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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.
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In situ X-ray scattering kinetics and population balance modeling of crystal nucleation and growth.
We use photocatalytic reduction to synthesize mono and bimetallic nanoparticles. This approach reveals a new formation pathway involving continuous nucleation and allows the reaction to be turned on and off without impacting particle outcomes.
Correction for ‘Anomalously abrupt switching of wurtzite-structured ferroelectrics: simultaneous non-linear nucleation and growth model’ by Keisuke Yazawa et al. , Mater. Horiz. , 2023, https://doi.org/10.1039/D3MH00365E.
Here, we report the size-controlled synthesis of ultrasmall (3–8 nm), phase-pure, and stoichiometric Cu 3 VS 4 nanocrystals via direct nucleation of the ternary sulvanite phase. An unusual redshift in optical absorption is observed with decreasing size and attributed to the plasmonic-like nature of valence band–intermediate band transitions.
Topological insulator Bi{sub 2}Te{sub 3} films have been grown by molecular beam epitaxy on Si (111) substrates. The structural properties of the ultra-thin films and their evolution in morphology during the growth have been investigated. The growth starts by a nucleation of separate islands and subsequently turns into a layer-by-layer growth mode. Despite this, the grown film is found to be single crystalline and fully relaxed from the first atomic layer.
This letter describes the fast growth of ultrananocrystalline diamond (UNCD) films by bias-enhanced nucleation and growth process in CH{sub 4}/Ar plasma. The UNCD grains were formed at the beginning of the film's growth without the necessity of forming the amorphous carbon interlayer, reaching a thickness of ∼380 nm in 10 min. Transmission electron microscopic investigations revealed that the application of bias voltage induced the formation of graphitic phase both in the interior and at the interface regions of UNCD films that formed interconnected paths, facilitating the transport of electrons and resulting in enhanced electron field emission properties.
The oxygen precipitation of highly (17.5 mΩ cm) and moderately (4.5 Ω cm) boron (B) doped silicon (Si) crystals at 780 °C is investigated by following in-situ the evolution of diffraction Pendellösung oscillations. All samples show an initial diffusion-driven growth process which may change over into Ostwald ripening. For the highly doped sample and involving a nucleation step at 450 °C for 30 h, the precipitate density ρ is enhanced by a factor of 8 as compared to the moderately doped sample. The influence of a high B concentration on ρ is dramatically higher for the samples directly heated to 780 °C, where an enhancement factor of 80 is found. Considering Ostwald ripening as a second growth regime reveals consistent ripening rates and surface energies σ with those found at 900 °C in a previous publication.
The crack-free metal-organic chemical vapor deposition (MOCVD) grown AlGaN/GaN heterostructures on Si substrate with modified growth conditions of AlN nucleation layer (NL) and its influence on the electrical and structural properties of conductive GaN layer are presented. From the Hall electrical measurements, a gradual decrease of two-dimensional electron gas (2DEG) concentration near heterointerface as the function of NL thickness is observed possibly due to the reduction in difference of piezoelectric polarization charge densities between AlGaN and GaN layers. It also indicates that the minimum tensile stress and a relatively less total dislocation density for high pressure grown NL can ensure a 20 % increment in mobility at room temperature irrespective of the interface roughness. The thickness and pressure variations in NL and the subsequent changes in growth mode of AlN contributing to the post growth residual tensile stress are investigated using X-ray diffraction and Raman scattering experiments, respectively. The post growth intrinsic residual stress in top layers of heterostructures arises from lattice mismatches, NL parameters and defect densities in GaN. Hence, efforts to reduce the intrinsic residual stress in current conducting GaN layer give an opportunity to further improve the electrical characteristics of AlGaN/GaN device structures on Si.
In vertebrates, insufficient availability of calcium and inorganic phosphate ions in extracellular fluids leads to loss of bone density and neuronal hyper-excitability. To counteract this problem, calcium ions are usually present at high concentrations throughout bodily fluids—at concentrations exceeding the saturation point. This condition leads to the opposite situation where unwanted mineral sedimentation may occur. Remarkably, ectopic or out-of-place sedimentation into soft tissues is rare, in spite of the thermodynamic driving factors. This fortunate fact is due to the presence of auto-regulatory proteins that are found in abundance in bodily fluids. Yet, many important inflammatory disorders such as atherosclerosis and osteoarthritis are associated with this undesired calcification. Hence, it is important to gain an understanding of the regulatory process and the conditions under which it can go awry. In this manuscript, we extend mean-field continuum classical nucleation theory of the growth of clusters to encompass surface shielding. We use this formulation to study the regulation of sedimentation of calcium phosphate salts in biological tissues through the mechanism of post-nuclear shielding of nascent mineral particles by binding proteins. We develop a mathematical description of this phenomenon using a countable system of hyperbolic partial differential equations. A critical concentration of regulatory protein is identified as a function of the physical parameters that describe the system.
Protein aggregation is of great importance in biology, e.g., in amyloid fibrillation. The aggregation processes that occur at the cellular scale must be highly stochastic in nature because of the statistical number fluctuations that arise on account of the small system size at the cellular scale. We study the nucleated reversible self-assembly of monomeric building blocks into polymer-like aggregates using the method of kinetic Monte Carlo. Kinetic Monte Carlo, being inherently stochastic, allows us to study the impact of fluctuations on the polymerization reactions. One of the most important characteristic features in this kind of problem is the existence of a lag phase before self-assembly takes off, which is what we focus attention on. We study the associated lag time as a function of system size and kinetic pathway. We find that the leading order stochastic contribution to the lag time before polymerization commences is inversely proportional to the system volume for large-enough system size for all nine reaction pathways tested. Finite-size corrections to this do depend on the kinetic pathway.
We discuss the microscopic mechanisms by which low-temperature amorphous states, such as ultrastable glasses, transform into equilibrium fluids, after a sudden temperature increase. Experiments suggest that this process is similar to the melting of crystals, thus differing from the behaviour found in ordinary glasses. We rationalize these observations using the physical idea that the transformation process takes place close to a “hidden” equilibrium first-order phase transition, which is observed in systems of coupled replicas. We illustrate our views using simulation results for a simple two-dimensional plaquette spin model, which is known to exhibit a range of glassy behaviour. Our results suggest that nucleation-and-growth dynamics, as found near ordinary first-order transitions, is also the correct theoretical framework to analyse the melting of ultrastable glasses. Our approach provides a unified understanding of multiple experimental observations, such as propagating melting fronts, large kinetic stability ratios, and “giant” dynamic length scales. We also provide a comprehensive discussion of available theoretical pictures proposed in the context of ultrastable glass melting.
Nonequilibrium molecular dynamics simulations of shock loaded single-crystal Al in the $\langle$100$\rangle$, $\langle$110$\rangle$, $\langle$111$\rangle$, and $\langle$123$\rangle$ orientations are conducted to study elastic and plastic shockwave formation and details associated with dislocation activity. A computer vision-based approach is implemented to capture the presence of dislocations and describe their spatial characteristics in the zone of nucleation behind the propagating shockwave. The methodology developed relies on the sequences of images extracted during shock loading that show dislocation activity within a cross section of the sample. Results reveal that the spacing between activated slip systems is orientation dependent and exhibits a modest reduction for the $\langle$100$\rangle$ and $\langle$111$\rangle$ orientations as shock pressure increases. Comparisons are made to existing theoretical models. Such relationships between shock pressure and dislocation activity, extracted from molecular dynamics simulations, can be used to inform higher length scale simulations or modeling of dislocation-based plasticity during shock.
Nucleation and growth are studied in a system that undergoes diffusion-controlled condensation under gradual changes in parameters, such as cooling. Here, it is demonstrated that when the Gibbs–Thompson effect becomes negligible, the system falls into a universal regime. i.e., the final droplet size distribution remains invariant under certain rescaling of system parameters. An approximate yet very accurate analytic form is obtained for the final droplet size distribution in this regime.
Molecular dynamics simulations of helium implantation have been performed in the MoNbTaTi complex concentrated alloy (CCA) to determine the impact of composition on helium clustering and bubble nucleation. It was found that compositions with lower interstitial atomic volume resulted in smaller cluster sizes, higher helium-to-vacancy ratios, and larger migration barriers. As the atomic volume decreases, it is harder to accommodate additional helium in the lattice and for helium to diffuse between interstitial sites, resulting in smaller cluster sizes. In particular, increasing molybdenum directly correlated with a decreased interstitial atomic volume and increased migration barrier. Niobium exhibited the opposite trend, where more niobium in the material resulted in larger interstitial atomic volumes and cluster sizes but lower migration barriers. The atomic volume was determined to be an indicator of the susceptibility of the material to helium bubble growth and could potentially be used as a metric to screen compositions for resistance to helium damage. In this way, properties such as available interstitial volumes could be used to screen materials more rapidly given the vast compositional space of CCAs.
Crystal nucleation and growth at a liquid–liquid interface is studied on the atomic scale by in situ Å-resolution X-ray scattering methods for the case of liquid Hg and an electrochemical dilute electrolyte containing Pb 2+ , F - , and Br - ions. In the regime negative of the Pb amalgamation potential Φ rp = -0.70 V, no change is observed from the surface-layered structure of pure Hg. Upon potential-induced release of Pb 2+ from the Hg bulk at Graphic, the formation of an intriguing interface structure is observed, comprising a well-defined 7.6-Å–thick adlayer, decorated with structurally related 3D crystallites. Both are identified by their diffraction peaks as PbFBr, preferentially aligned with their Graphic axis along the interface normal. X-ray reflectivity shows the adlayer to consist of a stack of five ionic layers, forming a single-unit-cell–thick crystalline PbFBr precursor film, which acts as a template for the subsequent quasiepitaxial 3D crystal growth. This growth behavior is assigned to the combined action of electrostatic and short-range chemical interactions.
Significance Many marine organisms build complex CaCO 3 shells, which record an archive of past climate in their trace chemistry. Organic–mineral interactions are a crucial, poorly understood aspect of shell formation, which may alter shell composition and bias climate records. We map the chemistry of an organic template preserved within a type of shell that is widely used in studies of past climate. We find that the organic template embedded within this shell is enriched in Na and Mg, and can locally influence shell composition. Atom-scale maps of template chemistry offer a detailed view of the chemical interactions at an organic mineral template, and suggest that elements other than Ca 2+ may be important in defining the energetics of CaCO 3 nucleation during biomineralization.
Significance The Earth’s climate is affected by the radiative properties of clouds. In clouds containing both supercooled water droplets and ice particles (mixed-phase clouds), cloud lifetime and albedo are affected by the presence of ice nucleating particles (INP). After decades of research, the importance of black carbon (BC) as an INP remains unresolved. In this work, we determined the contribution of BC to INP concentrations ([INP]) from real-world wildfires and prescribed burns. We found that BC does not contribute significantly to [INP] in near-field biomass burning plumes. These results were applied as parameterizations to global climate model output. Combined with previous work on diesel-engine exhaust, we find that BC does not contribute significantly to global [INP] relevant to mixed-phase clouds.
Significance Ion distributions at charged solid–water interfaces, referred to as the electrical double layer (EDL), are poorly understood at high ion concentrations, in part due to the lack of molecular-scale descriptions of the interactions between adsorbed hydrated ions. Here, direct visualization of the salinity-dependent evolution of EDL structure reveals molecular origins of nonclassical transformation of the EDL, in which charge overscreening and heterogeneous nucleation are driven by ion–ion correlations at the interfaces. This manifestation of the atomistic basis of nonclassical behaviors provides a much-needed understanding of the impact of ion cooperativity at charged interfaces for the development of predictive models for element transport in natural environments and advanced technologies for material growth and synthesis in saline environments.