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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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215 records · Page 12

Highly tunable structure-by-design polymer brush membranes for organic solvent nanofiltration

Synthetic polymeric nanofiltration membrane processes offer an alternate low-energy option to energy-intensive distillation to fractionate similar size organic solvents for chemical, petroleum, food and biotechnology industries. Here, in this study, we synthesize and test a new class of structure-by-design hydrophilic polymeric brush membranes, that address the limitations of commercial polymer membranes, are tunable and exhibit commercially relevant filtration performance. Because these brush membranes are grafted by Single Electron Transfer-Living Radical Polymerization (SET-LRP) and replace statistically random phase inversion or interfacial polymerization used for synthesizing commercial polymer membranes, their porous structure can be remodeled by varying their morphology and chemistry. We graft hydroxyethyl methacrylate (HEMA) brush structures with short and long crosslinkers, demonstrate two competing phenomena - pore stiffening and opening - and obtain high selectivity at reasonable permeability for commercially relevant methanol/toluene separation. This new class of stable, tunable, and scalable membranes offers exciting opportunities to reduce energy for separation of organic solvents.

42 ENGINEERING↗

Synthesis and Performance Evaluation of Unsaturated Polyester Blends of Resins and Its Application on Non-woven/Fabric Jute Fibers Reinforced Composites

The present study focuses on the generation of eco-friendly value added product by utilizing bio-based material as reinforced and matrix phase. Processing of soy and alkyd resin as matrix was carried out by utilization of soy flour and Ricinodendron heudelotii oil, followed essential modification in few inferior properties of soy flour resin by blending with alkyd resin. Separate sets of resin were prepared by maintaining 0%, 5% and 10% of alkyd resin in 100 g of soy flour resin respectively in each set to attain a comparative study on performance of prepared sets of resin blend. Subsequently, performance evaluation of polyester blends was evaluated by processing with non-woven/fabric jute fibers reinforced composites. The blend of R. heudelotii oil based alkyd and soy-flour resin in processing of composites was the noval approach of the study. The resins blend were characterized by FT–IR, viscosity and zeta potential measurements while thermo-mechanical analyses, water absorbancy and surface analyses were performed in composites. Significant increases noticed in the viscosity of blend, the blend containing 10% alkyd resin is two times more viscous compared to soy-flour resin. Furthermore, improvement in properties including water absorption, thermo-mechanical properties and better fiber-matrix interfacial adhesion of the composite could be observed. Higher glass transition temperature T{sub g} value i.e. 126.8 °C obtained for composites with 10% blend as matrix might emphasizes on increase of the degree of cross linking provided by the α-eleostearic fatty acid chain moiety. The enhancements in properties indicate extending opportunities for fiber-reinforced composites in several industries including building material, furniture, aerospace, nano etc.

36 MATERIALS SCIENCE↗

Plasma kinetic effects on interfacial mix and burn rates in multispatial dimensions

The physics of mixing in plasmas is of great significance to inertial confinement fusion and high energy density laboratory experiments. Two- and three-dimensional (2D and 3D) particle-in-cell simulations with a binary collision model are used to explore kinetic effects arising during the mixing of plasma media. The applicability of the one-dimensional (1D) ambipolarity condition is evaluated in 2D and 3D simulations of a plasma interface with a sinusoidal perturbation. The 1D ambipolarity condition is found to remain valid in 2D and 3D, as electrons and ions flow together required for $J$ = 0. Simulations of perturbed interfaces show that diffusion-induced total pressure imbalance and hydroflows flatten fine interface structures and drive rapid atomic mix. The atomic mix rate from a structured interface is faster than the ~$\sqrt{\bar{t}}$ scaling obtained from 1D theory in the small-Knudsen-number limit. Plasma kinetic effects inhibit the growth of the Rayleigh-Taylor instability at small wavelengths and result in a nonmonotonic growth rate scaling with wavenumber k with a maximum at a low k value, much different from $\sqrt{Agk}$ (where A is the Atwood number and g is the gravitational constant) as expected in the absence of plasma kinetic effects. Simulations under plasma conditions relevant to MARBLE separated-reactant experiments on Omega and the NIF show kinetic modification of DT fusion reaction rates. With non-Maxwellian distributions and relative drifts between D and T ions, DT reactivity is higher than that inferred from rates using stationary Maxwellian distributions. Reactivity is additionally revealed to be reduced in the presence of finite-Knudsen-layer losses.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Deliberate Modification of Fe 3 O 4 Anode Surface Chemistry: Impact on Electrochemistry

Fe 3 O 4 nanoparticles (NPs) with an average size of 8-10 nm have been successfully functionalized with various surface-treatment agents to serve as model systems for probing surface chemistry-dependent electrochemistry of the resulting electrodes. The surface-treatment agents used for the functionalization of Fe 3 O 4 anode materials were systematically varied to include aromatic or aliphatic structures: 4-mercaptobenzoic acid (MBA), benzoic acid (BA), 3-mercaptopropionic acid (MPA), and propionic acid (PA). Both structural and electrochemical characterizations have been used to systematically correlate the electrode functionality with the corresponding surface chemistry. Surface treatment with ligands led to better Fe 3 O 4 dispersion, especially with the aromatic ligands. Electrochemistry was impacted where the PA and BA-treated Fe 3 O 4 systems without the -SH group demonstrated higher rate capability than their thiol-containing counterparts and the pristine Fe 3 O 4 . Specifically, the PA system delivered the highest capacity and cycling stability amongst all samples tested. Notably, the aromatic BA system outperformed the aliphatic PA counterpart during extended cycling under high current density, due to the improved charge transfer and ion transport kinetics as well as better dispersion of Fe 3 O 4 NPs, induced by the conjugated system. Our surface engineering of the Fe 3 O 4 electrode presented herein, highlights the importance of modifying the structure and chemistry of surface-treatment agents as a plausible means of enhancing interfacial charge transfer within metal oxide composite electrodes without hampering the resulting tap density of the resulting electrode.

25 ENERGY STORAGE↗

Tailoring the Physicochemical Properties of Nb Thin Films via Surface Engineering Methods

The modification of surface oxide layers formed on niobium (Nb) thin films via chemical mechanical planarization (CMP) and accelerated neutral atom beam (ANAB) processing provides a promising route toward tailoring their emergent properties and performance when used as superconducting qubits. Here, in this study, we show that CMP- and ANAB-formed Nb oxides are significantly thinner and smoother than the native oxide, as revealed by transmission electron microscopy (TEM) and atomic force microscopy. Scanning TEM and energy-dispersive X-ray spectroscopy along with X-ray photoelectron spectroscopy identified an oxidation gradient within the native and surface-engineered oxides. The topside layer is dominated by Nb 5+ (Nb 2 O 5 ), with various Nb suboxides present closer to the oxide/metal interface. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) depth profiling confirmed the presence of an oxygen content gradient and demonstrated the enhanced resistance of the CMP- and ANAB-formed oxides to oxygen surface exchange and subsequent diffusion via 18 O 2 isotopic labeling experiments. ToF-SIMS also identified an interfacial layer containing trapped hydrogen (H)-containing species at the Nb oxide/metal interface. In situ ToF-SIMS and TEM revealed migration of the H/OH interfacial layer coinciding with decomposition of the surface oxide. Furthermore, our density functional theory calculations indicated that both H from moisture present in ambient air and bulk H in Nb films tend to segregate at the interface. These findings underscore the importance of understanding surface oxidation mechanisms, hydrogen incorporation, and their impact on the designed functionalities of Nb-based devices.

36 MATERIALS SCIENCE↗

Adding GaAs Monolayers to InAs Quantum-Dot Lasers on (001) InP

In a modification of the basic configuration of InAs quantum-dot semiconductor lasers on (001)lnP substrate, a thin layer (typically 1 to 2 monolayer thick) of GaAs is incorporated into the active region. This modification enhances laser performance: In particular, whereas it has been necessary to cool the unmodified devices to temperatures of about 80 K in order to obtain lasing at long wavelengths, the modified devices can lase at wavelengths of about 1.7 microns or more near room temperature. InAs quantum dots self-assemble, as a consequence of the lattice mismatch, during epitaxial deposition of InAs on ln0.53Ga0.47As/lnP. In the unmodified devices, the quantum dots as thus formed are typically nonuniform in size. Strainenergy relaxation in very large quantum dots can lead to poor laser performance, especially at wavelengths near 2 microns, for which large quantum dots are needed. In the modified devices, the thin layers of GaAs added to the active regions constitute potential-energy barriers that electrons can only penetrate by quantum tunneling and thus reduce the hot carrier effects. Also, the insertion of thin GaAs layer is shown to reduce the degree of nonuniformity of sizes of the quantum dots. In the fabrication of a batch of modified InAs quantum-dot lasers, the thin additional layer of GaAs is deposited as an interfacial layer in an InGaAs quantum well on (001) InP substrate. The device as described thus far is sandwiched between InGaAsPy waveguide layers, then further sandwiched between InP cladding layers, then further sandwiched between heavily Zn-doped (p-type) InGaAs contact layer.

Qiu, Yueming↗

Open millifluidics based on powder-encased channels

Millifluidics, the manipulation of liquid flow in millimeter-sized channels, has been a revolutionary concept in chemical processing and engineering. The solid channels that contain the liquids, though, are not flexible in their design and modification, and prevent contact with the external environment. All-liquid constructs, on the other hand, while flexible and open, are imbedded in a liquid environment. Here, we provide a route to circumvent these limitations by encasing the liquids in a hydrophobic powder in air that jams on the surface, containing and isolating flowing fluids, offering flexibility and adaptability in design, as manifest in the ability to reconfigure, graft, and segment the constructs. Along with the open nature of these powder-contained channels that allow arbitrary connections/disconnections and substance addition/extraction, numerous applications can be opened in the biological, chemical, and material arenas.

36 MATERIALS SCIENCE↗

Generation of nanocrystalline surface layer in short pulse laser processing of metal targets under conditions of spatial confinement by solid or liquid overlayer

The effect of spatial confinement by a solid or liquid overlayer on short pulse laser-induced surface microstructure modification is investigated in a series of large-scale atomistic simulations performed for Ag targets irradiated in the regime of melting and resolidification, below the thresholds for laser spallation and ablation. For Ag targets with free surfaces, the formation of a nanocrystalline region with random crystallographic grain orientation is observed under irradiation conditions leading to the generation of numerous sub-surface voids that slow down the solidification process. When no voids are generated, the resolidification produces grains misoriented with respect to the bulk of the target by just several degrees and separated from each other by low angle grain boundaries or dislocation walls. The presence of a liquid or solid overlayer suppresses nucleation of sub-surface voids, provides an additional pathway for cooling through the heat conduction to the overlayer, and facilitates the formation of nanocrystalline structure in a region of the metal target adjacent to the overlayer. Moreover, the stabilizing effect of the solid overlayer may result in an incomplete melting of metal in the vicinity of the interface, making it possible for grains growing from the interface to retain “memory” of the target orientation and to produce nanocrystalline interfacial region with small misorientation of grains with respect to the bulk of the target. In all simulations, the nanocrystalline layers generated by laser processing of single crystal Ag targets are characterized by a high density of stacking faults, twin boundaries, and point defects produced in the course of the rapid resolidification.

Chemistry↗

Influence of Longer Range Transfer of Vapor Interface Modified Caging Constraints on the Spatially Heterogeneous Dynamics of Glass-Forming Liquids

Based on the elastically collective nonlinear Langevin equation (ECNLE) theory of bulk relaxation in glass-forming liquids, and our recent ideas of how interface-nucleated modification of caging constraints are spatially transferred into the interior of a thick film, we present a force-based theory for dynamical gradients in thick films with one vapor interface that includes collective elasticity effects. Quantitative applications to the foundational hard sphere fluid and polymer melts of diverse fragilities are presented. In this work, we predict a roughly exponential spatial variation of the total activation barrier which is nonperturbatively modified to similar to 10 particle diameters into the film. This leads, to leading order, to the prediction of a reduced alpha relaxation time gradient of a double-exponential form characterized by a nearly constant spatial decay length, in qualitative accord with simulations. The relaxation acceleration at the surface grows exponentially with increasing packing fraction or decreasing temperature. The rate of increase with cooling of the alpha time strongly weakens upon approaching the vapor interface, with the top two layers remaining liquid-like down to similar to ~80-85% of the bulk glass transition temperature. These spatially heterogeneous changes of the temperature variation of the alpha time result in a large and long-range gradient of the local glass transition temperature. An average interfacial layer thickness relevant to ensemble-averaged dielectric and other experiments is also computed. It is predicted to be rather large at the bulk glass transition temperature, decreasing roughly linearly with heating. Remarkably, to leading order the ratio of this layer-averaged interfacial relaxation time to its bulk analogue is invariant to chemistry, volume fraction, and temperature and of modest absolute magnitude. Spatially inhomogeneous power law decoupling of the alpha relaxation time from its bulk value is predicted, with an effective exponent that decays to zero with distance from the free surface in a nearly exponential manner, trends which are in qualitative accord with recent simulations. Finally, this behavior and the double-exponential alpha time gradient are related and can be viewed as consequences of an effective quasi-universal factorization of the total barrier in films into the product of its bulk-temperature-dependent value times a function solely of location in the film.

36 MATERIALS SCIENCE↗

Decoupling first-cycle capacity loss mechanisms in sulfide solid-state batteries

Solid-state batteries (SSBs) promise more energy-dense storage than liquid electrolyte lithium-ion batteries (LIBs). However, first-cycle capacity loss is higher in SSBs than in LIBs due to interfacial reactions. The chemical evolution of key interfaces in SSBs has been extensively characterized. Electrochemically, however, we lack a versatile strategy for quantifying the reversibility of solid electrolyte (SE) redox for established and next-generation SSB electrolytes. In this work, we perform tailored electrochemical tests and operando X-ray diffraction to disentangle reversible and irreversible sources of capacity loss in positive electrodes composed of Li 6 PS 5 Cl SE, Li(Ni 0.5 Mn 0.3 Co 0.2 )O 2 (NMC), and carbon conductive additives. We leverage an atypically low voltage cutoff (2.0 V vs. Li/Li + ) to quantify the reversibility of SE redox. Using slow (5.5 mA g NMC −1 ) cycling paired with >100 h low-voltage holds, our cells achieve a surprising 96.2% first-cycle coulombic efficiency, which is higher than previously reported (mean: 72%, maximum: 91.6% across surveyed literature). We clarify that sluggish NMC relithiation kinetics have been historically mistaken for permanently irreversible capacity loss. In conclusion, through systematic decoupling of loss mechanisms, we uncover the unexpected reversibility of SE redox and isolate the major contributors to capacity loss, outlining a strategy for accurate assessment of next-generation SE materials and interface modifications.

54 ENVIRONMENTAL SCIENCES↗

Modification of Jet Velocities in an Explosively Loaded Copper Target with a Conical Cavity

Here, in this work, the design and execution of an experiment with the goal of demonstrating control over the evolution of a copper jet is described. Simulations show that when using simple multi-material buffers placed between a copper target with a conical cavity and a cylinder of high-explosive, a variety of jetting behaviors occur based on material placement, including both jet velocity augmentation and mitigation. A parameter sweep was performed to determine optimal buffer designs in two configurations. Experiments using the optimal buffer designs verified the effectiveness of the buffers at altering jet velocities. Similar trends were shown between the experimental results and the modeling.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Control of Surface Chemical Reactions through Solid Stiffness

Control of surface reactions is commonly achieved by modification of surface electronic structures. Here, we discover an alternative pathway for controlling surface reactions by tuning the mechanical stiffness of the underlying material. We find that in addition to the typically assumed surface electronic contribution right at the reactive site, the contribution from the deformation of the bulk region plays a vital role in controlling surface reactions. The underlying mechanism is an elastic relaxation of the solid, which depends on the material’s stiffness and can be modified by tuning bulk stoichiometry. The effect of bulk stiffness on surface reactions has been demonstrated by considering hydrogen scission reaction and oxygen incorporation reaction during corrosion of amorphous SiC in water and air, respectively. Finally, our results imply that tuning of bulk stiffness by modifying stoichiometry can provide an effective method for controlling surface reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Interfacial charge transfer driven by surface termination-controlled Ti 2 C MXene for enhanced hydrogen storage in magnesium

Two-dimensional transition metal carbides and nitrides (MXenes) with layered structure and high conductivity have been effectively utilized in various energy materials, including as a catalytic support of MgH 2 for hydrogen storage. However, the terminal groups formed on the surface during the etching step tend to deactivate reactive Mg metal and add dead mass, thereby deteriorating the catalytic role of MXene in hydrogen sorption of Mg. For this work, we exploited a molten-salt derived MXene with easily modifiable –Cl terminations, compared to conventional –O, –OH and –F groups, and synthesized a composite of Mg and delaminated Ti 2 CCl x MXene to improve the hydrogen storage performance of Mg through charge transfer. This strategy enables the formation of an intimate interface between Mg and MXene, facilitating charge transfer and thereby boosting the catalytic effect. The resulting composite demonstrates significantly enhanced hydrogen sorption kinetics by modulating Mg–H bond strength. This novel approach of modifying surface terminations leverages the unique properties of MXene as a superior support for active materials, offering broader applications in energy materials.

2D material↗

Designing Principle For Ni-rich Cathode Materials With High Energy Density For Practical Applications

Nickel(Ni)-rich lithium transition metal oxides (e.g. LiNi0.8Co0.15Al0.05O2 (NCA), LiNi1-x-yMnxCoyO2 (x+y<1) (NMC)) with layered structure are regarded as promising cathode candidates for constructing high energy density lithium ion batteries, so as to promote the market penetration of zero-emission electric vehicles. However, the poor structural and interfacial stability of Ni-rich NMC or NCA still hamper their large-scale applications. This review article mainly summarizes the recent progress achieved in the development of Ni-rich cathode materials, with an aim to provide important clues for future design Ni-rich cathodes and eventually enable their practical applications. Firstly, we introduce the improved method for the synthesis of Ni-rich cathode materials and discuss the relationships between the synthesis method, physicochemical properties, and the electrochemical performances of the cathode materials. Secondly, the insightful understandings on the capacity and voltage fading mechanism as well as the reasons of poor structure stability are comprehensively overviewed. Then, we summarize the main progress regarding to the novel approaches and attempts to prolong the cycling lifetime of Ni-rich materials and safety. Finally, we end up this review by proposing new perspectives and insights to stimulate more revolutionary strategies to boost the practical applications of Ni-rich cathodes.

high energy density, Ni-rich materials, modificati↗

Bio-inspired Surface Structures to Mitigate Interfacial Particle Adhesion and Erosion - A Review

Lunar dust known as regolith is a huge challenge for lunar exploration missions. Formed over millennia by a complex process involving impacts of meteoroids and micrometeoroids on the lunar surface, lunar dust is porous, highly abrasive with sharp jagged edges, chemically reactive, electrostatically charged and sometimes magnetic. The chemical composition and thickness of the dust layer also varies in different regions of the lunar surface. From samples obtained by previous lunar missions, the average particle size is below 100 microns. This dust has the tendency to strongly adhere to any exposed surfaces, and often degrades the material functionality to eventually cause failure. Any material on the lunar surface is also subject to harsh temperature cycles ranging from -178 ̊C to + 123 ̊C and extreme ultraviolet radiation. While on the lunar surface, different classes of materials would be required for different applications. Advanced materials have been and will be used throughout the lunar lander, habitat, and mission equipment. Examples include: polymeric materials for astronaut protective clothing; metals and ceramics for the lunar lander legs and habitats, and excavating equipment; and semiconductors for solar panels and on-board electronics. In all these applications, the surfaces of the materials are expected or understood to be exposed to the extreme lunar environment condition that includes the regolith dust. During the Apollo missions, the dust clung to and abraded the astronaut’s suits, degraded seals, optics, clogged sensors and reduced performance of thermal radiators. The lunar dust adheres to the surface by various mechanisms, which include electrostatic and Coulombic interactions, Van-der-Waals forces, magnetic forces, mechanical interlocking, chemical bonding and donor-acceptor interactions. There are three primary strategies for developing technologies to minimize the lunar dust adhesion: active, passive and a combination of active and passive. In the active approach, an external energy is needed to prevent or remove particles from collecting on the surface. Mechanically powered brushes and electrodynamic dust screens are two examples. In the passive approach, no external power is needed, and the material surface properties are able to mitigate dust adhesion. A well-known example of this strategy is the low work function coatings for non-stick surfaces. In most cases a combination of active and passive methods might be needed to optimally manage the lunar regolith. The passive method is significantly more attractive as it does not require any external power or an additional control subsystem. These approaches optimize the mission payload and reduce risk. Surface modification to minimize the dust adhesion is thus very important to lunar missions. Here, naturally evolved surface structures might provide guidance for solutions. There are several factors that have to be considered for minimizing particle adhesion to a surface. These include the substrate material properties, surface topography, chemistry, and the characteristics of the adhering particles. When engineering a surface, the substrate material chosen would be dependent on the needs of the application. Tailoring the surface microstructure or chemistry opens up more possibilities for its optimal utilization

Lunar Dust↗

Nonvolatile Ionic Modification of the Dzyaloshinskii-Moriya Interaction

The possibility of tuning the Dzyaloshinskii-Moriya interaction (DMI) by electric (E)-field gating in ultrathin magnetic materials has opened up new perspectives in terms of controlling the stabilization of chiral spin structures. The most recent efforts have used voltage-induced charge redistribution at the interface between a metal and an oxide to modulate the DMI. This approach is attractive for active devices but tends to be volatile, making it energy-demanding, and it is limited by Coulomb screening in the metal. Here we demonstrate nonvolatile E-field manipulation of the DMI by ionic-liquid gating of Pt/Co/Hf ⁢O 2 ultrathin films. The E-field effect on the DMI scales with the E-field exposure time, and we propose that it is linked to the migration of oxygen species from the Hf⁢ O 2 layer into the Co and Pt layers and subsequent anchoring. Here, this effect permanently changes the properties of the material, showing that E fields can be used not only for local gating in devices but also as a highly scalable materials design tool for postgrowth tuning of the DMI.

Domain walls↗

High-performance LiNi 0.8 Mn 0.1 Co 0.1 O 2 cathode by nanoscale lithium sulfide coating via atomic layer deposition

The commercialization of nickel-rich LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) has been hindered by its continuous loss of practical capacity and reduction in average working voltage. To address these issues, surface modification has been well-recognized as an effective strategy. Different from the coatings reported in literature to date, in this work, we for the first time report a sulfide coating, amorphous Li 2 S via atomic layer deposition (ALD). Here, our study revealed that the conformal nano-Li 2 S coating shows exceptional protection over the NMC811 cathodes, accounting for the dramatically boosted capacity retention from ~11.6% to ~71% and the evidently mitigated voltage reduction from 0.39 to 0.18 V after 500 charge–discharge cycles. In addition, the Li 2 S coating remarkably improved the rate capability of the NMC811 cathode. Our investigation further revealed that all these beneficial effects of the ALD-deposited nano-Li 2 S coating lie in the following aspects: (i) maintain the mechanical integrity of the NMC811 electrode; (ii) stabilize the NMC electrode/electrolyte interface; and (iii) suppress the irreversible phase transition of NMC structure. Particularly, this study also has revealed that the nano-Li 2 S coating has played some unique role not associated with traditional non-sulfide coatings such as oxides. In this regard, we disclosed that the Li 2 S layer has reacted with the released O 2 from the NMC lattices, and thereby has dramatically mitigated electrolyte oxidation and electrode corrosion. Thus, this study is significant and has demonstrated that sulfides may be an important class of coating materials to tackle the issues of NMCs and other layered cathodes in lithium batteries.

36 MATERIALS SCIENCE↗