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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 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Pore-Scale Modeling of Mineral Growth and Nucleation in Reactive Flow

A fundamental understanding of mineral precipitation kinetics relies largely on microscopic observations of the dynamics of mineral surfaces exposed to supersaturated solutions. Deconvolution of tightly bound transport, surface reaction, and crystal nucleation phenomena still remains one of the main challenges. Particularly, the influence of these processes on texture and morphology of mineral precipitate remains unclear. This study presents a coupling of pore-scale reactive transport modeling with the Arbitrary Lagrangian-Eulerian approach for tracking evolution of explicit solid interface during mineral precipitation. It incorporates a heterogeneous nucleation mechanism according to Classical Nucleation Theory which can be turned “on” or “off.” This approach allows us to demonstrate the role of nucleation on precipitate texture with a focus at micrometer scale. In this work precipitate formation is modeled on a 10 micrometer radius particle in reactive flow. The evolution of explicit interface accounts for the surface curvature which is crucial at this scale in the regime of emerging instabilities. The results illustrate how the surface reaction and reactive fluid flow affect the shape of precipitate on a solid particle. It is shown that nucleation promotes the formation of irregularly shaped precipitate and diminishes the effect of the flow on the asymmetry of precipitation around the particle. The observed differences in precipitate structure are expected to be an important benchmark for reaction-driven precipitation in natural environments.

58 GEOSCIENCES↗
DOE OSTI2023

Assessing an aqueous flow cell designed for in situ crystal growth under X-ray nanotomography and effects of radiolysis products

Nucleation and growth of minerals has broad implications in the geological, environmental and materials sciences. Recent developments in fast X-ray nanotomography have enabled imaging of crystal growth in solutions in situ with a resolution of tens of nanometres, far surpassing optical microscopy. Here, a low-cost, custom-designed aqueous flow cell dedicated to the study of heterogeneous nucleation and growth of minerals in aqueous environments is shown. To gauge the effects of radiation damage from the imaging process on growth reactions, radiation-induced morphological changes of barite crystals (hundreds of nanometres to ∼1 µm) that were pre-deposited on the wall of the flow cell were investigated. Under flowing solution, minor to major crystal dissolution was observed when the tomography scan frequency was increased from every 30 min to every 5 min (with a 1 min scan duration). The production of reactive radicals from X-ray induced water radiolysis and decrease of pH close to the surface of barite are likely responsible for the observed dissolution. The flow cell shown here can possibly be adopted to study a wide range of other chemical reactions in solutions beyond crystal nucleation and growth where the combination of fast flow and fast scan can be used to mitigate the radiation effects.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Multiscale hierarchical and heterogeneous mechanical response of additively manufactured novel Al alloy investigated by high-resolution nanoindentation mapping

Smart alloying and microstructural engineering mitigate challenges associated with laser-powder bed fusion additive manufacturing (L-PBFAM). A novel Al–Ni–Ti–Zr alloy utilized grain refinement by heterogeneous nucleation and eutectic solidification to achieve superior performance-printability synergy. Conventional mechanical testing cannot delineate complex micromechanics of such alloys. This study combined multiscale nanomechanical and microstructural mapping to illustrate mechanical signatures associated with hierarchical heat distribution and rapid solidification of L-PBFAM. The disproportionate hardening effect imparted by Al 3 (Ti,Zr) precipitates in the pool boundaries and the semi-solid zone was successfully demonstrated. Nanomechanical response associated with heterogeneity in particle volume fraction and coherency across melt pool was interpreted from nanoindentation force–displacement curves. The hardness map effectively delineated the weakest and strongest sections in the pool with microscopic accuracy. The presented approach serves as a high throughput methodology to establish the chemistry-processing-microstructure-properties correlation of newly designed alloys for L-PBFAM.

36 MATERIALS SCIENCE↗
DOE OSTI2023

SAF Combustion & Soot Processes [Slides]

The atomization, mixing, combustion and emissions characteristics of aviation fuels were measured using a novel approach based on a non-continuous injection scheme called the single-hole atomizer (SHA). High-speed microscopy revealed differences between fuels in terms of evaporation and mixing regimes over conditions relevant to modern and next generation aero-engine combustors. Measurements of liquid and vapor penetration, mixing fields, combustion and emissions metrics (ignition delay, lift-off length, PAH formation, soot mass) highlighted the effects of fuels and combustor conditions. The experimental results are being leveraged to adjust and validate chemical and CFD models. Detailed analysis of sampled soot showed subtle differences in soot morphology between fuels. The results revealed the presence of contaminants potentially affecting surface chemistry and the nucleation propensity of water droplets on particles. Chemical mechanisms for NJFCP A-2, C-1 and C-4 showed good performance over a large parameter space. Spray breakup at relight conditions is vastly different from the atomization observed at high pressure. CFD simulations of the SHA target conditions confirmed the good behavior of the C-1 kinetic mechanism. The simulations support the strong relationship between low and high temperature reactions. New altitude chamber facility to enable detailed characterization of the heterogeneous nucleation process of water on aerosol particles.

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

Mechanistic Insights into Defect-Mediated Crystallization Revealed by Lattice Strain Evolution

Structural defects and lattice strain are intrinsic to many crystalline materials, yet their roles in controlling chemical reaction mechanisms and directing crystallization pathways remain poorly understood. Here, in this study, we revealed the three-dimensional evolution of strain and dislocation defects at the nanoscale during the growth of heterogeneously nucleated barite (BaSO 4 ) and calcite (CaCO 3 ) crystals by using coherent X-ray scattering, electron microscopy, and molecular simulations. Unlike barite, which formed with minimal internal strain, calcite developed dislocation defects and exhibited spatially varying strain that increased during growth. During growth in Sr-rich solutions, calcite likely incorporates Sr 2+ into the defects, which further modulates the local lattice structure and increases both the compressive and tensile strain. These findings suggest that calcite crystallization was likely dominated by attachment of precursor phases, which gave rise to defect-enriched domain structures not predicted by classical growth models. By linking defect formation to ion incorporation and growth dynamics, this work provides fundamental insight into how lattice-level strain heterogeneity governs the chemical reactivity of ionic crystals.

Bragg coherent diffractive imaging↗
DOE OSTI2024

Formation and coarsening of epitaxially-supported metal nanoclusters

This mini-review describes developments over the last ~30 years in characterizing the nucleation & growth of epitaxially-supported metal nanoclusters (NCs) or islands during vapor deposition, as well as their post-deposition coarsening. A beyond-mean-field treatment for homogeneous nucleation & growth corrects the deficiencies of traditional treatments in describing, e.g., the island size distribution, but also necessitates consideration of the spatial distribution of islands and their capture zones. We discuss advances in modeling capabilities, including those based upon on an ab-initio level treatment of periphery diffusion kinetics, for description of the non-equilibrium growth shapes of these NCs, focusing on 2D NCs. For post-deposition coarsening of arrays of NCs, there is generally a competition between Ostwald Ripening (OR) and Smoluchowski Ripening (SR). SR is also known as Particle Migration & Coalescence. For 2D NCs in homoepitaxial systems, conventional OR is observed on pristine fcc(111) surfaces, dramatically enhanced OR in the presence of even trace amounts of chalcogens for Cu(111) and Ag(111), and anomalous OR on anisotropic fcc(110) surfaces. The unexpected discovery of SR for fcc(100) homoepitaxial systems prompted extensive analysis of the underlying diffusivities of 2D NCs as a function of size, as well as of NC coalescence dynamics. A comprehensive understanding of these processes is now available. Self-assembly of 3D NCs during deposition, issues related to heterogeneous nucleation, directed assembly, NC growth structure selection, and coarsening are addressed. Finally, for SR of 3D epitaxial NCs, recent insights into the size-dependence of diffusivity are described.

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

Directing Assembly of Mesoscale Multi‐Shell Morphologies of DNA Origami Crystals

Nature builds hierarchically ordered materials, such as seashells, wood, and bones, through spatially and temporally regulated growth. Mimicking such a level of control in synthetic systems remains challenging, particularly in achieving multiscale organizations with prescribed nanoscale arrangements and desired material morphologies. In this study, we introduce a DNA-based self-assembly strategy for constructing diverse multi-shell mesoscale morphologies from nanoscale lattices, enabling prescribed structural, and compositional 3D material patterns. Using DNA origami frames as modular monomers, we direct anisotropic epitaxial growth through addressable DNA frame binding motifs and encapsulate nanoparticles (NPs) in desired 3D patterns. Sequential monomer addition under thermodynamically favorable conditions enables shell growth through heterogeneous nucleation while minimizing unwanted homogeneous nucleation. Here, we demonstrate that DNA-encoded addressability enables epitaxial shell growth along specific lattice directions, yielding crystals with multilayered mesoscale organization, including tube-like (sushi roll) and plate-like (macaron) morphologies. Shell-specific NP configurations and compositions are achieved through addressable and differentiated placement of NPs within each shell, as validated by small-angle x-ray scattering and cross-sectional scanning transmission electron microscopy. We further demonstrate addressable NP release and reveal that shells modulate release kinetics. Together, these findings establish a platform for fabricating DNA origami crystals with programmable mesoscale morphologies, nanoscale structure, composition, and transport properties.

3D patterning↗
DOE OSTI2024

Precision Calcination Mechanism of CaCO 3 to High-Porosity Nanoscale CaO CO 2 Sorbent Revealed by Direct In Situ Observations

Deploying energy storage and carbon capture at scale is hindered by the substantial endothermic penalty of decomposing CaCO 3 to CaO and CO 2 , and the rapid loss of CO 2 absorption capacity by CaO sorbent particles due to sintering at the high requisite decomposition temperatures. The decomposition reaction mechanism underlying sorbent deactivation remains unclear at the atomic level and nanoscale due to past reliance on postmortem characterization methods with insufficient spatial and temporal resolution. Thus, elucidating the important CaCO 3 decomposition reaction pathway requires direct observation by time-resolved (sub-)nanoscale methods. Here, chemical and structural dynamics during the decomposition of CaCO 3 nanoparticles to nanoporous CaO particles comprising high-surface-area CaO nanocrystallites are examined. Comparing in situ transmission electron microscopy (TEM) and synchrotron X-ray diffraction experiments gives key insights into the dynamics of nanoparticle calcination, involving anisotropic CaCO 3 thermal distortion before conversion to thermally dilated energetically stable CaO crystallites. Time-resolved TEM uncovered a novel CaO formation mechanism involving heterogeneous nucleation at extended CaCO 3 defects followed by sweeping reaction front motion across the initial CaCO 3 particle. These observations clarify longstanding, yet incomplete, reaction mechanisms and kinetic models lacking accurate information about (sub-)nanoscale dynamics, while also demonstrating calcination of CaCO 3 without sintering through rapid heating and precise temperature control.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Multi-Step Crystallization of Self-Organized Spiral Eutectics

A method for the solidification of metallic alloys involving spiral self-organization is presented as a new strategy for producing large-area chiral patterns with emergent structural and optical properties, with attention to the underlying mechanism and dynamics. This study reports the discovery of a new growth mode for metastable, two-phase spiral patterns from a liquid metal. Crystallization proceeds via a non-classical, two-step pathway consisting of the initial formation of a polytetrahedral seed crystal, followed by ordering of two solid phases that nucleate heterogeneously on the seed and grow in a strongly coupled fashion. Crystallographic defects within the seed provide a template for spiral self-organization. These observations demonstrate the ubiquity of defect-mediated growth in multi-phase materials and establish a pathway toward bottom-up synthesis of chiral materials with an inter-phase spacing comparable to the wavelength of infrared light. Given that liquids often possess polytetrahedral short-range order, our results are applicable to many systems undergoing multi-step crystallization.

36 MATERIALS SCIENCE↗
DOE OSTI2020

In-situ re-crystallization of heavily-irradiated Gd 2 Ti 2 O 7

Gadolinium titanate (Gd 2 Ti 2 O 7 , or GTO) and other lanthanide pyrochlores are interesting candidates for actinide waste disposal and fast ion conduction because the relevant material properties are intimately dependent on local cation structure. Therefore, a deep understanding of the kinetics associated with cation ordering and disordering is required if such material properties are to be tuned for specific device designs. To this end, single crystals of GTO were irradiated with 190 keV helium ions to a total fluence of 1 × 10 17 ions/cm 2 , amorphizing the sample surface to a depth of ~1 μm and resulting in significant He bubble accumulation. FIB lamellae lifted out from the irradiated sections were examined during heat treatment in the (scanning) transmission electron microscope. Two distinct stages of the re-crystallization of the amorphized material were observed. The material near the end of the ions’ range transformed first and with the same orientation as the pristine material. This was due to the close proximity of the pristine material and the presence of small defect fluorite seeds, but the propagation of this growth front was frustrated by the large pores (formerly bubbles) in the He accumulation layer. This was followed by heterogeneous nucleation of new crystallites at random orientations at the top of the He accumulation layer, which is attributed to the high surface area associated with the many small He bubbles in that region. Finally, it is inferred that the kinetics of grain growth in this material are significantly faster than the kinetics of grain nucleation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

A spall and diffraction study of nanosecond pressure release across the iron ε-α phase boundary

The extreme response of polycrystalline iron at high pressures and high strain rates is revealed by means of high-power laser pulses. The compression portion of the pulse coupled with x-ray diffraction identifies the expected body-centered cubic (α) to hexagonal close packed (ε) displacive transformation. Upon release, observation shows that the complete reverse transformation takes approximately 8 ns and that the structure returns to its initial microstructural configuration, in a reversible transformation path. This is in good agreement with molecular dynamics (MD) simulations which predict an inverse dependence between transformation time and strain rate. The grain size is reduced from μm to nm range during compression and begins increasing back to the original grain size on decompression. The kinetics of the transition is dictated by heterogenous nucleation as it follows the Johnson-Mehl-Avrami-Kolmogorov equation with the appropriate time exponent of ~1. This is confirmed by MD simulations which also identify profuse twinning and dislocation generation. Here, the tensile pulse generated upon reflection at the free surface is captured by time-resolved free surface velocity measurements from which a peak tensile stress of 7 GPa is obtained, in stark contrast with its quasi-static value of ~200 MPa. At these strain rates, the strength of grain interiors, which is determined by twinning and slip exceeds the strength of the boundaries, and failure initiates preferentially in the latter.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Ultrafine-grained Fe-TiB 2 high-modulus nanocomposite steel with high strength and isotropic mechanical properties by laser powder bed fusion

Fe-TiB 2 metal matrix composite, also called high-modulus steels (HMSs), are of great interest for applications in fuel-efficient transportation infrastructure, aerospace, and wear industries due to their high specific stiffness and yield strength. However, conventional cast Fe-TiB 2 HMSs often contain coarse and sharp-edged TiB 2 particles which easily trigger premature cracking during loading. Here, we synthesized a Fe-TiB 2 nanocomposite HMS via laser powder bed fusion (LPBF) additive manufacturing of mixed micro-sized powders of Fe, Ti, and Fe 2 B. We investigated the microstructure formation and mechanical behavior of the Fe-TiB 2 HMS. We found that in situ chemical reaction of Ti and Fe 2 B enables the formation of TiB 2 particles at nanoscale during rapid solidification of LPBF. These nanoscale TiB 2 particles can serve as heterogeneous nucleation sites and promote the formation of ultrafine and equiaxed α-Fe grains with random crystallographic textures, which differ from many other additively manufactured (AM) metal alloys characteristic of strong crystallographic textures. As such, isotropic mechanical properties were achieved in the AM Fe-TiB 2 nanocomposite HMS with a high elastic modulus of ~ 240 GPa, an exceptional yield strength of ~ 1450 MPa, and a large plasticity of ~ 20% under compression. Quantitative analysis reveals that the high yield strength primarily originates from strengthening contributions of the ultrafine grains with an average grain size of ~450 nm, the nanoscale TiB 2 reinforcing particles of 20–180 nm, and a high density of printing-induced dislocations of the order of 10 15 m –2 . In situ synchrotron high-energy X-ray diffraction unveils the load partitioning from the softer α-Fe matrix to the stiffer and stronger TiB 2 nanoparticles, contributing to the sustained strain hardening during compression. Our work not only provides a general pathway for achieving high-performance metal matrix nanocomposites by in situ chemical reaction and precipitation of ceramic nanoparticles during additive manufacturing, but also offers mechanistic insights into the deformation mechanism of nanoparticle-reinforced HMS composites.

36 MATERIALS SCIENCE↗
DOE OSTI2023

C@SnS 2 core-shell 0D/2D nanocomposite with excellent electrochemical performance as lithium-ion battery anode

C@SnS 2 core-shell 0D/2D nanocomposite was successfully prepared by a one-step hydrothermal method. The SnS 2 nanosheets were heterogeneously nucleated and grown on the surface of carbon spheres. As an anode for lithium-ion batteries, the electrochemical performance of the C@SnS 2 composite outperforms that of SnS 2 nanoflowers. After 100 cycles, the reversible discharge specific capacity reaches an impressive value of 802 mAh g -1 at a current density of 100 mA g -1 . Even after 600 cycles, the discharge specific capacity remains a value of 442 mAh g -1 , under a high current density of 1 A g -1 . Further, this remarkable lithium-ion storage performance can be attributed to the unique core-shell nanostructure and the synergy between SnS 2 nanosheets and carbon spheres. This study advances our understanding of the vital role of carbon in fabricating nano-heterojunction or composite electrodes and provides a feasible route to significantly improve the electrochemical properties of SnS 2 and other metal sulfides.

25 ENERGY STORAGE↗
DOE OSTI2021

Evolution of glass structure during femtosecond laser assisted crystallization of LaBGeO 5 in glass

Single crystal LaBGeO 5 architecture formed in La 2 O 3 -B 2 O 3 -2GeO 2 glass serves as a model system for understanding of the transformation from glass to single crystal under fs laser irradiation. This transformation is highly sensitive to glass composition, raising the need to understand how the glass structure and composition evolve during crystallization. In this work, micro X-ray absorption spectroscopy and X-ray fluorescence mapping were used to study the glass structure and composition preceding LaBGeO5 crystallization in the region surrounding the single crystal growth front. The results show precipitation of germanium nanoparticles, as well as anisotropic segregation of Ge and La prior to LaBGeO5 crystallization, which are explained assuming electromigration in high fields within the plasma formed by the fs laser irradiation. However, these nanoparticles do not serve as sites for heterogeneous nucleation. Furthermore, the similarity of local structure around Ge in the starting glass and the ultimate crystal appears to enhance the crystallization process.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Microstructural evolution of rapidly solidified hypoeutectic Al 10Cu alloy during non-isothermal annealing transients induced by nano-second laser pulses

The evolution of characteristic nonequilibrium features presenting in morphologically distinct regions of rapid solidification (RS) microstructures in a hypoeutectic Al—10Cu (atomic %) in response to non-isothermal annealing transients has been studied by transmission electron microscopy (TEM). The capabilities of the Movie-Mode Dynamic TEM (MM-DTEM) instrument were used to expose select regions of the RS microstructure to sequences of rapid heating and cooling transients induced by nanosecond laser pulses while permitting in-situ observation. Partial melting, microstructural scale coarsening, morphological changes of the nonequilibrium features in the multi-phase RS microstructure, and solid-state phase transformation were observed. Heterogeneous nucleation of nanoscale θ-Al 2 Cu phase involved metastable supersaturated α-Al and the θ'-Al 2 Cu phases, establishing different sets of orientation relationships for the stable θ-Al 2 Cu and α-Al phases. Replacement of banded morphology grains that formed under conditions driven farthest from equilibrium by an equiaxed nanocrystalline structure comprised of α-Al phase, the primary solidification product, and an intergranular network of Al 2 Cu crystals has been attributed to local remelting. Here the experimental approach explored, permitted discovery of mechanistic details of location-specific transformation pathways activated in the multi-phase RS microstructure of hypoeutectic Al—Cu during subsequent nonisothermal transients.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Clarifying the formation of equiaxed grains and microstructural refinement in the additive manufacturing of Ti-Cu

Controlling microstructural evolution in metallic additive manufacturing (AM) is difficult, especially in producing refined as-built grains instead of coarse, directional grains. Traditional solutions involve adding inoculants to AM feedstocks, but titanium (Ti) alloys cannot employ this approach without producing detrimental secondary phases. Ti-Cu (Ti-copper) alloys offer a solution through constitutional supercooling and/or solid state thermal cycling under AM conditions. This work analyzes a compositionally graded directed energy deposition (DED) Ti-Cu build, single-melt laser tracks, and dilatometric heat treatments to evaluate if, when, and by what mechanism(s) microstructural refinement occurs. Refinement by inoculation of unmelted powder particles was also considered. Constitutional supercooling produced no net microstructural refinement as any equiaxed dendrites which form are remelted with new deposition. This finding agreed with solidification modeling of powder bed fusion-laser beam (PBF-LB) and DED builds. Solid state thermal cycling refined microstructures only during ex-situ dilatometric heat treatments, suggesting build parameter optimization is needed to achieve refinement in-situ. Accidental heterogeneous nucleation on unmelted Ti powder, originating from the different thermophysical properties of Ti and Cu, provided the most significant microstructural refinement. This work systematically assesses the microstructural refinement mechanisms of Ti-Cu in AM builds and offers insights into microstructural control in eutectoid alloys.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Symmetry in Seeded Metal Nanocrystal Growth

Symmetry underpins the structure and function of the world around us and is also captured in modern nanomaterials, where changing the symmetry of a nanocrystal or the interparticle spacing and orientation of nanocrystal building blocks in a superlattice can give new function. However, the synthesis and assembly of nanocrystals have been limited largely to simple compositions and structures. It remains a grand challenge to achieve nanocrystals with compositional and structural complexity while maintaining the monodispersity required for their use. This Account will illustrate through recent examples that seeded methods enable the synthesis of compositionally and structurally complex multimetallic crystals with defined and predictable symmetries for applications in plasmonics and catalysis. This outcome arises because the barrier for heterogeneous nucleation (i.e., seeded) is lower than that of homogeneous nucleation, where seeds can serve as preferential sites for the growth of complex structures and crystal phases. Our analysis begins by considering metal overgrowth from single-crystalline seeds of different shapes and symmetries, where the kinetics of adatom addition to seeds relative to their diffusion across seeds accounts for the expressed nanocrystal shapes. These results are then compared to overgrowth from seeds with different internal structures (i.e., planar defects), where the relationships between nanocrystal size and volumetric strain energy and surface energy are discussed. A major finding from this analysis is that often the underlying symmetry of seeds can be predictably transferred to the final crystals during overgrowth processes. Consequences of this finding are the predictable syntheses of crystals with different hierarchies akin to snowcrystals as well as nanocrystals with complex compositions (e.g., quaternary nanoparticles). Yet, there are subtle aspects to seeded growth that pave a path toward examples where nanocrystal symmetry has been reduced compared to the original seeds in a controlled manner. As we found, both the concentrations of metal precursors and capping agents can impact whether symmetry is transferred or reduced during overgrowth. Examples from our laboratory will be placed in context to other reported strategies for symmetry breaking. As will be argued, understanding what conditions favor symmetry preservation versus symmetry reduction during seeded crystal growth is central to accessing next-generation crystal forms. The Account concludes by outlining synthetic challenges associated with forming nanoscale heterostructures with precise 3-D placement of different materials within a given nanocrystal as well as facet control within different material domain and interface engineering. Furthermore, we envision meeting these challenges through regioselective and chemoselective seeded syntheses for which a foundation is outlined herein.

36 MATERIALS SCIENCE↗