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At least 181 records · Page 10

Study of Ice Particle Formation and Lifetime in Space Environment

The ice particles are formed when liquid and/or humid gases vent to the space. These submicroscopic ice particles are potential contamination sources of the environments during Skylab operations. The critical size of ice particle and its nucleation rate based on the theory of homogeneous and heterogeneous nucleation by sublimation are analyzed. The equations which are pertinent for studying the growth and evaporation of the ice particles are formulated. The mechanisms affecting the lifetime of ice particle are discussed. The gas dynamic techniques for experimental study of ice particle formation are proposed.

Jeng, D.↗

Crystal nucleation in amorphous (Au/100-y/Cu/y/)77Si9Ge14 alloys

Because, unlike most metallic glasses, melt-spun alloys of the series (Au/100-y/Cu/y/)77Si9Ge14 exhibit well separated glass transition and kinetic crystallization temperatures, crystallization can be studied in the fully relaxed amorphous phase. An isothermal calorimetric analysis of the devitrification kinetics of the amorphous alloy indicates sporadic nucleation and a constant growth rate. It is found for the cases of alloys with y values lower than 25 that the classical theory of homogeneous nucleation is consistent with observations, including transient effects. An analysis of the crystallization kinetics shows that slow crystal growth rates play an important role in glass formation in these alloys. Although the reduced glass transition temperature increases with Cu content, glass formation is more difficult at high Cu contents, perhaps because of a difference in nucleus composition.

Thompson, C. V.↗

Nucleation and growth of molybdenum disulfide grown by thermal atomic layer deposition on metal oxides

To enable greater control over thermal atomic layer deposition (ALD) of molybdenum disulfide (MoS 2 ), here we report studies of the reactions of molybdenum hexafluoride (MoF 6 ) and hydrogen sulfide (H 2 S) with metal oxide substrates from nucleation to few-layer films. In situ quartz crystal microbalance experiments performed at 150, 200, and 250 °C revealed temperature-dependent nucleation behavior of the MoF 6 precursor, which is attributed to variations in surface hydroxyl concentration with temperature. In situ Fourier transform infrared spectroscopy coupled with ex situ x-ray photoelectron spectroscopy (XPS) indicated the presence of molybdenum oxide and molybdenum oxyfluoride species during nucleation. Density functional theory calculations additionally support the formation of these species as well as predicted metal oxide to fluoride conversion. Residual gas analysis revealed reaction by-products, and the combined experimental and computational results provided insights into proposed nucleation surface reactions. With additional ALD cycles, Fourier transform infrared spectroscopy indicated steady film growth after ~13 cycles at 200 °C. XPS revealed that higher deposition temperatures resulted in a higher fraction of MoS 2 within the films. Deposition temperature was found to play an important role in film morphology with amorphous films obtained at 200 °C and below, while layered films with vertical platelets were observed at 250 °C. Finally, these results provide an improved understanding of MoS 2 nucleation, which can guide surface preparation for the deposition of few-layer films and advance MoS 2 toward integration into device manufacturing.

36 MATERIALS SCIENCE↗

The Birth of Minerals: From Single Step to Multiple Step Mechanisms

Mineral formation from ions in aqueous solutions begins with complex initial stages, where amorphous and liquid-like precursors play pivotal roles before crystalline growth occurs. Both classical and non-classical nucleation and growth theories, introduced in previous chapters, offer explanations, each with their own strengths and limitations, for the complex intermediate phases observed in experimental research. Analytical techniques play a critical role in detecting and characterizing precursor phases, offering valuable insights into nucleation and growth mechanisms across various temporal and spatial scales. In conclusion, molecular dynamics and modelling provide in-depth perspectives on these phases, allowing for a closer examination of their nucleation and growth mechanisms at the molecular level, and revealing the intricate processes that govern their behaviour.

amorphous↗

The kinetics of lunar glass formation, revisited

The nucleation frequency of Lunar Composition 70019, a lithified soil breccia from the center of a small crater in the Taurus-Littrow Valley, is determined using a relation that describes nucleation throughout the volume of a liquid together with measurements of the time required at temperatures of 780 to 930 C to obtain sensibly crystalline bodies. Curves indicating the time required at a given temperature to reach a particular fraction crystallized are shown to have the general form predicted by kinetic analysis. Nucleation frequencies are evaluated by applying such analysis to a curve representing the transition between glassy material and material with a sensible degree of crystallinity. The results obtained are found to be in excellent agreement with the values expected from the classical theory of homogeneous nucleation, indicating that such nucleation represents the dominant contribution to crystal formation, at least over the range of undercoolings covered (250 to 400 C).

Klein, L. C.↗

The melt memory effects in polymer crystallization

This paper presents a systematic review of the literature on the melt memory effects observed in polymers, an area that has engendered considerable debate for over 50 years. Recent advances in experimental techniques have provided fresh insights into how a polymer's thermal history influences its recrystallization behavior. It has been observed that given other conditions unchanged, the crystallization temperature during recrystallization decreases with an increase in the melt temperature T s above the melting point T m until a critical melt temperature is attained. This phenomenon also extends to the half-time of crystallization and the secondary structures, such as lamellar thickness, of semi-crystalline polymers. Despite these findings, a comprehensive constitutive model that encapsulates polymer melt memory effects remains elusive. Cutting-edge instrumentation, including in situ small and wide-angle X-ray scattering, temperature-controlled Fourier transform infrared spectroscopy, and flash differential scanning calorimetry, have posed significant challenges to the traditional nucleation and growth models established in the 1970s. These models are foundational to our understanding of polymer crystallization, which is an integral part of polymer processing and production. In this review, the historical contours of this discourse are traced, with an examination of both the recent experimental breakthroughs and theoretical advancements pertinent to polymer melt memory effects. In conclusion, this paper delves into the prevailing theories of polymer nucleation and crystallization and engages with theoretical discussions and numerical simulations that attempt to elucidate and rationalize these melt memory phenomena.

36 MATERIALS SCIENCE↗

Revealing and Engineering Assembly Pathways of 3D DNA Origami Crystals

Recent developments in nanomaterial self-assembly demonstrate the capability to create tailored nanostructures by engineering both the binding coordination and specificity of interactions between material subunits. DNA origami frames allow for the design and fabrication of a broad variety of ordered 3D nanoscale architectures through self-assembly, facilitated by frame-to-frame bonds with designable strength and specificity. While the bond design is critical to lattice formation, the assembly process itself is often dependent on a thermal pathway. Highly ordered nanoscale frameworks, assembled from DNA frames, are predominantly crystallized through thermal annealing pathways that typically follow a “slow” cooling approach, with experiments on the time scale of days yielding DNA origami crystals in the range of 1−10 μm. This extended assembly time scale hinders the study of crystal formation pathways, necessitating a deeper understanding of factors governing successful annealing. Lack of insight into time scale also presents a practical limitation for material fabrication. Here, we investigate key factors affecting lattice assembly pathways and demonstrate that precise engineering of assembly conditions greatly reduces assembly times by up to nearly 2 orders of magnitude. We evaluate the nucleation and growth of crystals via optical and electron microscopy, and small-angle X-ray scattering techniques, mapping the time−temperature-transformation of superlattices from the melt through single-crystal optical tracking. The results show that origami frame assembly can be described by classical nucleation and growth theory, which can, in turn, be used to prescribe the growth of the crystals. Lastly, these findings are applied to demonstrate thermal pathway-dependent assembly, forming distinct assemblies based on different thermal annealing profiles.

36 MATERIALS SCIENCE↗

Relative phase stability of L1 2 and DO 22 /DO 23 structures in Al 3 Nb, Al 3 Zr and Al 3 V compounds

The relative stability of the different tri-aluminide (Al 3 M) phases in three binary systems (M = Zr, Nb and V) was assessed for their potential to form fine cubic L1 2 precipitates in additively manufactured alloys. Supersaturated thin films of Al-(8–30) at% M were sputtered and heat treated during in-situ x-ray diffraction (XRD) measurements to observe the temperature ranges of stability for each phase. As-sputtered films were then processed with laser tracks simulating additive manufacturing solidification conditions, and the formation of phases in the laser tracks was correlated with density functional theory (DFT) and nucleation rate calculations. We found that the metastable L1 2 structure is highly competitive with the stable DO 23 structure in the Al-Zr system, but much less stable than the DO 22 structure in the Al-Nb system, and both the DO 22 and Al 8 V 5 structure in the Al-V system. Furthermore, these experimental results were found to be in good agreement with the DFT and kinetic calculations, as we determined that the metastable L1 2 in Al-Zr only requires a small amount of undercooling to favor its nucleation over the stable DO 23 , suggesting additive manufacturing can be a viable pathway to develop Al-Zr alloys strengthened by a high volume fraction of L1 2 Al 3 Zr phase.

Perrin, Alice E. [Oak Ridge National Laboratory (O↗

Theory of time-dependent rupture in the Earth

Fracture mechanics is used to develop a theory of earthquake mechanism which includes the phenomenon of subcritical crack growth. The following phenomena are predicted: slow earthquakes, multiple events, delayed multiple events (doublets), postseismic rupture growth and afterslip, foreshocks, and aftershocks. The theory predicts a nucleation stage prior to an earthquake, and suggests a physical mechanism by which one earthquake may 'trigger' another.

Das, S.↗

X-Ray Characterization of Structural Defects in Seeded and Self-Seeded ZnSe Crystal Grown by PVT in Horizontal and Vertical Configurations

As part of a pre-flight ground based investigation of crystal growth of II-VI compound semiconductors, a number of ZnSe boules have been grown by physical vapor transport (PVT) at Marshall Space Flight Center. Boules were grown in both horizontal and vertical configurations and seeded and self-seeded growth techniques were employed. As-grown and/or cleaved boules were examined by a combination of synchrotron white beam x-ray topography (SWBXT) and high resolution triple axis diffraction (HRTXD) to characterized the structural defects and correlate them with the growth conditions. Horizontal grown boules tend to grow away from the ampoule wall (contactless growth) and generally exhibit large (110) facets parallel to the gravity vector. Vertical grown boules grew to the full diameter of the ampoule and exhibited no faceting. X-ray topography combined with back reflection x-ray diffraction revealed the presence of lamellar twins (180 deg type about the [111] axis) in horizontal grown boules while vertically grown boules contain a few large grains, some of which are twinned. X-ray topographs and reciprocal space maps recorded from the boules show the better crystal quality of horizontal grown boules. The relationship between crystal quality and gravity vector is investigated. Further, an attempt is made to extend the Hurle theory of twin nucleation in Czochralski grown crystals to explain the twinning mechanisms in horizontal grown boules.

Raghothamachar, B.↗

Influence of Nucleation Mechanisms on the Radiative Properties of Deep Convective Clouds and Subvisible Cirrus in CRYSTAL/FACE

During the past few years we have conducted work on several different topics, as reflected by our publications. As one of the Co-Project scientists for The Cirrus Regional Study of Tropical Anvils and Cirrus Layers - Florida Area Cirrus Experiment (CRYSTAL FACE) we worked to help design the mission and then conduct it in the field. Another major activity during the past two years has been to pull together various groups to formulate plans for follow on missions to CRYSTAL FACE. We organized a workshop at the University of Colorado during the summer of 2003 to assess the best locations for future missions. Working with a group of about 10 scientists from around the country we prepared a science-planning document (Tropical Composition, Cloud and Climate Coupling Experiment (TC(sup 4)) that outlined the rationale, locations, strategy to accomplish the goals, and possible payloads for a set of three tropical missions. We also prepared background materials for various NRAs being prepared at NASA Headquarters for missions in Costa Rica, Darwin and Guam. In conjunction with the group at NASA Ames we have helped build a new numerical model for deep convection and have applied that model to simulate the CRYSTAL data. Our goal in particular has been to better understand how convection distributes water vapor isotopes. CRYSTAL observations of water isotopes are very different from those suggested by previous workers who assumed the isotopes would obey Rayleigh fractionation. The water isotope study has several implications. First it is a check on the realism of the deep convection model. Second, the isotopes are a measure of the precipitation removal in the atmosphere. Hence they provide a constraint on a parameter that is difficult to otherwise measure. Finally it has been suggested that isotopes may be the key to unraveling the water transport into the stratosphere and upper troposphere. Such transport is critical both for the radiation balance and for stratospheric chemistry. Ours is the first model that is able to treat this transport. Our initial results have just been submitted to Geophys. Res. Lett (Smith et al., 2005). Essentially we are able to explain the vertical profiles of isotopes in the tropical tropopause transition layer. We are also able to account for stratospheric humidity and isotope abundances with this model. We have also been heavily involved in trying to improve our understanding of nitric acid condensation on ice. Gao et al (2004) have shown that water supersaturations above ice occur when the atmosphere is supersaturated with respect to nitric acid trihydrate. As one of the co-authors of that work, we suggested the mechanism that may explain why this is occurring. Essentially, ice does not like to grow near unit supersaturation, but does so because the water molecules can find sites on the ice surface to attach themselves to before they fly off the ice surface. This phenomena was well known in the 1960s when it was a source of debate about whether condensation and evaporation coefficients for ice would be the same. Evaporation does not require any molecular orientation, while condensation does, so it was possible that the coefficients would differ. They don't differ because the water molecules rapidly move across the surface and find places to attach. Nitric acid may be occupying these preferred sites and therefore the water molecules can't find a desirable place to attach. We anticipate that this research will be the subject of laboratory work during the coming few years. Another possibility that has been suggested is that cubic ice is forming in clouds. We have measured the vapor pressure of cubic ice, and plan to publish that result in the next few months. We have also been working on additional aspects of the condensation of nitric acid on ice. With Y. Kondo we studied the condensation of NOy on ice using the SOLVE data. Gamblin et al. have continued this work. The CRYSTAL NOy and HNO, groups have shown th their data can be fit using standard Langmuir isotherms as suggested in some, but not all, laboratory studies. We have found in the SOLVE data set that this is not the case. Moreover some laboratory studies show there are important kinetic effects that may be occurring in the atmosphere limiting the transfer of nitric acid to the ice. The SOLVE data seem consistent with these studies. We are currently re-analyzing the CRYSTAL data to look for these kinetic effects. There are a number of implications of these studies. One of the more interesting is that the nitric acid coating on ice can be used as a cloud clock to determine how long the cloud parcel has been in existence. We have also been involved with several laboratory studies. We have worked to improve the database on ice optical constants, which are critical for remote sensing. We have also studied the ways in which ice nucleates on clays. We suspect now that the standard theories used for depositional ice nucleation are completely incorrect. Further work will be needed to develop a new theory.

Toon, Owen B.↗

Experimental and Computational Studies of Crystal Nucleation in Composition Gradients (Final Report)

The major goals of this project were to develop and validate a predictive nucleation model that incorporates composition gradients and is applicable to a large range of metallic systems which form both stochiometric and non-stochiometric compounds. Computationally we planned to expand the extent of thermodynamics-based theories and lay the groundwork to improve the general understanding and predictive capabilities of the role that gradients play in phase formation, glass formability and stability, and nucleation and growth events. To address these goals, we used Molecular Dynamics (MD) simulations and both isothermal and isochronal nanocalorimetric experiments on amorphous phases with a controlled composition gradient with the hopes of validating and improving the classical nucleation model and its use in solid solutions. While the computations were successful and identified ways to improve the classical nucleation model, the in situ nanocalorimetry studies proved very challenging due to unexpected difficulties in fabricating effective calorimeters and samples. Thus, we could not experimentally validate our predicted influence of composition gradients on nucleation. Nonetheless, important insights were gained and modifications to the classical nucleation theory were suggested.

36 MATERIALS SCIENCE↗

Combined homogeneous and heterogeneous crystal nucleation in glasses

The temperature dependence of combined homogeneous and heterogeneous crystal nucleation is examined within the framework of the classical theory. It is demonstrated that nucleation can have a local maximum rate at one or two temperatures. The physical parameters which cause large changes in the structure of the nucleation curve are elucidated. Also, the influence of saturation effects on the structure of nucleation curves is illustrated. The utilization of these results for the interpretation of experiments and for the production of controlled crystal nucleation in glass is considered.

Weinberg, Michael C.↗

Cluster-dynamics-based parameterization for sulfuric acid–dimethylamine nucleation: comparison and selection through box and three-dimensional modeling

Clustering of gaseous sulfuric acid (SA) enhanced by dimethylamine (DMA) is a major mechanism for new particle formation (NPF) in polluted atmospheres. However, uncertainty remains regarding the SA–DMA nucleation parameterization that reasonably represents cluster dynamics and is applicable across various atmospheric conditions. This uncertainty hinders accurate three-dimensional (3-D) modeling of NPF and the subsequent assessment of its environmental and climatic impacts. Here we extensively compare different cluster-dynamics-based parameterizations for SA–DMA nucleation and identify the most reliable one through a combination of box model simulations, 3-D modeling, and in situ observations. Results show that the parameterization derived from Atmospheric Cluster Dynamic Code (ACDC) simulations, incorporating the latest theoretical insights (DLPNO-CCSD(T)/aug-cc-pVTZ//ωB97X-D/6-311++G(3df,3pd) level of theory) and adequate representation of cluster dynamics, exhibits dependable performance in 3-D NPF simulation for both winter and summer conditions in Beijing and shows promise for application in diverse atmospheric conditions. Another ACDC-derived parameterization, replacing the level of theory with RI-CC2/aug-cc-pV(T+d)Z//M06-2X/6–311++G(3df,3pd), also performs well in NPF modeling at relatively low temperatures around 280 K but exhibits limitations at higher temperatures due to inappropriate representation of SA–DMA cluster thermodynamics. Additionally, a previously reported parameterization incorporating simplifications is applicable for simulating NPF in polluted atmospheres but tends to overestimate particle formation rates under conditions of elevated temperature (>∼300 K) and low-condensation sink (<∼3×10 -3 s −1 ). Our findings highlight the applicability of the new ACDC-derived parameterization, which couples the latest SA–DMA nucleation theory and holistic cluster dynamics, in 3-D NPF modeling. The ACDC-derived parameterization framework provides a valuable reference for developing parameterizations for other nucleation systems.

Shen, Jiewen↗

Statistical evaluation of microscale stress conditions leading to void nucleation in the weak shock regime

Here, we investigate the heterogeneity of the stress state driven by anisotropic deformation response at the single crystal level through five statistical volume element (SVE) calculations of polycrystalline BCC tantalum. This work focuses on grain boundaries as a prominent material defect type prone to void nucleation based upon experimental observations of predominantly intergranular void nucleation in this material. The SVEs are constructed to be statistically representative of larger volumes of material and are meshed such that mean and standard deviation of grain size and orientation information is reconstructed. The computational meshes feature hexahedral (brick) elements and smooth conformal grain boundaries where significant stress concentration is known to occur, a tail effect of interest in the extreme events process of dynamic ductile damage. An existing micromechanical crystallographic plasticity model shown to capture the single crystal behavior of BCC tantalum well is used to perform the polycrystal calculations. The model includes representation of the non-Schmid effect of non-planar screw dislocation kinetics in tantalum. A three-dimensional stress state time profile predicted by damage modeling of a flyer plate impact experiment is applied as boundary conditions to each SVE. Resulting grain boundary stress state statistics are strongly non-Gaussian. Significant structural evolution is observed within the compressive hold before unloading into tension in the stress profile. Strong angular dependence of grain boundary traction magnitude with shock direction is observed. Non-Schmid effects continue to suggest their influence on propensity of microstructural defect types to nucleate voids. A general void nucleation criterion is proposed using probability theory. The general framework is specified to polycrystalline BCC tantalum in the weak shock regime to include the SVE calculations and literature molecular dynamics calculations of grain boundary void nucleation strength. Probability density functions (PDFs) are used to describe the interaction between the local stress state heterogeneity and the distributed grain boundary void nucleation strength state. A causation entropy maximization procedure removes the requirement for ad hoc selection of a PDF functional form and provides a rigorous procedure for data-based PDF determination. The resulting physically informed PDF describes the spatial appearance frequency of nucleated voids as a function of applied macroscale pressure. Lower length scale physics are thus packaged in a precise and computationally efficient way to provide computational plasticity insight to macroscale dynamic ductile damage models.

36 MATERIALS SCIENCE↗

Undercooling of materials during solidification in space

A theoretical research program was undertaken on the under cooling and solidification of materials under variable external field conditions. A catalog of theories and models of nucleation of solid phases in the melt is provided, as is a discussion of the relation of undercooling to intermolecular potentials, the dependence of growth rate on undercooling, the influence of undercooling on liquid-solid interface stability and solid structure, the direct effects of external fields on melts, the relation of solid physical properties to structure and the role of nucleants in solidification. Results of the theoretical analysis of several experiments related to the space processing applications program are given, and recommendations for future experiments and further theoretical developments along with procedures for correlation of theory and experiment are specified.

Miller, R. I.↗

Extended inflation from higher dimensional theories

The possibility is considered that higher dimensional theories may, upon reduction to four dimensions, allow extended inflation to occur. Two separate models are analayzed. One is a very simple toy model consisting of higher dimensional gravity coupled to a scalar field whose potential allows for a first-order phase transition. The other is a more sophisticated model incorporating the effects of non-trivial field configurations (monopole, Casimir, and fermion bilinear condensate effects) that yield a non-trivial potential for the radius of the internal space. It was found that extended inflation does not occur in these models. It was also found that the bubble nucleation rate in these theories is time dependent unlike the case in the original version of extended inflation.

Holman, Richard↗

Colossal grain growth in Cd(Se,Te) thin films and their subsequent use in CdTe epitaxy by close-spaced sublimation

Many technologies deposit thin films on inexpensive substrates, resulting in small grains due to classic nucleation and grain growth theory. For example, state-of-the-art solar cells are made by depositing CdSeTe and CdTe layers on inexpensive glass coated with nanocrystalline transparent conducting oxides (TCOs), like SnO 2 . Characteristically, the grain size of these films is on the order of the film thickness, i.e. a few microns. CdTe small-grain films have poor electro-optical properties and require CdCl 2 passivation which fails to fully passivate grain boundaries, causes carrier compensation, and prevents implementing other II–VI alloys and materials to improve performance. Here, we present a method to increase grain size to 1 mm in CdSe x Te 1-x thin films deposited on glass/TCO substrates without CdCl 2 treatment. The colossal grain growth is driven by mechanisms distinct from classic nucleation, grain growth, and Ostwald ripening and only occurs at low selenium content (x ~ 0.1). We also demonstrate how these films can serve as templates for subsequent large-grain epitaxy of other compositions like CdTe, again without exposure to CdCl 2 . The results open new paths for thin film solar cell technology, and thin film devices in general.

36 MATERIALS SCIENCE↗