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At least 1,405 records · Page 78

Redox-homogeneous, gel electrolyte-embedded high-mass-loading cathodes for high-energy lithium metal batteries

Lithium metal batteries have higher theoretical energy than their Li-ion counterparts, where graphite is used at the anode. However, one of the main stumbling blocks in developing practical Li metal batteries is the lack of cathodes with high-mass-loading capable of delivering highly reversible redox reactions. To overcome this issue, here we report an electrode structure that incorporates a UV-cured non-aqueous gel electrolyte and a cathode where the LiNi 0.8 Co 0.1 Mn 0.1 O 2 active material is contained in an electron-conductive matrix produced via simultaneous electrospinning and electrospraying. This peculiar structure prevents the solvent-drying-triggered non-uniform distribution of electrode components and shortens the time for cell aging while improving the overall redox homogeneity. Moreover, the electron-conductive matrix eliminates the use of the metal current collector. When a cathode with a mass loading of 60 mg cm -2 is coupled with a 100 µm thick Li metal electrode using additional non-aqueous fluorinated electrolyte solution in lab-scale pouch cell configuration, a specific energy and energy density of 321 Wh kg -1 and 772 Wh L -1 (based on the total mass of the cell), respectively, can be delivered in the initial cycle at 0.1 C (i.e., 1.2 mA cm -2 ) and 25 °C.

25 ENERGY STORAGE↗

Anderson localization and Brewster anomalies in photonic disordered quasiperiodic lattices

A comprehensive study of the properties of light propagation through one-dimensional photonic disordered quasiperiodic superlattices, composed of alternating layers with random thicknesses of air and a dispersive metamaterial, is theoretically performed. The superlattices consist of the successive stacking of N quasiperiodic Fibonacci or Thue-Morse heterostructures. The width of the slabs in the photonic superlattice may randomly fluctuate around its mean value, which introduces a structural disorder into the system. It is assumed that the left-handed layers have a Drude-type dispersive response for both the dielectric permittivity and magnetic permeability, and Maxwell's equations are solved for oblique incidence by using the transfer-matrix formalism. The influence of both quasiperiodicity and structural disorder on the localization length and Brewster anomalies are thoroughly discussed.

36 MATERIALS SCIENCE↗

High-Frequency Testing of Composite Fan Vanes With Erosion-Resistant Coating Conducted

The mechanical integrity of hard, erosion-resistant coatings were tested using the Structural Dynamics Laboratory at the NASA Glenn Research Center. Under the guidance of Structural Mechanics and Dynamics Branch personnel, fixturing and test procedures were developed at Glenn to simulate engine vibratory conditions on coated polymer-matrix- composite bypass vanes using a slip table in the Structural Dynamics Laboratory. Results from the high-frequency mechanical bench testing, along with concurrent erosion testing of coupons and vanes, provided sufficient confidence to engine-endurance test similarly coated vane segments. The knowledge gained from this program will be applied to the development of oxidation- and erosion-resistant coatings for polymer matrix composite blades and vanes in future advanced turbine engines. Fan bypass vanes from the AE3007 (Rolls Royce America, Indianapolis, IN) gas turbine engine were coated by Engelhard (Windsor, CT) with compliant bond coatings and hard ceramic coatings. The coatings were developed collaboratively by Glenn and Allison Advanced Development Corporation (AADC)/Rolls Royce America through research sponsored by the High-Temperature Engine Materials Technology Project (HITEMP) and the Higher Operating Temperature Propulsion Components (HOTPC) project. High-cycle fatigue was performed through high-frequency vibratory testing on a shaker table. Vane resonant frequency modes were surveyed from 50 to 3000 Hz at input loads from 1g to 55g on both uncoated production vanes and vanes with the erosion-resistant coating. Vanes were instrumented with both lightweight accelerometers and strain gauges to establish resonance, mode shape, and strain amplitudes. Two high-frequency dwell conditions were chosen to excite two strain levels: one approaching the vane's maximum allowable design strain and another near the expected maximum strain during engine operation. Six specimens were tested per dwell condition. Pretest and posttest inspections were performed optically at up to 60 magnification and using a fluorescent-dye penetrant. Accumulation of 10 million cycles at a strain amplitude of two to three times that expected in the engine (approximately 670 Hz and 20g) led to the development of multiple cracks in the coating that were only detectable using fluorescent-dye penetrant inspection. Cracks were prevalent on the trailing edge and on the convex side of the midsection. No cracking or spalling was evident using standard optical inspection at up to 60 magnification. Further inspection may reveal whether these fine cracks penetrated the coating or were strictly on the surface. The dwell condition that simulated actual engine conditions produced no obvious surface flaws even after up to 80 million cycles had been accumulated at strain amplitudes produced at approximately 1500 Hz and 45g.

Bowman, Cheryl L.↗

Structural properties of pure and Fe-doped Yb films prepared by vapor condensation

Ytterbium and iron-doped ytterbium films were prepared by vapor quenching on Kapton substrates at room temperature. Structural characterization was performed by X-ray diffraction and transmission electron microscopy. The aim was to study the microstructure of pure and iron-doped films and thereby to understand the effects induced by iron incorporation. A coexistence of face centered cubic and hexagonal close packed-like structures was observed, the cubic-type structure being the dominant contribution. There is an apparent thickness dependence of the cubic/hexagonal relative ratios in the case of pure ytterbium. Iron-clusters induce a crystalline texture effect, but do not influence the cubic/hexagonal volume fraction. A schematic model is proposed for the microstructure of un-doped and iron-doped films including the cubic- and hexagonal-like structures, as well as the iron distribution in the ytterbium matrix. - Highlights: • Pure and Fe-doped Yb films have been prepared by vapor condensation. • Coexistence of fcc- and hcp-type structures was observed. • No oxide phases have been detected. • Fe-clustering does not affect the fcc/hcp ratio, but favors a crystalline texture. • A schematic model is proposed to describe microscopically the microstructure.

36 MATERIALS SCIENCE↗

Compact representations of structured BFGS matrices

For general large-scale optimization problems compact representations exist in which recursive quasi-Newton update formulas are represented as compact matrix factorizations. For problems in which the objective function contains additional structure, recent structured quasi-Newton methods exploit available second-derivative information and approximate unavailable second derivatives. Here, this article develops the compact representations of two structured Broyden-Fletcher-Goldfarb-Shanno update formulas. The compact representations enable efficient limited memory and initialization strategies. Two limited memory line search algorithms are described for which extensive numerical results demonstrate the efficacy of the algorithms, including comparisons to IPOPT on large machine learning problems, and to L-BFGS on a real world large scale ptychographic imaging application.

97 MATHEMATICS AND COMPUTING↗

Surface characterization of carbon fiber polymer composites and aluminum alloys after laser interference structuring

Here, the increasing use of Carbon Fiber-reinforced Polymer matrix Composites (CFPC) and aluminum alloys as lightweight materials in the automotive and aerospace industries demands enhanced surface preparation and control of surface morphology prior to joining. In this study, surfaces of both composite and aluminum were prepared for joining using an Nd:YAG laser in a two-beam interference setup, enabling the (a) structuring of the AL 5182 surface, (b) removal of the resin layer on top of carbon fibers, and (c) structuring of the carbon fibers. CFPC specimens of T700S carbon fiber, Prepreg - T8 3 epoxy, 5 ply thick, 0/90o plaques were used. The effect of laser fluence, scanning speed, and number of shots-per-spot was investigated on the removal rate of the resin without an excessive damage of the fibers. Optical micrographs, 3D imaging, and scanning electron microscope (SEM) imaging were used to study the effect of the laser processing on surface morphology.

36 MATERIALS SCIENCE↗

The Influence of Modification on Crystal Lattice Stability of Austenite in Stainless Steel

Using the methods of electron diffraction microscopy and X-ray diffraction analysis, the influence of alloying of the austenitic steel, Grade 110H13, with chromium and vanadium, as well as high-melting, ultrafine-grained TiO{sub 2}, ZrO{sub 2} powders and Na{sub 3}AlF{sub 6} cryolite on its structural-phase state and microstructure is investigated. It is shown that the matrix of non-modified steel is completely austenitic and consists of an iron-based solid solution and the interstitial (C, N, O and other) and substitutional (Cr, V and other) atoms simultaneously. Alloying with chromium and vanadium changes neither its phase composition nor defect structure, while alloy modification results in qualitatively new structural features: γ → ε-transformation, high-intensity microtwinning, defect structure changes, and a sharp increase in the scalar dislocation density. The features of the deformation-induced microtwinning and ε-martensite plates identified in the modified steel promote revealing additional microtwin systems in the matrix γ-phase, which result in structural changes making it possible to classify it as a γ′-phase. It is found out that an introduction of modifying additions gives rise to the following sequence of structural-phase transformations: γ→γ′→(γ′ +ε). The experimental data obtained demonstrate that as a result of modification the crystal lattice transits into a low-stability state. This transition is accompanied by marked structural-phase changes consisting in the formation of several microtwin systems and γ → ε-transformation. These structural-phase changes in the modified steel are due to the crystal-lattice transition into the low-stability state, followed by new structural-phase alterations.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Compression panel studies for supersonic cruise vehicles

Results of analytical and experimental studies are summarized for titanium, boron fiber reinforced aluminum matrix composite, Borsic fiber reinforced aluminum matrix composite, and titanium sheathed Borsic fiber reinforced aluminum matrix composite stiffened panels. The results indicate that stiffened panels with continuous joints (i.e., brazed, diffusion bonded or adhesive bonded joints) are more structurally efficient than geometrically similar panels with discrete joints (i.e., spotwelded or bolted joints). In addition, results for various types of fiber reinforced aluminum matrix stiffened panels indicate that titanium sheathed Borsic fiber reinforced aluminum matrix composite panels are the most structurally efficient. Analytical results are also presented for graphite fiber reinforced polyimide matrix composite stiffened panels and superplastically formed and diffusion bonded titanium sandwich panels.

Mcwithey, R. R.↗

Decomposition Algorithm for Global Reachability on a Time-Varying Graph

A decomposition algorithm has been developed for global reachability analysis on a space-time grid. By exploiting the upper block-triangular structure, the planning problem is decomposed into smaller subproblems, which is much more scalable than the original approach. Recent studies have proposed the use of a hot-air (Montgolfier) balloon for possible exploration of Titan and Venus because these bodies have thick haze or cloud layers that limit the science return from an orbiter, and the atmospheres would provide enough buoyancy for balloons. One of the important questions that needs to be addressed is what surface locations the balloon can reach from an initial location, and how long it would take. This is referred to as the global reachability problem, where the paths from starting locations to all possible target locations must be computed. The balloon could be driven with its own actuation, but its actuation capability is fairly limited. It would be more efficient to take advantage of the wind field and ride the wind that is much stronger than what the actuator could produce. It is possible to pose the path planning problem as a graph search problem on a directed graph by discretizing the spacetime world and the vehicle actuation. The decomposition algorithm provides reachability analysis of a time-varying graph. Because the balloon only moves in the positive direction in time, the adjacency matrix of the graph can be represented with an upper block-triangular matrix, and this upper block-triangular structure can be exploited to decompose a large graph search problem. The new approach consumes a much smaller amount of memory, which also helps speed up the overall computation when the computing resource has a limited physical memory compared to the problem size.

Kuwata, Yoshiaki↗

Thermal conductivity and thermal expansion of graphite fiber/copper matrix composites

The high specific conductivity of graphite fiber/copper matrix (Gr/Cu) composites offers great potential for high heat flux structures operating at elevated temperatures. To determine the feasibility of applying Gr/Cu composites to high heat flux structures, composite plates were fabricated using unidirectional and cross-plied pitch-based P100 graphite fibers in a pure copper matrix. Thermal conductivity of the composites was measured from room temperature to 1073 K, and thermal expansion was measured from room temperature to 1050 K. The longitudinal thermal conductivity, parallel to the fiber direction, was comparable to pure copper. The transverse thermal conductivity, normal to the fiber direction, was less than that of pure copper and decreased with increasing fiber content. The longitudinal thermal expansion decreased with increasing fiber content. The transverse thermal expansion was greater than pure copper and nearly independent of fiber content.

Ellis, David L.↗

Thermal conductivity and thermal expansion of graphite fiber-reinforced copper matrix composites

The high specific conductivity of graphite fiber/copper matrix (Gr/Cu) composites offers great potential for high heat flux structures operating at elevated temperatures. To determine the feasibility of applying Gr/Cu composites to high heat flux structures, composite plates were fabricated using unidirectional and cross-plied pitch-based P100 graphite fibers in a pure copper matrix. Thermal conductivity of the composites was measured from room temperature to 1073 K, and thermal expansion was measured from room temperature to 1050 K. The longitudinal thermal conductivity, parallel to the fiber direction, was comparable to pure copper. The transverse thermal conductivity, normal to the fiber direction, was less than that of pure copper and decreased with increasing fiber content. The longitudinal thermal expansion decreased with increasing fiber content. The transverse thermal expansion was greater than pure copper and nearly independent of fiber content.

Ellis, David L.↗

Self-standing elastomeric composites based on lithium ferrites and their dielectric behavior

Lithium ferrite (LiFe{sub 5}O{sub 8}) is an attractive material for technological applications due to its physical properties, which are significantly dependent on the preparation method and raw materials. In this work, LiFe{sub 5}O{sub 8} crystallites were obtained by controlled heat-treatment process at 1100 °C, of a homogeneous mixture of Li{sub 2}O-Fe{sub 2}O{sub 3} powders, prepared by wet ball-milling and using lithium and iron nitrates as raw materials. The main goal was the preparation of a flexible and self-standing tick composite film by embedding lithium ferrite particles in a polymeric matrix, taking advantage of the good mechanical properties of the polymer and of the electrical and dielectric properties of the ferrite. The selected polymer matrix was styrene-b-isoprene-b-styrene copolymer. To prepare the composites, the lithium ferrite particles were chemically modified in order to functionalize their surface. To analyse the influence of the particles surface modification, different composites were made, with modified and unmodified particles. The structure of the obtained composites was studied by FTIR, XRD, TGA, and DSC techniques. The dielectric properties were analysed, in the frequency range between 10 Hz and 1 MHz and in function of temperature in the range between −73 °C and 127 °C. These properties were related with the structure and concentration of the particles in the matrix network. The composites with the modified particles present higher dielectric constant, maintaining values of loss tangent sufficiently low (<10{sup −2}) that can be considered interesting for technological applications.

36 MATERIALS SCIENCE↗

Charge storage and tunneling mechanism of Ni nanocrystals embedded HfO{sub x} film

A nano-floating gate memory structure based on Ni nanocrystals (NCs) embedded HfO{sub x} film is deposited by means of radio-frequency magnetron sputtering. Microstructure investigations reveal that self-organized Ni-NCs with diameters of 4-8 nm are well dispersed in amorphous HfO{sub x} matrix. Pt/Ni-NCs embedded HfO{sub x}/Si/Ag capacitor structures exhibit voltage-dependent capacitance-voltage hysteresis, and a maximum flat-band voltage shift of 1.5 V, corresponding to a charge storage density of 6.0 × 10{sup 12} electrons/cm{sup 2}, is achieved. These capacitor memory cells exhibit good endurance characteristic up to 4 × 10{sup 4} cycles and excellent retention performance of 10{sup 5} s, fulfilling the requirements of next generation non-volatile memory devices. Schottky tunneling is proven to be responsible for electrons tunneling in these capacitors.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Long-Term Durability of a Matrix for High-Temperature Composites Predicted

Polymer matrix composites (PMC's) are being increasingly used in applications where they are exposed for long durations to harsh environments such as elevated temperatures, moisture, oils and solvents, and thermal cycling. The exposure to these environments leads to the degradation of structures made from these materials. This also affects the useful lifetimes of these structures. Some of the more prominent aerospace applications of polymer matrix composites include engine supports and cowlings, reusable launch vehicle parts, radomes, thrust-vectoring flaps, and the thermal insulation of rocket motors. This demand has led to efforts to develop lightweight, high-strength, high-modulus materials that have upper-use temperatures over 316 C. A cooperative program involving two grants to the Massachusetts Institute of Technology and in-house work at the NASA Glenn Research Center was conducted to identify the mechanisms and the measurement of mechanical and physical properties that are necessary to formulate a mechanism-based model for predicting the lifetime of high-temperature polymer matrix composites. The polymer that was studied was PMR-15 polyimide, a leading matrix resin for use in high-temperature-resistant aerospace composite structures such as propulsion systems. The temperature range that was studied was from 125 to 316 C. The diffusion behavior of PMR-15 neat resin was characterized and modeled. Thermogravimetric analysis (TGA) was also conducted in nitrogen, oxygen, and air to provide quantitative information on thermal and oxidative degradation reactions. A new low-cost technique was developed to collect chemical degradation data for isothermal tests lasting up to 4000 hr in duration. In the temperature range studied, results indicate complex behavior that was not observed by previous TGA tests, including the presence of weight-gain reactions. These were found to be significant in the initial periods of aging from 125 to 225 C. Two types of weight loss reactions dominated at aging temperatures above 225 C. One was concentrated at the surface of the polymer and was very active at temperatures above 225 C. The second was observed to dominate in the latter stages of aging at temperatures below 260 C. This three-reaction model satisfactorily explains past findings that the degradation mechanism of PMR-15 appears to change around 316 C. It also indicates that the second weight gain mechanism is a significant factor at temperatures below 204 C. On the basis of these results, a predictive model was developed for the thermal degradation of PMR-15 at 316 C. A comparison of data generated by this model with actual experimental data is shown in the following figure.

Bowles, Kenneth J.↗

Biochemical and structural controls on the decomposition dynamics of boreal upland forest moss tissues

Mosses contribute an average of 20 % of boreal upland forest net primary productivity and are frequently observed to degrade slowly compared to vascular plants. If this is caused primarily by the chemical complexity of their tissues, moss decomposition could exhibit high temperature sensitivity (measured as Q 10 ) due to high activation energy, which would imply that soil organic carbon (SOC) stocks derived from moss remains are especially vulnerable to decomposition with warming. Alternatively, the physical structure of the moss cell-wall biochemical matrix could inhibit decomposition, resulting in low decay rates and low temperature sensitivity. We tested these hypotheses by incubating mosses collected from two boreal forests in Newfoundland, Canada, for 959 days at 5°C and 18°C, while monitoring changes in the moss tissue composition using total hydrolyzable amino acid (THAA) analysis and 13 C nuclear magnetic resonance (NMR) spectroscopy. Less than 40 % of C was respired in all incubations, revealing a large pool of apparently recalcitrant C. The decay rate of the labile fraction increased in the warmer treatment, but the total amount of C loss increased only slightly, resulting in low Q 10 values (1.23–1.33) compared to L horizon soils collected from the same forests. NMR spectra were dominated by O-alkyl C throughout the experiment, indicating the persistence of potentially labile C. The accumulation of hydroxyproline (derived primarily from plant cell-wall proteins) and aromatic C indicates the selective preservation of biochemicals associated with the moss cell wall. This was supported by scanning electron microscope (SEM) images of the moss tissues, which revealed few changes in the physical structure of the cell wall after incubation. This suggests that the moss cell-wall matrix protected labile C from microbial decomposition, accounting for the low temperature sensitivity of moss decomposition despite low decay rates. Climate drivers of moss biomass and productivity, therefore, represent a potentially important regulator of boreal forest SOC responses to climate change that needs to be assessed to improve our understanding of carbon–climate feedbacks.

54 ENVIRONMENTAL SCIENCES↗

Developing a Novel Hydrogen Sponge with Ideal Binding Energy and High Surface Area for Practical Hydrogen Storage

This Phase I (5 quarters) research project was to examine the validity of a new class of boron-containing polymer (B-polymer) frameworks, serving as the adsorbents for the practical onboard H2 storage applications. Three B-polymer frameworks were synthesized and investigated, which include B-poly(butyenylstyrene) (B-PBS) framework (A), B-poly(phenyldiacetyene) (B-PPDA) framework (B), and B-poly(phenyltriacetylene) (B-PPTA) framework (C). They are 2-D polymer structures with the repeating cyclic units that spontaneously form open morphology and the B-doped (p-type) π-electrons delocalized surfaces. The ideal B-polymer framework shall exhibit open micropores (pore size in the range of 1-1.5nm) with high surface area (>3000 m 2 /g), and the B-dopants in the conjugated framework shall provide high surface energy for interacting with H 2 molecules (an ideal H 2 binding energy in the range of 15-25 kJ/mol). The pore size distribution and H2 binding energy were investigated at both Penn State and NREL laboratories. So far, the experimental results show the successful synthesis of B-polymer frameworks with the relatively well-defined planar (2-D) structures. The intrinsically formed porous morphology exhibits a broad pore size distribution (in the range of 0.5-10 nm) with specific surface area (~1000 m 2 /g). The miss-alignment between 2-D layers may block some micropore channels and limit gas diffusion throughout the entire matrix. In addition, the 2-D planar conjugated structure may also allow free π-electrons delocalization throughout the framework, which significantly reduces the acidity of B-moieties (electron-deficiency).The resulting 2-D B-polymer frameworks only exhibit a small increase of H 2 binding energy in the range of 8-9 KJ/mole (quite constant over the whole sorption range).

08 HYDROGEN↗

Numerical simulation of effective mechanical properties of stochastic composites with consideration for structural evolution under intensive dynamic loading

Mechanical behavior of stochastic metal-ceramic composites with the aluminum matrix under high-rate deformation at shock-wave loading is numerically simulated with consideration for structural evolution. Effective values of mechanical parameters of metal-ceramic composites Al B{sub 4}C, Al SiC, and Al Al{sub 2}O{sub 3} are evaluated depending on different concentration of ceramic inclusions.

36 MATERIALS SCIENCE↗

Chitosan as a Canvas for Studies of Macromolecular Controls on CaCO 3 Biological Crystallization

A mechanistic understanding of how macromolecules, typically as an organic matrix, nucleate and grow crystals to produce functional biomineral structures remains elusive. Advances in structural biology indicate that polysaccharides (e.g., chitin) and negatively charged proteoglycans (due to carboxyl, sulfate, and phosphate groups) are ubiquitous in biocrystallization settings and play greater roles than currently recognized. This review highlights studies of CaCO 3 crystallization onto chitinous materials and demonstrates that a broader understanding of macromolecular controls on mineralization has not emerged. With recent advances in biopolymer chemistry, it is now possible to prepare chitosan-based hydrogels with tailored functional group compositions. By deploying these characterized compounds in hypothesis-based studies of nucleation rate, quantitative relationships between energy barrier to crystallization, macromolecule composition, and solvent structuring can be determined. Finally, this foundational knowledge will help researchers understand composition-structure-function controls on mineralization in living systems and tune the designs of new materials for advanced applications.

15 GEOTHERMAL ENERGY↗