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Bulk Formation of Metallic Glasses and Amorphous Silicon from the Melt

By using metallic glass compositions with a high relative glass transition temperature, such as Pd40Ni40P20, homogeneous nucleation also becomes negligible. Large (5g) masses of this alloys were obtained using a molten B2O3 flux. Presently, bulk glass formation in iron based glasses is being investigated. It is expected that if an undercooling of about 250K can be achieved in a Ge or Si melt, formation of the amorphous semiconductor phase (rather than the crystal) may be kinetically favored. The volumetric behavior of undercooled liquid Ga droplet dispersion is investigated by dilatometry. A theoretical model (both analytical and numerical) was developed for transient nucleation in glass forming melts. The model, originally designed for isothermal conditions, was extended to continuous quenching. It is being applied to glass formation in various metallic and oxide systems. A further refinement will be the inclusion of diffusion controlled interfacial rearrangements governing the growth of the crystal embryos.

Spaepen, F.↗

Structural Characterization of Solar Silicon

Compared to single crystal silicon, solar silicon generally contains large residual stresses and numerous structural defects. During subsequent processing, the defect structure can undergo further changes since, at the high temperatures required for diffusion, dislocations are sufficiently mobile to rearrange themselves in patterns which reduce long range residual stresses. This process, which is similar to the polygonization of strained metals, has no counterpart in single crystal silicon. Many of the solar silicon materials are grown from graphite dies and crucibles and therefore contain carbon concentrations in excess of 1E18. The interactions between carbon, crystal defects, intrinsic point defects, oxygen and diffusing dopants are discussed.

Ast, D. G.↗

Cast iron freezing mechanisms

This task focused on liquid phase sintering and infiltration studies of refractory metals and metal composites. Particular emphases was placed on those powered metal compacts which produce liquid alloys in sintering. For this class of materials, heating to a two phase region causes the constituent components to react, forming an alloy liquid which must wet the solid phase. Densification is initially driven by the free energy effects which cause rapid rearrangement. Further densification occurs by evaporation and condensation, surface diffusion, bulk flow, and volume diffusion.

Lillybeck, N. P.↗

Thermodynamic Derivation of the Activation Energy for Ice Nucleation

Cirrus clouds play a key role in the radiative and hydrological balance of the upper troposphere. Their correct representation in atmospheric models requires an understanding of the microscopic processes leading to ice nucleation. A key parameter in the theoretical description of ice nucleation is the activation energy, which controls the flux of water molecules from the bulk of the liquid to the solid during the early stages of ice formation. In most studies it is estimated by direct association with the bulk properties of water, typically viscosity and self-diffusivity. As the environment in the ice-liquid interface may differ from that of the bulk, this approach may introduce bias in calculated nucleation rates. In this work a theoretical model is proposed to describe the transfer of water molecules across the ice-liquid interface. Within this framework the activation energy naturally emerges from the combination of the energy required to break hydrogen bonds in the liquid, i.e., the bulk diffusion process, and the work dissipated from the molecular rearrangement of water molecules within the ice-liquid interface. The new expression is introduced into a generalized form of classical nucleation theory. Even though no nucleation rate measurements are used to fit any of the parameters of the theory the predicted nucleation rate is in good agreement with experimental results, even at temperature as low as 190 K, where it tends to be underestimated by most models. It is shown that the activation energy has a strong dependency on temperature and a weak dependency on water activity. Such dependencies are masked by thermodynamic effects at temperatures typical of homogeneous freezing of cloud droplets; however, they may affect the formation of ice in haze aerosol particles. The new model provides an independent estimation of the activation energy and the homogeneous ice nucleation rate, and it may help to improve the interpretation of experimental results and the development of parameterizations for cloud formation.

Cirrus clouds↗

Gas release and ordering of carbon in the Allende meteorite

An attempt is made to ascertain whether the inert gas atoms leave their carrier phases by volume diffusion, with intact internal phase frameworks, or are instead expelled from the solids as a results of substantial rearrangement, during release from samples of the Allende carbonaceous meteorite. Gas release over the 300-1100 C range was followed by Raman spectroscopic studies in the 1360 and 1580/cm wavelength bands of carbon. The results obtained indicate that the gas release at high temperatures is causally related to the ordering of carbon.

Heymann, D.↗

The Melting of Aqueous Foams

Diffusing-wave spectroscopy measurements show that ordinarily solid aqueous foams flow by a series of stick-slip avalanche-like rearrangements of neighboring bubbles from one tight packing configuration to another. Contrary to a recent prediction, the distribution of avalanche sizes do not obey a power-law distribution characteristic of self-organized criticality. This can be understood from a simple model of foam mechanics based on bubble-bubble interactions.

Durian, Douglas J.↗

Foam Optics and Mechanics

The Foam Optics and Mechanics (FOAM) project will exploit the microgravity environment to more accurately measure the rheological and optical characteristics of wet aqueous foams. Using both rheology and laser light scattering diagnostics, the goal is to quantify the unusual elastic character of foams in terms of their underlying microscopic structure and dynamics. Of particular interest is determining how the elastic character vanishes, i.e., how the foam 'melts' into a simple viscous liquid, as a function of both increasing liquid content and increasing shear strain rate. The unusual elastic character of foams will be quantified macroscopically by measurement of the shear stress as a function of shear strain rate and of time following a step strain. Such data will be analyzed in terms of a yield stress, shear moduli, and dynamical time scales. Microscopic information about bubble packing and rearrangement dynamics, from which the macroscopic non-Newtonian properties ultimately arise, will be obtained non-invasively by multiple-light scattering: diffuse transmission spectroscopy (DTS) and diffusing wave spectroscopy (DWS). Quantitative trends with materials parameters, most importantly average bubble size and liquid content, will be sought in order to elucidate the fundamental connection between the microscopic structure and dynamics and the macroscopic rheology.

Durian, Douglas J.↗

Microgravity Foam Structure and Rheology

To exploit rheological and multiple-light scattering techniques, and ultimately microgravity conditions, in order to quantify and elucidate the unusual elastic character of foams in terms of their underlying microscopic structure and dynamics. Special interest is in determining how this elastic character vanishes, i.e. how the foam melts into a simple viscous liquid, as a function of both increasing liquid content and shear strain rate. The unusual elastic character of foams will be quantified macroscopically by measurement of the shear stress as a function of static shear strain, shear strain rate, and time following a step strain; such data will be analyzed in terms of a yield stress, a static shear modulus, and dynamical time scales. Microscopic information about bubble packing and rearrangement dynamics, from which these macroscopic non-Newtonian properties presumably arise, will be obtained non-invasively by novel multiple-light scattering diagnostics such as Diffusing-Wave Spectroscopy (DWS). Quantitative trends with materials parameters, such as average bubble size, and liquid content, will be sought in order to elucidate the fundamental connection between the microscopic structure and dynamics and the macroscopic rheology.

Durian, Douglas J.↗

Irreversible wave-mean flow interactions in a mechanistic model of the stratosphere

A wave-1 minor warming is simulated in a mechanistic, global, primitive equation model. The modification of the zonal flow by the rearrangement of potential vorticity on a middle stratopheric isentrope is compared in a fully nonlinear model and in a model with only one wave and the zonal flow (a quasi-linear model). The permanent rearrangement of potential vorticity during the wave episode is more intense and more localized meridionally in the fully nonlinear model, which is able to capture the process of planetary wave breaking in some detail. Additional experiments reveal that the differences between the quasi-linear and nonlinear models persist for a broad range of wave amplitudes, and that the quasi-linear model can qualitatively reproduce the modification of the zonal flow by the wave when the diffusive dissipation of the wave is enhanced. These results are discussed in the context of the theory of barotropic Rossby waves in shear flows, and in comparison with recent numerical simulations of the middle atmosphere.

Robinson, Walter A.↗

Effect of salinity on the preservation of biomarkers in hypersaline microbial mat kerogens

Kerogen is the residue that remains after the minerals and organic compounds have been extracted from a rock using acid and organic solvents, respectively [1]. It is not only the largest organic carbon sink in the geological record but the best-preserved fraction due to its recalcitrance and ability to retain syngenetic source information during deposition [2]. Due to the complex, macromolecular, cross-linked polymeric structure of kerogen, it is difficult to analyse intact, often requiring breakdown into smaller subunits through thermal (pyrolysis) or chemical treatment (chemolysis) [3]. Saline and hypersaline environments host diverse microbial communities, which can trap and bind organic matrices such as cellular components (e.g., extracellular polymeric substances, cell wall, peptidoglycan, sheath material, etc.) with sediments, forming layered, laminated structures called microbial mats. Here we present depth profiles of two hypersaline cores through a microbial mat with differing total salinities. We looked at the composition of organic compounds released from kerogen during high temperature, hydrogen-assisted, pyrolysis to understand the effect of salinity on the composition and timing of their incorporation [4]. Field Site: The Exportadora del Sal S. A. (ESSA) saltern of Guerrero Negro (Baja California Sur, Mexico) lies within a typical sabhka environment adjacent to Laguna Ojo de Liebre. Note the spatial extent of the 13 major ponds of the ESSA system. The GN ponds thrive under well-monitored and stable conditions with steady state accretion and degradation of mat layers (around 0.5–1.4 cm per year). Organic mats typically attain up to 10 cm in thickness, depending on the location, which represents about 60 years of growth since these ponds were established. Sedimentation rate is rapid in these non-lithifying and non-mineralising mats, 1–1.5 cm per year. This environment is ideal for investigating in situ lipid preservation and diagenesis without the influence of constantly changing physical parameters. Methods: P4n5 and P5AB cores were collected as ~9 cm and 6.5 cm fresh cores, respectively, in June 2001 and September 2010, respectively from the ESSA saltern. The P4n5 core (9-9.1% salinity) was taken from Pond 4 near 5 and sub-divided into 10 layers. The P5AB core (11.2% salinity) was taken from Pond 5A near 5B and sub-divided into 8 layers. Lyophilised microbial mat powders were solvent-extracted using a modified Bligh-Dyer method and analysed by gas chromatography-mass spectrometry (GC-MS). Additionally, a subset of layers—layer 4 and layer 7—which represented active biomass and sediment-processed, respectively, were subjected to mild-acid methanolysis. The respective residues from conventional solvent extraction and acid methanolysis were loaded with a molybdenum sulfide catalyst and placed into a stainless-steel reactor. Samples were run on the hydropyrolysis set up (heated to 500 °C with 13-15 MPa of H2 pressure), extracted, and analysed by GC-MS. Results: Molecular profiles from the two ponds were significantly different and reflect the contributions of different photosynthetic and respiratory microbial communities to preserved organic matter. For example, the higher salinity P5AB core showed evidence of greater archaeal inputs (similarly observed in lab culture experiments [5]) as well as potential kerogen-bound carotenoids/carotenoid rearranged products or fragments. A hydrophobic emulsion formed during the acid methanolysis processing of layer 4 from both P4n5 and P5AB and layer 7 of P5AB. Hydropyrolysis of this hydrophobic residues released a greater abundance of polycyclic lipids relative to the pre-extracted control. Implications and Future Work: Catalytic hydropyrolysis of kerogen can rapidly generate abundant saturated pyrolysate products from the bound biomarker pool without altering the structures or stereochemistries of the products [6]. Chemical processing of solvent-extractable residues indicated that cellular matrices such as extracellular polymeric substances (EPS) may play a role in the sequestration of polycyclic lipid biomarkers such as steranes and hopanes. Their higher relative abundance compared to the pre-extracted control in the higher salinity layers and cores preliminarily aligns with this hypothesis, although further experiments are required to confirm this. It has been well-documented that EPS plays an important role in mineralisation, specifically carbonate formation, in microbial ecosystems. EPS can enhance calcium carbonate precipitation by providing diffusion-limited sites that create alkalinity gradients in response to microbial processes [7]. It has been experimentally demonstrated that salinity influences the total amount of EPS (both loosely- and tightly-bound) which increases with increasing salinity [8]. The higher salinity at Guerrero Negro switches the microbial population from filamentous Microcoleus to being dominated by Phormidium, Oscillatoria, and unicellular cyanobacteria. We demonstrated that lipid binding into kerogen via strong covalent linkages occurs at the very earliest stages of sedimentary diagenesis. We are currently investigating the influence of salinity on organic preservation through experimental and modelling approaches. Understanding how key biomarkers transform into preserved organic matter (i.e., from precursor biolipids to bound geolipids) in brine ecosystems will aid the search for organic biosignatures on other planetary bodies, especially Icy Moons and modern Mars.

hypersaline↗