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At least 1,099 records · Page 61

Giant nonlinear optical responses from photon-avalanching nanoparticles

Avalanche phenomena use steeply nonlinear dynamics to generate disproportionately large responses from small perturbations, and are found in a multitude of events and materials. Photon avalanching enables technologies such as optical phase-conjugate imaging, infrared quantum counting and efficient upconverted lasing. However, the photon-avalanching mechanism underlying these optical applications has been observed only in bulk materials and aggregates, limiting its utility and impact. In this study we report the realization of photon avalanching at room temperature in single nanostructures-small, Tm 3+ -doped upconverting nanocrystals-and demonstrate their use in super-resolution imaging in near-infrared spectral windows of maximal biological transparency. Avalanching nanoparticles (ANPs) can be pumped by continuous-wave lasers, and exhibit all of the defining features of photon avalanching, including clear excitation-power thresholds, exceptionally long rise time at threshold, and a dominant excited-state absorption that is more than 10,000 times larger than ground-state absorption. Beyond the avalanching threshold, ANP emission scales nonlinearly with the 26th power of the pump intensity, owing to induced positive optical feedback in each nanocrystal. This enables the experimental realization of photon-avalanche single-beam super-resolution imaging with sub-70-nanometre spatial resolution, achieved by using only simple scanning confocal microscopy and without any computational analysis. Pairing their steep nonlinearity with existing super-resolution techniques and computational methods, ANPs enable imaging with higher resolution and at excitation intensities about 100 times lower than other probes. The low photon-avalanching threshold and excellent photostability of ANPs also suggest their utility in a diverse array of applications, including sub-wavelength imaging and optical and environmental sensing.

36 MATERIALS SCIENCE↗

Ionic Liquids as Additives to Polystyrene- Block -Poly(Methyl Methacrylate) Enabling Directed Self-Assembly of Patterns with Sub-10 nm Features

Polystyrene- block -poly(methyl methacrylate) (PS- b -PMMA) is one of the prototypical block copolymers in directed self-assembly (DSA) research and development, with standardized protocols in place for processing on industrially relevant 300 mm wafers. Scaling of DSA patterns to pitches below 20 nm using PS- b -PMMA, however, is hindered by the relatively low Flory–Huggins interaction parameter, $χ$. In this work, we investigate the approach of adding small amounts of ionic liquids (ILs) into PS- b -PMMA, which selectively segregates into the PMMA domain and effectively increases the $χ$ parameter and thus the pattern resolution. The amount of IL additive is small enough to result in limited changes in PS- b -PMMA’s surface and interfacial properties, thus maintaining industry-friendly processing by thermal annealing with a free surface. Three different ILs are studied comparatively regarding their compositional process window, capability of increasing $χ$, and thermal stability. By adding ~3.1 vol % of the champion IL into a low-molecular-weight PS- b -PMMA ( M n = 10.3k- b -9.5k), we demonstrated DSA on chemically patterned substrates of lamellar structures with feature sizes <8.5 nm. Compatibility of the PS- b -PMMMA/IL blends with the standardized processes that have been previously developed suggests that such blend materials could provide a drop-in solution for sub-10 nm lithography with the processing advantages of PS- b -PMMA.

36 MATERIALS SCIENCE↗

Electrochemical measurement and analysis of YCl 3 , ScCl 3 , GdCl 3 and MgCl 2 in molten eutectic LiCl-KCl

For this work, electrochemical measurements of YCl 3 , ScCl 3 , GdCl 3 and MgCl 2 were obtained in molten LiCl-KCl eutectic at 773 K using a three-electrode configuration. Tungsten rods were used as the working and counter electrodes. Two quasi- and one reference electrode(s) (glassy carbon, nickel wire, and Ni/NiO) were used to collect electrochemical measurements of the analyte salts. Cyclic voltammetry data were analyzed to calculate values of diffusion coefficient, exchange current density, and charge transfer resistance and were determined to be on the order of 10 –5 cm 2 s –1 , 10 –2 A cm –2 , and 10 0 Ω; respectively. In general, the values of diffusion coefficients were found to be consistent with those reported of high-temperature molten salts. Relatively large values of exchange current density corresponded with smaller values of charge transfer resistance. These values were found to be reasonable in comparison to results available in the literature. The measured cyclic voltammograms were normalized with respect to both lithium reduction and chloride ion oxidation potentials. Such a normalization technique is effective for comparing experimentally obtained cyclic voltammetry data to those that have been published. An analysis of experimentally obtained results indicates the relation of electrode reactions (e.g., differences of reduction potentials) are independent of the choice of reference electrode. Additionally, the choice of reference electrode did not affect the electrochemical window, exchange current density, or diffusion coefficient values.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Double-Layer Morphologies from a Silicon-Containing ABA Triblock Copolymer

A combined experimental and self-consistent-field theoretical (SCFT) investigation of the phase behavior of poly(stryrene-b-dimethylsiloxane-b-styrene) (PS-b-PDMS-b-PS, or SDS32) thin films during solvent vapor annealing is presented. The morphology of the triblock copolymer is described as a function of the as-cast film thickness and the ratio of two different solvent vapors, toluene and heptane. SDS32 formed terraced bilayer morphologies even when the film thickness was much lower than the commensurate thickness. The morphology transitioned between bilayer cylinders, bilayer perforated lamellae, and bilayer lamellae, including mixed structures such as a perforated lamella on top of a layer of in-plane cylinders, as the heptane fraction during solvent annealing increased. SCFT modeling showed the same morphological trends as a function of the block volume fraction. In comparison with diblock PS-b-PDMS with the same molecular weight, the SDS32 offers a simple route to produce a diversity of well-ordered bilayer structures with smaller feature sizes, including the formation of bilayer perforated lamellae over a large process window.

36 MATERIALS SCIENCE↗

A processing diagram for high-density Ti-6Al-4V by selective laser melting

Density optimization is the first critical step in building additively manufactured parts with highquality and good mechanical properties. In earlier work, we developed an approach that combines simulations and experiments to identify processing parameters for high-density parts. Here we present the results for Ti-6Al-4V using the laser powder-bed-fusion technique. We show how simple, but approximate, simulations are used to design parameters for a limited set of single track experiments. The resulting melt-pool characteristics are then used to identify processing parameters for high-density pillars. From these experimental data, a processing diagram based on the normalized energy density concept is constructed, illustrating an optimized processing window for high- or low-density samples. Excellent mechanical properties are obtained for Ti-6Al-4V samples built from the optimized window. We discuss the limitations and implications of the processing diagram on the microstructure and mechanical properties.

36 MATERIALS SCIENCE↗

Materials for Energy Management across the Electromagnetic Spectrum (MEMES) (LDRD Report)

Electrification of the United States has been a major driver of economic growth, powering industrialization, modern manufacturing, and the digital economy. Today, further economic and environmental benefits can be realized by improving the energy efficiency of the technologies we have come to rely on. This project focused on enhancing the energy efficiency of two cornerstone technologies of modern society: electronic displays and building climatization. While these two technologies operate in different parts of the electromagnetic spectrum (the visible and infrared, respectively), they share a common potential technological solution: electrically-driven displays that change reflectivity. In this work, we developed the first multipixel multicolor reflective display that achieves multi-colorization with fast-changing structural color. In the course of this demonstration, we quantified the structural changes that occur across different time and length scales and resolved device sealing issues, enabling operation of these devices over months (as opposed to days previously). We furthermore developed two reflectivity changing devices in the infrared and demonstrated how these technologies can be used to reduce climatization demands for both smart window and smart wall technologies. Implementing such a device in a scaled down mock room resulted in 10 degree Celsius change.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Disintegration of Meatball Electrodes for LiNi x Mn y Co z O 2 Cathode Materials

Mechanical degradation of Li-ion batteries caused by the repetitive swelling and shrinking of electrodes upon electrochemical cycles is now well recognized. Structural disintegration of the state-of-art cathode materials of a hierarchical structure is relatively less studied. In this paper, we track the microstructural evolution of different marked regimes in LiNi x Mn y Co z O 2 (NMC) electrodes after lithiation cycles. Decohesion of primary particles constitutes the major mechanical degradation in the NMC materials, which results in the loss of connectivity of the conductive network and impedance increase. We find that the structural disintegration is largely dependent on the charging rate – slow charging causes more damage, and is relatively insensitive to the cyclic voltage window. We use finite element modeling to study the evolution of Li concentration and stresses in a NMC secondary particle and employ the cohesive zone model to simulate the interfacial fracture between primary particles. Finally, we reveal that microcracks accumulate and propagate during the cyclic lithiation and delithiation at a slow charging rate.

25 ENERGY STORAGE↗

A miniature multi-anvil apparatus using diamond as anvils—MDAC: Multi-axis diamond anvil cell

The diamond anvil cell (DAC) has been widely used in high-pressure research. Despite significant progress over the past five decades, the opposed anvil geometry in the DAC inevitably leads to a disk-shaped sample configuration at high pressure. This intrinsic limitation is largely responsible for the large pressure and temperature gradients in the DAC, which often compromise precise experiments and their characterizations. Here, we designed and fabricated a multi-axis diamond anvil cell (MDAC) by adopting the concept of a multi-anvil apparatus but using single crystal diamonds as the anvil material. Preliminary data show that the MDAC can generate extreme pressure conditions above 100 GPa. The advantages of the MDAC over a traditional opposed anvil DAC include thicker, voluminous samples, quasi-hydrostatic, or designed deviatoric stress conditions, and multidirectional access windows for optical applications and x-ray probes. In this article, we present the design and performance of a prototype MDAC, as well as the application prospects in high-pressure research.

47 OTHER INSTRUMENTATION↗

Reconnaissance of marine resources

A test area along the NW Coast of Africa was used during the Skylab mission to study the distribution of temperature and plankton. The S190B Earth Terrain Camera with a spectral film response of 0.4-0.7 micrometers allowed qualitative estimates of the distribution patterns of suspended material. Differentiation between inorganic particles and phytoplankton could be made by comparing the green band and the red band of the S190A Camera System. The pictorial display of data obtained from the S191 scanning radiometer in the 10-11 micrometer atmospheric window allowed a detailed interpretation of the temperature distribution in the area where cold upwelled water reaches the euphotic zone. The comparison between infrared data and the imageries taken simultaneously indicated the origin of the cold water as well as the pathway within the Canary current. A fish survey carried out almost simultaneously in the area, by echosounding, showed high correlation between the position of good fishing grounds and the distribution of plankton as detected by remote sensing detectors on Skylab.

Szekielda, K.-H.↗

Tough, processable simultaneous semi-interpenetrating polyimides

A high temperature semi-interpenetrating polymer network (semi-IPN) was developed which had significantly improved processability, damage tolerance, and mechanical performance when compared to the commercial Thermid materials. This simultaneous semi-IPN was prepared by mixing a thermosetting polyimide with a thermoplastic monomer precursor solution (NR150B2) and allowing them to react upon heating. This reaction occurs at a rate which decreases the flow and broadens the processing window. Upon heating at a higher temperature, there is an increase in flow. Because of the improved flow properties, broadened processing window and enhanced toughness, high strength polymer matrix composites, adhesives and molded articles can now be prepared from the acetylene endcapped polyimides which were previously inherently brittle and difficult to process.

Pater, Ruth H.↗

Very Large Area/Volume Microwave ECR Plasma and Ion Source

The present invention is an apparatus and method for producing very large area and large volume plasmas. The invention utilizes electron cyclotron resonances in conjunction with permanent magnets to produce dense, uniform plasmas for long life ion thruster applications or for plasma processing applications such as etching, deposition, ion milling and ion implantation. The large area source is at least five times larger than the 12-inch wafers being processed to date. Its rectangular shape makes it easier to accommodate to materials processing than sources that are circular in shape. The source itself represents the largest ECR ion source built to date. It is electrodeless and does not utilize electromagnets to generate the ECR magnetic circuit, nor does it make use of windows.

Foster, John E.↗

Automatic mesh adaptivity for CADIS and FW-CADIS neutronics modeling of difficult shielding problems

The CADIS and FW-CADIS hybrid Monte Carlo/deterministic techniques dramatically increase the efficiency of neutronics modeling, but their use in the accurate design analysis of very large and geometrically complex nuclear systems has been limited by the large number of processors and memory requirements for their preliminary deterministic calculations and final Monte Carlo calculation. Three mesh adaptivity algorithms were developed to reduce the memory requirements of CADIS and FW-CADIS without sacrificing their efficiency improvement. First, a macro-material approach enhances the fidelity of the deterministic models without changing the mesh. Second, a deterministic mesh refinement algorithm generates meshes that capture as much geometric detail as possible without exceeding a specified maximum number of mesh elements. Finally, a weight window coarsening algorithm de-couples the weight window mesh and energy bins from the mesh and energy group structure of the deterministic calculations in order to remove the memory constraint of the weight window map from the deterministic mesh resolution. The three algorithms were used to enhance an FW-CADIS calculation of the prompt dose rate throughout the ITER experimental facility. Using these algorithms resulted in a 23.3% increase in the number of mesh tally elements in which the dose rates were calculated in a 10-day Monte Carlo calculation and, additionally, increased the efficiency of the Monte Carlo simulation by a factor of at least 3.4. The three algorithms enabled this difficult calculation to be accurately solved using an FW-CADIS simulation on a regular computer cluster, obviating the need for a world-class super computer. (authors)

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Space Weathering in the Fine Size Fractions of Lunar Soils: Soil Maturity Effects

The effects of space weathering on the optical properties of lunar materials have been well documented. These effects include a reddened continuum slope, lowered albedo, and attenuated absorption features in reflectance spectra of lunar soils as compared to finely comminuted rocks from the same Apollo sites. However, the regolith processes that cause these effects are not well known, nor is the petrographic setting of the products of these processes fully understood. A Lunar Soil Characterization Consortium has been formed with the purpose of systematically integrating chemical and mineralogical data with the optical properties of lunar soils. Understanding space-weathering effects is critical in order to fully integrate the lunar sample collection with remotely-sensed data from recent robotic missions (e.g., Lunar Prospector, Clementine, and Galileo) We have shown that depositional processes (condensation of impact-derived vapors, sputter deposits, accreted impact material, e.g., splash glass, spherules, etc.) are a major factor in the modification of the optical surfaces of lunar regolith materials. In mature soils, it is the size and distribution of the nanophase metal in the soil grains that has the major effect on optical properties. In this report, we compare and contrast the space-weathering effects in an immature and a mature soil with similar elemental compositions. For this study, we analyzed <10 micron sieve fractions of two Apollo 17 soils, 79221 (mature, Is/FeO = 81) and 71061 (immature, Is/FeO = 14). Details of the sieving procedures and allocation scheme are given else where. The results of other detailed chemical, mineralogical, and spectroscopic analyses of these soil samples are reported elsewhere. A representative sample of each soil was embedded in low-viscosity epoxy, and thin sections (about 70nm thick) were obtained through ultra microtomy. The thin sections used for these analyses typically contained cross sections of up to 500 individual grains. The thin sections were studied using a JEOL 2010 transmission electron microscope (TEM) equipped with a thin window energy-dispersive X-ray (EDX) spectrometer. An individual thin section was selected from each soil, and for each grain in the section we determined (1) the elemental composition by EDX; (2) whether the grain was crystalline or glassy using electron diffraction and darkfield imaging; (3) the presence or absence of rims and accreted material; and (4) the distribution of nanophase Fe where present. Most of the categories are self-evident; however, we divide the agglutinate derived material into agglutinitic glass (glass with approximately the same composition as the bulk soil that contains nanophase Fe with or without vesicles) and agglutinate fragments, which are composed of crystalline grains and agglutinitic glass. Lithic fragments are defined as polymineralic grains with no glass. Pyroxene grains have been divided into high- and low-Ca groups. As expected, there are a number of differences in the petrography of the <10-microns fractions of 79221 and 71061 given the great difference in their respective maturities, but we focus here on two major distinctions: agglutinate content and the number of grains with micropatina. Slightly over 50% of the particles in 79221 consist of agglutinitic glass and agglutinate fragments, while the remainder are predominantly crystalline mineral grains. The agglutinic glass particles contain abundant nanophase Fe and vesicles. Angular particles are rare, with most showing smooth, rounded exteriors, Of the mineral grains analyzed thus far, over 90% of the grains have amorphous rims that contain nanophase Fe (these rims are believed to have formed by vapor deposition and irradiation effects). The nanophase Fe in these rims probably accounts for a significant fraction of the increase in Is/FeO measured in these size fractions. In addition to the rims, the majority of particles also show abundant accreted material in the form of glass splashes and spherules that also contain nanophase Fe. In stark contrast, the surfaces of the mineral grains in the 71061 sample are relatively prisitine, as only about 14% of the mineral grains in the sample exhibited amorphous rims. Furthermore, the mineral particles are more angular and show greater surface roughness than in the mature sample. Accreted material on particle surfaces is rare. Agglutinitic material is a major component of the 71061 sample; however, nanophase Fe and vesicles are not as well developed as in the 79221 sample. It is now recognized that nanophase Fe is probably the main agent in modifying the optical properties of lunar soil grains. The most important result of this study is the observation that in the fine size fractions of mature soils, nearly every grain has nanophase Fe within 100 run of the particle surface. (Additional Information contained in original)

Keller, L. P.↗

Developing a Scalable System for Biorecovery of Critical Materials from Industrial Waste with Gluconobacter Oxydans

Organic acid production by Gluconobacter oxydans has been proposed as part of a potential economical and environmentally friendly heterotrophic bioleaching process for recovery of rare earth elements from industrial waste. To provide organic acids in a quantity and at a rate useful for commercial bioleaching, continuous culture of the acid-producing organism will be necessary. The objective of this research project was to determine optimal conditions for continuous cultivation of G. oxydans for production of organic acids. Cultures were subjected to dilution rates ranging from .05 hr -1 to .38 hr -1 to determine the optimum conditions for production of lixiviant agents. Previous studies have identified methods for maximizing production of gluconic acid and 2,5-diketogluconic acid from G. oxydans , yet the utilization of these and other unidentified G. oxydans metabolites for leaching of rare earth metals is largely unexplored. Continuous cultures exhibited sustained organic acid production for at least 110 hours, while batch fermentations showed slowed growth rates after 16 hours. Several parameters, namely optical density, dissolved oxygen, organic acid concentration and pH, were monitored to characterize the steady state conditions of the fermentation process. The observed trend was increasing acidity with decreasing dilution rates, as the lowest dilution rate of 0.05 hr -1 yielded the highest gluconic acid concentration of 176 mM and lowest pH of 2.20. Trace amounts of 2,5-diketogluconic acid were detected only at the 0.05 hr-1 dilution rate, likely because the pH of the bioreactors was not maintained within the window for gluconate dehydrogenase activity [Silberbach, M., et al., Appl Microbiol Biotechnol, 2003. 62(1): p. 92-8].

60 APPLIED LIFE SCIENCES↗

Operating Hardware Impact on the Heat Transfer Properties of Windows

Despite significant advancements in fenestration technology in the last two decades, the thermal transmittance of fenestration products is still significantly higher than that of walls. This corresponds to 60% of the total energy loss of a modern building envelope through the windows. Hence, further development and improvements of fenestration products are necessary. Increasingly stringent codes and standards for fenestration stimulate industry to work on improved solutions. Thus, it is crucial that assessment techniques are able to account for innovations accurately. The thermal effects of non-continuous hardware in window frames are currently ignored by international rating procedures. A preliminary investigation conducted by our team showed significant performance degradation in two of the three out-opening casement profiles caused by the presence of operating hardware. Frames with the structure made of vinyl and fiberglass consist of many air cavities that are penetrated by operating hardware made of highly conductive materials. In these frames, in order to have an accurate assessment, it may be required to employ three-dimensional modeling due to the convective nature of heat transfer within the cavities. However, in this study, we demonstrate that the three-dimensional (3D) effects of non-continuous hardware can be approximated accurately with simpler two-dimensional (2D) simulations. We then develop a simplified model based on weighted average capable of replacing the time- and computation-intensive 3D simulations with 2D simulations and validate it against market available frames and their corresponding hardware. Validation results show that our approximation technique results in discrepancies lower than 0.05 W/(m2K), or 3% of the total thermal transmittance. Thus, we conclude that simplified 2D simulation models may be used for predicting hardware impact in window frames with reasonable accuracy. As windows and glazing structures are becoming ever better thermally insulated, it is becoming even more important to be able to model the impact of the operating hardware on the total thermal performance in order to design the best windows possible and not let the operating hardware ruin an otherwise well-proven design, which is hence addressed in this study.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Dynamic mode decomposition of nonequilibrium electron-phonon dynamics: accelerating the first-principles real-time Boltzmann equation

Abstract Nonequilibrium dynamics governed by electron–phonon ( e -ph) interactions plays a key role in electronic devices and spectroscopies and is central to understanding electronic excitations in materials. The real-time Boltzmann transport equation (rt-BTE) with collision processes computed from first principles can describe the coupled dynamics of electrons and atomic vibrations (phonons). Yet, a bottleneck of these simulations is the calculation of e –ph scattering integrals on dense momentum grids at each time step. Here we show a data-driven approach based on dynamic mode decomposition (DMD) that can accelerate the time propagation of the rt-BTE and identify dominant electronic processes. We apply this approach to two case studies, high-field charge transport and ultrafast excited electron relaxation. In both cases, simulating only a short time window of ~10% of the dynamics suffices to predict the dynamics from initial excitation to steady state using DMD extrapolation. Analysis of the momentum-space modes extracted from DMD sheds light on the microscopic mechanisms governing electron relaxation to a steady state or equilibrium. The combination of accuracy and efficiency makes our DMD-based method a valuable tool for investigating ultrafast dynamics in a wide range of materials.

36 MATERIALS SCIENCE↗

Polarized near-infrared intersubband absorptions in CdSe colloidal quantum wells

Colloidal quantum wells are two-dimensional materials grown with atomically-precise thickness that dictates their electronic structure. Although intersubband absorption in epitaxial quantum wells is well-known, analogous observations in non-epitaxial two-dimensional materials are sparse. Here in this paper, we show that CdSe nanoplatelet quantum wells have narrow (30–200 meV), polarized intersubband absorption features when photoexcited or under applied bias, which can be tuned by thickness across the near-infrared (NIR) spectral window (900–1600 nm) inclusive of important telecommunications wavelengths. By examination of the optical absorption and polarization-resolved measurements, the NIR absorptions are assigned to electron intersubband transitions. Under photoexcitation, the intersubband features display hot carrier and Auger recombination effects similar to excitonic absorptions. Sequenced two-color photoexcitation permits the sub-picosecond modulation of the carrier temperature in such colloidal quantum wells. This work suggests that colloidal quantum wells may be promising building blocks for NIR technologies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗