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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 685 records · Page 38
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Genesis of Nanogalvanic Corrosion Revealed in Pearlitic Steel

Nanoscale, localized corrosion underpins billions of dollars in damage and material costs each year; however, the processes responsible have remained elusive due to the complexity of studying degradative material behavior at nanoscale liquid–solid interfaces. Recent improvements to liquid cell scanning/transmission electron microscopy and associated techniques enable this first look at the nanogalvanic corrosion processes underlying this widespread damage. Nanogalvanic corrosion is observed to initiate at the near-surface ferrite/cementite phase interfaces that typify carbon steel. In minutes, the corrosion front delves deeper into the material, claiming a thin layer of ferrite around all exposed phase boundaries before progressing laterally, converting the ferrite to corrosion product normal to each buried cementite grain. Over the following few minutes, the corrosion product that lines each cementite grain undergoes a volumetric expansion, creating a lateral wedging force that mechanically ejects the cementite grains from their grooves and leaves behind percolation channels into the steel substructure.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Unveiling the Interfacial Reconstruction Mechanism Enabling Stable Growth of the Delafossite PdCoO 2 on Al 2 O 3 and LaAlO 3

Delafossites, composed of noble metal (A + ) and strongly correlated sublayers (BO 2 – ), form natural superlattices with highly anisotropic properties. These properties hold significant promise for various applications, but their exploitation hinges on the successful growth of high-quality thin films on suitable substrates. Unfortunately, the unique lattice geometry of delafossites presents a significant challenge to thin-film fabrication. Different delafossites grow differently, even when deposited on the same substrate, ranging from successful epitaxy to complete growth suppression. These variations often lack a clear correlation to obvious causes like lattice mismatch. Unidentified stabilization mechanisms appear to enable growth in certain cases, allowing these materials to form stable thin films or act as buffer layers for subsequent delafossite growth. This study employs advanced scanning transmission electron microscopy techniques to investigate the nucleation mechanism underlying the stable growth of PdCoO 2 films on Al 2 O 3 and LaAlO 3 substrates grown via molecular-beam epitaxy. Our findings reveal the presence of a secondary phase within the substrate surface that stabilizes the films. This mechanism deviates from the conventional understanding of strain relief mechanisms at oxide heterostructure interfaces and differs significantly from those observed for Cu-based delafossites.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Surface-Active ß-Caryophyllene Oxidation Products at the Air/Aqueous Interface

We examine synthesized standards of structurally related ß-caryophyllene ozonolysis products at the air/water and air/(NH4)2SO4 (aq) interface using polarization-resolved standard- and high-resolution vibrational sum frequency generation (SFG) spectroscopy in the C–H and O–H stretching regions. ß-Caryophyllene aldehyde (1), the most surface-active molecule in the suite, appears to undergo a change in its molecular orientation distribution when transitioning from low to high relative surface coverage. We also report that the water molecules present at the outermost layer of the aqueous interface are displaced by ß-caryophyllene aldehyde (1) on both the (NH4)2SO4 (aq) and water subphases. Additionally, the more weakly hydrogen-bonded water network observed around ~3400 cm-1 seems to be perturbed to a greater extent by ß-caryophyllene aldehyde (1) than the more strongly hydrogen-bonded population observed at ~3200 cm-1 on the (NH4)2SO4 (aq) subphase, while this effect is not observed on the water subphase. We provide surface spectroscopic evidence for the “salting out” effect of (NH4)2SO4 in aqueous environments and discuss the implications for understanding the organization of surface-localized molecules present in aqueous cloud-forming droplets containing dissolved aerosol cloud condensation nuclei (CCN) in the atmosphere. Despite the importance of elucidating the surface activity and interfacial organization of individual molecules in aqueous media, future work will focus on how the combined effects of several surface-active constituents dictate overall cloud activation potentials of aerosol particles.

Sum frequency generation (SFG) spectroscopy, ?-car↗
DOE OSTI2024

Dynamic Bubbling Balanced Proactive CO 2 Capture and Reduction on a Triple-Phase Interface Nanoporous Electrocatalyst

The formation and preservation of the active phase of the catalysts at the triple-phase interface during CO 2 capture and reduction is essential for improving the conversion efficiency of CO 2 electroreduction toward value-added chemicals and fuels under operational conditions. Designing such ideal catalysts that can mitigate parasitic hydrogen generation and prevent active phase degradation during the CO 2 reduction reaction (CO 2 RR), however, remains a significant challenge. Herein, we developed an interfacial engineering strategy to build a new SnO x catalyst by invoking multiscale approaches. This catalyst features a hierarchically nanoporous structure coated with an organic F-monolayer that modifies the triple-phase interface in aqueous electrolytes, substantially reducing competing hydrogen generation (less than 5%) and enhancing CO 2 RR selectivity (~90%). This rationally designed triple-phase interface overcomes the issue of limited CO 2 solubility in aqueous electrolytes via proactive CO 2 capture and reduction. Concurrently, we utilized pulsed square-wave potentials to dynamically recover the active phase for the CO 2 RR to regulate the production of C1 products such as formate and carbon monoxide (CO). This protocol ensures profoundly enhanced CO 2 RR selectivity (~90%) compared with constant potential (~70%) applied at -0.8 V (V vs RHE). We further achieved a mechanistic understanding of the CO 2 capture and reduction processes under pulsed square-wave potentials via in situ Raman spectroscopy, thereby observing the potential-dependent intensity of Raman vibrational modes of the active phase and CO 2 RR intermediates. Finally, this work will inspire material design strategies by leveraging triple-phase interface engineering for emerging electrochemical processes, as technology moves toward electrification and decarbonization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Defect-driven selective metal oxidation at atomic scale

Nanoscale materials modified by crystal defects exhibit significantly different behaviours upon chemical reactions such as oxidation, catalysis, lithiation and epitaxial growth. However, unveiling the exact defect-controlled reaction dynamics (e.g. oxidation) at atomic scale remains a challenge for applications. Here, using in situ high-resolution transmission electron microscopy and first-principles calculations, we reveal the dynamics of a general site-selective oxidation behaviour in nanotwinned silver and palladium driven by individual stacking-faults and twin boundaries. The coherent planar defects crossing the surface exhibit the highest oxygen binding energies, leading to preferential nucleation of oxides at these intersections. Planar-fault mediated diffusion of oxygen atoms is shown to catalyse subsequent layer-by-layer inward oxide growth via atomic steps migrating on the oxide-metal interface. These findings provide an atomistic visualization of the complex reaction dynamics controlled by planar defects in metallic nanostructures, which could enable the modification of physiochemical performances in nanomaterials through defect engineering.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Evidence for non-electrostatic interactions between a pyrophosphate-functionalized uranyl peroxide nanocluster and iron (hydr)oxide minerals

We report the terminal oxygen atoms of the pyrophosphate groups in the uranyl peroxide nanocluster U 24 Pp 12 ([(UO 2 ) 24 (O 2 ) 24 (P 2 O 7 ) 12 ] 48- ) are not fully satisfied by bond valence considerations and can become protonated. This functionality could allow for specific interactions with mineral surfaces, as opposed to the electrostatically-driven interactions observed between non-functionalized uranyl peroxide nanoclusters and mineral surfaces. The sorption of U 24 Pp 12 to goethite and hematite was studied using batch sorption experiments as a function of U 24 Pp 12 concentration, mineral concentration, and pH. A suite of spectroscopic techniques, scanning electron microscopy, and electrophoretic mobility measurements were used to examine the minerals before and after reaction with U 24 Pp 12 , leading to a proposed conceptual model for U 24 Pp 12 interactions with goethite. The governing rate laws were determined and compared to those previously determined for a non-functionalized uranyl peroxide nanocluster. The rate of uranyl peroxide nanocluster sorption depends on the charge density and functionalized component of the uranyl peroxide cage. Electrophoretic mobility and attenuated total reflectance Fourier transform infrared spectroscopy analyses show that an inner-sphere complex forms between the U 24 Pp 12 cluster and the goethite surface through the terminal pyrophosphate groups, leading to a proposed conceptual model in which U 24 Pp 12 interacts with the triply-coordinated reactive sites on the (110) plane of goethite. Finally, these results demonstrate that the behavior of U 24 Pp 12 at the iron (hydr)oxide-water interface is unique relative to interactions of the uranyl ion and non-functionalized uranyl peroxide nanoclusters.

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

Enhancement of thermal stability and water resistance in yttrium-doped GeO{sub 2}/Ge gate stack

We have systematically investigated the material and electrical properties of yttrium-doped GeO{sub 2} (Y-GeO{sub 2}) on Germanium (Ge). A significant improvement of both thermal stability and water resistance were demonstrated by Y-GeO{sub 2}/Ge stack, compared to that of pure GeO{sub 2}/Ge stack. The excellent electrical properties of Y-GeO{sub 2}/Ge stacks with low D{sub it} were presented as well as enhancement of dielectric constant in Y-GeO{sub 2} layer, which is beneficial for further equivalent oxide thickness scaling of Ge gate stack. The improvement of thermal stability and water resistance are discussed both in terms of the Gibbs free energy lowering and network modification of Y-GeO{sub 2}.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Biomimetic composite architecture achieves ultrahigh rate capability and cycling life of sodium ion battery cathodes

Sodium ion batteries are an emerging candidate to replace lithium ion batteries in large-scale electrical energy storage systems due to the abundance and widespread distribution of sodium. Despite the growing interest, the development of high-performance sodium cathode materials remains a challenge. In particular, polyanionic compounds are considered as a strong cathode candidate owing to their better cycling stability, a flatter voltage profile, and stronger thermal stability compared to other cathode materials. Here, we report the rational design of a biomimetic bone-inspired polyanionic Na3V2(PO4)3-reduced graphene oxide composite (BI-NVP) cathode that achieves ultrahigh rate charging and ultralong cycling life in a sodium ion battery. At a charging rate of 1 C, BI-NVP delivers 97% of its theoretical capacity and is able to retain a voltage plateau even at the ultra-high rate of 200 C. It also shows long cycling life with capacity retention of 91% after 10 000 cycles at 50 C. The sodium ion battery cells with a BI-NVP cathode and Na metal anode were able to deliver a maximum specific energy of 350 W h kg−1 and maximum specific power of 154 kW kg−1. In situ and postmortem analyses of cycled BI-NVP (including by Raman and XRD spectra) HRTEM, and STEM-EELS, indicate highly reversible dilation–contraction, negligible electrode pulverization, and a stable NVP-reduced graphene oxide layer interface. The results presented here provide a rational and biomimetic material design for the electrode architecture for ultrahigh power and ultralong cyclability of the sodium ion battery full cells when paired with a sodium metal anode.

25 ENERGY STORAGE↗
DOE OSTI2022

Epitaxial SrTiO 3 films with dielectric constants exceeding 25,000

Significance Semiconductor interfaces are among the most important in use in modern technology. The properties they exhibit can either enable or disable the characteristics of the materials they connect for functional performance. While much is known about important junctions involving conventional semiconductors such as Si and GaAs, there are several unsolved mysteries surrounding interfaces between oxide semiconductors. Here we resolve a long-standing issue concerning the measurement of anomalously low dielectric constants in SrTiO 3 films with record high electron mobilities. We show that the junction between doped and undoped SrTiO 3 required to make dielectric constant measurements masks the dielectric properties of the undoped film. Through modeling, we extract the latter and show that it is much higher than previously measured.

36 MATERIALS SCIENCE↗
DOE OSTI2020

FEBIP for functional nanolithography of 2D nanomaterials

Lithographic patterning on emerging nanomaterials is one of essential ingredients for the development of new functional nanomaterial and device systems. Focused electron beam induced processing (FEBIP) in combination with an on-demand reconfigurable precursor injection system enables the highest resolution and controllability of nanolithography on two-dimensional (2D) nanomaterials. FEBIP allows for localized atomic-to-nanoscale engineering of nanomaterials and devices in a multi-mode format including geometrical patterning, functionalization/defect formation/doping, metal/metal oxide deposition, interface fusion and activation, active channel cleaning. This chapter discusses the scientific bases and showcases the state-of-the-art FEBIP technologies with a specific focus on functional lithography of 2D nanomaterials and provides future prospects of FEBIP technologies to address real industrial needs for the development of high-performance, next-generation functional devices.

2D materials, nanolithography, focused electron be↗
DOE OSTI2013

Quantum confinement induced magnetism in LaNiO3-LaMnO3 superlattices

The emergence of magnetic reconstructions at the interfaces of oxide heterostructures are often explained via subtle modifications in the electronic densities, exchange couplings, or strain. Here, an additional possible route for induced magnetism is studied in the context of the (LaNiO3)n/(LaMnO3)n superlattices using a hybrid tightbinding model. In the LaNiO3 region, the induced magnetizations decouple from the intensity of charge leakage from Mn to Ni, but originate from the spin-filtered quantum confinement present in these nanostructures. In general, the induced magnetization is the largest for the (111)-stacking and the weakest for the (001)-stacking superlattices; results compatible with the exchange bias effects reported byGibert et al. [Nat.Mater. 11, 195 (2012)].

Dong, Shuai↗
DOE OSTI2014

Thickness Dependent Carrier Density at the Surface of SrTiO3 (111) Slabs

We investigate the surface electronic structure and thermodynamic stability of the SrTiO3 (111) slabs using density functional theory. We observe that, for Ti-terminated slabs it is indeed possible to create a two-dimensional electron gas (2DEG). However, the carrier density of the 2DEG displays a strong thickness dependence due to the competition between electronic reconstruction and polar distortions. As expected, having a surface oxygen atom at the Ti termination can stabilize the system, eliminating any electronic reconstruction, thereby making the system insulating. An analysis of the surface thermodynamic stability suggests that the Ti terminated (111) surface should be experimentally realizable. This surface may be useful for exploring the behavior of electrons in oxide (111) interfaces and may have implications for modern device applications.

Sivadas, Mr. Nikhil↗