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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 469 records · Page 26

Morphology, microstructure, and doping behaviour: A comparison between different deposition methods for poly-Si/SiO x passivating contacts

In this work, we study how crystallographic structures, optoelectronic properties, and nanoscale surface morphologies of ex situ phosphorus-doped polycrystalline silicon (poly-Si)/SiO x passivating contacts, formed by different deposition methods (sputtering, plasma-enhanced chemical vapour deposition [PECVD], and low-pressure chemical vapour deposition [LPCVD]), are investigated and compared. Across all these deposition technologies, we noted the same trend: higher diffusion temperatures yield films that are more crystalline but that have rougher surface morphologies due to bigger surface crystal grains. Also, the recrystallization process of the as-deposited Si films starts from the SiO x interface, rather than from the film surface and bulk. However, there are some distinct differences among these technologies. First, the LPCVD method yields the lowest deposition rate, roughest surfaces, and smallest degree of crystallinity on finished poly-Si films. In contrast, the PECVD method has the highest deposition rate and smoothest surfaces for both as-deposited Si and annealed poly-Si films. Second, as-deposited sputtered and PECVD Si films contain only an amorphous phase, whereas as-deposited LPCVD films already has some crystalline phase. Third, the LPCVD phosphorus in-diffusion into the substrate depends strongly on the initial film thickness, whereas for the other two methods, it is weakly dependent on thickness. Finally, the passivation quality of every poly-Si film type has different responses to the film thickness and diffusion temperature, suggesting that the ex situ doping optimization should be performed independently.

14 SOLAR ENERGY↗

Investigation of Nucleation and Growth at a Liquid–Liquid Interface by Solvent Exchange and Synchrotron Small-Angle X-Ray Scattering

Hybrid nanomaterials possess complex architectures that are driven by a self-assembly process between an inorganic element and an organic ligand. The properties of these materials can often be tuned by organic ligand variation, or by swapping the inorganic element. This enables the flexible fabrication of tailored hybrid materials with a rich variety of properties for technological applications. Liquid-liquid interfaces are useful for synthesizing these compounds as precursors can be segregated and allowed to interact only at the interface. Although procedurally straightforward, this is a complex reaction in an environment that is not easy to probe. Here, we explore the interfacial crystallization of mithrene, a supramolecular multi-quantum well. This material sandwiches a well-defined silver-chalcogenide layer between layers of organic ligands. Controlling mithrene crystal size and morphology to be useful for applications requires understanding details of its crystal growth, but the specific mechanism for this reaction remain only lightly investigated. We performed a study of mithrene crystallization at an oil-water interfaces to elucidate how the interfacial free energy affects nucleation and growth. We exchanged the oil solvent on the basis of solvent viscosity and surface tension, modifying the dynamic contact angle and interfacial free energy. We isolated and characterized the reaction byproducts via scanning electron microscopy (SEM). We also developed a high-throughput small angle X-ray scattering (SAXS) technique to measure crystallization at short reaction timescales (minutes). Our results showed that modifying interfacial surface energy affects both the reaction kinetics and product size homogeneity and yield. Our SAXS measurements reveal the onset of crystallinity after only 15 min. These results provide a template for exploring directed synthesis of complex materials via experimental methods.

Schriber, Elyse A.↗

Surface characterization and methane activation on SnO x /Cu 2 O/Cu(111) inverse oxide/metal catalysts

To activate methane at low or medium temperatures is a difficult task and a pre-requisite for the conversion of this light alkane into high value chemicals. In this work, we report the preparation and characterizations of novel SnO x /Cu 2 O/Cu(111) interfaces that enable low-temperature methane activation. Scanning tunneling microscopy identified small, well-dispersed SnO x nanoclusters on the Cu 2 O/Cu(111) substrate with an average size of 8 Å, and such morphology was sustained up to 450 K in UHV annealing. Ambient pressure X-ray photoelectron spectroscopy showed that hydrocarbon species (CH x groups), the product of methane activation, were formed on SnO x /Cu 2 O/Cu(111) at a temperature as low as 300 K. An essential role of the SnO x –Cu 2 O interface was evinced by the SnO x coverage dependence. Systems with a small amount of tin oxide, 0.1–0.2 ML coverage, produced the highest concentration of adsorbed CH x groups. Calculations based on density functional theory showed a drastic reduction in the activation barrier for C–H bond cleavage when going from Cu 2 O/Cu(111) to SnO x /Cu 2 O/Cu(111). On the supported SnO x , the dissociation of methane was highly exothermic (ΔE ~ –35 kcal mol –1 ) and the calculated barrier for activation (~20 kcal mol –1 ) could be overcome at 300–500 K, target temperatures for the conversion of methane to high value chemicals.

36 MATERIALS SCIENCE↗

Microstructural evolution and growth behavior of intermetallic compounds at the liquid Al/solid Fe interface by synchrotron X-ray radiography

Highlights: • A layered and tongue-like η phase was in-situ observed by synchrotron radiation X-ray radiography. • The coalescence of η phase bottom resulted in dissolution, further increasing the growth rate. • The θ phase growth behavior with different morphologies during cooling was analyzed. - Abstract: The growth of Inter-Metallic Compounds (IMCs) with dissolution was investigated on the liquid Al/solid Fe interconnection by using synchrotron radiation real-time imaging technology. At the initial stage of holding at 850 °C, a layer of the η-Fe{sub 2}Al{sub 5} phase formed at the interface, and tongue-like η grew into α-Fe. The tongue-like η phase had a stronger (001) texture than the layered phase. The coalescence of tongue-like η started at the bottom, followed by the dissolution of IMCs, which leads to a further increase in its growth rate. During solidification stage, the dotted, needle-like and flake θ-FeAl{sub 3} phases were sequentially formed.

36 MATERIALS SCIENCE↗

Numerical Analysis of Molten Pool Behavior and Spatter Formation with Evaporation During Selective Laser Melting of 316L Stainless Steel

During the selective laser-melting process, material evaporation and resultant spatter are common phenomena that bring about many defects. However, the underlying physical phenomena such as molten pool behavior and spatter formation, as evaporation occurred, are sparsely understood and difficult to observe during the process. Thus, a three–dimensional powder-scale model was established to investigate the thermal and flow behavior of the molten pool, the morphology evolution of the molten pool and keyhole, and the spatter formation with evaporation in the selective laser-melting processing of 316L stainless steel. Phase transitions and variations in interfacial force were taken into account in this model. The modified phase-field method was applied to trace the melt–gas interface. The results showed that keyhole formed in molten pool under recoil pressure, and that there were some differences in the temperature distribution and flow behavior inside and outside the keyhole. In addition, the dimension and surface morphology of the molten pool and keyhole depth altered and gradually stabilized during the process. Moreover, droplet spatter formation at rear of molten pool proceeded roughly as follows: the backward ejection of melt vapor would induce a depression in molten pool and a bump on the molten pool surface, the bump moved backward and subsequently a liquid column formed, then the liquid column formed a neck and gradually pinched off, resulting in the droplet spatter. Furthermore, the characteristic morphology of the scan track and dimension of the molten pool were obtained through experiments, which showed good agreement with the simulation results.

36 MATERIALS SCIENCE↗

Carbon nanotube-based mixed-matrix membranes with supramolecularly engineered interface for enhanced gas separation performance

Here in this study, novel nanocomposite membranes were fabricated from single-walled carbon nanotubes (SWNTs) and a triptycene-containing polyimide. The desirable interfacial morphology and homogenous dispersion of SWNTs were achieved by strong π-π stacking and supramolecular shape-fitting interactions between the nanotube and the paddlewheel-shaped triptycene moieties in polymer matrix. Mixed-matrix membranes (MMMs) containing 2–15 wt% of as-purchased SWNTs (AP-SWNTs) were prepared and tested for their gas transport properties. While all MMMs showed greatly enhanced permeabilities with well-maintained selectivities, a non-linear dependence of permeability on filler content was observed. Another series of MMMs with purified SWNTs (P-SWNTs) and acid-treated SWNT (A-SWNTs) were also prepared. The functionalized A-SWNT MMM exhibited the best separation performance at 2 wt% filler content among all MMMs, which can be attributed to the improved interfacial affinity with carboxylic acid functionalized surface of A-SWNTs.

42 ENGINEERING↗

Irradiation resistance of nanostructured interfaces in Zr–Nb metallic multilayers

We report that irradiation resistance of metallic nanostructured multilayers is determined by the interactions between defects and phase boundaries. However, the dose-dependent interfacial morphology evolution can greatly change the nature of the defect–boundary interaction mechanisms over time. In the present study, we used atomistic models combined with a novel technique based on the accumulation of Frenkel pairs to simulate irradiation processes. We examined dose effects on defect evolutions near zirconium–niobium multilayer phase boundaries. Our simulations enabled us to categorize defect evolution mechanisms in bulk phases into progressing stages of dislocation accumulation, saturation, and coalescence. In the metallic multilayers, we observed a phase boundary absorption mechanism early on during irradiation, while at higher damage levels, the increased irradiation intermixing triggered a phase transformation in the Zr–Nb mixture. Lastly, this physical phenomenon resulted in the emission of a large quantity of small immobile dislocation loops from the phase boundaries.

36 MATERIALS SCIENCE↗

Dispersity-Driven Stabilization of Coexisting Morphologies in Asymmetric Diblock Copolymer Thin Films

Despite decades of research, characterization of the effects of polymer chain dispersity on the structural properties of block copolymer thin films remains challenging. Here we present an integrated experimental and modeling approach to characterize the morphology of thin films containing asymmetric diblock copolymers. Specifically, we used synergistic neutron reflectivity (NR) and self-consistent field theory (SCFT)-based modeling to realize unexpected morphology of thin films containing asymmetric copolymers. Using NR, a highly stable and reproducible mixed phase of coexisting cylinders and lamellar domains was discovered in asymmetric poly(deuterated-styrene-b-n butyl methacrylate) (dPS-PBMA) copolymer thin films containing 34% volume fraction of dPS. SCFT reveals how to obtain such a thermodynamically stable morphology in the presence of disperse majority block and asymmetric interactions of polymer species with surfaces. Stabilization of the coexisting domains is a consequence of the depth segregation based on chain-length distribution. The asymmetric chains microphase-separate into cylindrical domains close to the substrate and near-symmetric chains form lamellar domains at the air interface. In the absence of dispersity, the coexistence of cylindrical and lamellar domains is thermodynamically unstable because of the absence of depth segregation. Overall, such an effect of dispersity on diblock copolymer thin-film morphology reveals a unique and powerful strategy to create coexisting nanoscale domains and tailor properties of thin films.

36 MATERIALS SCIENCE↗

Effect of Crucible Diameter Reduction on the Convection, Macrosegregation, and Dendritic Morphology during Directional Solidification of Pb-2.2 Wt Pct Sb Alloy

The Pb-2.2 wt pct Sb alloy has been directionally solidified in 1-, 2-, 3-, and 7-mm-diameter crucibles with planar and dendritic liquid-solid interface orphology. For plane front solidification, the experimentally observed macrosegregation along the solidified length follows the relationship proposed by Favier. Application of a 0.4 T transverse magnetic field has no effect on the extent of convection. Reducing the ampoule diameter appears to decrease the extent of convection. However, extensive convection is still present even in the 1-mm-diameter crucible. An extrapolation of the observed behavior indicated that nearly diffusive transport conditions require ampoules that are about 40 microns in diameter. Reduction of the crucible diameter does not appear to have any significant effect on the primary dendrite spacing. However, it results in considerable distortion of the dendrite morphology and ordering. This is especially true for the 1-mm diameter samples.

Chen, Jun↗

Integrating fine root diameter and watershed mapping to characterize rhizosphere hydrology

Root morphology and soil hydraulic characteristics were integrated using watershed distance mapping to show water distribution and uptake across the plant-soil interface. Poplar (Populus deltoides, P. trichocarpa), maize (Zea mays), juniper (Juniperus virginiana), grape (Vitis rotundifolia) and maple (Acer saccharum) seedlings were grown in sand, after which root diameter and soil water dynamics were assessed via sequential neutron radiography. Three local soil regions (root-soil interface or edge, rhizosphere, bulk soil) were classified based on both radial distance from the root surface and diameter of the nearest root, from which changes in water content and distribution were characterized using digital image processing. Water content dynamics across the rhizosphere showed two different species-independent processes: a consistently elevated water content at the root-soil edge interface which increased with root diameter, and hysteresis as the rhizosphere transitioned to bulk soil (~0.5 cm from the root), independent of root diameter. Water uptake per unit root surface area declined exponentially with root diameter, independent of species. Results highlight the species-independent hydrologic characteristics of the rhizosphere and the potential for evaluating them in a local spatially connected soil context. Avenues for improved integration of soil and root characteristics are discussed.

59 BASIC BIOLOGICAL SCIENCES↗

Perovskite-Sensitized Upconversion under Operando Conditions

Perovskite-sensitized upconversion (UC) has resulted in near-infrared-to-visible UC at solar-relevant fluxes. However, the successful implementation of UC devices into operating solar cells will result in exposure to similar environmental stressors as for the commercial photovoltaics (PVs), mainly elevated temperatures, and continuous irradiation. In this article, we investigated the effects of these two stressors, heat and light, on the triplet generation process at the perovskite/rubrene interface. Following exposure to both stressors, local discrepancies across the upconversion device were discovered. Here, the first region showed changes to the morphology, and no detectable upconverted emission was observed. Through the combination of optical microscopy and spectroscopy, crystallization of the organic semiconductor layer, degradation of dibenzotetraphenylperiflanthene, and concurrent degradation of the perovskite sensitizer were found. These effects culminate in a reduction in both triplet generation and triplet–triplet annihilation. In the second region, no changes to the morphology were present and visible UC emission was observed following exposure to both stressors. To probe the triplet sensitization process at elevated temperatures, transient absorption spectroscopy was performed. The presence of the excited spin-triplet state of rubrene at 60 °C highlighted successful triplet generation even at elevated temperatures. This work emphasizes the challenges and continued potential for the integration of perovskite-sensitized UC into commercial photovoltaic devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Unveiling the Reactivity of Fluoropolymers with Sodium Metal: Mechanistic Insights and Battery Implications

Poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) has broad applications across various metal-ion battery systems, such as a binder for electrodes, a supporting matrix for electrolytes, and a separator material. Due to its excellent mechanical properties, PVDF-HFP has become an excellent candidate for fabricating gel and solid-state electrolytes in sodium-based batteries. However, in this study, we noticed notable side reactions occurring at the interface of PVDF-HFP membranes and Na metal. These reactions not only alter chemical compositions but also further affect the surface morphology and adhesive properties of membranes. Similar phenomena are observed in other polyfluoroalkyl-based membranes (PVDF and PTFE). Therefore, we systematically studied the reaction mechanisms between the Na metal and these polymers. The influence of different functional groups (−F, −CF 3 , −H) and their arrangement on the reaction extent has also been discussed. Finally, we concluded with the key factors driving these side reactions and provided new perspectives for designing polymers tailored for sodium-based batteries.

Interfacial side reactions↗

Industrial potential, uses, and performance of sputtered and ion plated films

The sputtering and ion plating technology is reviewed in terms of their potential, uses and performance. It offers the greatest flexibility in coating preparation, since coatings can be tailored in any preferred chemical combination, and graded type interfaces (ceramic to metal seals) can be formed. Sputtered and ion plated film characteristics such as the degree of adherence, coherence and morphological growth which contribute to film performance and reliability are described and illustrated as used in practice. It is concluded that the potential future of sputtered and ion plated films for industrial applications will depend primarily upon greater comprehension of materials selection, possible elimination of restrictions for coating/substrate combinations and the awareness of utilizing the proper deposition parameters.

Spalvins, T.↗

The characterization of Mode I delamination failure in non-woven, multidirectional laminates

The uniform double cantilever beam test and SEM are presently used for the characterization of Mode I delamination behavior in fiber-reinforced epoxy laminates. Delamination failure assumes forms that depend on ply orientation, test specimen geometry, and matrix toughness, but the calculated fracture energy is noted to be heavily dependent on fracture surface morphology. A material property concept that is independent of both test specimen geometry and the orientation of the plies constituting the delaminating interface is elucidated, through the definition of interlaminar fracture solely in terms of an interlaminar separation that includes no fiber breakage or pull-out. This value, which dissipates the lowest possible amount of energy during crack growth, is the controlling factor for laminate toughness.

Chai, H.↗

Creep and fracture of dispersion-strengthened materials

The creep and fracture of dispersion strengthened materials is reviewed. A compilation of creep data on several alloys showed that the reported values of the stress exponent for creep varied between 3.5 and 100. The activation energy for creep exceeded that for lattice self diffusion in the matrix in the case of some materials and a threshold stress behavior was generally reported in these instances. The threshold stress is shown to be dependent on the interparticle spacing and it is significantly affected by the initial microstructure. The effect of particle size and the nature of the dispersoid on the threshold stress is not well understood at the present time. In general, most studies indicate that the microstructure after creep is similar to that before testing and very few dislocations are usually observed. It is shown that the stress acting on a dispersoid due to a rapidly moving dislocation can exceed the particle yield strength of the G sub p/1000, where G sub p is the shear modulus of the dispersoid. The case when the particle deforms is examined and it is suggested that the dislocation creep threshold stress of the alloy is equal to the yield strength of the dispersoid under these conditions. These results indicate that the possibility that the dispersoid creep threshold stress is determined by either the particle yield strength or the stress required to detach a dislocation from the dispersoid matrix interface. The conditions under which the threshold stress is influenced by one or the other mechanism are discussed and it is shown that the particle yield strength is important until the extent of dislocation core relaxation at the dispersoid matrix interface exceeds about 25 pct. depending on the nature of the particle matrix combination. Finally, the effect of grain boundaries and grain morphology on the creep and fracture behavior of dispersoid strengthened alloys is examined.

Raj, Sai V.↗

Novel High Efficient Organic Photovoltaic Materials: Appendix for Summary of Research

There are many different kinds of conjugated polymers that may be useful in photovoltaic devices. So far, the most popular and successful conjugated polymers used in photovoltaic devices include poly(1,4-)phenylenevinylenes (PPV), C60 and their derivatives. The discovery of electro-luminescence in PPV has stimulated a great deal of interest in developing "plastic" solid-state semiconductor devices. The overall synthetic methodology for the preparation of PPV can be divided into three main categories: (1) side chain derivatization, (2) precursor approach, and (3) in-situ polymerization. In this project, the first method was adopted. As discussed in project proposal and literatures, the overall efficiency of photovoltaic devices containing conjugated polymers is determined by the materials ability to generate excitons from incoming radiation, and then to separate the charges at donor/acceptor interfaces, and then to transport charges to respective electrodes. Given that effective exciton diffusion range are typical less then 30 nm, unique morphological structures are needed. This need led to several research groups to the idea that interpenetrating or bi-continuous networks of donor (electron donating) and acceptor (electron withdrawing) polymers should give better results. One approach involved the use of functionalized PPV. The attachment of electron withdrawing cyano groups to a PPV forms the CN-PPV, making it a strong electron acceptor. Underivatized PPV is a generally considered a hole-transporting material. Using blends of MEH-PPV, a soluble donor PPV derivative, as a hole transporter and CN-PPV as an electron transporter, a quantum efficiencies of up to 6% was achieved.

Sun, Sam↗

Survey of ion plating sources

Ion plating is a plasma deposition technique where ions of the gas and the evaporant have a decisive role in the formation of a coating in terms of adherence, coherence, and morphological growth. The range of materials that can be ion plated is predominantly determined by the selection of the evaporation source. Based on the type of evaporation source, gaseous media and mode of transport, the following will be discussed: resistance, electron beam sputtering, reactive and ion beam evaporation. Ionization efficiencies and ion energies in the glow discharge determine the percentage of atoms which are ionized under typical ion plating conditions. The plating flux consists of a small number of energetic ions and a large number of energetic neutrals. The energy distribution ranges from thermal energies up to a maximum energy of the discharge. The various reaction mechanisms which contribute to the exceptionally strong adherence - formation of a graded substrate/coating interface are not fully understood, however the controlling factors are evaluated. The influence of process variables on the nucleation and growth characteristics are illustrated in terms of morphological changes which affect the mechanical and tribological properties of the coating.

Spalvins, T.↗

Rapid Access to Diverse Multicomponent Hierarchical Nanostructures from Mixed–Graft Block Copolymers

Multicomponent nanostructured materials assembled from molecular building blocks received wide attention due to their precisely integrated multifunctionalities. However, discovery of these materials with desirable composition and morphology was limited by their low synthetic scalability and narrow structural tuning window with given building blocks. Here, we report a scalable and diversity-oriented synthetic approach to hierarchically structured nanomaterials based on a few readily accessible building blocks. Mixed-graft block copolymers containing sequence-defined side chains were prepared through ring-opening metathesis copolymerization of three or four types of macromonomers. Intramolecularly defined interfaces promoted the formation of ordered hierarchical structures with lattice sizes tunable across multiple length scales. Finally, the same set of macromonomers were arranged and combined in different ways, providing access to diverse morphologies in the resultant structures.

36 MATERIALS SCIENCE↗