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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 379 records · Page 21
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Automated processing of environmental transmission electron microscopy images for quantification of thin film dewetting and carbon nanotube nucleation dynamics

We report scalable production of carbon nanotubes (CNTs) requires catalysts and reaction conditions that provide high nucleation efficiency. In situ characterization methods such as environmental transmission electron microscopy (ETEM) can reveal fundamental mechanisms of synthesis, but to date have primarily provided qualitative observations on small sample sizes. Here, quantitative analysis is performed using high-resolution, high-rate video capture of ETEM experimentation coupled with automated image processing, involving computer vision algorithms and convolutional neural networks. By this approach, we detect distinct nanoparticle formation from an alumina-supported iron thin film and subsequent CNT nucleation from the nanoparticles. The statistical summary of particles in each video shows that, compared to a H 2 -only atmosphere, pretreatment of the catalyst with carbon added to the H 2 atmosphere results in a smaller average particle diameter, a 2-fold increase in particle density (to 5300 particles/μm 2 ), a 3-fold increase in CNT nucleation efficiency (to 92%), and more than a 5-fold increase in CNT density (to 4800/μm 2 ). Addition of carbon during exposure to H 2 is also more effective than NH 3 at dewetting the catalyst film and increasing the CNT nucleation efficiency, in spite of NH 3 being a stronger reducing agent for iron. Insights from this study are applicable to improving CNT yield and productivity in both batch-style and continuous processes.

25 ENERGY STORAGE↗
DOE OSTI2019

Electrophoretic and potentiometric signatures of multistage CaCO3 nucleation

HYPOTHESIS: Calcium carbonate nucleation is often a complex and multistep process that is difficult to follow in situ. The time-resolved electrochemical and electrophoretic methods can provide a new insight into the nucleation pathway. EXPERIMENTS: Here, we used a combination of speciation calculations with time-resolved electrophoretic and potentiometric methods to monitor calcium carbonate precipitation from a slightly supersaturated solution. FINDINGS: After an initial mixing period of three minutes in which metastable CaCO 3 phases may have nucleated and subsequently dissolved due to locally-high supersaturations, bulk solution pH and Ca 2+ concentrations stabilize before decreasing in tandem with the precipitation of a CaCO 3 phase. After an hour, the precipitate is dominated by calcite that grows at the expense of dissolving vaterite. The time-dependent electrokinetic potential shows analogous signatures of multistage nucleation process: initial rapid changes in ζ-potential are followed by much slower equilibration starting about one hour after reagents are mixed. The changes in ζ-potential, solution pH, saturation indexes, and particle morphology are consistent with vaterite to calcite transformation via dissolution of the former and recrystallization of the latter. These findings highlight the potential use of ζ-potential measurements for monitoring polymorphic transformations of carbonate phases in-situ.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Dislocation nano-hydrides in nickel: Nucleation, evolution and effects on dislocation behaviors

Nano-hydrides have been predicted to precipitate at the core of edge dislocations in the Ni-H system, a mechanism that may promote hydrogen embrittlement. However, nano-hydride nucleation, growth, and effects on dislocation behavior have seldom been explored. This work combines molecular dynamics grand canonical Monte Carlo (MD-GCMC) simulations and continuum modeling to uncover a wide range of phenomena linked to dislocation nano-hydrides. Simulations reveal that nano-hydrides can be stabilized at dislocation cores with all character angles, including screw segments, due to the hydrostatic stresses around the cores of the Shockley partials. Nano-hydride nucleation takes place in these regions, and growth is dictated by the character angle θ of the perfect dislocation. The equilibrium stacking fault width d eq varies dynamically to increase the local hydrostatic stress field and facilitate the formation of the nano-hydride, forming a constriction-like feature and leading to three distinct behaviors: d eq decreases for θ > 30°, d eq remains unchanged for θ = 30°, and d eq increases for θ < 30°. Remote hydrostatic and Escaig stresses are also shown to influence the nucleation stage, implying stress concentrations such as those ahead of crack tips may facilitate nano-hydride precipitation. Moreover, we identify a new hydrogen-induced 60° dislocation reaction that emits a Shockley partial on a conjugate plane, with potential implications for twin nucleation. Testable predictions from this study are then used to reinterpret previous results from the literature. In conclusion, these findings provide a comprehensive framework to assess nano-hydride formation and evolution at dislocations in nickel and other face-centered cubic metals, with important implications to hydrogen embrittlement.

Dislocations↗
DOE OSTI2015

Effect of starting microstructure upon the nucleation sites and distribution of graphite particles during a graphitising anneal of an experimental medium-carbon machining steel

The potential for using graphite particles as an internal lubricant during machining is considered. Graphite particles were found to form during graphitisation of experimental medium-carbon steel alloyed with Si and Al. The graphite nucleation sites were strongly influenced by the starting microstructure, whether ferrite–pearlite, bainite or martensite, as revealed by light and electron microscopy. Favourable nucleation sites in the ferrite–pearlite starting microstructure were, not unexpectedly, found to be located within pearlite colonies, no doubt due to the presence of abundant cementite as a source of carbon. In consequence, the final distribution of graphite nodules in ferrite–pearlite microstructures was less uniform than for the bainite microstructure studied. In the case of martensite, this study found a predominance of nucleation at grain boundaries, again leading to less uniform graphite dispersions. - Highlights: • Metallography of formation of graphite particles in experimental carbon steel. • Potential for using graphite in steel as an internal lubricant during machining. • Microstructure features expected to influence improved machinability studied. • Influence of pre-anneal starting microstructure on graphite nucleation sites. • Influence of pre-anneal starting microstructure on graphite distribution. • Potential benefit is new free-cutting steel compositions without e.g. Pb alloying.

36 MATERIALS SCIENCE↗
DOE OSTI2012

Effect of La{sub 2}O{sub 3}, CoO, Cr{sub 2}O{sub 3} and MoO{sub 3} nucleating agents on crystallization behavior and magnetic properties of ferromagnetic glass-ceramic in the system Fe{sub 2}O{sub 3}{center_dot}CaO{center_dot}ZnO{center_dot}SiO{sub 2}

Highlights: Black-Right-Pointing-Pointer Crystallization of magnetic glass ceramic with different nucleating agents. Black-Right-Pointing-Pointer The effect of La{sub 2}O{sub 3}, CoO, Cr{sub 2}O{sub 3} and MoO{sub 3} as nucleating agents was studied. Black-Right-Pointing-Pointer XRD for as prepared samples revealed crystallization of pure magnetite. Black-Right-Pointing-Pointer Heat treatment revealed minor calcium silicate, hematite and cristobalite. Black-Right-Pointing-Pointer TEM revealed crystallization of crystallite size in the range 50-100 nm. -- Abstract: Preparation and characterization of ferromagnetic glass ceramic in the system Fe{sub 2}O{sub 3}{center_dot}CaO{center_dot}ZnO{center_dot}SiO{sub 2} with different nucleating agents was studied. The effect of La{sub 2}O{sub 3}, CoO, Cr{sub 2}O{sub 3} and MoO{sub 3} as nucleating agents was investigated. Differential thermal analysis; X-ray diffraction and transmission electron microscope were used to investigate thermal behavior, sequence of crystallization and microstructure of the samples. XRD analysis for as prepared samples revealed the crystallization of single magnetite phase. Heat treatment at 900 Degree-Sign C/2 h revealed the appearance of minor amounts of calcium silicate, hematite and cristobalite beside magnetite. TEM revealed crystallization of crystallite size in the range 50-100 nm. Lattice parameters, cell volume and crystallite size were stimulated from XRD data. Magnetic properties of quenched samples were measured under 20 kG.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Ion redistributions at interfaces facilitate nucleation and growth of branched Ag 3 PO 4 polypods

Branched structures are of spectacular interest due to their improved light-harvesting, direct carrier transportation pathway, high surface area, and controllable electronic structures. Understanding their growth mechanisms and controlling factors enables the design of materials with improved functions. Interfaces of liquid-solid and air-liquid are known to change the chemical and physical properties of the liquid solution. However, their role in crystal growth, especially of branched structures, is seldom investigated. In this work we synthesized branched silver phosphate polypods in a thin layer of aqueous solution at room temperature taking advantage of the unique properties near the interfaces. The branched crystals nucleate and grow with a liquid thickness of 810 µm or below requiring the presence of both the gas-liquid and liquid-solid interfaces. The hydrophilicity of the solid substrate also facilitates nucleation and growth. Our results indicate that the synergism of long-range electric fields (ion distributions) at the interfaces promotes not only the nucleation and growth of silver phosphate but also the formation of branched structures. This work can be a reference for facilitating crystal nucleation and growth and controlling structures with specific morphologies, such as branched ones, by understanding and mimicking the properties at the interfaces.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Probing the Mechanism of Cadmium Sulfide Cluster Nucleation and Growth via Sequential Infiltration Synthesis

Few-atom metal chalcogenide clusters may be realized through the sequential infiltration of metal–organic precursors in polymer films. However, the underlying nucleation and growth mechanisms that allow for cluster synthesis with near atomic-scale precision are not fully resolved. The kinetics of the sequential infiltration synthesis (SIS) method that control the nucleation and growth mechanisms of primarily Cd 4 S 4 -core clusters within a poly­(4-vinylpyridine) (P4VP) matrix are probed with in situ UV–visible absorbance spectroscopy. Density functional theory (DFT) calculations that allow simulation of the optical properties of cluster fragments further reveal the thermodynamics that guide cluster growth within the P4VP matrix. Here, we conclude that a reactive capture mechanism for cluster nucleation and growth is dominant, although transient dimethyl cadmium adduction to the polymer backbone may contribute to cluster nucleation under shorter metal–organic purge process conditions. Grazing incidence X-ray diffraction (GI-XRD) and X-ray absorption spectroscopy (XAS) analyses further corroborate the cluster size and atom connectivity throughout the stepwise synthesis.

Jayaweera, Nuwanthaka P. [Argonne National Laborat↗
DOE OSTI2016

Measurement of the Dewetting, Nucleation, and Deactivation Kinetics of Carbon Nanotube Population Growth by Environmental Transmission Electron Microscopy

Understanding the collective growth of carbon nanotube (CNT) populations is key to tailoring their properties for many applications. During the initial stages of CNT growth by chemical vapor deposition, catalyst nanoparticle formation by thin-film dewetting and the subsequent CNT nucleation processes dictate the CNT diameter distribution, areal density, and alignment. Here, in this study, we use in situ environmental transmission electron microscopy (E-TEM) to observe the catalyst annealing, growth, and deactivation stages for a population of CNTs grown from a thin-film catalyst. Complementary in situ electron diffraction and TEM imaging show that, during the annealing step in hydrogen, reduction of the iron oxide catalyst is concomitant with changes in the thin-film morphology; complete dewetting and the formation of a population of nanoparticles is only achieved upon the introduction of the carbon source, acetylene. The dewetting kinetics, i.e., the appearance of distinct nanoparticles, exhibits a sigmoidal (autocatalytic) curve with 95% of all nanoparticles appearing within 6 s. After nanoparticles form, they either nucleate CNTs or remain inactive, with incubation times measured to be as small as 3.5 s. Via E-TEM we also directly observe the crowding and self-alignment of CNTs after dewetting and nucleation. In addition, in situ electron energy loss spectroscopy reveals that the collective rate of carbon accumulation decays exponentially. We conclude that the kinetics of catalyst formation and CNT nucleation must both be addressed in order to achieve uniform and high CNT density, and their transient behavior may be a primary cause of the well-known nonuniform density of CNT forests.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Molecular Dynamics Simulation Study of the Early Stages of Nucleation of Iron Oxyhydroxide Nanoparticles in Aqueous Solutions

Nucleation is a fundamental step in crystal growth. Of environmental and materials relevance are reactions that lead to nucleation of iron oxyhydroxides in aqueous solutions. These reactions are difficult to study experimentally due to their rapid kinetics. Here, we used classical molecular dynamics simulations to investigate nucleation of iron hydroxide/oxyhydroxide nanoparticles in aqueous solutions. Results show that in a solution containing ferric ions and hydroxyl groups, iron–hydroxyl molecular clusters form by merging ferric monomers, dimers, and other oligomers, driven by strong affinity of ferric ions to hydroxyls. When deprotonation reactions are not considered in the simulations, these clusters aggregate to form small iron hydroxide nanocrystals with a six-membered ring-like layered structure allomeric to gibbsite. By comparison, in a solution containing iron chloride and sodium hydroxide, the presence of chlorine drives cluster assembly along a different direction to form long molecular chains (rather than rings) composed of Fe–O octahedra linked by edge sharing. Further, in chlorine-free solutions, when deprotonation reactions are considered, the simulations predict ultimate formation of amorphous iron oxyhydroxide nanoparticles with local atomic structure similar to that of ferrihydrite nanoparticles. Overall, our simulation results reveal that nucleation of iron oxyhydroxide nanoparticles proceeds via a cluster aggregation-based nonclassical pathway.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Importance of Nucleation during Morphology Evolution of the Blade-Cast PffBT4T-2OD-Based Organic Solar Cells

Different temperatures, solvents, and additives are used as influencing parameters to drive molecular packing and phase separation for the development of the controlled evolution of nanostructures for organic solar cells (OSCs). The temperature-dependent aggregation (TDA) features of polymers are explored by investigating aggregation in solution and solid thin-film states using solution small-angle neutron scattering (SANS), soft/hard X-ray scattering, and transmission electron microscopy (TEM) characterizations. In situ grazing incidence wide angle X-ray scattering (GIWAXS) reveals that the nucleation process is highly significant and responsible for the ultimate film morphology. Processing conditions such as temperatures, solvents, and additives were used to influence the nucleation and evolution of film morphology. The nucleation process may improve the polymer packing and phase separation. It may also translate into optimized multilength scale domains and efficient charge percolation pathways, a strong implication to control the nucleation process for the efficient separation and transportation of charges in bulk heterojunction (BHJ) devices.

14 SOLAR ENERGY↗
DOE OSTI2025

Overcoming Secondary Nucleation of Misoriented Domains during Wafer-Scale Epitaxy of Single-Crystal Graphene on Ge(110)

The wafer-scale synthesis of single-crystal graphene on technologically important substrates is a major challenge inhibiting the development of next-generation devices that harness the exceptional electronic, thermal, and mechanical properties of single-crystal graphene. Here, in this work, the factors controlling the domain orientation of graphene grown epitaxially on Ge(110) are elucidated, and this insight is utilized to produce graphene with minimal polycrystallinity. In the early stages of growth, most graphene islands have unidirectionally aligned lattices. However, we discover a secondary nucleation phenomenon in which misoriented graphene domains nucleate near/from the island edges, introducing defective grain boundaries and significantly increasing polycrystallinity throughout growth. We find that secondary nucleation occurs when islands grow over Ge steps, which form because of an interplay between the island growth and Ge surface topography evolution. Strategies for suppressing secondary nucleation are developed, enabling the synthesis of graphene in which the predominant crystal orientation has high coverage >99% and low rotational spread <0.6°. This work overcomes the irreproducibility of graphene epitaxy on Ge(110) reported in the literature, providing a route toward the large-area synthesis of single-crystal graphene on technologically useful semiconductors.

chemical vapor deposition↗
DOE OSTI2014

Effect of otoconial proteins fetuin A, osteopontin, and otoconin 90 on the nucleation and growth of calcite

Here, we investigated the roles of three proteins associated with the formation of otoconia including fetuin A, osteopontin (OPN), and otoconin 90 (OC90). In situ atomic force microscopy (AFM) studies of the effects of these proteins on the growth of atomic steps on calcite surfaces were performed to obtain insight into their effects on the growth kinetics. We also used scanning electron microscopy to examine the effects of these proteins on crystal morphology. All three proteins were found to be potent inhibitors of calcite growth, although fetuin A promoted growth at concentrations below about 40 nM and only became an inhibitor at higher concentrations. We then used in situ optical microscopy to observe calcite nucleation on films of these proteins adsorbed onto mica surfaces. By measuring the calcite nucleation rate as a function of supersaturation, the value of the interfacial energy that controls the free energy barrier to heterogeneous nucleation was determined for each protein. OPN and OC90 films led to significantly reduced interfacial energies as compared to the value for homogeneous calcite nucleation in bulk solution. The value for fetuin A was equal to that for bulk solution within experimental error. Zeta potential measurements showed all of the proteins possessed negative surface charge and varied in magnitude according to sequence fetuin A > OC90 > OPN. In addition, the interfacial energies exhibited an inverse scaling with the zeta potential. In analogy to previous measurements on polysaccharide films, this scaling indicates the differences between the proteins arise from the effect of protein surface charge on the solution–substrate interfacial energy.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2014

Multivalent Macromolecules Redirect Nucleation-Dependent Fibrillar Assembly into Discrete Nanostructures

Manipulating the size and shape of noncovalent multivalent assemblies is an ongoing challenge in the field of supramolecular polymers. Following a mechanistic approach, we reasoned that nucleation–elongation kinetics presents unique opportunities for controlled growth since the final outcome is likely to depend on the structure and dynamics of critical-nucleus formation. Taking fibrillar assembly of amyloid β (Aβ) peptide as the model system of nucleation-dependent supramolecular polymerization, here we report multivalent polymer–peptide conjugates (mPPCs) that redirect fibrillar assembly of Aβ to form discrete nanostructures. The mPPCs were rationally designed to target Aβ intermediates formed prior to critical nucleation. Atomic force microscopy and transmission electron microscopy studies show that in the presence of mPPCs, Aβ self-assembles into zero-dimensional discrete nanostructures with lateral dimensions approximately in 5–35 nm, while Aβ alone self-assembles into one-dimensional fibrils in micrometer. Thioflavin T kinetics fluorescence assays demonstrate that mPPCs suppress Aβ fibrillogenesis. As a result, the mPPCs may thus represent a prototypical molecular design of multivalent macromolecules able to control the final shape of supramolecular polymers assembled via a nucleation-dependent mechanism.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Heterogeneous nucleation and shape transformation of multicomponent metallic nanostructures

To be able to control the functions of engineered multicomponent nanomaterials, a detailed understanding of heterogeneous nucleation at the nanoscale is essential. Here, by using in situ synchrotron X-ray scattering, we show that in the heterogeneous nucleation and growth of Au on Pt or Pt-alloy seeds the heteroepitaxial growth of the Au shell exerts high stress (similar to 2 GPa) on the seed by forming a core/shell structure in the early stage of the reaction. The development of lattice strain and subsequent strain relaxation, which we show using atomic-resolution transmission electron microscopy to occur through the slip of {111} layers, induces morphological changes from a core/shell to a dumbbell structure, and governs the nucleation and growth kinetics. We also propose a thermodynamic model for the nucleation and growth of dumbbell metallic heteronanostructures.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Direct observation of dual-step twinning nucleation in hexagonal close-packed crystals

Design and processing of advanced lightweight structural alloys based on magnesium and titanium rely critically on a control over twinning which, however, remains elusive to date and is dependent on an explicit understanding on the twinning nucleation mechanism in hexagonal close-packed (HCP) crystals. Here, by using in-situ high resolution transmission electron microscopy, we directly reveal a “dual-step” twinning nucleation mechanism in HCP rhenium nanocrystals. It is found that nucleation of the predominant {10 -12} twinning is initiated by disconnections on the Prismatic¦Basal interfaces which establish the lattice correspondence of the twin with a minor deviation from the ideal orientation. Subsequently, the minor deviation is corrected by the formation of coherent twin boundaries through rearrangement of the disconnections on the Prismatic¦Basal interface; thereafter, the coherent twin boundaries propagate by twinning disconnections. The findings provide much-needed high-resolution evidences to the twinning nucleation mechanism in HCP crystals, with crucial implications for engineering advanced structural alloys.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Step engineering for nucleation and domain orientation control in WSe 2 epitaxy on c -plane sapphire

In this study, epitaxial growth of two-dimensional transition metal dichalcogenides on sapphire has emerged as a promising route to wafer-scale single-crystal films. Steps on the sapphire act as sites for transition metal dichalcogenide nucleation and can impart a preferred domain orientation, resulting in a substantial reduction in mirror twins. Here we demonstrate control of both the nucleation site and unidirectional growth direction of WSe 2 on c-plane sapphire by metal–organic chemical vapour deposition. The unidirectional orientation is found to be intimately tied to growth conditions via changes in the sapphire surface chemistry that control the step edge location of WSe 2 nucleation, imparting either a 0° or 60° orientation relative to the underlying sapphire lattice. The results provide insight into the role of surface chemistry on transition metal dichalcogenide nucleation and domain alignment and demonstrate the ability to engineer domain orientation over wafer-scale substrates.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Temperature Dependence in Heterogeneous Nucleation with Application to the Direct Determination of Cluster Energy on Nearly Molecular Scale

A re-examination of measurements of heterogeneous nucleation of water vapor on silver nanoparticles is presented here using a model-free framework that derives the energy of critical cluster formation directly from measurements of nucleation probability. Temperature dependence is correlated with cluster stabilization by the nanoparticle seed and previously found cases of unusual increasing nucleation onset saturation ratio with increasing temperature are explained. A necessary condition for the unusual positive temperature dependence is identified, namely that the critical cluster be more stable, on a per molecule basis, than the bulk liquid to exhibit the effect. Temperature dependence is next examined in the classical Fletcher model, modified here to make the energy of cluster formation explicit in the model. The contact angle used in the Fletcher model is identified as the microscopic contact angle, which can be directly obtained from heterogeneous nucleation experimental data by a recently developed analysis method. Here an equivalent condition, increasing contact angle with temperature, is found necessary for occurrence of unusual temperature dependence. Our findings have immediate applications to atmospheric particle formation and nanoparticle detection in condensation particle counters (CPCs).

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

A correlation between grain boundary character and deformation twin nucleation mechanism in coarse-grained high-Mn austenitic steel

Abstract In polycrystalline materials, grain boundaries are known to be a critical microstructural component controlling material’s mechanical properties, and their characters such as misorientation and crystallographic boundary planes would also influence the dislocation dynamics. Nevertheless, many of generally used mechanistic models for deformation twin nucleation in fcc metal do not take considerable care of the role of grain boundary characters. Here, we experimentally reveal that deformation twin nucleation occurs at an annealing twin (Σ3{111}) boundary in a high-Mn austenitic steel when dislocation pile-up at Σ3{111} boundary produced a local stress exceeding the twining stress, while no obvious local stress concentration was required at relatively high-energy grain boundaries such as Σ21 or Σ31. A periodic contrast reversal associated with a sequential stacking faults emission from Σ3{111} boundary was observed by in-situ transmission electron microscopy (TEM) deformation experiments, proving the successive layer-by-layer stacking fault emission was the deformation twin nucleation mechanism, different from the previously reported observations in the high-Mn steels. Since this is also true for the observed high Σ-value boundaries in this study, our observation demonstrates the practical importance of taking grain boundary characters into account to understand the deformation twin nucleation mechanism besides well-known factors such as stacking fault energy and grain size.

36 MATERIALS SCIENCE↗