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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 559 records · Page 31

New Materials for Structural Composites and Protective Coatings

The objective of this Phase I project was to create novel conductive materials that are lightweight and strong enough for multiple ground support equipment and Exploration applications. The long-term goal is to combine these materials within specially designed devices to create composites or coatings with diagnostic capabilities, increased strength, and tunable properties such as transparency, electroluminescence, and fire resistance. One such technology application is a smart windows system. In such a system, the transmission of light through a window is controlled by electrical power. In the future, these materials may also be able to absorb sunlight and convert it into electrical energy to produce light, thereby creating a self-sufficient lighting system. This experiment, conducted in collaboration with the Georgia Institute of Technology, demonstrated enhancements in fabricating fiber materials from carbon nanotubes (CNT). These nanotubes were grown as forests in an ultra-high-purity chemical vapor deposition (CVD) furnace and then drawn, using novel processing techniques, into fibers and yarns that would be turned into filaments. This work was submitted to the Journal of Advanced Functional Materials. The CNT fibers were initially tested as filament materials at atmospheric pressure; however, even under high current loads, the filaments produced only random sparking. The CNT fibers were also converted into transparent, hydrophobic, and conductive sheets. Filament testing at low vacuum pressures is in progress, and the technology will be enhanced in 2008. As initial proof of the smart-windows application concept, the use of CNT sheets as composites/ protective coatings was demonstrated in collaboration with Nanocomp Technologies of Concord, New Hampshire.

Source record↗

Statistical White-Line Analysis in High-Throughput TXM-XANES for Chemical State Quantification

The transmission X-ray microscopy (TXM) based X-ray absorption near-edge structure (XANES) technique provides three-dimensional mapping of element-specific chemical states at nanometer-scale spatial resolution and micrometer-scale fields of view. However, compared to conventional volume-averaged XANES (VA-XANES) measurements, the inherently small voxel size in TXM-XANES leads to a lower signal-to-noise ratio, making full-spectrum analysis computationally demanding and less robust. Here, we present the structural and compositional conditions for a statistical white-line analysis framework under which chemical state information can be directly extracted from the white-line peak position in voxel spectra without the need for voxel-wise background subtraction or normalization, under well-defined structural and compositional conditions. The method is validated on layered oxide cathode materials, where low-order polynomial fitting accurately reproduces white-line features, and the extracted energy distributions correlate strongly with VA-XANES results. This statistical approach enables high-throughput, dose-efficient, and noise-robust chemical state quantification in TXM-XANES, offering broad applicability to functional materials requiring nanoscale oxidation-state mapping.

TXM↗

Dark field X-ray microscopy below liquid-helium temperature: The case of NaMnO 2

Dark field X-ray microscopy (DFXM) is an experimental technique employed to investigate material properties by probing their ‘mesoscale,’ or microscale structures, in a bulk-sensitive manner using hard X-rays at synchrotron radiation sources. However, challenges remain when it comes to applications of this technique to examine low-temperature phenomena in quantum materials, which exhibit complex phase transitions at cryogenic temperatures. One such material is NaMnO 2 , which hosts an antiferromagnetic transition at 45 K that is suspected to coincide with local structural transitions from its majority monoclinic phase to nanoscale triclinic domains. Direct observation of local heterogeneities and this effect at low temperatures in NaMnO 2 is an important step in understanding this material and serves as an ideal candidate study for expanding the DFXM experimental design space. This paper details a foundational high-resolution DFXM study, down to liquid-helium temperature and below, conducted to explore phase transitions in NaMnO 2 . In conclusion, the outlined experiment ushers in the evaluation of other functional materials at low temperatures using this technique.

36 MATERIALS SCIENCE↗

In-situ synthesized N-doped ZnO for enhanced CO 2 sensing: Experiments and DFT calculations

Chemiresistive CO 2 sensing is attractive due to low cost and ease of chip-level integration. Our previous studies (Yong Xia, 2021) showed the well-developed ZnO material fabricated by in-situ annealing exhibited good CO 2 sensing performance. Here, we have expanded on those studies, including CO 2 cyclic tests under both dry air and N 2 background whereby a much higher response to CO 2 in N 2 background was observed. In this study, detailed density functional theory calculations were conducted to understand the behavior. The results indicated nitrogen doping is mainly responsible for the observed response. In the presence of pre-adsorbed O 2 , N-doped ZnO can no longer interact with CO 2 , which agrees well with the observation of higher response in N 2 background. Furthermore, density of states analysis showed N sp 2 hybridized orbital and N 2p orbital of the N dopant mixed with sp 2 hybridized orbital of C atom and 2p orbitals of C/O atoms in CO 2 to form σ and π bonds, respectively. However, they mixed with O 2s/2p orbitals of O atom in O 2 when pre-adsorbed O 2 was present, hindering CO 2 interaction with N-doped ZnO, and resulting in limited response in air. The illustrated mechanism does not only further the understanding of metal oxide-based CO 2 sensing, but also guide the design of new functional materials for CO 2 sensing or capture.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Emergent multiferroism with magnetodielectric coupling in EuTiO 3 created by a negative pressure control of strong spin-phonon coupling

Negative pressure has emerged as a powerful tool to tailor the physical properties of functional materials. However, a negative pressure control of spin-phonon coupling for engineering magnetism and multiferroicity has not been explored to date. Here, using uniform three-dimensional strain-induced negative pressure in nanocomposite films of (EuTiO 3 ) 0.5 :(MgO) 0.5 , we demonstrate an emergent multiferroicity with magnetodielectric coupling in EuTiO 3 , matching exactly with density functional theory calculations. Density functional theory calculations are further used to explore the underlying physics of antiferromagnetic-paraelectric to ferromagnetic-ferroelectric phase transitions, the spin-phonon coupling, and its correlation with negative pressures. The observation of magnetodielectric coupling in the EuTiO 3 reveals that an enhanced spin-phonon coupling originates from a negative pressure induced by uniform three-dimensional strain. Our work provides a route to creating multiferroicity and magnetoelectric coupling in single-phase oxides using a negative pressure approach.

36 MATERIALS SCIENCE↗

Synthesis and crystal chemical evolution of fresnoite powders

(Ba,Sr){sub 2}TiSi{sub 2}O{sub 8} fresnoite powders were prepared via a Pechini process in which citric acid and ethylene glycol were used as complexing agents. The resulting gel contained a homogeneous distribution of the metal ions that suppressed the formation of (Ba,Sr)TiO{sub 3} perovskite as a secondary phase during calcination. Phase development was examined as by isochronal and isothermal reaction analysis. A combination of thermo- and differential gravimetric analysis (TGA-DGA), quantitative X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) confirmed that calcination at 900 Degree-Sign C/12 h yielded finely crystalline ({approx}70 nm) Ba{sub 2}TiSi{sub 2}O{sub 8} (BTS) and Sr{sub 2}TiSi{sub 2}O{sub 8} (STS). The endmembers and compositional intermediates crystallized directly from the Pechini resin and indirectly through reaction of (Ba,Sr)CO{sub 3}, (Ba,Sr)TiO{sub 3} and a silica-rich glass intermediates. This new method for preparing fresnoite yields materials suitable for consolidation as dense monolithic dielectrics or for use as high surface area catalytic powders. - Graphical abstract: The Pechini synthesis of (Ba, Sr){sub 2}TiSi{sub 2}O{sub 8} titano-silicate fresnoites delivers finely divided precursors for applications as diverse as solid electrolytes and photocatalysis that exploit the unique Ti-O and Si-O bonding and structural morphology of these materials. Highlights: Black-Right-Pointing-Pointer A Pechini method for synthesizing (Ba,Sr){sub 2}TiSi{sub 2}O{sub 8} fresnoites is demonstrated. Black-Right-Pointing-Pointer The method minimizes a persistent glassy intermediate phase. Black-Right-Pointing-Pointer The Pechini process is generally applicable for tailoring fresnoites as functional materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Well-Tunable, 3D-printable, and Fast Autonomous Self-Healing Elastomers

Self-healing elastomers provide extended longevity of functional materials, due to their unique adaptability and durability. However, a major scientific challenge remains in developing materials with a rapid healing process combined with decent mechanical properties, that can be prepared by a relatively simple synthesis approach. Herein, we report a versatile design approach on self-healing elastomers by incorporating two different hydrogen bonding containing monomers, i.e., 2-[[(butylamino)carbonyl]oxy]ethyl acrylate (BCOE) and 2-ureido-4[1H]pyrimidinone (UPy) functionalized ethyl methacrylate. Poly(BCOE-r-UPy)s are synthesized by reversible addition-fragmentation chain-transfer (RAFT) polymerization, and controlling the ratio of two monomers enables well-tunable mechanical properties with tensile strength ranging from 0.04 to 6.3 MPa and tensile strain up to 3,000 %. The characteristic dissociation energy is calculated from a temperature dependence of terminal relaxation followed by subtracting the segmental relaxation. The rapid autonomous self-healing is achieved when the molar composition of Poly(BCOE-r-UPy) is tailored to BCOE/UPy = 99/1. The self-healing process is monitored in situ by a helium-ion microscope, and its macroscopic study using tensile tests indicates that Poly(BCOE-r-UPy1) with 1 % molar ratio of UPy recovers 70 % of its original toughness at ambient temperature within 10 mins. 3D printing of Poly(BCOE-r-UPy) affords a self-healable 3D structure, demonstrating the adaptability of Poly(BCOE-r-UPy) for on-demand fabrication. The simplicity of synthesis, well-tunable mechanical properties, unique self-healability, and 3D printing capability of Poly(BCOE-r-UPy)s indicate their potential for a range of applications.

36 MATERIALS SCIENCE↗

Combining Experimental and Theoretical Techniques to Gain an Atomic Level Understanding of the Defect Binding Mechanism in Hard Carbon Anodes for Sodium Ion Batteries

Sodium ion batteries (NIBs) are an attractive alternative to lithium–ion batteries in applications that require large–scale energy storage due to sodium's high natural abundance and low cost. Hard carbon (HC) is the most promising anode material for NIBs; however, there is a knowledge gap in the understanding of the sodium binding mechanism that prevents a rational design of HC. This study tunes sucrose–derived HC via synthesis temperature then evaluates the structural, physical, and electrochemical properties. Neutron total scattering is used to generate structural models by fitting pair distribution functions (PDF) with a combination of molecular dynamics and reverse Monte Carlo methods. From this model, the number and type of structural features are identified, quantified, and correlated to the galvanostatic charge/discharge. A method of PDF “fingerprinting” binding sites using Na probe atoms is developed and analyzing these PDFs reveals an atomistic view of ion binding sites responsible for “defect” storage mechanisms. Combining these techniques results in an atomic–level study that provides a big picture of the Na–binding mechanism in NIBs, which allows for more precise tuning of the structure–property relationships in the future. Finally, the methodologies developed will also enable new strategies for the analysis of amorphous functional materials.

25 ENERGY STORAGE↗

Synthesis and Properties of Nanostructured Exotic Superconductors (Final Report)

Superconductors are materials that conduct electricity with no resistance, i.e. no energy dissipation. In future electrically activated nanodevices, the use of superconducting interconnects is highly desirable, since it circumvents the damaging heat produced by energy dissipation in normal nano-conductors whose high resistance is inversely proportional to its cross-section area. Furthermore, the wave functions of the charge carriers - Cooper pairs will be strongly modified in a superconductor when they are squeezed into a small volume comparable to the coherence length or penetration depth. Thus, superconducting nanostructures provide unique platforms to investigate and discover novel superconducting phenomena in confined geometries. The objective of this DOE funded project was the development of novel approaches to synthesizing a new class of superconducting nanostructures such as nanowires and nanoribbons that are stable in atmosphere, enabling the exploration of superconducting properties and potential applications of individual nanostructures. We also pursued the modification of properties of the fabricated nanostructures by introducing artificial defects through nanoengineering. We developed a conversion approach comprised of two-steps to synthesize NbSe 2 and NbN nanowires/ribbons that were not achievable using other routes: first, we synthesized one-dimensional (1D) nanostructures of NbSe 3 and second, we converted these into desired 1D superconducting nanostructures of NbSe 2 and NbN by adjusting the composition of NbSe 3 nanostructure precursors while maintaining their shapes. Novel phenomena such as resistance oscillations with increasing magnetic fields were observed in both NbSe 2 and NbN nanowires/ribbons. By replacing the catalytic microparticles used in conventional whisker growth with the same kind of nanoparticles that are available now commercially, we improved whisker technologies for nanofabrication of high-T c superconductor nanowires/ribbons: we succeeded in the growth of Bi 2 Sr 2 CaCu 2 O 8+x (BSCCO-2212) and YBa 2 Cu 3 O 7-x (YBCO) nanowires and nanoribbons by annealing glassy precursors with alumina nanoparticles as growth sites. The high-quality whiskers enabled us to observe the ‘matching effect’ that represents itself as dips in the field dependence of the magnetoresistance and the influence of the periodic defects on the melting behavior of vortex matter. We also observed N-shaped V-I characteristics similar to those observed in semiconductor and plasma devices for the first time. Each nanofabrication technique has its advantages and drawbacks. For example, electron-beam lithography (EBL), in combination thin film deposition, has been widely used to fabricate nanowires (nanobridge) with well-defined cross-sections. However, electron-beam resist usually contaminates the sample up to a few hundred nanometers and hence degrades the quality of the entire nanowires if their widths are only a few hundred nanometers. We found that e-beam resist can degrade the superconducting critical temperature of a Nb nanowire from 9 K down to below 4 K if its width is less than 200 nm. We investigated the suitability of the various nanofabrication methods for achieving high-quality samples with desired properties. For example, we developed a novel way to achieve high quality Nb nanostrips with transverse dimensions of 150 nm or smaller. In the new process a superconducting bridge a few micrometers wide is fabricated with EBL. Subsequently, focused-ion-beam (FIB) is used to mill nano- 2 grooves to isolate an uncontaminated area of the microbridge to form a nanostrip. The high-quality superconducting Nb nanostrips with well-defined rectangular cross-sections fabricated using this new technique have enabled experimental confirmation of the theoretically predicted confinement-induced anisotropy effect on the magnetoresistance and critical field. We also found that FIB milling is more suitable than EBL in producing a pinning potential array with desired barrier between them into a MoGe film, which enabled us to realize the predicted vortex ices for the first time. By utilizing a filtration membrane as the substrate, we developed a new method to achieve networks of superconducting MoGe nanowires with transverse dimensions smaller than 10 nm. We observed superconducting confinement effect such as thermally activated phase slips and Little-Parks effect in these new samples. This research significantly advanced our knowledge on confined superconductors, in both their synthesis and physical properties. Though the new fabrication methods developed in this project aimed to achieve samples for studying new phenomena in confined superconductors, they can be utilized to obtain nanostructures of other functional materials. For example, we utilized the method developed to produce superconducting nanowire networks for the fabrication of networks of ultrasmall palladium (Pd) nanowires, which take advantage of single Pd nanowires while eliminating their nanofabrication obstacles, resulting in high-performance hydrogen sensors that are much more cost effective than those based on single Pd nanowires fabricated with lithography methods.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Multivalent, multiflavored droplets by design

Nature self-assembles functional materials by programming flexible linear arrangements of molecules and then folding them to make 2D and 3D objects. To understand and emulate this process, we have made emulsion droplets with specific recognition and controlled valence. Uniquely monovalent droplets form dimers: divalent lead to polymer-like chains, trivalent allow for branching, and programmed mixtures of different valences enable a variety of designed architectures and the ability to subsequently close and open structures. Our functional building blocks are a hybrid of micrometer-scale emulsion droplets and nanoscale DNA origami technologies. Functional DNA origami rafts are first added to droplets and then herded into a patch using specifically designated “shepherding” rafts. Additional patches with the same or different specificities can be formed on the same droplet, programming multiflavored, multivalence droplets. The mobile patch can bind to a patch on another droplet containing complementary functional rafts, leading to primary structure formation. Further binding of nonneighbor droplets can produce secondary structures, a third step in hierarchical self-assembly. The use of mobile patches rather than uniform DNA coverage has the advantage of valence control at the expense of slow kinetics. Droplets with controlled flavors and valences enable a host of different material and device architectures.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Electric-field control of tri-state phase transformation with a selective dual-ion switch

Materials can be transformed from one crystalline phase to another by using an electric field to control ion transfer, in a process that can be harnessed in applications such as batteries, smart windows and fuel cells. Increasing the number of transferrable ion species and of accessible crystalline phases could in principle greatly enrich material functionality. However, studies have so far focused mainly on the evolution and control of single ionic species (for example, oxygen, hydrogen or lithium ions). In this paper, we describe the reversible and non-volatile electric-field control of dual-ion (oxygen and hydrogen) phase transformations, with associated electrochromic and magnetoelectric effects. We show that controlling the insertion and extraction of oxygen and hydrogen ions independently of each other can direct reversible phase transformations among three different material phases: the perovskite SrCoO 3-δ , the brownmillerite SrCoO 2.5 , and a hitherto-unexplored phase, HSrCoO 2.5 . By analysing the distinct optical absorption properties of these phases, we demonstrate selective manipulation of spectral transparency in the visible-light and infrared regions, revealing a dual-band electrochromic effect that could see application in smart windows. Moreover, the starkly different magnetic and electric properties of the three phases—HSrCoO 2.5 is a weakly ferromagnetic insulator, SrCoO 3-δ is a ferromagnetic metal, and SrCoO 2.5 is an antiferromagnetic insulator—enable an unusual form of magnetoelectric coupling, allowing electric-field control of three different magnetic ground states. Finally, these findings open up opportunities for the electric-field control of multistate phase transformations with rich functionalities.

36 MATERIALS SCIENCE↗

Integrating Machine Learning Potential and X-ray Absorption Spectroscopy for Predicting the Chemical Speciation of Disordered Carbon Nitrides

Precise determination of atomic structural information in functional materials holds transformative potential and broad implications for emerging technologies. Spectroscopic techniques, such as X-ray absorption near-edge structure (XANES), have been widely used for material characterization; however, extracting chemical information from experimental probes remains a significant challenge, particularly for disordered materials. We present an integrated approach that combines atomic simulations, data-driven techniques, and experimental measurements to investigate chemical speciation of amorphous carbon nitride systems as a case study. Here, we discuss the development of machine learning potentials that can efficiently explore the vast configuration space of amorphous carbon nitrides. By employing statistical methods, this structural database enables the elucidation of the most representative local structures and how they evolve with chemical compositions and density. Density functional theory simulations are used to establish a correlation between the local structure and spectroscopic signatures, which then serve as the basis for interpreting and extracting chemical content from experimental data. Although our framework is specifically demonstrated for XANES and carbon nitrides, the approach described herein is readily adaptable as applied to other experimental characterization probes and materials classes.

36 MATERIALS SCIENCE↗

Crystallization-induced emission enhancement of alkyl chain-dependent pyrene-based luminogens: Visual detection of nitro-explosives

In view of the widespread applications and urgent need for efficient blue emitting materials, the synthesis of such materials has seen renewed interest. In the present work, three alkyl chain-dependent blue emitting pyrene-based luminogens were synthesized and characterized. Here, the experimental results show that these luminogens exhibited high photoluminescence efficiency both in solution (>86%) and in the solid state (>35%). Interestingly, 1,3,6,8-tetrakis (pentylphenyl)pyrene (TPPy), as a photoelectric functional material, was endowed with higher quantum yield (72%) and competitiveness due to a remarkable crystallization-induced emission enhancement (CIEE) property. More importantly, TPPy exhibits high sensitivity and selectivity for ortho-nitroaniline (o-NA) with low limit of detection (9.99 × 10 -8 M), which is mainly due to the distinctive odd-even effects of the terminal alkyl chain. The results demonstrate that this type of luminogen can potentially be utilized for practical applications in the field of contaminant or explosive detection as a sensitive and portable fluorimeter.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Anomalous water expulsion from carbon-based rods at high humidity

Managing water is critical for industrial applications including CO2 capture, catalysis, bio-oil separations and energy storage. Various classes of materials have been designed for these applications, achieving specific water adsorption capacities at a given relative humidity (RH). Three water adsorption-desorption mechanisms are common to inorganic materials: (1) chemisorption, which may lead to the modification of the first coordination sphere; (2) simple adsorption, which is reversible in nature; or (3) capillary condensation, which is irreversible in nature. Regardless of sorption mechanism, all materials known today increase water adsorption capacity with increasing RH; none exhibit repeated adsorption of water at low humidity and release at high humidity. We present here a material that breaks from this convention: a new class of nitrogen containing carbon rods along with nonstoichiometric FeXSY that adsorb water at low humidity, and spontaneously expel half of the adsorbed water when the RH exceeds a 50–80% threshold. Monolayers of water form on the surfaces of the carbon rods, with the amount of water adsorbed directly linked to the aspect ratio of the rods and the available surface area. This unprecedented water expulsion is a reversible physical process. Once a complete monolayer is formed, adjacent rods in the bundles begin to adhere together via formation of a bridging monolayer, reducing the surface area available for water to adhere to. We believe the unique surface chemistry of these carbon rods can be used on other functionalized materials. Such behaviour offers a paradigm shift in water purification and separation: water could be repeatedly adsorbed from a low humidity vapour stream and then expelled into a pure water vapour stream, or humidity-responsive membranes could change their water permeance or selectivity as a function of RH.

36 MATERIALS SCIENCE↗

A novel multifunctional NiTi/Ag hierarchical composite

Creating multifunctional materials is an eternal goal of mankind. As the properties of monolithic materials are necessary limited, one route to extending them is to create a composite by combining contrasting materials. The potential of this approach is neatly illustrated by the formation of nature materials where contrasting components are combined in sophisticated hierarchical designs. In this study, inspired by the hierarchical structure of the tendon, we fabricated a novel composite by subtly combining two contrasting components: NiTi shape-memory alloy and Ag. The composite exhibits simultaneously exceptional mechanical properties of high strength, good super-elasticity and high mechanical damping, and remarkable functional properties of high electric conductivity, high visibility under fluoroscopy and excellent thermal-driven ability. All of these result from the effective-synergy between the NiTi and Ag components, and place the composite in a unique position in the properties chart of all known structural-functional materials providing new opportunities for innovative electrical, mechanical and biomedical applications. Furthermore, this work may open new avenues for designing and fabricating advanced multifunctional materials by subtly combining contrasting multi-components.

ELECTRONIC DEVICES↗