCO 3 . Meanwhile, adsorbed sulfate on CaCO 3 nuclei may poison the surface of smaller CaCO 3 nuclei, inhibiting Ostwald ripening. These revealed sulfate's active roles in controlling CaCO 3 formation advance our understanding of sulfate-incorporated biomineralization and scaling phenomena in natural and engineered aquatic environments.