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At least 649 records · Page 36

Nucleation Selectivity and Lateral Coalescence of GaAs over Graphene on Ge(111)

Here we use epitaxial lateral overgrowth (ELO) to produce semimetallic graphene nanostructures embedded in a semiconducting GaAs matrix for potential applications in plasmonics, THz generation and detection, and tunnel junctions in multijunction solar cells. We show that (1) the combination of low sticking coefficient and fast surface diffusion on graphene enhances nucleation selectivity at exposed regions of the substrate and (2) high growth temperatures favor efficient lateral overgrowth, coalescence, and planarization of epitaxial GaAs films over the graphene nanostructures. Our work provides a more complete understanding of ELO using graphene masks, as opposed to more conventional dielectric masks, and enables new types of metal/semiconductor nanocomposites.

36 MATERIALS SCIENCE↗

Synergistic CuWO 4 /NiS 2 Binary Nanostructures for Efficient Photocatalytic Hydrogen Production

A viable and ecologically safe method for producing green hydrogen is photocatalytic hydrogen (H 2 ) production. However, the development of effective semiconductor materials with improved activity and long-term stability is still a major obstacle. Here, in this work, we report the development of a broadband-gap, UV light-responsive CuWO 4 /NiS 2 nanocomposite using simple hydrothermal and wet impregnation techniques. The hybrid systems, with photocatalytic presentation, were thoroughly assessed using spectroscopic, photophysical, and microscopic characterization methods. The optimized CuWO 4 /NiS 2 nanostructure demonstrated an impressive H 2 generation rate of 28.2 mmol h –1 g –1 under light irradiation, which is roughly 2.71 and 3.28 times greater than those of pristine CuWO 4 (10.4) and NiS 2 (8.6 mmol h -1 g (cat) -1 ), respectively. The enhanced presentation is ascribed to the synergetic interface between the coupled semiconductors, which facilitates the formation of a nanostructure. This arrangement inhibits electron–hole recombination and encourages effective charge carrier parting. Additionally, compared with pristine CuWO 4 and NiS 2 , respectively, the CuWO 4 /NiS 2 composite showed a noticeably greater photocurrent density. The developed nanostructured CuWO 4 /NiS 2 displayed a 28.6% quantum efficiency at 450 nm. These outcomes validate CuWO 4 /NiS 2 ’s significant aptitude as a non-noble-metal photocatalyst for the production of sustainable hydrogen.

CuWO4/NiS2↗

Investigating Silver Nanoparticle Interactions with Quaternary Ammonium Functionalized Triblock Copolymers and Their Effect on Midblock Crystallinity

Interactions between silver nanoparticles and a cationic triblock copolymer significantly alter bulk material properties and can be tuned by functionalizing the polymer with different quaternary ammonium cations (QACs). In this work, poly-chloromethylstyrene-b-polycyclooctene-b-polychloromethylstyrene (PCMS-b-PCOE-b-PCMS) was quaternized with either methylpiperidinium (MPRD) or trimethylammonium (TMA). The surface interacting groups were identified using FT-IR to be the phenyl rings, the QACs from the outer blocks, and vinyl groups from the PCOE midblock. Changes in thermal characteristics and crystallinity were highly dependent on the QAC, uncovering differences in the nature of the interactions between silver and TMA or MPRD. Interactions induced by TMA greatly hinder crystalline domain formation and give rise to a higher water content, while MPRD promotes certain crystalline orientations and provides a greater degree of crystallinity with a lower water content. In this work, our findings demonstrate that bulk polymer characteristics can be tuned, a highly desirable attribute for many nanocomposite materials.

36 MATERIALS SCIENCE↗

Amplifying Nanoparticle Reinforcement through Low Volume Topologically Controlled Chemical Coupling

Here, we present a streamlined method to covalently bond hydroxylated carbon nanotubes (CNOH) within a polyphenol matrix, all achieved through a direct, solvent-free process. Employing an extremely small concentration of CNOH (0.01% w/w) along with topologically contrasting linkers led to a maximum of 5-fold increase in modulus and a 25% enhancement in tensile strength compared to the unaltered matrix, an order of magnitude greater reinforcement (w/w) compared to state-of-the-art melt-processed nanocomposites. Through dynamic mechanical analysis, low field solid-state nuclear magnetic resonance spectroscopy, and molecular dynamics simulations, we uncovered the profound influence of linker’s conformational degrees of freedom on the segmental dynamics and therefore the material’s properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Void-interface wetting to crossing transition owing to bubble to void transformation

Understanding cavity-interface interaction is crucial in designing high-strength, radiation-tolerant nanocomposites. In this work, bubbles near the Cu–Nb interface in Nb could be absorbed by Cu voids wetting the interface due to the high system energy difference produced by the huge pressure difference between the bubbles and voids and high mobility of bubbles, and no bubble-denuded zone forms owing to fast Brownian motion of bubbles, which keeps bubbles distributed homogeneously. However, owing to the low system energy difference generated by the low internal pressure difference and low mobility, voids near the Cu–Nb interface in Nb would simply coalesce with Cu voids wetting the interface, leading to the void-interface wetting to crossing transition and the formation of void-denuded zones due to the negligible migration of internal Nb voids.

36 MATERIALS SCIENCE↗

Correlation between the temperature evolution of the interfacial region and the growing dynamic cooperativity length scale

Here, we study experimentally the temperature evolution of the thickness of the interfacial layer, L int (T), between bulk matrices and the surface of nanoparticles in nanocomposites through broadband dielectric spectroscopy. Analyses revealed a power-law dependence between the logarithm of structural relaxation time in the interfacial layer, τ int (T), and the L int (T): ln τ i n t ( T ) / τ 0 ∝ L i n t β ( T ) / T , with τ 0 ~ 10 –12 s, and β index ~0.67 at high temperatures and ~1.7 at temperatures close to the glass transition temperature. In addition, our analysis revealed that the L int (T) is comparable to the length scale of dynamic heterogeneity estimated from previous nonlinear dielectric measurements and the four-point NMR [ξ NMR (T)], with L int (T) ~ ξ NMR (T). These observations may suggest a direct correlation between the L int (T) and the size of the cooperatively rearranging regions and have strong implications for understanding the dynamic heterogeneity and cooperativity in supercool liquids and their role in interfacial dynamics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Metal (Cu,Al)/CNT Composite Wires for Energy Efficient Motors

This report summarizes the main results of research project on Metal/CNT nanocomposites conducted at University of Central Florida (UCF). It should be noted that the project was budgeted for three years, but the budget period 3 was unfortunately not funded and conducted in COVID19 pandemic years due to many reasons. The demonstration plan on the small motors was also removed according to the discussion with the DOE program manager. All research activities were focused on the (Cu,Al)/CNT material development and wire extrusion. Existing methods to fabricate Metal/CNTs were usually suffering from agglomeration of CNTs due to their density and stiffness differences. A new method is studied by the UCF research team, where CNTs are surface treated firstly, then coated with pure metals (i.e., Al, Cu, and Nickle). The metal encapsulation on CNT is expected to significantly improve the interfacial bonding between CNTs and the intimated metal matrices. The coated CNT powders were used to make sample materials through sintering, then a customized wire extrusion process was employed to fabricate wires. Measurement of material property improvements in mechanical strength, thermal conductivity, and electrical conductivity were conducted on both cylinder samples and extruded wires. In addition to the sintering process, casting on metal coated CNT powder was also investigated. The best results we achieved are summarized as follows. (1) The measured thermal conductivity of Al/CNT composite made with Ni-encapsulated CNTs and pure Al powders is about 85% better than that of pure aluminum fabricated. The measured electrical conductivity of fabricated Al/CNT is about 14-20% better than that of pure aluminum. (2) The measured electrical conductivity of Cu/CNT is about 14.5% better than that of pure copper fabricated. (3) The mechanical strengths of both Cu/CNT and Al/CNT (with about 1% wt. CNTs) are 70% better than pure metals although losing some material ductility. (4) Two-stage wire extrusion at high temperatures were designed and successfully conducted to fabricate wires of Metal/CNTs.

36 MATERIALS SCIENCE↗

Fundamentals of Scalable Nanoparticle Assembly in Engineering Polymres

Systematically improving the properties of polymer nanocomposites is contingent on effectively controlling nanoparticle (NP) dispersion; further, it is necessary to attain this at scale if these methods are to impact practical applications. While most past work has focused on amorphous polymers, ≈ 70% of all polymers sold annually are semicrystalline. Inspired by this apparent disconnect, our work in the current DOE funded grant and this renewal proposal employs a novel handle, polymer crystallization, to organize NPs into the various amorphous zones of the lamellar semicrystalline morphology (interlamellar, interfibrillar and interspherulitic domains) of stereoregular polymers. We hypothesize that the isothermal crystallization rate of a polymer host, G, and NP diffusivity, are the two relevant control parameters in this context. In the case where the NPs are miscible in the melt, they remain spatially well-dispersed when the polymer is crystallized at a rate that is fast relative to NP diffusion. In contrast, monolayer-thick NP sheets with intersheet spacing of ~10-100nm form in slowly crystallized samples. This sheet stacking is remarkably similar to that seen in natural materials, e.g., Nacre. There is also ordering of the NPs at the larger interfibrillar scale. Importantly, the relative fraction of engulfed, interlamellar and interfibrillar NPs is determined by G. Further, the modulus of these materials can increase by a factor of 2-3 due to the organization state of the NPs, while leaving fracture toughness unaffected. We have established the broad applicability of this approach in two polymers, polyethylene (PE) and polyethyleneoxide (PEO). To achieve this goal we developed a method for grafting long PE chains from NPs with controlled graft density and molecular weight, giving us the ability to tailor their dispersion in the PE melt prior to crystallization. In this renewal proposal, we will develop the fundamental, quantitative understanding that will allow us to independently tailor polymer crystallization rate, NP diffusivity and NP agglomeration state in semicrystalline polymers so as to facilely control NP ordering and hence properties. A program that tightly integrates experiment and theory is proposed, and a key outcome of this research will be a three-dimensional design map for different regimes of NP organization (and hence properties) that can be achieved by polymer crystallization. A second independent outcome is the role of directional solidification and how it competes with the rates of polymer crystallization and NP mobility to affect the organization of the NP.

36 MATERIALS SCIENCE↗

Heterogeneous Morphologies and Hardness of Co-Sputtered Thin Films of Concentrated Cu-Mo-W Alloys

Heterogeneous microstructures in Cu-Mo-W alloy thin films formed by magnetron co-sputtering immiscible elements with concentrated compositions are characterized using scanning transmission electron microscopy (STEM) and nanoindentation. In this work, we modified the phase separated structure of a Cu-Mo immiscible system by adding W, which impedes surface diffusion during film growth. The heterogeneous microstructures in the Cu-Mo-W ternary system exhibited bicontinuous matrices and agglomerates composed of Mo(W)-rich phase. This is unique, as these are the slower-diffusing species, contrasting past reports of binary Cu-Mo thin films that exhibited Cu-rich agglomerates. The bicontinuous matrices comprised of Cu-rich and Mo(W)-rich phases exhibited bilayer thicknesses of less than 5 nm. The hardness of these thin films measured using nanoindentation is reported and compared to similar multilayers and nanocomposites in binary systems.

36 MATERIALS SCIENCE↗

Increased Tensile Strength of Carbon Nanotube Yarns and Sheets through Chemical Modification and Electron Beam Irradiation

The inherent strength of individual carbon nanotubes offers considerable opportunity for the development of advanced, lightweight composite structures. Recent work in the fabrication and application of carbon nanotube (CNT) forms such as yarns and sheets has addressed early nanocomposite limitations with respect to nanotube dispersion and loading; and has pushed the technology toward structural composite applications. However, the high tensile strength of an individual CNT has not directly translated to macro-scale CNT forms where bulk material strength is limited by inter-tube electrostatic attraction and slippage. The focus of this work was to assess post processing of CNT sheet and yarn to improve the macro-scale strength of these material forms. Both small molecule functionalization and e-beam irradiation was evaluated as a means to enhance tensile strength and Youngs modulus of the bulk CNT material. Mechanical testing results revealed a tensile strength increase in CNT sheets by 57 when functionalized, while an additional 48 increase in tensile strength was observed when functionalized sheets were irradiated; compared to unfunctionalized sheets. Similarly, small molecule functionalization increased yarn tensile strength up to 25, whereas irradiation of the functionalized yarns pushed the tensile strength to 88 beyond that of the baseline yarn.

composites↗

An Overview of Air-Breathing Propulsion Efforts for 2015 SBIR Phase I

NASA's Small Business Innovation Research (SBIR) program focuses on technological innovation by investing in development of innovative concepts and technologies to help NASA mission directorates address critical research needs for Agency programs. This report highlights 24 of the innovative SBIR 2015 Phase I projects that emphasize one of NASA Glenn Research Center's six core competencies-Air-Breathing Propulsion. The technologies cover a wide spectrum of applications such as hybrid nanocomposites for efficient aerospace structures; plasma flow control for drag reduction; physics-based aeroanalysis methods for open rotor conceptual designs; vertical lift by series hybrid power; fast pressure-sensitive paint systems for production wind tunnel testing; rugged, compact, and inexpensive airborne fiber sensor interrogators based on monolithic tunable lasers; and high sensitivity semiconductor sensor skins for multi-axis surface pressure characterization. Each featured technology describes an innovation and technical objective and highlights NASA commercial and industrial applications. This report provides an opportunity for NASA engineers, researchers, and program managers to learn how NASA SBIR technologies could help their programs and projects, and lead to collaborations and partnerships between the small SBIR companies and NASA that would benefit both.

aerospace structures↗

Additive Manufacturing of Frequency-Agile W-Band Packaging

Abstract —In this paper we demonstrate a fully additively manufactured packaged W-band amplifier with integrated bypass capacitors. This package was fabricated using a chip-first approach and aerosol jet printing. Package substrates (dielectrics), conductors and interconnects are printed around a bare die attached to a carrier. This package uses shaped ramp interconnects, allowing for frequency agnostic package performance of the interconnect with no impedance discontinuity, within the physical limits of the printer. High dielectric constant thin films of a polymer-matrix nanocomposite for bypass capacitors were printed using multi-material aerosol jet printing. The maximum measured packaged gain is 14.9 dB in the W-band, compared to the maximum bare die gain of 15.5 dB in the same frequency range. From 75 - 92 GHz, the average package loss is 1.1 dB including 3 mm transmission line, interconnects, and a GSG launch structure correlating to an average loss of 0.37 dB/mm.

Additive manufacturing, aerosol jet printing, hete↗

Biogenic Straw Aerogel Thermal Insulation Materials

Biogenic wheat straw is a carbon-storing building insulation material. However, the enzymatic hydrolysis ratio of its cellulose is relatively low due to the presence of hemicellulose and lignin hindering its thermal insulation performance. In this work, we report aerogel and straw composites with thermal conductivity of 35 mW m –1 K –1 , while high cellulose fiber conversion in straw is obtained by using a hybrid mechanical and chemical process. Furthermore, we show that the in-situ cellulose-reinforced silica aerogel nanocomposites exhibit an optimal thermal conductivity of 32 mW m –1 K –1 by using 50 wt% of aerogel. Moreover, the hydrophobic aerogel-cellulose composites show a low density, high porosity (90 %), high compression modulus (1.9 MPa), superhydrophobicity, and superior reusability. This work provides a cost-effective and facile method to manufacture biogenic composites from agriculture waste materials, promising for carbon-sequestration building insulation applications.

36 MATERIALS SCIENCE↗

Highly-Cyclable Room-Temperature Phosphorene Polymer Electrolyte Composites for Li Metal Batteries

Despite significant interest toward solid-state electrolytes owing to their superior safety in comparison to liquid-based electrolytes, sluggish ion diffusion and high interfacial resistance limit their application in durable and high-power density batteries. Here, a novel quasi-solid Li + ion conductive nanocomposite polymer electrolyte containing black phosphorous (BP) nanosheets is reported. The developed electrolyte is successfully cycled against Li metal (over 550 h cycling) at 1 mA cm -2 at room temperature. The cycling overpotential is dropped by 75% in comparison to BP-free polymer composite electrolyte indicating lower interfacial resistance at the electrode/electrolyte interfaces. Molecular dynamics simulations reveal that the coordination number of Li + ions around (trifluoromethanesulfonyl)imide (TFSI - ) pairs and ethylene-oxide chains decreases at the Li metal/electrolyte interface, which facilitates the Li + transport through the polymer host. Here, density functional theory calculations confirm that the adsorption of the LiTFSI molecules at the BP surface leads to the weakening of N and Li atomic bonding and enhances the dissociation of Li + ions. This work offers a new potential mechanism to tune the bulk and interfacial ionic conductivity of solid-state electrolytes that may lead to a new generation of lithium polymer batteries with high ionic conduction kinetics and stable long-life cycling.

2D materials↗

Interfacial-Strain-Controlled Ferroelectricity in Self-Assembled BiFeO 3 Nanostructures

Self-assembled BiFeO 3 -CoFe 2 O 4 (BFO-CFO) vertically aligned nanocomposites are promising for logic, memory, and multiferroic applications, primarily due to the tunability enabled by strain engineering at the prodigious epitaxial vertical interfaces. However, local investigations directly revealing functional properties in the vicinity of such critical interfaces are often hampered by the size, geometry, microstructure, and concomitant experimental artifacts. Ferroelectric switching in the presence of lateral distributions of vertical strain thus remains relatively unexplored, with broader implications for all strain-engineered functional devices. Additionally, by implementing tomographic atomic force microscopy, 3D domain orientation mapping, and spatially-resolved ferroelectric switching movies, local tensile strain significantly impacts the ferroelectric switching, principally by retarding domain nucleation in the BFO nearest to the vertically epitaxial tensile-strained interfaces. The relaxed centers of the BFO pillars become preferred domain nucleation and growth sites for low biases, with up to an order of magnitude change in the edge:center switching ratio for high biases. The new, multi-dimensional imaging approach—and its corresponding insights especially for directly strained interface effects on local properties—thereby advances the fundamental understanding of polarization switching and provides design principles for optimizing functional response in confined nanoferroic systems.

36 MATERIALS SCIENCE↗