Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “NUCLEATION”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 469 records · Page 26
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Understanding Metal–Organic Framework Nucleation from a Solution with Evolving Graphs

A mechanistic understanding of metal–organic framework (MOF) synthesis and scale-up remains underexplored due to the complex nature of the interactions of their building blocks. In this work, we investigate the collective assembly of building units at the early stages of MOF nucleation, using MIL-101(Cr) as a prototypical example. Using large-scale molecular dynamics simulations, we observe that the choice of solvent (water and N,N-dimethylformamide), the introduction of ions (Na+ and F–) and the relative populations of MIL-101(Cr) half-secondary building unit (half-SBU) isomers have a strong influence on the cluster formation process. Additionally, the shape, size, nucleation and growth rates, crystallinity, and short and long-range order largely vary depending on the synthesis conditions. We evaluate these properties as they naturally emerge when interpreting the self-assembly of MOF nuclei as the time evolution of an undirected graph. Solution-induced conformational complexity and ionic concentration have a dramatic effect on the morphology of clusters emerging during assembly. While pure solvents lead to the rapid formation of a small number of large clusters, the presence of ions in aqueous solutions results in smaller clusters and slower nucleation. This diversity is captured by the key features of the graph representation. Principle component analysis on graph properties reveals that only a small number of molecular descriptors is needed to deconvolute MOF self-assembly. Furthermore, descriptors such as the average coordination number between half-SBUs and fractal dimension are of particular interest as they can be can be followed experimentally by techniques like by time-resolved spectroscopy. Ultimately, graph theory emerges as an approach that can be used to understand complex processes revealing molecular descriptors accessible by both simulation and experiment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Thermodynamic Control of Interface Directs MnO 2 Nucleation Chemistry for Dense and Conformal Electrodeposition

Manganese dioxide (MnO 2 ) is widely recognized as a promising material for high-energy-density energy storage systems due to its broad applicability and facile electrodeposition. However, achieving uniform, thin, and high-mass-loading MnO 2 coatings on high-surface-area electrodes remains a significant challenge. Conventional electrodeposition methods typically yield nonuniform, thick layers with poor conductivity and limited material utilization, restricting their practical use. Here, we uncover a thermodynamically engineered vanadyl/pervanadyl (VO 2+ /VO 2 + ) interface that fundamentally reshapes MnO 2 electrodeposition chemistry, enabling highly uniform and dense coatings. Here, combining in situ AFM measurement, Classical Nucleation Theory, and Johnson–Mehl–Avrami–Kolmogorov modeling, we show that this interface reduces early-stage detectable MnO 2 island size by 35-fold and shifts the MnO 2 growth from diffusion-limited to reaction-limited progressive nucleation. This thermodynamically controlled interface yields highly dense and conformal MnO 2 films with record-high mass loading of 241 mg cm –2 (1607 mg cm –3 ) on 3D-printed graphene aerogels, without compromising porosity or inducing thickness gradient. As a prototype demonstration, the resulting MnO 2 electrodes deliver record-setting volumetric performance in both capacitors (106 F cm –3 ) and Zn//MnO 2 pouch cells (162 mAh cm –3 ). Beyond energy storage, our findings demonstrate the significance of thermodynamic interface control in MnO 2 nucleation chemistry for achieving dense and uniform coatings on various substrates, with implications for electrocatalysis, semiconductor processing, and advanced materials manufacturing.

Batteries↗
DOE OSTI2014

Nucleation of Iron Oxide Nanoparticles Mediated by Mms6 Protein in Situ

Biomineralization proteins are widely used as templating agents in biomimetic synthesis of a variety of organic–inorganic nanostructures. However, the role of the protein in controlling the nucleation and growth of biomimetic particles is not well understood, because the mechanism of the bioinspired reaction is often deduced from ex situ analysis of the resultant nanoscale mineral phase. Here we report the direct visualization of biomimetic iron oxide nanoparticle nucleation mediated by an acidic bacterial recombinant protein, Mms6, during an in situ reaction induced by the controlled addition of sodium hydroxide to solution-phase Mms6 protein micelles incubated with ferric chloride. Using in situ liquid cell scanning transmission electron microscopy we observe the liquid iron prenucleation phase and nascent amorphous nanoparticles forming preferentially on the surface of protein micelles. Our results provide insight into the early steps of protein-mediated biomimetic nucleation of iron oxide and point to the importance of an extended protein surface during nanoparticle formation.

36 MATERIALS SCIENCE↗
DOE OSTI2018

In situ study of nucleation and growth dynamics of Au nanoparticles on MoS 2 nanoflakes

Two-dimensional (2D) substrates decorated with metal nanoparticles offer new opportunities to achieve high-performance catalytic behavior. However, little is known on how the substrates control the nucleation and growth processes of the nanoparticles. This paper presents the visualization of dynamic nucleation and growth processes of gold nanoparticles on ultrathin MoS 2 nanoflakes by in situ liquid-cell transmission electron microscopy (TEM). The galvanic displacement resulting in Au nuclei formation on MoS 2 was observed in real time inside the liquid cell. We found that the growth mechanism of Au particles on pristine MoS 2 is in between diffusion-limited and reaction-limited, possibly due to the presence of electrochemical Ostwald ripening. A larger size distribution and more orientation variation is observed for the Au particles along the MoS 2 edge than on the interior. Differing from pristine MoS 2 , sulfur vacancies on MoS 2 induce Au particle diffusion and coalescence during the growth process. Density functional theory (DFT) calculations show that the size difference is because the exposed molybdenum atoms at the edge with dangling bonds can strongly interact with Au atoms, whereas sulfur atoms on the MoS 2 interior have no dangling bonds and weakly interact with gold atoms. In addition, S vacancies on MoS 2 generate strong nucleation centers that can promote diffusion and coalescence of Au nanoparticles. Furthermore, the present work provides key insights into the role of 2D materials in controlling the size and orientation of noble metal nanoparticles vital to the design of next generation catalysts.

2D materials↗
DOE OSTI2012

The influence of Mg doping on the nucleation of self-induced GaN nanowires

GaN nanowires were grown without any catalyst by plasma-assisted molecular beam epitaxy. Under supply of Mg, nanowire nucleation is faster, the areal density of wires increases to a higher value, and nanowire coalescence is more pronounced than without Mg. During nanowire nucleation the Ga desorption was monitored in-situ by line-of-sight quadrupole mass spectrometry for various substrate temperatures. Nucleation energies of 4.0{+-}0.3 eV and 3.2{+-}0.3 eV without and with Mg supply were deduced, respectively. This effect has to be taken into account for the fabrication of nanowire devices and could be employed to tune the NW areal density.

36 MATERIALS SCIENCE↗
DOE OSTI2012

In situ study of self-assembled GaN nanowires nucleation on Si(111) by plasma-assisted molecular beam epitaxy

Nucleation of GaN nanowires grown by plasma-assisted molecular beam epitaxy is studied through a combination of two in situ tools: grazing incidence x-ray diffraction and reflection high energy electron diffraction. Growth on bare Si(111) and on AlN/Si(111) is compared. A significantly larger delay at nucleation is observed for nanowires grown on bare Si(111). The difference in the nucleation delay is correlated to a dissimilarity of chemical reactivity between Al and Ga with nitrided Si(111).

36 MATERIALS SCIENCE↗
DOE OSTI2012

Role of nucleation sites on the formation of nanoporous Ge

The role of nucleation sites on the formation of nanoporous Ge was investigated. Three Ge films with different spherical or columnar pore morphologies to act as inherent nucleation sites were sputtered on (001) Ge. Samples were implanted 90 Degree-Sign from incidence at 300 keV with fluences ranging from 3.0 Multiplication-Sign 10{sup 15} to 3.0 Multiplication-Sign 10{sup 16} Ge{sup +}/cm{sup 2}. Electron microscopy investigations revealed varying thresholds for nanoporous Ge formation and exhibited a stark difference in the evolution of the Ge layers based on the microstructure of the initial film. The results suggest that the presence of inherent nucleation sites significantly alters the onset and evolution of nanoporous Ge.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2012

Selective nucleation induced by defect nanostructures: A way to control cobalt disilicide precipitation during ion implantation

In this paper, we show a way to control cobalt disilicide precipitation during Co ion implantation at high temperatures (650 Degree-Sign C) by affecting radiation defects involved in precipitate nucleation and growth. We demonstrate that the relative shares of different precipitate types nucleated by implantation are strongly affected by defect microstructures deliberately created in investigated samples prior to cobalt implantation. Especially interesting is the effect of a dense ensemble of extremely small (1-3 nm) cavities, which promotes the formation of a relatively uniform layer of coherent cobalt disilicide precipitates with a narrow size distribution. In order to better understand the mechanism of the microstructural influence on the precipitate nucleation modes during Co implantation, we investigate the disilicide precipitation using different implantation setups and compare the results with those for cavity-free Si specimens implanted in similar conditions.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2013

Nucleation of single GaN nanorods with diameters smaller than 35 nm by molecular beam epitaxy

Nucleation mechanism of catalyst-free GaN nanorod grown on Si(111) is investigated by the fabrication of uniform and narrow (<35 nm) nanorods without a pre-defined mask by molecular beam epitaxy. Direct evidences show that the nucleation of GaN nanorods stems from the sidewall of the underlying islands down to the Si(111) substrate, different from commonly reported ones on top of the island directly. Accordingly, the growth and density control of the nanorods is exploited by a “narrow-pass” approach that only narrow nanorod can be grown. The optimal size of surrounding non-nucleation area around single nanorod is estimated as 88 nm.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2014

Microwave plasma enhanced chemical vapor deposition of nanocrystalline diamond films by bias-enhanced nucleation and bias-enhanced growth

Effects of biasing voltage-current relationship on microwave plasma enhanced chemical vapor deposition of ultrananocrystalline diamond (UNCD) films on (100) silicon in hydrogen diluted methane by bias-enhanced nucleation and bias-enhanced growth processes are reported. Three biasing methods are applied to study their effects on nucleation, growth, and microstructures of deposited UNCD films. Method A employs 320 mA constant biasing current and a negative biasing voltage decreasing from −490 V to −375 V for silicon substrates pre-heated to 800 °C. Method B employs 400 mA constant biasing current and a decreasing negative biasing voltage from −375 V to −390 V for silicon pre-heated to 900 °C. Method C employs −350 V constant biasing voltage and an increasing biasing current up to 400 mA for silicon pre-heated to 800 °C. UNCD nanopillars, merged clusters, and dense films with smooth surface morphology are deposited by the biasing methods A, B, and C, respectively. Effects of ion energy and flux controlled by the biasing voltage and current, respectively, on nucleation, growth, microstructures, surface morphologies, and UNCD contents are confirmed by scanning electron microscopy, high-resolution transmission-electron-microscopy, and UV Raman scattering.

36 MATERIALS SCIENCE↗
DOE OSTI2014

The nucleation process and the roles of structure and density fluctuations in supercooled liquid Fe

We observed homogeneous nucleation process of supercooled liquid Fe by molecular dynamics simulations. Using bond-orientational order parameters together with Voronoi polyhedron method, we characterized local structure, calculated the volume of Voronoi polyhedra of atoms and identified the structure and density fluctuations. We monitored the formation of nucleus and analyzed its inner structure. The birth and growth of the pre-nucleus and nucleus are accompanied with aggregating and disaggregating processes in the time scale of femtosecond. Only the initial solid-like clusters (ISLC), ranging from 1 to 7 atoms, pop up directly from liquid. The relation between the logarithm of number of clusters and the cluster size was found to be linear for ISLCs and was observed to be parabolic for all solid-like clusters (SLC) due to aggregating and disaggregating effects. The nucleus and pre-nuclei mainly consist of body centered cubic (BCC) and hexagonal close packed atoms, while the BCC atoms tend to be located at the surface. Medium-range structure fluctuations induce the birth of ISLCs, benefit the aggregation of embryos and remarkably promote the nucleation. But density fluctuations contribute little to nucleation. The lifetime of most icosahedral-like atoms (ICO) is shorter than 0.7 ps. No obvious relationship was found between structure/density fluctuations and the appearance of ICO atoms.

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

Temperature dependent nucleation, propagation, and annihilation of domain walls in all-perpendicular spin-valve nanopillars

We present a study of the temperature dependence of the switching fields in Co/Ni-based perpendicularly magnetized spin-valves. While magnetization reversal of all-perpendicular Co/Ni spin valves at ambient temperatures is typically marked by a single sharp step change in resistance, low temperature measurements can reveal a series of resistance steps, consistent with non-uniform magnetization configurations. We propose a model that consists of domain nucleation, propagation, and annihilation to explain the temperature dependence of the switching fields. Interestingly, low temperature (<30 K) step changes in resistance that we associate with domain nucleation have a bimodal switching field and resistance step distribution, attributable to two competing nucleation pathways.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Viscosity of interfacial water regulates ice nucleation

Ice formation on solid surfaces is an important phenomenon in many fields, such as cloud formation and atmospheric icing, and a key factor for applications in preventing freezing. Here, we report temperature-dependent nucleation rates of ice for hydrophilic and hydrophobic surfaces. The results show that hydrophilic surface presents a lower ice nucleation rate. We develop a strategy to extract the thermodynamic parameters, J{sub 0} and Γ, in the context of classical nucleation theory. From the extracted J{sub 0} and Γ, we reveal the dominant role played by interfacial water. The results provide an insight into freezing mechanism on solid surfaces.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2014

Role of filament annealing in the kinetics and thermodynamics of nucleated polymerization

The formation of nanoscale protein filaments from soluble precursor molecules through nucleated polymerization is a common form of supra-molecular assembly phenomenon. This process underlies the generation of a range of both functional and pathological structures in nature. Filament breakage has emerged as a key process controlling the kinetics of the growth reaction since it increases the number of filament ends in the system that can act as growth sites. In order to ensure microscopic reversibility, however, the inverse process of fragmentation, end-to-end annealing of filaments, is a necessary component of a consistent description of such systems. Here, we combine Smoluchowski kinetics with nucleated polymerization models to generate a master equation description of protein fibrillization, where filamentous structures can undergo end-to-end association, in addition to elongation, fragmentation, and nucleation processes. We obtain self-consistent closed-form expressions for the growth kinetics and discuss the key physics that emerges from considering filament fusion relative to current fragmentation only models. Furthermore, we study the key time scales that describe relaxation to equilibrium.

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

In-situ high resolution transmission electron microscopy observation of silicon nanocrystal nucleation in a SiO{sub 2} bilayered matrix

Solid-state nucleation of Si nanocrystals in a SiO{sub 2} bilayered matrix was observed at temperatures as low as 450 °C. This was achieved by aberration corrected high-resolution transmission electron microscopy (HRTEM) with real-time in-situ heating up to 600 °C. This technique is a valuable characterization tool especially with the recent interest in Si nanostructures for light emitting devices, non-volatile memories, and third-generation photovoltaics which all typically require a heating step in their fabrication. The control of size, shape, and distribution of the Si nanocrystals are critical for these applications. This experimental study involves in-situ observation of the nucleation of Si nanocrystals in a SiO{sub 2} bilayered matrix fabricated through radio frequency co-sputtering. The results show that the shapes of Si nanocrystals in amorphous SiO{sub 2} bilayered matrices are irregular and not spherical, in contrast to many claims in the literature. Furthermore, the Si nanocrystals are well confined within their layers by the amorphous SiO{sub 2}. This study demonstrates the potential of in-situ HRTEM as a tool to observe the real time nucleation of Si nanocrystals in a SiO{sub 2} bilayered matrix. Furthermore, ideas for improvements on this in-situ heating HRTEM technique are discussed.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2014

Surface dislocation nucleation controlled deformation of Au nanowires

We investigate deformation in high quality Au nanowires under both tension and bending using in-situ transmission electron microscopy. Defect evolution is investigated during: (1) tensile deformation of 〈110〉 oriented, initially defect-free, single crystal nanowires with cross-sectional widths between 30 and 300 nm, (2) bending deformation of the same wires, and (3) tensile deformation of wires containing coherent twin boundaries along their lengths. We observe the formation of twins and stacking faults in the single crystal wires under tension, and storage of full dislocations after bending of single crystal wires and after tension of twinned wires. The stress state dependence of the deformation morphology and the formation of stacking faults and twins are not features of bulk Au, where deformation is controlled by dislocation interactions. Instead, we attribute the deformation morphologies to the surface nucleation of either leading or trailing partial dislocations, depending on the Schmid factors, which move through and exit the wires producing stacking faults or full dislocation slip. The presence of obstacles such as neutral planes or twin boundaries hinder the egress of the freshly nucleated dislocations and allow trailing and leading partial dislocations to combine and to be stored as full dislocations in the wires. We infer that the twins and stacking faults often observed in nanoscale Au specimens are not a direct size effect but the result of a size and obstacle dependent transition from dislocation interaction controlled to dislocation nucleation controlled deformation.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Effective binary theory of multi-component nucleation

Classical theory of multi-component nucleation [O. Hirschfelder, J. Chem. Phys. 61, 2690 (1974)] belongs to the class of the so-called intractable problems: it requires computational time which is an exponential function of the number of components N. For a number of systems of practical interest with N > 10, the brute-force use of the classical theory becomes virtually impossible and one has to resort to an effective medium approach. We present an effective binary model which captures important physics of multi-component nucleation. The distinction between two effective species is based on the observation that while all N components contribute to the cluster thermodynamic properties, there is only a part of them which trigger the nucleation process. The proposed 2D-theory takes into account adsorption by means of the Gibbs dividing surface formalism and uses statistical mechanical considerations for the treatment of small clusters. Theoretical predictions for binary-, ternary-, and 14-component mixtures are compared with available experimental data and other models.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Systematic coarse-graining in nucleation theory

In this work, we show that the standard method to obtain nucleation rate-predictions with the aid of atomistic Monte Carlo simulations leads to nucleation rate predictions that deviate 3 − 5 orders of magnitude from the recent brute-force molecular dynamics simulations [Diemand et al., J. Chem. Phys. 139, 074309 (2013)] conducted in the experimental accessible supersaturation regime for Lennard-Jones argon. We argue that this is due to the truncated state space the literature mostly relies on, where the number of atoms in a nucleus is considered the only relevant order parameter. We here formulate the nonequilibrium statistical mechanics of nucleation in an extended state space, where the internal energy and momentum of the nuclei are additionally incorporated. We show that the extended model explains the lack in agreement between the molecular dynamics simulations by Diemand et al. and the truncated state space. We demonstrate additional benefits of using the extended state space; in particular, the definition of a nucleus temperature arises very naturally and can be shown without further approximation to obey the fluctuation law of McGraw and LaViolette. In addition, we illustrate that our theory conveniently allows to extend existing theories to richer sets of order parameters.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗