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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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At least 973 records · Page 54
All sourcesNASA NTRSDOE OSTI
DOE OSTI2016

Nucleation of graphene layers on magnetic oxides: Co 3 O 4 (111) and Cr 2 O 3 (0001) from theory and experiment

We report directly grown strongly adherent graphene on Co 3 O 4 (111) by carbon molecular beam epitaxy (C MBE) at 850 K and density functional theory (DFT) findings that the first graphene layer is reconstructed to fit the Co 3 O 4 surface, while subsequent layers retain normal graphene structure. This adherence to the Co 3 O 4 structure results from partial bonding of half the carbons to top oxygens of the substrate. This structure is validated by X-ray photoelectron spectroscopy and low-energy electron diffraction studies, showing layer-by-layer graphene growth with ~0.08 electrons/carbon atom transferred to the oxide from the first graphene layer, in agreement with DFT. In contrast, for Cr 2 O 3 DFT finds no strong bonding to the surface and C MBE on Cr 2 O 3 (0001) yields only graphite formation at 700 K, with C desorption above 800 K. As a result, strong graphene-to-oxide charge transfer aids nucleation of graphene on incommensurate oxide substrates and may have implications for spintronics.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Nucleation and Growth of PbBrF Crystals at the Liquid Mercury–Electrolyte Interface Studied by Operando X-ray Scattering

In this work, detailed in operando studies of electrochemically induced PbBrF deposition at the liquid mercury/liquid electrolyte interface are presented. The nucleation and growth were monitored using time-resolved X-ray diffraction and reflectivity combined with electrochemical measurements, revealing a complex potential-dependent behavior. PbBrF deposition commences at potentials above –0.7 V with the rapid formation of an ultrathin adlayer of one unit cell thickness, on top of which (001)-oriented three-dimensional crystallites are formed. Two potential regimes are identified. At low overpotentials, slow growth of a low surface density film of large crystals is observed. At high overpotentials, crossover to a potential-independent morphology occurs, consisting of a compact PbBrF deposit with a saturation thickness of 25 nm, which forms within a few minutes. This potential behavior can be rationalized by the increasing supersaturation near the interface, caused by the potential-dependent Pb2+ deamalgamation, which changes from a slow reaction-controlled process to a fast transport-controlled process in this range of overpotentials. In addition, growth on the liquid substrate is found to involve complex micromechanical effects, such as crystal reorientation and film breakup during dissolution.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Nucleation and Initial Stages of Growth during the Atomic Layer Deposition of Titanium Oxide on Mesoporous Silica

A chemical approach to the deposition of thin films on solid surfaces is highly desirable but prone to affect the final properties of the film. To better understand the origin of these complications, the initial stages of the atomic layer deposition of titania films on silica mesoporous materials were characterized. Adsorption-desorption measurements indicated that the films grow in a layer-by-layer fashion, as desired, but initially exhibit surprisingly low densities, about one-quarter of that of bulk titanium oxide. Electron microscopy, X-ray diffraction, UV/visible, and X-ray absorption spectroscopy data pointed to the amorphous nature of the first monolayers, and EXAFS and 29 Si CP/MAS NMR results to an initial growth via the formation of individual tetrahedral Ti-oxide units on isolated Si-OH surface groups with unusually long Ti-O bonds. Here, density functional theory calculations were used to propose a mechanism where the film growth starts at the nucleation centers to form an open 2D structure.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Nucleation Selectivity and Lateral Coalescence of GaAs over Graphene on Ge(111)

Here we use epitaxial lateral overgrowth (ELO) to produce semimetallic graphene nanostructures embedded in a semiconducting GaAs matrix for potential applications in plasmonics, THz generation and detection, and tunnel junctions in multijunction solar cells. We show that (1) the combination of low sticking coefficient and fast surface diffusion on graphene enhances nucleation selectivity at exposed regions of the substrate and (2) high growth temperatures favor efficient lateral overgrowth, coalescence, and planarization of epitaxial GaAs films over the graphene nanostructures. Our work provides a more complete understanding of ELO using graphene masks, as opposed to more conventional dielectric masks, and enables new types of metal/semiconductor nanocomposites.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Comprehensive Insights into Nucleation, Autocatalytic Growth, and Stripping Efficiency for Lithium Plating in Full Cells

Synchrotron high-energy X-ray diffraction is used to enable nondestructive detection and quantification of heterogeneous lithium plating in working batteries. In this study a LiNi 0.5 Mn 0.3 Co 0.2 O 2 /graphite pouch cell was operated under 6C fast-charge rate for greater than 1200 cycles. The magnitude and spatial distribution of lithium plating, lithium stripping, and the effect of metallic lithium deposition on lithium intercalation into graphite were quantified. Fully intercalated graphite (LiC 6 ) was detected after discharge with a lateral distribution closely correlated with lithium plating, which can be used as a higher-sensitivity indicator for lithium plating. Over an extended cycle life, the overall metallic lithium concentration followed a sigmoidal curve indicating two-stage continuous nucleation and autocatalytic growth. The lithium stripping efficiency underwent an exponential decay as a function of cycle life as the buildup of metallic lithium hindered the efficient dissolution back into the electrolyte. The findings provide direct insights into the characteristics of lithium plating and stripping under realistic fast-charge conditions.

25 ENERGY STORAGE↗
DOE OSTI2019

Characteristics of ice nucleating particles in and around California winter storms

A major component of California’s yearly precipitation comes from wintertime atmospheric river (AR) events which bring large amounts of moisture from the tropics up to the midlatitudes. Understanding these systems, specifically the effects of aerosol particles on precipitation associated with these storms, was a major focus of the 2015 Atmospheric Radiation Measurement (ARM) Cloud Aerosol Precipitation Experiment (ACAPEX), which was part of the wintertime CalWater 2015 campaign. The measurement campaign provided sampling platforms on four aircraft, including the ARM Aerial Facility G-1, as well as the NOAA Ronald H. Brown research vessel and at a ground station in Bodega Bay, CA. Measurements of ice nucleating particles (INPs) were made with the Colorado State University (CSU) Continuous Flow Diffusion Chamber (CFDC) aboard the G-1, and aerosol filters were collected on the G-1, at the Bodega Bay site and on the Ronald H. Brown for post-processing via immersion freezing in the CSU Ice Spectrometer. Aerosol composition was measured aboard the G-1 with the Aerosol Time-of-Flight Mass Spectrometer (ATOFMS). Here we present INP concentrations and aerosol chemical compositions during the course of the aircraft campaign. During the AR event we found that marine aerosol was the dominant aerosol type and that marine INPs were dominant at cloud activation temperatures, which is in stark contrast to the dominance of dust INPs during the AR events in the CalWater 2011 campaign.

Levin, Ezra↗
DOE OSTI2020

Nucleation-controlled growth of superior lead-free perovskite Cs 3 Bi 2 I 9 single-crystals for high-performance X-ray detection

The organic-inorganic hybrid lead halide perovskites have emerged as a series of star materials for solar cells, lasers and detectors. However, the issues raised by the toxic lead element and marginal stability due to the volatile organic components have severely limited their potential applications. In this work, we develop a nucleation-controlled solution method to grow large size high-quality Cs 3 Bi 2 I 9 perovskite single crystals (PSCs). Using the technique, we harvest some centimeter-sized single crystals and achieved high device performance. We find that X-ray detectors based on PSCs exhibit high sensitivity of 1652.3 μC Gy air -1 cm -2 and very low detectable dose rate of 130 nGy air s -1 , both desired in medical diagnostics. In addition, its outstanding thermal stability inspires us to develop a high temperature X-ray detector with stable response at up to 100 °C. Furthermore, PSCs exhibit high X-ray imaging capability thanks to its negligible signal drifting and extremely high stability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

A multi-step nucleation process determines the kinetics of prion-like domain phase separation

Compartmentalization by liquid-liquid phase separation (LLPS) has emerged as a ubiquitous mechanism underlying the organization of biomolecules in space and time. Here, we combine rapid-mixing time-resolved small-angle X-ray scattering (SAXS) approaches to characterize the assembly kinetics of a prototypical prion-like domain with equilibrium techniques that characterize its phase boundaries and the size distribution of clusters prior to phase separation. We find two kinetic regimes on the micro- to millisecond timescale that are distinguished by the size distribution of clusters. At the nanoscale, small complexes are formed with low affinity. After initial unfavorable complex assembly, additional monomers are added with higher affinity. At the mesoscale, assembly resembles classical homogeneous nucleation. Careful multi-pronged characterization is required for the understanding of condensate assembly mechanisms and will promote understanding of how the kinetics of biological phase separation is encoded in biomolecules.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Visualization and validation of twin nucleation and early-stage growth in magnesium

The abrupt occurrence of twinning when Mg is deformed leads to a highly anisotropic response, making it too unreliable for structural use and too unpredictable for observation. Here, we describe an in-situ transmission electron microscopy experiment on Mg crystals with strategically designed geometries for visualization of a long-proposed but unverified twinning mechanism. Combining with atomistic simulations and topological analysis, we conclude that twin nucleation occurs through a pure-shuffle mechanism that requires prismatic-basal transformations. Also, we verified a crystal geometry dependent twin growth mechanism, that is the early-stage growth associated with instability of plasticity flow, which can be dominated either by slower movement of prismatic-basal boundary steps, or by faster glide-shuffle along the twinning plane. The fundamental understanding of twinning provides a pathway to understand deformation from a scientific standpoint and the microstructure design principles to engineer metals with enhanced behavior from a technological standpoint.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Nucleation-promoting and growth-limiting synthesis of disordered rock-salt Li-ion cathode materials

Disordered rock-salt oxides and oxyfluorides are promising positive electrode materials for high-performance lithium-ion batteries free of nickel and cobalt. However, conventional synthesis methods rely on post-synthesis pulverization to achieve cycling-appropriate particle sizes, offering limited control over particle microstructure and crystallinity. This accelerates degradation and complicates secondary particle processing. Here we present a synthesis strategy that enhances nucleation while suppressing particle growth and agglomeration across various disordered rock-salt compositions, including lithium–manganese–titanium oxide, lithium–manganese–niobium oxide, and lithium–nickel–titanium oxide systems. Applied to Li 1.2 Mn 0.4 Ti 0.4 O 2 , this method yields highly crystalline, well-dispersed sub-200 nm particles that form homogeneous electrode films with stable cycling behavior. Tested in cells with lithium metal as the counter electrode, these electrodes deliver ~200 mAh/g with 85% capacity retention relative to the first cycle after 100 cycles (20 mA/g, 1.5–4.8 V), and an average discharge voltage loss of 4.8 mV per cycle, compared to 38.6% retention and 7.5 mV loss per cycle for electrodes derived from pulverized solid-state particles. This approach suggests a route to enhance the performance and durability of disordered rock-salt electrodes for sustainable lithium-ion batteries.

Batteries↗
DOE OSTI2025

Quasicrystal stability and nucleation kinetics from density functional theory

The aperiodic order of quasicrystals bridges the amorphous and crystalline regime, so it has remained unclear whether quasicrystals are metastable or stable phases of matter. Density functional theory is often used to evaluate thermodynamic stability, but quasicrystals are long-range aperiodic and their energies cannot be calculated using conventional ab initio methods. Here, in this work, we perform first-principles calculations on quasicrystal nanoparticles of increasing size, from which we can directly extrapolate their bulk and surface energies. Using this technique, we determine with high confidence that the icosahedral quasicrystals ScZn 7.33 and YbCd 5.7 are ground-state phases, thus revealing that translational symmetry is not a necessary condition for the zero-temperature stability of inorganic solids. Although we found the ScZn 7.33 quasicrystal to be thermodynamically stable, we show on a mixed thermodynamic and kinetic phase diagram that its solidification from the melt is limited by nucleation, which illustrates why even stable materials may be kinetically challenging to grow. Our techniques broadly open the door to first-principles investigations into the structure–bonding–stability relationships of aperiodic materials.

density functional theory↗
DOE OSTI2023

Oriented nucleation in formamidinium perovskite for photovoltaics

The black phase of formamidinium lead iodide (FAPbI 3 ) perovskite shows huge promise as an efficient photovoltaic, but it is not favoured energetically at room temperature, meaning that the undesirable yellow phases are always present alongside it during crystallization. This problem has made it difficult to formulate the fast crystallization process of perovskite and develop guidelines governing the formation of black-phase FAPbI 3 . Here, we use in situ monitoring of the perovskite crystallization process to report an oriented nucleation mechanism that can help to avoid the presence of undesirable phases and improve the performance of photovoltaic devices in different film-processing scenarios. The resulting device has a demonstrated power-conversion efficiency of 25.4% (certified 25.0%) and the module, which has an area of 27.83 cm 2 , has achieved an impressive certified aperture efficiency of 21.4%.

14 SOLAR ENERGY↗
DOE OSTI2013

Ethanol assisted reduction and nucleation of ferromagnetic Co and Ni nanocrystalline particles

In this report, we demonstrate the ability of ethanol to act as a solvent and reducing agent to nucleate nanocrystalline Co and Ni particles. Under solvothermal conditions, Co and Ni particles can be produced at 200 degrees C. The Ni and Co particles crystallized into FCC and a mixture of FCC and HCP crystal phases, respectively. Ni particles possessed a spherical morphology with diameters in the range of 200 nm to 300 nm. Co particles took on an ellipsoidal morphology, with diameters greater than 500 nm. Magnetizations for the Ni and Co particles were commensurate with bulk values, showing their high crystallinity and the presence of little oxide impurity. By finding inexpensive solvents with a lowered environmental impact, steps towards a "greener" synthetic process for ferromagnetic nanoparticles can be established.

Huba, ZJ↗
DOE OSTI2018

Nanoscale in situ detection of nucleation and growth of Li electrodeposition at various current densities

Li metal batteries can store at least ten times more energy than currently existing Li-ion batteries. However, during routine charging and discharging, Li dendrites grow on the Li metal electrode, which can lead to capacity loss by the consumption of Li salt at the surface of the Li dendrites, and be a safety hazard resulting from the potential for short-circuits. Although past efforts have provided useful information about the morphology and surface area of Li dendrite formation at the microscale, a nanoscale understanding of nucleation and growth of Li nanoparticle electrodeposition is still elusive. In this study, using a new electrochemical cell for transmission mode grazing incidence small angle X-ray scattering, we obtained, for the first time, the primary nucleus size of Li nanoparticles, their size evolution and their fractal structures at various current densities and in real-time. The measured average radius of gyration, R g , at current densities of 0.1, 0.5, and 2.0 mA cm -2 is 5.4 ± 0.4, 4.5 ± 0.3, and 3.5 ± 0.3 nm, respectively. This variation in size with current density is noteworthy when recognizing that the surface area-to-volume ratio of the Li nanoparticles is 3.7 times higher at 2.0 mA cm -2 than at 0.1 mA cm -2 . We also compared a hierarchical fractal structure of Li particles from the nanometer to micrometer scale. Our findings illuminate the role of overpotential in the reactive surface area of Li dendrites at the nanoscale, and provide a novel research platform for suppressing Li dendrite formation in Li metal battery systems.

25 ENERGY STORAGE↗
DOE OSTI2021

LaMer's 1950 model of particle formation: a review and critical analysis of its classical nucleation and fluctuation theory basis, of competing models and mechanisms for phase-changes and particle formation, and then of its application to silver halide, semiconductor, metal, and metal-oxide nanoparticles

Are classical nucleation theory and the 1950 LaMer model of particle formation supported for a wide range of particle formations, or do competing models in the form of chemical reaction mechanisms have better experimental support? Read on to find out.

Whitehead, Christopher B.↗
DOE OSTI2021

Manipulation of amorphous precursors to enhance zeolite nucleation

Crystallization in media comprised of amorphous precursors is becoming a more common phenomenon for numerous synthetic, biological, and natural materials that grow by a combination of classical and nonclassical pathways. Amorphous phases can exhibit a wide range of physicochemical properties that may evolve during the course of nucleation and crystal growth. This creates challenges for establishing causal relationships between amorphous precursor properties and their effect(s) on the selection of mechanistic pathways of crystallization and ultimately the properties of the crystalline product. In this study, we examine ways to manipulate the composition and colloidal stability of amorphous (alumino)silicate precursors that are prevalent in nanoporous zeolite syntheses. Changes in the amorphous precursor properties are evaluated on the basis of their ability to enhance rates of crystal formation. Here, we use fumed silica as the primary silicon source and examine the effects of infusing the source or growth medium with additional alkali metal, which serves as an inorganic structure-directing agent to facilitate the formation of porous crystal structures. We also assess the impact of adding a polymer additive, which reduces the colloidal stability of precursors, wherein we posit that the confined pockets of solution within the interstitial spaces of the precursor aggregates play an important role in regulating the rate of zeolite crystallization. Three commercially relevant zeolites (mordenite, SSZ-13, and ZSM-5) were selected for this study based on their diverse frameworks and methods of preparation. Here our findings reveal that alkali infusion significantly reduces the crystallization times for mordenite and SSZ-13, but has little impact on ZSM-5 synthesis. Conversely, we find that polymer addition markedly enhanced the rates of crystallization among all three zeolites, suggesting that this method may be a general approach to reduce zeolite synthesis times. Given the relatively high costs associated with commercial zeolite production, identifying new methods to improve the efficiency of hydrothermal syntheses can have significant practical implications beyond the fundamental benefits of developing new routes to tailor nonclassical crystallization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗