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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 37 records · Page 2

Shape Control of Colloidal Semiconductor Nanocrystals through Thermodynamically Driven Aggregative Growth

The optoelectronic properties of colloidal semiconductor nanocrystals (NCs) can be manipulated by changing their geometric shapes. The precise synthetic control over particle morphologies, however, has remained elusive. Conventional growth techniques rely on the kinetic assembly of atomic units, where supersaturation and precipitation processes can lead to a broad distribution of particle shapes. In this paper, we demonstrate that replacing atomic precursors with small-size nanocrystals as building blocks for larger colloids offers an easier, more predictive control over nanoparticle shape evolution. The reported growth strategy is illustrated via shape-selective syntheses of CdSe and CdS NC cubes, spheres, rods, as well as unprecedented “donut” and ring-like structures. Growth of desired particle morphologies was achieved by choosing an appropriate reaction solvent that minimizes the surface free energy through a unique shape formation. This so-called "aggregative growth mechanism" is explained using a thermodynamic model for interacting viscous colloids. We expect that this novel growth strategy will offer a viable platform for shape–selective synthesis of many inorganic colloids, providing pathways to optimizable optoelectronic materials.

36 MATERIALS SCIENCE↗

The Tiny Heater: Creating Heat with Hybrid Nano-Antennas [LDRD HQ Highlights Article]

SRNL scientists demonstrate that an electromagnetic field, either as a light or magnetic field, is selectively coupled to shape-selective hybrid nano-antennas for efficient thermal processes. Localized heating occurs extremely fast, reducing the ‘wasted' thermal load on the environment. Being non-contact, efficient, and highly selective, the required input energy is greatly diminished. By strategically placing nano-antennas at desired locations, heat can be controlled at the nano-level. The location for nano-antennas, and the subsequent energy deposition, may be fine-tuned through specific chemical, steric, or magnetic interactions. The nano-antennas, composed of combinations of plasmonic, magnetic, and hydride components, are used for controlled release of hydrogen isotopes, chemotherapy drugs, environmental contaminants, enhanced catalytic processes, (bio)imaging and therapeutics.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Developing New Polymeric Powder Feedstocks for Selective Laser Sintering: Emphasizing Particle Size and Shape

Although selective laser sintering is considered a major player in the additive manufacturing community, significant limitations exist when it comes to processing the polymeric powder feedstocks in the laser sintering machine. While these limitations – such as inadequate and uneven heating and complex thermal phenomena leading to curling and shrinkage – cannot be ignored and are being addressed in the community, it is also vitally important to turn our attention to the expansion of commercially available powder feedstocks. A major drawback of SLS is the lack of available feedstocks. At Los Alamos National Laboratory, a primary desire for advancement in the manufacturing or development of new feedstocks lies in the nuclear weapons applications program. New feedstocks with greater thermal stability and performance would provide the opportunity for insertion of production parts, rather than just prototype parts. Additionally, the ability to print with so-called commodity polymers like polyethylene and polypropylene poses great economic advantages for prototyping and production of large batches of parts. However, a gap exists between the Lab’s needs and what is commercially available – a gap which could be filled by collaboration with the broader industrial sector. Furthermore, connecting with and building relationships with industry partners allows for greater control and input in the developmental process of new powders. This would provide reliable feedstocks, improved quality assurance, and overall higher performance of processes across the additive manufacturing community.

36 MATERIALS SCIENCE↗

Carbon fiber design improvements based on economic models

Circular fiber geometries are predominant in commercial carbon fiber material systems, but the use of this fiber shape has numerous limitations. Circular geometries have continuous symmetry, which is helpful for various processing considerations, but also have the largest possible maximum diffusion thickness for a given fiber area. This characteristic means that circular carbon fibers always have the highest material processing cost and lowest production throughput compared to any other fiber shape with the same area and tow count. To quantify material cost and other benefits for non-circular carbon fiber geometries, process models for polyacrylonitrile based carbon fiber production are developed in relationship to the carbon fiber shape, size, and tow count. For a given fiber shape, precursor production costs are shown to favor maximizing fiber size while conversion costs are minimized by the smallest fiber size. These competing cost trends result in a numerically optimal fiber size for a given shape and tow count, while both cost components are decreased by increasing tow count. Cost–performance tradeoffs for three lobe fiber geometries are studied by supplementing the cost trends with a numerical failure model to predict compressive strength for discrete shape variants. The shape selection is shown to be more sensitive to variations in cost than compressive strength while suboptimal shape designs can improve manufacturing robustness and achievable fiber volume fractions. Finally, an optimal three lobe carbon fiber is identified that balances the set of considerations while reducing costs and embodied energy and increasing production throughput compared to a commercial carbon fiber.

Carbon fiber↗

Effect of penetrant–polymer interactions and shape on the motion of molecular penetrants in dense polymer networks

The diffusion of dilute molecular penetrants within polymers plays a crucial role in the advancement of material engineering for applications such as coatings and membrane separations. The potential of highly cross-linked polymer networks in these applications stems from their capacity to adjust the size and shape selectivity through subtle changes in network structures. In this paper, we use molecular dynamics simulation to understand the role of penetrant shape (aspect ratios) and its interaction with polymer networks on its diffusivity. We characterize both local penetrant hopping and the long-time diffusive motion for penetrants and consider different aspect ratios and penetrant–network interaction strengths at a variety of cross-link densities and temperatures. The shape affects the coupling of penetrant motion to the cross-link density- and temperature-dependent structural relaxation of networks and also affects the way a penetrant experiences the confinement from the network meshes. The attractive interaction between the penetrant and network primarily affects the former since only the system of dilute limit is of present interest. These results offer fundamental insights into the intricate interplay between penetrant characteristics and polymer network properties and also suggest future directions for manipulating polymer design to enhance the separation efficiency.

Chemistry↗

Facet-Dependent Hydrogen Evolution Reaction on M 2 P (M = Ni, Co, Fe) Single Crystals

Transition-metal phosphides (MPs) are promising earth-abundant catalysts for hydrogen evolution reactions (HERs) due to their remarkable activity and stability. To further improve their properties, facet control is a key strategy. The growth of shape-selected nanoparticles may substantially enhance electrocatalytic activity, but this approach requires fundamental studies of facet-specific catalytic properties. There are only a few reports on the facet effects of MPs, which leads to a limited understanding of the activity of each facet and hampers catalyst design. Here, in this study, we grew large hexagonal-prism-shaped single crystals of three representative M 2 P (M = Ni, Co, and Fe) catalysts using metal flux routes. Two facets of M 2 P single crystals were tested to study facet-dependent HER activities, and it was consistently demonstrated that for all M 2 P crystals, a tip facet [(0001) for Ni 2 P/Fe 2 P and (010) for Co 2 P] had a higher activity than the side facet [(101̅0) for Ni 2 P/Fe 2 P and (100) for Co 2 P]. HER activity between the same facet elucidated the activity ordered between different transition metals as Fe 2 P > Co 2 P > Ni 2 P under low-potential regions. At high applied potentials, this trend is reversed due to the differences in Tafel slopes, with Ni 2 P becoming the most active catalyst, such that the activity of the (0001) facet of Ni 2 P approaches that of Pt. The calculated surface density of states (DOS) of each facet and its local curvature were found to be a useful descriptor for the activity trends among different transition metals of the same facets.

Co2P↗

Using Electrochemistry to Benchmark, Understand, and Develop Noble Metal Nanoparticle Syntheses

The complex chemical nature of metal nanoparticle synthesis presents obstacles for the mechanistic understanding of nanoparticle growth and predictive synthesis design, despite significant progress in this area. Real-time characterization of the chemical processes that take place throughout nanoparticle growth will enable progress toward addressing outstanding challenges in metal nanoparticle synthesis, such as mitigating synthetic reproducibility issues, defining chemical mechanisms that direct nanoparticle growth, and designing synthetic conditions for previously unachievable combinations of nanoparticle shape and composition. In this Perspective, we present open-circuit potential (OCP) measurements as an in situ, real-time method for characterizing chemical changes during nanoparticle growth and discuss the method’s strengths in comparison to and in combination with other characterization techniques. We propose the use of OCP measurements as benchmarks for troubleshooting irreproducibility and streamlining synthetic optimization. Finally, we explore possibilities for using the increased parameter space accessible by electrodeposition to accelerate the development of shape-selective nanoparticle syntheses.

benchmarking↗

Center for Gas Separations (CGS)

The total energy consumption in the U.S. has been rising steadily for decades, and it currently amounts to ~98,000 TBtu/yr, with approximately 30% of this total attributable to the industrial sector. Reasonable estimates indicate that 45–55% of total industry energy consumption derives from chemical separations, and for example, over 120 TBtu/yr alone is used in carrying out olefin/paraffin separations via energy-intensive cryogenic distillation. Therefore, the pursuit of new, even radically different approaches to some of the most energy-intensive industrial separations processes is an imperative scientific pursuit for reducing energy consumption toward a more sustainable future. Adsorbent and membrane-based separations can require a fraction of the energy needed for distillation methods, and as such are considered promising solutions for balancing increasing energy demand in the U.S. with the need for a massive reduction in energy consumption. Although considerable research effort has been devoted to the design of materials capable of carrying out various gas separations, usually operating through size-selective, chemisorptive, or physisorptive mechanisms, it remains a great challenge to design materials that function adequately for real-world applications. Indeed, the chemical and physical differences between molecules in gas mixtures of interest are often small, and therefore it is necessary, through the use of nanoscience and synthetic chemistry, to engineer unprecedented molecular-level control in adsorbate–adsorbent interactions. The overarching mission of the Center for Gas Separations (CGS) was to discover fundamental innovations that have the potential to dramatically reduce the energy associated with critical gas separations. In particular, the CGS developed novel synthetic routes, guided by molecular chemistry principles, as well as advanced characterization and computational methods, that have enabled the discovery of new materials and membranes tailor-made to exhibit exceptional performance for a range of gas separations processes, as required in the clean use of fossil fuels and in reducing CO 2 emissions from industry. A challenge of this magnitude required the collaboration and synergy of a large team of researchers with expertise in materials synthesis, characterization, and computations. During the 11-year project period, the CGS created a range of new materials within the family of highly-tunable, porous solids known as metal–organic frameworks (MOFs). These new frameworks demonstrate novel mechanisms for key industrial gas separations, including revolutionary new cooperative adsorption processes that enable low-energy CO 2 and CO capture, and are capable of efficiently separating olefins from paraffins, O 2 from air, and the shape-selective separation of alkane isomers. In addition, the CGS developed new strategies for incorporating these materials into composite membranes toward highly efficient and selective membrane-based separations. As a testament to the success of the CGS, two start-up companies, Mosaic Materials,4 Inc. and Flux Technology, Inc., grew out of these research efforts, and these companies are seeking to commercialize MOF and composite membranes materials for key separations in industry, including large-scale CO 2 capture and hydrocarbon separations, respectively. Another company, framergy, Inc., licensed IP resulting from CGS research toward the commercialization of adsorbents for various energy-relevant applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ethylene Dehydroaromatization over Ga‐ZSM‐5 Catalysts: Nature and Role of Gallium Speciation

Abstract Bifunctional catalysis in zeolites possessing both Brønsted and Lewis acid sites offers unique opportunities to tailor shape selectivity and enhance catalyst performance. Here, we examine the impact of framework and extra‐framework gallium species on enriched aromatics production in zeolite ZSM‐5. We compare three distinct methods of preparing Ga‐ZSM‐5 and reveal direct (single step) synthesis leads to optimal catalysts compared to post‐synthesis methods. Using a combination of state‐of‐the‐art characterization, catalyst testing, and density functional theory calculations, we show that Ga Lewis acid sites strongly favor aromatization. Our findings also suggest Ga(framework)–Ga(extra‐framework) pairings, which can only be achieved in materials prepared by direct synthesis, are the most energetically favorable sites for reaction pathways leading to aromatics. Calculated acid site exchange energies between extra‐framework Ga at framework sites comprised of either Al or Ga reveal a site‐specific preference for stabilizing Lewis acids, which is qualitatively consistent with experimental measurements. These findings indicate the possibility of tailoring Lewis acid siting by the placement of Ga heteroatoms at distinct tetrahedral sites in the zeolite framework, which can have a marked impact on catalyst performance relative to conventional H‐ZSM‐5.

Zhou, Yunwen↗

Zeolite Nanosheets Stabilize Catalyst Particles to Promote the Growth of Thermodynamically Unfavorable, Small–Diameter Carbon Nanotubes

A challenge in the synthesis of single–wall carbon nanotubes (SWCNTs) is the lack of control over the formation and evolution of catalyst nanoparticles and the lack of control over their size or chirality. Here, zeolite MFI nanosheets (MFI–Ns) are used to keep cobalt (Co) nanoparticles stable during prolonged annealing conditions. Environmental transmission electron microscopy (ETEM) shows that the MFI–Ns can influence the size and shape of nanoparticles via particle/support registry, which leads to the preferential docking of nanoparticles to four or fewer pores and to the regulation of the SWCNT synthesis products. The resulting SWCNT population exhibits a narrow diameter distribution and SWCNTs of nearly all chiral angles, including sub–nm zigzag (ZZ) and near–ZZ tubes. Theoretical simulations reveal that the growth of these unfavorable tubes from unsupported catalysts leads to the rapid encapsulation of catalyst nanoparticles bearing them; their presence in the growth products suggests that the MFI–Ns prevent nanoparticle encapsulation and prologue ZZ and near–ZZ SWCNT growth. Furthermore, these results thus present a path forward for controlling nanoparticle formation and evolution, for achieving size– and shape–selectivity at high temperature, and for controlling SWCNT synthesis.

36 MATERIALS SCIENCE↗

Tunable Solid Acid Catalyst Thin Films Prepared by Atomic Layer Deposition

Solid acid catalysts, including zeolites and amorphous silica-aluminas (ASAs), are industrially important materials widely used in the fuel and petrochemical industries. The versatility of zeolites is due to the Brønsted acidity of the bridging hydroxyl and shape selectivity that can be tailored during and after synthesis. This is in contrast to amorphous silica-alumina, where tailoring acidity is a major challenge as the Brønsted acid structure in ASA is still debated. In both cases, however, the pore size and acidity cannot be tuned independently, and this is particularly limiting in the application of biomass conversion, where zeolite pores are too small for the molecules of interest. Herein, we present a method using atomic layer deposition (ALD) to prepare thin films of solid acid materials where the ratio of Brønsted to Lewis acid sites can be tuned precisely. This capability, combined with the sub-nm pore size control afforded by ALD yields a powerful and flexible method for synthesizing solid acid catalysts inside virtually any mesoporous host. We demonstrate the utility of these materials in two acid-catalyzed reactions relevant to biomass conversion: (1) Meerwein–Ponndorf–Verley–Oppenauer (MPVO) reaction and dehydration of fructose and (2) cascade reaction of glucose to 5-hydroxymethylfurfural. Finally, we propose a plausible structure for the Brønsted acid sites in our materials based on infrared spectroscopy and solid-state nuclear magnetic resonance measurements and density functional theory calculations and argue that this same structure might apply to conventional ASAs as well.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthetic galaxy clusters and observations based on Dark Energy Survey Year 3 Data

ABSTRACT We develop a novel data-driven method for generating synthetic optical observations of galaxy clusters. In cluster weak lensing, the interplay between analysis choices and systematic effects related to source galaxy selection, shape measurement, and photometric redshift estimation can be best characterized in end-to-end tests going from mock observations to recovered cluster masses. To create such test scenarios, we measure and model the photometric properties of galaxy clusters and their sky environments from the Dark Energy Survey Year 3 (DES Y3) data in two bins of cluster richness $\lambda \in [30; 45)$, $\lambda \in [45; 60)$ and three bins in cluster redshift ($z\in [0.3; 0.35)$, $z\in [0.45; 0.5)$ and $z\in [0.6; 0.65)$. Using deep-field imaging data, we extrapolate galaxy populations beyond the limiting magnitude of DES Y3 and calculate the properties of cluster member galaxies via statistical background subtraction. We construct mock galaxy clusters as random draws from a distribution function, and render mock clusters and line-of-sight catalogues into synthetic images in the same format as actual survey observations. Synthetic galaxy clusters are generated from real observational data, and thus are independent from the assumptions inherent to cosmological simulations. The recipe can be straightforwardly modified to incorporate extra information, and correct for survey incompleteness. New realizations of synthetic clusters can be created at minimal cost, which will allow future analyses to generate the large number of images needed to characterize systematic uncertainties in cluster mass measurements.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Investigating event-shape methods in the search for the chiral magnetic effect in relativistic heavy ion collisions

The chiral magnetic effect (CME) is a phenomenon in which electric charge is separated by a strong magnetic field from local domains of chirality imbalance and parity violation in quantum chromodynamics. The CME-sensitive observable, the charge-dependent three-point azimuthal correlator Δ⁢𝛾 , is contaminated by a major physics background proportional to the particle's elliptic flow anisotropy 𝑣 2 . Event-shape engineering (ESE) binning events in dynamical fluctuations of 𝑣 2 and event-shape selection (ESS) binning events in statistical fluctuations of 𝑣 2 are two methods to search for the CME by projecting Δ⁢𝛾 to the measured anisotropy 𝑣 2 = 0 intercept. Here, we conduct a systematic study of these two methods using physics models as well as toy model simulations. It is observed that the ESE method fulfills the general premise of measuring the CME but is statistically hungry. It is found that the intercept from the ESS method depends on the details of the event content, such as the mixtures of background-contributing sources, because of statistical fluctuations of intertwining variables used in the method, and is thus not practically useful to measure the CME.

Relativistic heavy-ion collisions↗

Elucidating the formation mechanisms of zeolites using data-driven modelling and in-situ characterization

Zeolites are the main solid catalysts used by the chemical industry. The use of zeolites in separations and as shape selective catalysts requires control of the width and connectivity of their pores. 235 distinct zeolite frameworks have been synthesized to date, of over 2 million that have been proposed. Recent work indicates that the limitation is in large part kinetic: new synthetic pathways are required to access new zeolites. Organic cations are used to direct the synthesis towards specific zeolites. However, the molecular mechanisms by which cations direct the nucleation towards specific zeolites is not known. Elucidating these mechanisms is key to realize new zeolites for catalysis and separations, and is the focus of this project. This project developed and implemented a synergistic, data-driven computational and experimental approach to resolve the molecular pathways of nucleation, growth, and polymorph selection of zeolites and the role of organic cations in directing their formation. The project developed computationally efficient and accurate models for the study of the nucleation and growth of pure silica zeolites in molecular simulations, using machine learning with data from experiments. Simulations with these models were integrated with scanning tunneling electron microscopy, computer vision, and deep learning to unveil the molecular pathways of formation of a zeolite. Of particular interest in this project was to elucidate the role of amorphous precursors in the nucleation of the zeolite. Previous experiments indicate that zeolites are born within non-crystalline aggregates in which the silicates and organic cations have local and medium range order similar to that of the zeolite. The organic cations that direct the formation of zeolites and those that direct the formation of ordered mesoporous silicas are similar. We hypothesized that the frustrated attraction that for large organic cations leads to the formation of stable mesophases that direct the synthesis of mesoporous silicas, could promote the formation of metastable mesophases that can assist in the nucleation and polymorph selection of zeolites. The simulations resolved how structure directing agents build crystalline order and showed that mesoscopic pre-ordering occurs is not required to facilitate the nucleation of zeolites, because the synthesis occurs at high driving forces, where the barriers for nucleation are negligible. This project unveiled that polymorph selection in zeolite synthesis occurs after nucleation, opening a distinct area of control through the kinetics of growth and not through nucleation barriers.

36 MATERIALS SCIENCE↗

Artificial zeolites

Zeolites are industrially important materials possessing high Bronsted acidity and shape-selectivity. However, their inherently small pores restrict application for catalytic conversion of bulky molecules. A method of synthesis of ‘artificial’ zeolites. The artificial zeolites have well-tailored Bronsted and Lewis acid sites prepared on mesostructured silica to circumvent this limitation. This novel approach utilizes atomic layer deposition to tailor both porosity and acid speciation, providing exquisite control over catalytic behavior and enabling systematic studies.

Elam, Jeffrey W.↗

Nonlocal Metasurface with Resonance-Selective Nonlinear Wavefront Shaping

We demonstrate a nonlinear nonlocal metasurface supporting quasi-trapped modes that enable helicity-dependent wavefront shaping at third-harmonic wavelengths. The geometric phase is selectively modified near resonance, revealing a mechanism for polarization-dependent nonlinear phase control.

Sedeh, Hooman [Duke University]↗

Improving indirect-drive ablator performance through pulse shaping and material selection in double shell implosions

The double shell path to inertially confined volumetric thermonuclear burn relies on efficient kinetic energy transfer from an outer ablator shell to an inner shell containing DT fuel at implosion velocities near 250 km/s. In order to experimentally realize adequate compression, target imperfections and assembly features must be tightly controlled. Pulse shape and ablator material are critical design choices that impact all aspects of the implosion. In this article, we evaluate three designs: an Al ablator with single-shock radiation drive, a CH ablator with single-shock drive, and a CH ablator with reduced-adiabat 2-shock drive. All designs use the same W inner (pusher) shell overcoated with a glow discharge polymer tamper and filled with liquid-density DT. One-dimensional HYDRA simulations revealed that the plastic ablator design required the use of the 2-shock drive to match the performance of the Al design. Two-dimensional simulations resolving broadband surface roughness up to modes of several hundred placed only on the ablator showed plastic to greatly outperform Al. The plastic ablator designs did exhibit higher levels of inner shell instability growth when surface roughness was only placed at the pusher/tamper interface, which was mitigated with higher foam cushion densities. A unique and additional benefit of a plastic ablator is also discussed, where heating of the ablator by Au M-band radiation is predicted to rapidly expand the hemi-shell surfaces, closing the equatorial joint gap ahead of the first shock. Taken together, the properties of the plastic ablator for indirect-drive double shell implosions appear promising in removing several long-standing fabrication challenges.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗