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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

High-temperature nanoindentation creep studies on castable and sintered nanostructured low-activation ferritic-martensitic alloys

In this article, we present the creep characteristics of two reduced activation ferritic-martensitic steels of identical starting compositions formed by different fabrication routes: a nanostructured ferritic alloy commonly referred to as a castable nanostructured alloy (CNA) and a sintered nanostructured alloy (SNA) variant. Through a series of nanoindentation experiments spanning a temperature range of 25 °C to 650 °C, with a maximum load of 100 mN, we find creep behaviors in the cast and sintered materials to be remarkably similar. The creep stress exponent (n) for CNA and SNA were found to be in the range of 8–35 and the activation volume was ∼14–42b 3 , underscoring a dominance of dislocation-mediated mechanisms in both alloys. Notably, we observed a decline in the creep stress exponent with increasing temperature, attributable to the heightened influence of thermally activated dislocations. This phenomenon suggests a potential transition in the deformation mechanism towards a thermally activated dislocation climb process, significantly impacting the observed creep behavior.

36 MATERIALS SCIENCE↗

Large-area nanostructured surfaces with tunable zeta potentials

Through a refined fabrication protocol based on block-copolymer self-assembly we synthesize nanostructured surfaces with conical nanopillars of different height (60, 120, and 200 nm) in hexagonal arrays with uniform spacing (~50 nm) over large areas (>cm 2 ). While the nanostructured surfaces fabricated on silicon substrates display superhydrophilic behavior, superhydrophobic properties are attained by coating with octadecyltrichlorosilane (OTS). Negative zeta potentials for all the studied surfaces are reported by electrokinetic flow measurements with aqueous KCl solutions at different concentrations (1 and 10 mM) and pH values between 4 and 8. While the surface nanostructure reduces the zeta potential magnitude, the hydrophobic OTS coating enhances it. Experimental results can be accounted for by a site-dissociation model for the surface charge density. The reported wetting properties and zeta potential tunability makes the studied surfaces particularly relevant for applications such as energy conversion and storage, membrane-based water treatment and molecular separation.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Using block-copolymer nanolithography as a tool to sensitively evaluate variation in chemical dry etching rates of semiconductor materials with sub-5 nm resolution

Ion implantation is a robust and established method to customize the electronic properties of Si. However, fabricating doped, ultrafine semiconductor nanostructures can be challenging. Ion implantation has well-established effects on the dry etch rates of Si, which becomes increasingly consequential as the target dimension shrinks below a few tens of nanometers. While dry etching arrays of block copolymer-templated nanoscale holes (pitch = 37.5 nm, diameter ~25 nm) into p-type, n-type, and undoped Si, we observed that the lateral etch rate was notably larger for the n-type regions than p-type or undoped regions. By doing image analyses on high resolution electron micrographs of the nanostructured hole arrays, we were able to extract the porosity and average radii of the holes with subnanometer sensitivity and compare the relative etch rates between different doping conditions. We found that degenerately doped n-type silicon consistently etches between approximately 17% and 27% faster in the lateral direction than p-type Si, resulting in significantly larger porosity and, consequently, less mechanical stability. Here, we demonstrate that top-down dimensional analysis of a densely packed porous nanostructure is a robust method for assessing extremely small differences in the lateral, chemical etch rate of doped Si to a degree of sensitivity that was previously unachievable. The minute, dense-packed nature of block copolymer self-assembled nanostructures is shown to be ideal for this application. This proposed method could be useful for designing fabrication processes for heterogeneous nanostructures, as slight dry etch rate variations that may be within process tolerance at the micrometer-scale appear to have nontrivial consequences at the nanometer scale.

42 ENGINEERING↗

Gradient nanostructuring via compositional means

Nanocrystalline metals are inherently unstable against thermal and mechanical stimuli, commonly resulting in significant grain growth. Also, while these metals exhibit substantial Hall-Petch strengthening, they tend to suffer from low ductility and fracture toughness. With regard to the grain growth problem, alloying elements have been employed to stabilize the microstructure through kinetic and/or thermodynamic mechanisms. And to address the ductility challenge, spatially-graded grain size distributions have been developed to facilitate heterogeneous deformation modes: high-strength at the surface and plastic deformation in the bulk. In the present work, we combine these two strategies and present a new methodology for the fabrication of gradient nanostructured metals via compositional means. Here, we have demonstrated that annealing a compositionally stepwise Pt-Au film with a homogenous microstructure results in a film with a spatial microstructural gradient, exhibiting grains which can be twice as wide in the bulk compared to the outer surfaces. Additionally, phase-field modeling was employed for the comparison with experimental results and for further investigation of the competing mechanisms of Au diffusion and thermally induced grain growth. This fabrication method offers an alternative approach for developing the next generation of microstructurally stable gradient nanostructured films.

36 MATERIALS SCIENCE↗

Rationally Programming Nanomaterials with DNA for Biomedical Applications

Abstract DNA is not only a carrier of genetic information, but also a versatile structural tool for the engineering and self‐assembling of nanostructures. In this regard, the DNA template has dramatically enhanced the scalability, programmability, and functionality of the self‐assembled DNA nanostructures. These capabilities provide opportunities for a wide range of biomedical applications in biosensing, bioimaging, drug delivery, and disease therapy. In this review, the importance and advantages of DNA for programming and fabricating of DNA nanostructures are first highlighted. The recent progress in design and construction of DNA nanostructures are then summarized, including DNA conjugated nanoparticle systems, DNA‐based clusters and extended organizations, and DNA origami‐templated assemblies. An overview on biomedical applications of the self‐assembled DNA nanostructures is provided. Finally, the conclusion and perspectives on the self‐assembled DNA nanostructures are presented.

59 BASIC BIOLOGICAL SCIENCES↗

Probing and Understanding the Spatial and Energy Distributions of Plasmonic Hot Carriers via Single-Molecule Quantum Transport

The generation of hot carriers in plasmonic nanostructures offers new transformative opportunities for a range of applications, including solar energy harvesting, photochemistry, and photodetection. To better understand such phenomena, this project aims to develop an experimental approach to study and understand hot carrier distributions in photoexcited plasmonic nanostructures. The developed experimental approach, combining scanning probe-based single-molecule quantum transport measurements with plasmonic excitation methods, leverages nanoscopic single molecules as quantum energy filters to selectively access hot carriers in a variety of plasmonic nanostructures. This report summarizes the key outcomes, impacts, and lessons learned in the first two years of the project. Over the past two years, important progress was made in achieving the project's goals, including the development of the scanning probe-based experimental platform, fabrication of plasmonic nanostructures, and design and synthesis of the desired molecular candidates. Insights from this research will pave the path toward the development of technologies that will improve the way we harvest solar energy and drive chemical reactions and ultimately help transition the U.S. to a clean and sustainable society.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Ordered Nanostructures Made Using Chaperonin Polypeptides

A recently invented method of fabricating periodic or otherwise ordered nanostructures involves the use of chaperonin polypeptides. The method is intended to serve as a potentially superior and less expensive alternative to conventional lithographic methods for use in the patterning steps of the fabrication of diverse objects characterized by features of the order of nanometers. Typical examples of such objects include arrays of quantum dots that would serve as the functional building blocks of future advanced electronic and photonic devices. A chaperonin is a double-ring protein structure having a molecular weight of about 60 plus or minus 5 kilodaltons. In nature, chaperonins are ubiquitous, essential, subcellular structures. Each natural chaperonin molecule comprises 14, 16, or 18 protein subunits, arranged as two stacked rings approximately 16 to 18 nm tall by approximately 15 to 17 nm wide, the exact dimensions depending on the biological species in which it originates. The natural role of chaperonins is unknown, but they are believed to aid in the correct folding of other proteins, by enclosing unfolded proteins and preventing nonspecific aggregation during assembly. What makes chaperonins useful for the purpose of the present method is that under the proper conditions, chaperonin rings assemble themselves into higher-order structures. This method exploits such higher-order structures to define nanoscale devices. The higher-order structures are tailored partly by choice of chemical and physical conditions for assembly and partly by using chaperonins that have been mutated. The mutations are made by established biochemical techniques. The assembly of chaperonin polypeptides into such structures as rings, tubes, filaments, and sheets (two-dimensional crystals) can be regulated chemically. Rings, tubes, and filaments of some chaperonin polypeptides can, for example, function as nano vessels if they are able to absorb, retain, protect, and release gases or chemical reagents, including reagents of medical or pharmaceutical interest. Chemical reagents can be bound in, or released from, such structures under suitable controlled conditions. In an example of a contemplated application, a two-dimensional crystal of chaperonin polypeptides would be formed on a surface of an inorganic substrate and used to form a planar array of nanoparticles or quantum dots. Through genetic engineering of the organisms used to manufacture the chaperonins, specific sites on the chaperonin molecules and, thus, on the two-dimensional crystals can be chemically modified to react in a specific manner so as to favor the deposition of the material of the desired nanoparticles or quantum dots. A mutation that introduces a cysteine residue at the desired sites on a chaperonin of Sulfolobus shibatae was used to form planar arrays of gold nanoparticles (see figure).

Trent, Jonathan↗

Synthesis of bulk reactive Ni–Al composites using high pressure torsion

Self-propagating exothermic reactions, for instance in the nickel-aluminum (Ni-Al) system, have been widely studied to create high performance intermetallic compounds or for in-situ welding. Their easy ignition once the phase spacing is reduced below the micron scale, makes top-down methods like high-energy ball milling, ideal to fabricate such reactive nanostructures. A major drawback of ball milling is the need of a sintering step to form bulk pieces of the reactive material. However, this is not possible, as the targeted reactions would already proceed. Therefore, we investigate the ability of high pressure torsion as an alternative process, capable to produce bulk nanocomposites from powder mixtures. Severe straining of powder mixtures with a composition of 50 wt% Ni and 50 wt% Al enables fabrication of self-reactive bulk samples with microstructures similar to those obtained from ball milling or magnetron sputtering. Additionally, samples deformed at ambient temperature are highly reactive and can be ignited significantly below the Al melting point, finally predominantly consisting of Al 3 Ni 2 and Al 3 Ni, independent of the applied strain. Although the reaction proceeds first at the edge of the disk, the strain gradient present in the disks does not prevent reaction of the whole sample.

36 MATERIALS SCIENCE↗

Scalable Graphene Oxide Hollow Fiber Membranes for Dye Desalination Enabled by Multi‐Purpose Polyamine Functionalization

2D nanosheets such as graphene oxide (GO) can be stacked to construct membranes with fine-tuned nanochannels to achieve molecular sieving ability. These membranes are often thin to achieve high water permeance, but their fabrication with consistent nanostructures on a large scale presents an enormous challenge. Herein, GO-based hollow fiber membranes (HFMs) are developed for dye desalination by synergistically combining chemical etching to form in-plane nanopores (10–30 nm) to increase water permeance and polyamine functionalization to improve underwater stability and enable facile large-scale production using existing membrane manufacturing processes. HFM modules with areas of 88 cm 2 and GO layer thicknesses of ≈500 nm are fabricated, and they exhibited a stable dye water permeance of 75 L m −2 h −1 bar −1 , rejection of >99.5% for Direct red and Congo red, and Na 2 SO 4 /dye separation factor of 300–500, superior to state-of-the-art commercial membranes. Furthermore, the versatility of this approach is also demonstrated using different short polyamines and porous substrates. This study reveals a scalable way of designing 2D materials into high-performance robust membranes for practical applications.

amine functionalization↗

Depolymerization as a Design Strategy: Depolymerization Etching of Polymerization-Induced Microphase Separations

Thermally triggered depolymerization has traditionally been viewed through the lens of sustainability and recycling, not as a constructive tool for materials design. Herein, we show that selective, thermally triggered depolymerization to gaseous monomer serves as a solvent-free strategy for generating porosity in nanostructured polymer materials, offering a means to bypass the mass transport limitations inherent in conventional solution-based etching. As a demonstration platform, we employed polymerization-induced microphase separation (PIMS) to generate disordered bicontinuous block copolymer structures with embedded depolymerizable domains. By incorporating a methacrylate block susceptible to thermal depolymerization within a cross-linked, depolymerization-resistant styrenic matrix, we developed a process we term depolymerization etching of polymerization-induced microphase separations (DEPIMS). This approach enables highly selective and efficient domain removal via reversion to monomer to produce mesoporous materials with high surface areas (>200 m 2 /g). Subsequent surface functionalization yielded mesoporous adsorbents with tunable uptake kinetics and among the highest dye adsorption capacities reported for PIMS-derived materials, demonstrating the adaptability of the DEPIMS platform for chemical separations. DEPIMS can also be extended to a gram-scale, one-pot approach to yield mesoporous materials with recoverable monomer in under 12 h. These findings reposition thermal depolymerization from a sustainability tool to a broadly enabling strategy for scalable, on-demand fabrication of functional nanostructured materials.

Depolymerization↗

Integration of Nanostructures into Microsensor Devices on Whole Wafers

Chemical sensors are used in a wide variety of applications, such as environmental monitoring, fire detection, emission monitoring, and health monitoring. The fabrication of chemical sensors involving nanostructured materials holds the potential for the development of sensor systems with unique properties and improved performance. However, the fabrication and processing of nanostructures for sensor applications currently are limited in the ability to control their location on the sensor, which in turn hinders the progress for batch fabrication. This report discusses the advantages of using nanomaterials in sensor designs, some of the challenges encountered with the integration of nanostructures into microsensor / devices, and then briefly describes different methods attempted by other groups to address this issue. Finally, this report will describe how our approach for the controlled alignment of nanostructures onto a sensor platform was applied to demonstrate an approach for the mass production of sensors with nanostructures.

Nanostructures (Devices)↗

Alignment frustration in block copolymer films with block copolymer grafted TiO 2 nanoparticles under soft-shear cold zone annealing

Block copolymers (BCPs) have received significant attention as promising candidates for sequestering nanoparticles and fabrication of aligned nanostructures with optimal optical or electrical properties. We investigate the influence of static and dynamic thermal field on the alignment of polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) BCP morphology with the loading of novel poly(methyl methacrylate-block-Polystyrene) (PMMA-b-PS)-grafted-TiO 2 nanoparticles (BCP-g-TiO 2 ). Observation of characteristics IR peaks for PMMA and PS in BCP-g-TiO 2 nanoparticles and Transmission Electron Microscopy (TEM) results of the outer coating of core nanoparticle, validate the grafting to approach in synthesizing BCP-g-TiO 2 . In this work, we report that under the sharp dynamic thermal field, at low loading of BCP-g-TiO 2 , there is good dispersion of nanoparticles in unidirectionally aligned BCP matrix in film interior probed by GISAXS, while, at high nanoparticle loading (~10 wt%), there is local frustration in the unidirectional alignment of the BCP matrix due to aggregation of BCP-g-TiO 2 nanoparticles. However, Grazing incidence small angle X-ray scattering (GISAXS) shows clearly that the BCP films remain largely locally ordered at the domain scale, despite these large perturbations to long-range ordering even at high loading level, while bringing in new TiO 2 functionality to the BCP films, such as UVO absorptivity or biofouling prevention, important to potential new applications of such membranes.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Raspberry colloid-templated approach for the synthesis of palladium-based oxidation catalysts with enhanced hydrothermal stability and low-temperature activity

It is becoming increasingly urgent to develop and utilize novel, more efficient and stable materials for mobile and stationary emission control applications as the deleterious consequences of anthropogenic air pollution are becoming more evident and pressing. Tightening regulations, particularly related to automotive exhaust treatment, together with continued improvements in engine design, that result in lowering the engine operating temperatures and inadvertently lead to the release of an overwhelming proportion of pollutants during the cold start, present new challenges for materials design, specifically for oxidation catalysts. In particular, improvements in the low-temperature activity while maintaining catalyst stability at high temperatures are required from the next-generation catalyst. Typical catalysts for removal of pollutants from automotive exhaust streams incorporate platinum group metals (PGMs). They tend to be inefficient at low temperatures (below 250 °C), thus accounting for the cold start problem, yet sinter and lose their activity at high temperatures that are frequently encountered during catalyst operation. High PGM loadings are often employed to compensate for catalyst inefficiencies and fast degradation, ultimately resulting in high-cost catalytic converters. Here, we have developed a new approach for the design and formation of catalytic materials that allows for both significantly more efficient PGM incorporation and improved overall catalyst performance at reduced PGM loadings. The method provides control over the composition and geometry of the support through self-assembly of sacrificial composite template — “raspberry” polymeric colloids decorated with catalytic particles — accompanied by infiltration with metal-oxide precursor and subsequent removal of the colloids. This method simultaneously structures the porous network and organizes the catalytic particles within it. Uniquely, the resulting catalytic particles are partially embedded in the support matrix and partially exposed to the pore interior, producing catalytic sites that are both stable and accessible. Herein, the feasibility of this novel and versatile approach for automotive catalytic conversion is demonstrated: the studies include testing alumina-based raspberry-colloid-templated (RCT) catalysts containing Pd nanoparticles (RCT Pd/Al2O3) for oxidation of propane and carbon monoxide under simulated diesel exhaust conditions and hydrothermal aging at 800 °C for 50 h in the simulated stream. The RCT Pd/Al2O3 catalysts exhibit exceptional activity toward CO oxidation, reduced reaction onset temperature, and high stability to elevated temperatures (demonstrated through prolonged exposure to temperatures up to 950 °C) and reactive gas streams, without migration, sintering or loss of the precious metal NPs. Notably, the novel catalyst shows the same or slightly better performance than the commercial catalysts even when the PGM load is reduced by ~80 % compared to the commercial counterparts. These results provide confidence for the utilization of the RCT approach for the fabrication of robust nanostructured catalysts for next-generation, energy-efficient catalytic converters with improved performance at low and high temperatures and reduced costs. The RCT methodology is, in addition, highly generalizable, and can thus be applied for the design of a wide range of catalytic systems in the automotive sector and beyond.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Chemical Redox Agent-Driven Noncorrosive Formation of Nanoporous Mg Structures for Advanced Hydrogen Storage

Light metal-based nanomaterials are widely used for energy storage due to their high energy density and surface-to-volume ratio. However, their high reactivity is paradoxically both the source of advantageous properties and a hurdle to the fabrication of stable nanostructures. Here, in this study, we demonstrate the formation of nanoporous Mg via chemical redox agent-driven dealloying, which ensures minimized surface passivation and results in fine nanostructures with <50 nm of interconnected metallic ligament despite the labile chemical properties of Mg. The thin passivation layer protects the metallic ligaments from severe coarsening by suppressing surface diffusion. The hydrogen storage performance of nanoporous Mg is investigated as an exemplar for energy applications, and the hydrogen ab/desorption kinetics is substantially enhanced compared to other nano-Mg with similar dimensions. Mesoscale simulations highlight the significance of the bicontinuous structure compared to the particle-like counterpart. This work offers valuable insights into the unexplored realm of reactive metal-based nanoporous structures, highlighting their potential for sustainable energy storage and carrier media.

08 HYDROGEN↗

Chemical Design of Spin Frustration to Realize Topological Spin Glasses

Patterning spins to generate collective behavior is at the core of condensed matter physics. Physicists develop techniques, including the fabrication of magnetic nanostructures and precision layering of materials specifically to engender frustrated lattices. As chemists, we can access such exotic materials through targeted chemical synthesis and create new lattice types by chemical design. Here, in this study, we introduce a new approach to induce magnetic frustration on a modified honeycomb lattice through a competition of alternating antiferromagnetic (AFM) and ferromagnetic (FM) nearest-neighbor interactions. By subtly modulating these two types of interactions through facile synthetic modifications, we created two systems: (1) a topological spin glass and (2) a frustrated spin-canted magnet with low-temperature exchange bias. To design this unconventional magnetic lattice, we used a metal–organic framework (MOF) platform, Ni 3 (pymca) 3 X 3 (NipymcaX where pymca = pyrimidine-2-carboxylato and X = Cl, Br). We isolated two MOFs, NipymcaCl and NipymcaBr, featuring canted Ni 2+ -based moments. Despite this similarity, differences in the single-ion anisotropies of the Ni 2+ spins result in distinct magnetic properties for each material. NipymcaCl is a topological spin glass, while NipymcaBr is a rare frustrated magnet with low-temperature exchange bias. Density functional theory calculations and Monte Carlo simulations on the NipymcaX lattice support the presence of magnetic frustration as a result of alternating AFM and FM interactions. Our calculations enabled us to determine the ground-state spin configuration and the distribution of spin–spin correlations relative to paradigmatic kagomé and triangular lattices. This modified honeycomb lattice is similar to the electronic Kekulé-O phase in graphene and provides a highly tunable platform to realize unconventional spin physics.

Exchange bias↗

Self-assembled Seashell Like Coatings for Large Area Robust Debris Shields for Next Generation Pulsed Power Drivers

During this LDRD project, our team developed a technology which enables the fabrication of novel nanostructures replicating seashell – “nature’s toughest material”. The resulting coatings exhibit high thermal stability up to 1650°C, which exceeds the hardness of Spectra® by ~44%, as well as the compressive strength of aluminum by ~57%. Coatings made with this technology are stronger, environmentally friendly, more sustainable, and more versatile than other comparable materials. Beryllium wafers, the current, most favorable shielding material in terms of thermal and mechanical properties, are very toxic and cost hundreds of times more than the new material developed in this project. The coatings on silicon wafer and stainless steel, respectively, have been tested as ride-along on the Z machine and clearly outperform the bare substrate. Use of this technology will have a profound global impact for pulsed power and fusion energy development, debris mitigation for spacecraft and satellites, durability of drill bits used in deep well drilling and tunnel boring operations, thermal protection of aircraft and manned spacecraft, and various other thermal and mechanical protection applications.

36 MATERIALS SCIENCE↗

Processing of Nanostructured Devices Using Microfabrication Techniques

Systems and methods that incorporate nanostructures into microdevices are discussed herein. These systems and methods can allow for standard microfabrication techniques to be extended to the field of nanotechnology. Sensors incorporating nanostructures can be fabricated as described herein, and can be used to reliably detect a range of gases with high response.

Hunter, Gary W↗

Diamond nanostructures with large surface area and method of producing the same

A method for forming diamond nanostructures with large specific area can include forming porous diamond nanostructures by means of selectively etching sp2-bonded carbon and partially removing sp3-bonded carbon in nanocrystalline diamond (NCD) and ultrananocrystalline diamond (UNCD® diamond). The diamond nanostructures achieved from the disclosed method can include a long shaft surrounded by a school of barbs. The nanostructure can provide a significantly larger surface area than diamond without such a nanostructure and its fabrication provides relative ease of manufacture compared to traditional techniques.

36 MATERIALS SCIENCE↗