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At least 415 records · Page 23

Nucleation, growth, and strain relaxation of lattice-mismatched 3-5 semiconductor epitaxial layers

We have investigated the early stages of evolution of highly strained 2-D InAs layers and 3-D InAs islands grown by metal-organic chemical vapor deposition (MOCVD) on (100) and (111)B GaAs substrates. The InAs epilayer/GaAs substrate combination has been chosen because the lattice-mismatch is severe (approximately 7.2 percent), yet these materials are otherwise very similar. By examining InAs-on-GaAs composites instead of the more common In(x)Ga(1-x)As alloy we remove an additional degree of freedom (x) and thereby simplify data interpretation. A matrix of experiments is described in which the MOCVD growth parameters - susceptor temperature, Thin flux, and AsH3 flux - have been varied over a wide range. Scanning electron microscopy, atomic force microscopy, transmission electron microscopy, and electron microprobe analysis have been employed to observe the thin film surface morphology. In the case of 3-D growth, we have extracted activation energies and power-dependent exponents that characterize the nucleation process. As a consequence, optimized growth conditions have been identified for depositing approximately 250 A thick (100) and (111)B oriented InAs layers with relatively smooth surfaces. Together with preliminary data on the strain relaxation of these layers, the above results on the evolution of thin InAs films indicate that the (111)B orientation is particularly promising for yielding lattice-mismatched films that are fully relaxed with only misfit dislocations at the epilayer/substrate interface.

Welser, R. E.↗

Nucleation, Growth, and Strain Relaxation of Lattice-Mismatched III-V Semiconductor Epitaxial Layers

We have investigated the early stages of evolution of highly strained 2-D InAs layers and 3-D InAs islands grown by metal-organic chemical vapor deposition (MOCVD) on (100) and (111) B GaAs substrates. The InAs epilayer / GaAs substrate combination has been chosen because the lattice-mismatch is severe (approx. 7.20%), yet these materials are otherwise very similar. By examining InAs-on-GaAs composites Instead of the more common In(x)Ga(1-x)As alloy, we remove an additional degree of freedom (x) and thereby simplify data interpretation. A matrix of experiments is described in which the MOCVD growth parameters -- susceptor temperature, TMIn flux, and AsH3 flux -- have been varied over a wide range. Scanning electron microscopy, atomic force microscopy, transmission electron microscopy, and electron microprobe analysis have been employed to observe the thin film surface morphology. In the case of 3-D growth, we have extracted activation energies and power-dependent exponents that characterize the nucleation process. As a consequence, optimized growth conditions have been identified for depositing approx. 250 A thick (100) and (111)B oriented InAs layers with relatively smooth surfaces. Together with preliminary data on the strain relaxation of these layers, the above results on the evolution of thin InAs films indicate that the (111)B orientation is particularly promising for yielding lattice-mismatched films that are fully relaxed with only misfit dislocations at the epilayer / substrate interface.

Welser, R. E.↗

Sizing of discontinuous natural fibers: Effect of sizing approach and sizing concentration on composite properties

Natural fiber reinforced composites (NFRCs) are gaining attention in automotive applications as an alternative to glass fiber composites due to their lightweight and renewable sourcing. However, the inherent hydrophilicity of natural fibers leads to poor compatibility with hydrophobic polymers which adversely affects the mechanical properties of the composites and can limit their application to non-structural parts. Sizing is a common approach used for synthetic fibers to improve the interface between fiber and matrix. However, there is limited study on the sizing of natural fibers, and hence the focus of this work. Here, in this study, two different approaches to sizing discontinuous coir fibers were investigated, namely; (1) ex-situ sizing and (2) in-situ sizing. A commercial polypropylene (PP) based sizing agent was used and the effects of varying sizing solution concentrations (1.5, 2.5, and 3.5 wt%) on the properties of the composites was studied. Results showed that composites prepared via the in-situ sizing process had better fiber–matrix adhesion and improved tensile properties compared to ex-situ sized composites. On studying the effect of different sizing concentrations on composite properties, we found that the tensile strength of the composites increased (by ∼ 42 %) up to 2.5 wt% sizing concentration (in solution) and then decreased. However, the impact strength decreased significantly on increasing the sizing content beyond 1.5 wt% (by ∼ 40 %). Additionally, the study was further extended to investigate the effect of sizing on different NFRCs (coir, banana, and cottonized hemp fiber) where effectiveness of sizing was found to be influenced by the fiber surface morphology.

36 MATERIALS SCIENCE↗

Linking structure to performance: Characterization of porous transport layers for high-pressure water electrolysis

Proton exchange membrane (PEM) water electrolysis is a promising technology to produce cost-efficient hydrogen. PEM electrolyzers offer a large current density range and the ability to operate at differential pressure which can be used to minimize both capital and operational expenditures. However, directly producing pressurized hydrogen at the cathode results in pushing the membrane against the anode porous transport layer (PTL). This can lead to detrimental effects, such as membrane deformation or ruptures, which depend on membrane properties as well as PTL material properties such as pore size, structure, and morphology. In this work, a range of sinter and felt-based commercial PTLs are evaluated for their contributions to the cell's electrochemical and H 2 crossover performance at cathode pressures up to 30 bar. X-ray tomography and post-operando optical microscopy are used to assess the morphology of the PTLs, and the PTL induced deformation experienced by the catalyst coated membrane (CCM), respectively. PTL samples with lower porosity were found to reduce both the cell voltage and the amount of H 2 permeating from the cathode to the anode exhaust, which was ascribed to improved catalyst layer contact and reduced membrane deformation, respectively. The best performing PTLs improved electrolyzer efficiency by ~1.5 kWh/kg H2 . Specifically, 1 kWh/kg H2 was gained due to reducing membrane deformation and decreasing H 2 crossover. The remainder 0.5 kWh/kg H2 were achieved by improving the electrical contact at the electrode/PTL interface which decreased cell voltage.

08 HYDROGEN↗

The surface chemistry of colloidal lead halide perovskite nanowires

This study explored the interplay between the ligand–surface chemistry of colloidal CsPbBr 3 nanowires (NWs) and their optical properties. The ligand equilibrium was probed using nuclear magnetic resonance spectroscopy, and by perturbing the equilibrium via dilution, the gradual removal of ligands from the CsPbBr 3 surface was observed. This removal was correlated with an increase in the surface defect density, as suggested by a broadening of the photoluminescence (PL) spectrum, a decrease in the PL quantum yield (PLQY), and quenching of the PL decay. These results highlight similar surface binding between the traditional CsPbBr 3 quantum dots and our NWs, thereby expanding the scope of well-established ligand chemistry to a relatively unexplored nanocrystal morphology. In conclusion, by controlling the dilution factor, it was revealed that CsPbBr 3 NWs achieve a PLQY of 72% ± 2% and a relatively long average PL lifetime of 400 ± 10 ns, without relying on additional surface passivation techniques, such as ligand exchange.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Investigation of the asymmetric misfit dislocation morphology in epitaxial layers with the zinc-blende structure

The source of the asymmetry in the dislocation morphology exhibited in the epitaxial growth of compound semiconductors on (100) was investigated. A thickness wedge of p- and n-type GaAs(0.95)P(0.05) was grown on GaAs by metalorganic chemical vapor deposition, and the effect of misorientation on the resolved shear stress for each slip system was calculated and eliminated as the source of the asymmetry. Another potential source of asymmetry, the thickness gradient, was also eliminated. Results show that the substrate misorientation and the thickness gradient do not significantly contribute to the asymmetry and that the dominant contributor to the asymmetry of misfit dislocations in the (001) epitaxial interface can be attributed to the differences in the Peierls barriers between the two types of dilocations in GaAsP/GaAs.

Fox, Bradley A.↗

Effect of feed-rod tilting on friction surfacing of steel

During the friction surfacing process, the forge-axial force, rotation rate, and traverse speed of the consumable feed-rod play crucial roles in determining the deposition rate and layer morphology. Although some researchers have studied the enhancement of deposition by introducing a backward tilt relative to the traverse direction, there has been limited investigation into the effects of other tilt orientations. Therefore, this study aims to provide a more comprehensive understanding of feed-rod tilting in friction surfacing. In this investigation, the consumable feed-rod undergoes tilting in four distinct directions: forward, backward, advancing side, and retreating side, each tested at two different tilt angles (1.5° and 3.0°). The results reveal that the feed-rod tilting can influence the deposition dynamics by altering the location and area of the rubbing interface situated between the feed-rod and the substrate. Moreover, the feed-rod tilting can significantly enhance the bond width, deposition rate, and deposition efficiency. The enhancement in deposition efficiency signifies a successful reduction in flash formation. Furthermore, a distinct layered microstructure is evident within each deposition layer, regardless of tilt conditions, indicating the unique deposition process inherent to friction surfacing. Finally, the innovative approach proposed in this study not only offers a straightforward and feasible means to improve deposition rate and efficiency but also expands the potential for constructing more intricate geometries or authentic surfaces.

36 MATERIALS SCIENCE↗

Observations Regarding Small Eolian Dunes and Large Ripples on Mars

Eolian bedforms occur at the interface between a planetary surface and its atmosphere; they present a proxy record of the influence of climate, expressed in sediment transport, over that surface. High resolution images (1.5 - 12 m/pixel) from the Mars Global Surveyor (MGS) Mars Orbiter Camera provide glimpses of the most recent events shaping the martian landscape. Thousands of images exhibit small transverse dunes or large eolian ripples that have crest-to-crest spacings of 10 to 60 m, heights of a few to 10 m. Bedforms of the size and patterns seen in the Mars photographs are rarely described among Earth's eolian landforms; in terms of size and morphology, most of these fall between traditional definitions of "ripples" and "dunes". Dunes are composed chiefly of materials transported by saltation, ripples are smaller forms moved along by the impact of saltating grains (traction). The largest reported eolian ripples on Earth (granule ripples, megaripples) are typically smaller than the bedforms observed on Mars; likewise, most dunes are typically larger. The small dunes and large ripples on Mars come in a variety of relative albedos, despite an early MGS impression that they are all of high albedo. Some ripples occur on the surfaces of sand dunes; these are most likely true granule ripples. However, most of these bedforms occur in troughs, pits, craters, and on deflated plains. Despite impressions early in the MGS mission, they do not occur everywhere (e.g., they are rare on the northern plains) but they do occur at a range of elevations from the highest volcanoes to the deepest basins. Where they occur on a hard substrate among larger sand dunes, the big dunes have over-ridden the smaller bedforms, indicating that the smaller features are older and perhaps indurated or very coarse-grained. At other locales, the small bedforms have been mantled by material settled from suspension, in other cases they are being exhumed and may be lithified. Still other examples are peppered with small impact craters, implying considerable age. These bedforms present a complicated record of the geologically-recent past, one that has involved changes in climate, sediment transport capabilities, and sediment sources and sinks over time.

Edgett, Kenneth S.↗

Thermoelectric Performance Enhancement by Surrounding Crystalline Semiconductors with Metallic Nanoparticles

Direct conversion of thermal energy to electricity by thermoelectric (TE) devices may play a key role in future energy production and utilization. However, relatively poor performance of current TE materials has slowed development of new energy conversion applications. Recent reports have shown that the dimensionless Figure of Merit, ZT, for TE devices can be increased beyond the state-of-the-art level by nanoscale structuring of materials to reduce their thermal conductivity. New morphologically designed TE materials have been fabricated at the NASA Langley Research Center, and their characterization is underway. These newly designed materials are based on semiconductor crystal grains whose surfaces are surrounded by metallic nanoparticles. The nanoscale particles are used to tailor the thermal and electrical conduction properties for TE applications by altering the phonon and electron transport pathways. A sample of bismuth telluride decorated with metallic nanoparticles showed less thermal conductivity and twice the electrical conductivity at room temperature as compared to pure Bi2Te3. Apparently, electrons cross easily between semiconductor crystal grains via the intervening metallic nanoparticle bridges, but phonons are scattered at the interfacing gaps. Hence, if the interfacing gap is larger than the mean free path of the phonon, thermal energy transmission from one grain to others is reduced. Here we describe the design and analysis of these new materials that offer substantial improvements in thermoelectric performance.

Kim, Hyun-Jung↗

Laser Ablation Surface Treatment of Structural Aerospace Composites and Metal Alloys for Adhesive Bonding

NASA Langley Research Center (LaRC) has been involved over the past decade in the development of laser ablation as a method to surface treat aerospace structural fiber reinforced composites (CFRPs) and metal alloys. [1- 18] Laser surface treatment has been shown to be a rapid, high precision, and reproducible method for surface treatment of these materials, and is amenable to automation. The laser ablation process removes surface contamination such as silicones, creates surface roughness, and chemically activates a surface for bonding. The degree of ablation is controllable by adjusting laser parameters. In the case of CFRPs, ablation can be performed without damage to any underlying carbon fibers. In the case of metal alloys, ablation is possible without surface embrittlement, heat damage or creation of undesirable grain structures or morphologies. The optimum laser treatment conditions are substrate dependent and generally are influenced by laser wavelength and pulse duration (typically fixed for a laser system), and laser power. In the case of metal alloys such as Ti-6Al-4V, the laser ablation process eliminates the need for several steps of the conventional processes, including hydrofluoric (HF) acid and caustic treatment. These steps are often conducted in dip tanks and require costly facilities and environmentally unfriendly liquids. In addition, the laser can create nano-porosity on the Ti-6Al-4V alloy surface allowing for sol-gel penetration and thereby creating a gradient interface with improved temperature and mechanical performance. NASA LaRC has also been involved with the development of in-line characterization methods compatible with the laser treatment process to rapidly determine the presence of key contaminates such as silicones that, even at very low concentrations, are a threat to adhesive bonding. A spectroscopic technique called micro-laser induced breakdown spectroscopy (u-LIBS) has been developed to rapidly detect silicones at concentrations below those known to cause bonding problems. This technique requires no sample preparation, vacuum or inert atmosphere, has no practical size limitations, and provides nearly instantaneous feedback to the operator. This presentation will give an overview and update of these developments with specific examples highlighted.

Connell, John W.↗

Transport–Friendly Microstructure in SSC–MEA: Unveiling the SSC Ionomer–Based Membrane Electrode Assemblies for Enhanced Fuel Cell Performance

The significant role of the cathodic binder in modulating mass transport within the catalyst layer (CL) of fuel cells is essential for optimizing cell performance. This investigation focuses on enhancing the membrane electrode assembly (MEA) through the utilization of a short-side-chain perfluoro-sulfonic acid (SSC-PFSA) ionomer as the cathode binder, referred to as SSC-MEA. This study meticulously visualizes the distinctive interpenetrating networks of ionomers and catalysts, and explicitly clarifies the triple-phase interface, unveiling the transport-friendly microstructure and transport mechanisms inherent in SSC-MEA. The SSC-MEA exhibits advantageous microstructural features, including a better-connected ionomer network and well-organized hierarchical porous structure, culminating in superior mass transfer properties. Relative to the MEA bonded by long-side-chain perfluoro-sulfonic acid (LSC-PFSA) ionomer, noted as LSC-MEA, SSC-MEA exhibits a notable peak power density (1.23 W cm –2 ), efficient O 2 transport, and remarkable proton conductivity (65% improvement) at 65 °C and 70% relativity humidity (RH). These findings establish crucial insights into the intricate morphology-transport-performance relationship in the CL, thereby providing strategic guidance for developing highly efficient MEA.

25 ENERGY STORAGE↗

Impact of Dilute DIO Additive on Local Microstructure of Fluorinated, pNDI‐Based Polymer Solar Cells

The performance of all‐polymer solar cells is often enhanced by incorporating solvent additives during solution processing. Here, in particular, blends based on the model all‐polymer system PBDBT:N2200 have been shown to have increased short‐circuit current and fill factor when processed with dilute diiodooctane (DIO). However, the morphological mechanism that drives the increase in performance is often not well understood due to limitations in common characterization techniques. In this study, it is shown that a combination of X‐ray techniques with cryogenic high‐resolution transmission electron microscopy (HRTEM) analysis can provide a quantitative and spatially resolved picture of polymer chain orientation and alignment in all‐polymer blends. It is found that DIO induces vertical phase separation in PBDBT‐2F:F‐N2200 and increases donor crystallite thickness in the pi‐stacking direction leading to an acceptor‐rich film surface. However, it is also shown that DIO does not disrupt the formation of face‐on donor–acceptor interfaces. These findings suggest that dilute DIO primarily affects crystalline domain formation in single component regions as opposed to mixed regions; thus, dilute DIO can impact vertical charge transport pathways without sacrificing donor–acceptor interfacial connectivity.

Cheng, Christina↗

Achieving Electrode Smoothing by Controlling the Nucleation Phase of Metal Deposition Through Polymer‐Substrate Binding

Polymer additives [like polyethylene oxide (PEO)] are widely used for smooth electrode deposition in aqueous zinc and many other battery systems. However, the precise mechanism by which they regulate morphology and suppress dendrite formation remains unclear. In this study, the knowledge gap is addressed by using in situ electrochemical atomic force microscopy to directly observe the interfacial evolution during Zn electrodeposition and polymer adsorption on Cu substrates in the presence of varying concentrations of ZnSO 4 and PEO. Contrary to previous literature assumptions, which emphasize the binding to the growing Zn crystal surfaces or Zn 2+ ions, the results demonstrate that PEO smooths Zn films by promoting nucleation of (002)-oriented Zn platelets through interactions with the Cu substrate. Density functional theory simulations support this finding by showing that PEO adsorption on Cu modifies the interfacial energy of Zn/Cu/electrolyte interfaces, favoring the stabilization of Zn (002) on the Cu substrate, as well as confines Zn electrodeposition to a narrow near-surface region. In conclusion, these findings elucidate a novel design principle for electrode smoothing, emphasizing the importance of substrate selection paired with polymer additives that exhibit an attractive interaction with the substrate but minimal interaction with growing crystals, offering a mechanistic perspective for improved battery performance.

Electrodeposition↗

A review of fluids under nanoconfinement: Reactivity, geomechanics, phase transitions, and flow

Due to its many industrial applications, the physics associated with the nanoconfinement of fluids has garnered great attention from the scientific community in roughly the last fifteen years. One pioneer of that research has been the Multi-Scale Fluid-Solid Interactions in Architected and Natural Materials (MUSE) Energy Frontier Research Center, which produced more than 50 journal articles from 2018 to 2023. We structure the findings of MUSE into four categories and contextualize the work with the broader literature. Here, the four categories are (1) the dependence of chemical reactions on the degree of confinement, which given the lower freedom of motion of molecules yet improved availability of reaction sites generally lead to enhancement from bulk reactions; (2) the mechanical properties of the porous matrix, which are dependent on the heterogeneity of the system in terms of both composition and structure; (3) the phase transitions under nanoconfinement, which are influenced by the pore size and morphology, surface chemistry, and substrate composition; and (4) the physical controls of slip flow, which demonstrate the importance of several factors, such as wettability. These aspects of nanoconfinement are becoming clearer, but there are other elements such as mathematical theory that are still being developed.

58 GEOSCIENCES↗

The Evolution of Dendrite Morphology during Isothermal Coarsening

Dendrite coarsening is a common phenomenon in casting processes. From the time dendrites are formed until the inter-dendritic liquid is completely solidified dendrites are changing shape driven by variations in interfacial curvature along the dendrite and resulting in a reduction of total interfacial area. During this process the typical length-scale of the dendrite can change by orders of magnitude and the final microstructure is in large part determined by the coarsening parameters. Dendrite coarsening is thus crucial in setting the materials parameters of ingots and of great commercial interest. This coarsening process is being studied in the Pb-Sn system with Sn-dendrites undergoing isothermal coarsening in a Pb-Sn liquid. Results are presented for samples of approximately 60% dendritic phase, which have been coarsened for different lengths of times. Presented are three-dimensional microstructures obtained by serial-sectioning and an analysis of these microstructures with regard to interface orientation and interfacial curvatures. These graphs reflect the evolution of not only the microstructure itself, but also of the underlying driving forces of the coarsening process. As a visualization of the link between the microstructure and the driving forces a three-dimensional microstructure with the interfaces colored according to the local interfacial mean curvature is shown.

Alkemper, Jens↗

Phase-field modeling of diffusion bonding in 316H stainless steel: Impact of processing conditions on grain morphology and bonding quality

A novel multi-phase, multi-component phase‐field model is presented to study the diffusion bonding of 316H stainless steel. Combined with targeted experimental investigations, this model simulates the bond-growth process and predicts the bonding quality. Unlike previous models, our approach captures the simultaneous evolution of voids and grain structures, while quantifying bonding quality using defined bonding ratio. A comprehensive analysis of bond process control is performed by changing temperature, pressure and surface roughness observing the resulting bond structure, which is consistent with experimental observations and analytical predictions. Temperature is determined to be the dominant factor, with the transition from a flat to a robust bond occurring between 1000 °C and 1050 °C. At the ideal bonding temperature of 1050 °C, a surface roughness exceeding 0.6 μm or an applied stress below 4 MPa results in poor bonding quality. Beyond this, higher pressures and smoother surfaces reduce void size, accelerate void shrinkage, and lead to improved bond integrity. This diffuse-interface model can be extended to other material systems if supplied with appropriate thermodynamic and kinetic data. In conclusion, this makes it an effective modeling platform for optimizing high-temperature diffusion bonding and developing reliable bonded components such as compact heat exchangers.

Diffusion bonding↗

Modeling Fatigue Damage Onset and Progression in Composites Using an Element-Based Virtual Crack Closure Technique Combined With the Floating Node Method

A new methodology is proposed to model the onset and propagation of matrix cracks and delaminations in carbon-epoxy composites subject to fatigue loading. An extended interface element, based on the Floating Node Method, is developed to represent delaminations and matrix cracks explicitly in a mesh independent fashion. Crack propagation is determined using an element-based Virtual Crack Closure Technique approach to determine mixed-mode energy release rates, and the Paris-Law relationship to obtain crack growth rate. Crack onset is determined using a stressbased onset criterion coupled with a stress vs. cycle curve and Palmgren-Miner rule to account for fatigue damage accumulation. The approach is implemented in Abaqus/Standard® via the user subroutine functionality. Verification exercises are performed to assess the accuracy and correct implementation of the approach. Finally, it was demonstrated that this approach captured the differences in failure morphology in fatigue for two laminates of identical stiffness, but with layups containing θdeg plies that were either stacked in a single group, or distributed through the laminate thickness.

De Carvalho, Nelson V.↗

The Isothermal Dendritic Growth Experiment (IDGE): USMP-4 One-Year-Report

Dendrites describe the tree-like crystal morphology commonly assumed in many material systems--particularly in metals and alloys that freeze from supercooled or supersaturated melts. There remains a high level of engineering interest in dendritic solidification because of the role of dendrites in the determination of cast alloy microstructures. Microstructure plays a key role in determining the physical properties of cast or welded products. In addition, dendritic solidification provides an example of non-equilibrium physics and is one of the simplest non-trivial examples of dynamic pattern formation, where an amorphous melt, under simple starting conditions, evolves into a complex ramified microstructure. Although it is well-known that dendritic growth is controlled by the transport of latent heat from the moving solid-melt interface as the dendrite advances into a supercooled melt, an accurate, and predictive model has not been developed. Current theories consider: 1) the transfer of heat or solute from the solid-liquid interface into the melt, and 2) the interfacial crystal growth and growth selection physics for the interface. However, the effects of gravity-induced convection on the transfer of heat from the interface prevent either element from being adequately tested solely under terrestrial conditions. The Isothermal Dendritic Growth Experiment (IDGE) constituted a series of three NASA-supported microgravity experiments, all of which flew aboard the space shuttle, Columbia. This experimental space flight series was designed and operated to grow and record dendrite solidification in the absence of gravity-induced convective heat transfer, and thereby produce a wealth of benchmark-quality data for testing solidification scaling laws. The data collection from the on-orbit phase of the IDGE flight series is now complete. We are currently completing analyses and moving towards final data archiving.

Glicksman, M. E.↗