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At least 235 records · Page 13

Programming Function via Soft Materials (PFvSM) (Final Report)

The PFvSM cluster at the University of Illinois greatly deepened the science of soft materials and expanded the means for embedding within them unprecedented functionalities. We pioneered a mesoscopic approach to materials design that combined leading competencies in fundamental experimental and theoretical soft matter science and fabrication that powerfully establishes equilibrium and nonequilibrium assembly of novel and complex building blocks as a preeminent contributor to progress in materials chemistry. Our cluster’s vision was an integrated program of work centered on soft matter science with the ultimate goal of impacting important energy technologies. As elementary units we employed function-encoded colloids, nanoparticles, large mesh fibrillar gels, deterministically fabricated networks and hybrid objects. These materials were employed as building blocks for diverse model systems that allowed fundamental soft matter principles of wide relevance to be established. Their assembly into materials with useful functional behavior provided new approaches to challenging problems in basic energy science including energy harvesting, transport and storage. To achieve these goals the cluster brought together a team of recognized world-leaders in materials synthesis and processing, in-situ characterization, theory and modeling, and materials design, integration and fabrication

36 MATERIALS SCIENCE↗

Ferroelectric Emission Cathodes for Low-Power Electric Propulsion

Low- or no-flow electron emitters are required for low-power electric thrusters, spacecraft plasma contactors, and electrodynamic tether systems to reduce or eliminate the need for propellant/expellant. Expellant-less neutralizers can improve the viability of very low-power colloid thrusters, field emission electric propulsion devices, ion engines, Hall thrusters, and gridded vacuum arc thrusters. The NASA Glenn Research Center (GRC) is evaluating ferroelectric emission (FEE) cathodes as zero expellant flow rate cathode sources for the applications listed above. At GRC, low voltage (100s to approx. 1500 V) operation of FEE cathodes is examined. Initial experiments, with unipolar, bipolar, and RF burst applied voltage, have produced current pulses 250 to 1000 ns in duration with peak currents of up to 2 A at voltages at or below 1500 V. In particular, FEE cathodes driven by RF burst voltages from 1400 to 2000 V peak to peak, at burst frequencies from 70 to 400 kHz, emitted average current densities from 0.1 to 0.7 A/sq cm. Pulse repeatability as a function of input voltage has been initially established. Reliable emission has been achieved in air background at pressures as high as 10(exp -6) Torr.

Kovaleski, Scott D.↗

Exploratory study of several advanced nuclear-MHD power plant systems.

In order for efficient multimegawatt closed cycle nuclear-MHD systems to become practical, long-life gas cooled reactors with exit temperatures of about 2500 K or higher must be developed. Four types of nuclear reactors which have the potential of achieving this goal are the NERVA-type solid core reactor, the colloid core (rotating fluidized bed) reactor, the 'light bulb' gas core reactor, and the 'coaxial flow' gas core reactor. Research programs aimed at developing these reactors have progressed rapidly in recent years so that prototype power reactors could be operating by 1980. Three types of power plant systems which use these reactors have been analyzed to determine the operating characteristics, critical parameters and performance of these power plants. Overall thermal efficiencies as high as 80% are projected, using an MHD turbine-compressor cycle with steam bottoming, and slightly lower efficiencies are projected for an MHD motor-compressor cycle.

Williams, J. R.↗

The Space Technology-7 Disturbance Reduction Systems

The Space Technology 7 Disturbance Reduction System (DRS) is an in-space technology demonstration designed to validate technologies that are required for future missions such as the Laser Interferometer Space Antenna (LISA) and the Micro-Arcsecond X-ray Imaging Mission (MAXIM). The primary sensors that will be used by DRS are two Gravitational Reference Sensors (GRSs) being developed by Stanford University. DRS will control the spacecraft so that it flies about one of the freely-floating Gravitational Reference Sensor test masses, keeping it centered within its housing. The other GRS serves as a cross-reference for the first as well as being used as a reference for .the spacecraft s attitude control. Colloidal MicroNewton Thrusters being developed by the Busek Co. will be used to control the spacecraft's position and attitude using a six degree-of-freedom Dynamic Control System being developed by Goddard Space Flight Center. A laser interferometer being built by the Jet Propulsion Laboratory will be used to help validate the results of the experiment. The DRS will be launched in 2008 on the European Space Agency (ESA) LISA Pathfinder spacecraft along with a similar ESA experiment, the LISA Test Package.

ODonnell, James R., Jr.↗

Accelerated annealing of colloidal crystal monolayers by means of cyclically applied electric fields

Abstract External fields are commonly applied to accelerate colloidal crystallization; however, accelerated self-assembly kinetics can negatively impact the quality of crystal structures. We show that cyclically applied electric fields can produce high quality colloidal crystals by annealing local disorder. We find that the optimal off-duration for maximum annealing is approximately one-half of the characteristic melting half lifetime of the crystalline phase. Local six-fold bond orientational order grows more rapidly than global scattering peaks, indicating that local restructuring leads global annealing. Molecular dynamics simulations of cyclically activated systems show that the ratio of optimal off-duration for maximum annealing and crystal melting time is insensitive to particle interaction details. This research provides a quantitative relationship describing how the cyclic application of fields produces high quality colloidal crystals by cycling at the fundamental time scale for local defect rearrangements; such understanding of dynamics and kinetics can be applied for reconfigurable colloidal assembly.

36 MATERIALS SCIENCE↗

Low thrust propulsion system effects on communication satellites.

Choice of type and placement of thrusters on spacecraft (s/c) should include consideration of their effects on other subsystems. Models are presented of the exhaust plumes of mercury, cesium, colloid, hydrazine, ammonia, and Teflon rockets. Effects arising from plume impingement on s/c surfaces, radio frequency interference, optical interference, and earth environmental contamination are discussed. Some constraints arise in the placement of mercury, cesium, and Teflon thrusters. Few problems exist with other thruster types, nor is earth contamination a problem.

Hall, D. F.↗

System with buffer for lateral flow on a porous membrane

Systems are described, based on a primary binding compound and a secondary binding compound used in combination with a support to detect a target in a sample. The systems includes at least one support structure, at least one small primary support portion containing at least one molecule covalently bound to a visual colloidal marker, a plurality of secondary support portions comprising secondary binding compounds that are covalently bound to the support portions and chemically active, at least one pH litmus indicator, at least one pH strip, a buffer for lateral flow on the porous membrane support that allows preservation and activity of binding compounds.

Bearinger, Jane P.↗

Electrical Switching of Nematic Plasmonic Nanocolloids for Infrared Solar Gain Control

Controlling solar gain is essential to reduce the energy consumption by residential and commercial buildings, which are responsible for ≈40% of all energy generated globally. However, the dynamic control of solar gain in the near-infrared that corresponds to ≈50% of the overall Sun's energy at the Earth's surface, separately from the visible spectral range has been a challenge, albeit commercial coatings provide passive control while retaining highly visible transmission. To address this problem, in this paper switchable silver colloids (SSCs) are demonstrated, colloidal analogs of the common silver coatings used for solar gain control. When dispersed in a nematic liquid crystal, orientations of such plasmonic silver nanoplates are controlled by ≈1 V low-voltage electric fields, allowing for sub-second switching of the near-infrared-based solar gain. Installed and retrofit products made from thin films of such nanoplate dispersions confined between glass and plastic substrates, respectively, exhibit electrically controlled infrared-based solar gain while retaining high visible-range transparency, low haze, and high color rendering index. Furthermore, this study's findings reveal a great potential of soft-matter systems in addressing energy-related problems.

36 MATERIALS SCIENCE↗

Applying colloidal silica suspensions injection and sequential gelation to block vertical water flow in well annulus: laboratory testing on rheology, gelation, and injection

We evaluated the application of silica suspension injection and sequential gelation to block vertical water flow in the annuli of long-screened wells. First, we studied the viscosity, rheological behavior, and gelation performance of colloidal silica suspensions in batch tests. Then, we tested the injection of silica suspensions and the water flow blocking efficiency of the later formed silica gel in column and bench-scale sandbox experiments. Micron-sized fumed powder silica suspensions and nanosized silica suspensions recovered from geothermal fluids were tested in this work. Fumed silica suspensions showed shear thinning, while nanosized silica suspensions exhibited Newtonian flow behavior. During the gelation process, the nanosized silica suspension changed from a Newtonian fluid to a shear thinning fluid while increasing its overall viscosity. At comparable concentrations, the nanosized silica suspensions have much lower viscosity than that of the fumed silica suspensions. Increases in the Na + concentration and silica particle concentration in these suspensions shortened the gelation time. Silica suspension gelation in sand columns completely blocked the water flow and sustained the injection pressure up to 50 psig (344.7 kPa). A silica suspension was successfully injected into the target zone in the annulus of a bench-scale sandbox mimicking long-screened wells in the field. The silica gel formed in the annulus effectively blocked chemical transport through the gelled zone. Our research reveals that a process using silica suspension injection and sequential gelation technology is promising for blocking the vertical water flow and chemical transport through the filter pack in targeted zones within the annulus of long-screened well systems.

54 ENVIRONMENTAL SCIENCES↗

Nonadditive Interactions Unlock Small-Particle Mobility in Binary Colloidal Monolayers

We examine the organization and dynamics of binary colloidal monolayers composed of micron-scale silica particles interspersed with smaller-diameter silica particles that serve as minority component impurities. These binary monolayers are prepared at the surface of ionic liquid droplets over a range of size ratios (σ = 0.16–0.66) and are studied with low-dose minimally perturbative scanning electron microscopy (SEM). The high resolution of SEM imaging provides direct tracking of all particle coordinates over time, enabling a complete description of the microscopic state. In these bidisperse size mixtures, particle interactions are nonadditive because interfacial pinning to the droplet surface causes the equators of differently sized particles to lie in separate planes. By varying the size ratio, we control the extent of nonadditivity in order to achieve phase behavior inaccessible to additive 2D systems. Across the range of size ratios, we tune the system from a mobile small-particle phase (σ < 0.24) to an interstitial solid (0.24 < σ < 0.33) and furthermore to a disordered glass (σ > 0.33). These distinct phase regimes are classified through measurements of hexagonal ordering of the large-particle host lattice and the lattice’s capacity for small-particle transport. Altogether, we explain these structural and dynamic trends by considering the combined influence of interparticle interactions and the colloidal packing geometry. Our measurements are reproduced in molecular dynamics simulations of 2D nonadditive disks, suggesting an efficient method for describing confined systems with reduced dimensionality representations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Selective Catalytic Behavior Induced by Crystal–Phase Transformation in Well–Defined Bimetallic Pt–Sn Nanocrystals

The Pt-Sn bimetallic system is a much studied and commercially used catalyst for propane dehydrogenation. The traditionally prepared catalyst, however, suffers from inhomogeneity and phase separation of the active Pt–Sn phase. Colloidal chemistry offers a route for the synthesis of Pt–Sn bimetallic nanoparticles (NPs) in a systematic, well-defined, tailored fashion over conventional methods. Here, the successful synthesis of well-defined ≈2 nm Pt, PtSn, and Pt 3 Sn nanocrystals with distinct crystallographic phases is reported; hexagonal close packing (hcp) PtSn and fcc Pt 3 Sn show different activity and stability depending on the hydrogen-rich or poor environment in the feed. Moreover, face centred cubic (fcc) Pt 3 Sn/Al 2 O 3 , which exhibited the highest stability compared to hcp PtSn, shows a unique phase transformation from an fcc phase to an L1 2 -ordered superlattice. Contrary to PtSn, H 2 cofeeding has no effect on the Pt 3 Sn deactivation rate. Finally, the results reveal structural dependency of the probe reaction, propane dehydrogenation, and provide a fundamental understanding of the structure–performance relationship on emerging bimetallic systems.

36 MATERIALS SCIENCE↗

Physics of Hard Spheres Experiment: Significant and Quantitative Findings Made

Direct examination of atomic interactions is difficult. One powerful approach to visualizing atomic interactions is to study near-index-matched colloidal dispersions of microscopic plastic spheres, which can be probed by visible light. Such spheres interact through hydrodynamic and Brownian forces, but they feel no direct force before an infinite repulsion at contact. Through the microgravity flight of the Physics of Hard Spheres Experiment (PHaSE), researchers have sought a more complete understanding of the entropically driven disorder-order transition in hard-sphere colloidal dispersions. The experiment was conceived by Professors Paul M. Chaikin and William B. Russel of Princeton University. Microgravity was required because, on Earth, index-matched colloidal dispersions often cannot be density matched, resulting in significant settling over the crystallization period. This settling makes them a poor model of the equilibrium atomic system, where the effect of gravity is truly negligible. For this purpose, a customized light-scattering instrument was designed, built, and flown by the NASA Glenn Research Center at Lewis Field on the space shuttle (shuttle missions STS 83 and STS 94). This instrument performed both static and dynamic light scattering, with sample oscillation for determining rheological properties. Scattered light from a 532- nm laser was recorded either by a 10-bit charge-coupled discharge (CCD) camera from a concentric screen covering angles of 0 to 60 or by sensitive avalanche photodiode detectors, which convert the photons into binary data from which two correlators compute autocorrelation functions. The sample cell was driven by a direct-current servomotor to allow sinusoidal oscillation for the measurement of rheological properties. Significant microgravity research findings include the observation of beautiful dendritic crystals, the crystallization of a "glassy phase" sample in microgravity that did not crystallize for over 1 year in 1g (Earth's gravity), and the emergence of face-centered-cubic (FCC) crystals late in the coarsening process (as small crystallites lost particles to the slow ripening of large crystallites). Significant quantitative findings from the microgravity experiments have been developed describing complex interactions among crystallites during the growth process, as concentration fields overlap in the surrounding disordered phase. Time-resolved Bragg scattering under microgravity captures one effect of these interactions quite conclusively for the sample at a volume fraction of 0.528. From the earliest time until the sample is almost fully crystalline, the size and overall crystallinity grow monotonically, but the number of crystallites per unit volume (number density) falls. Apparently nucleation is slower than the loss of crystallites because of the transfer of particles from small to large crystals. Thus, coarsening occurs simultaneously with growth, rather than following the completion of nucleation and growth as is generally assumed. In the same sample, an interesting signature appears in the apparent number density of crystallites and the volume fraction within the crystallites shortly before full crystallinity is reached. A brief upturn in both indicates the creation of more domains of the size of the average crystallite simultaneous with the compression of the crystallites. Only the emergence of dendritic arms offers a reasonable explanation. The arms would be "seen" by the light scattering as separate domains whose smaller radii of curvature would compress the interior phase. In fiscal year 1999, numerous papers, a doctoral dissertation, and the PHaSE final report were produced. Although this flight project has been completed, plans are in place for a follow-on colloid experiment by Chaikin and Russel that employs a light microscope within Glenn's Fluids and Combustion Facility on the International Space Station. PHaSE is providing us with a deeper understanding of the nure of phase transitions. The knowledge derived has added to the understanding of condensed matter. In addition, the burgeoning study of the dynamics of colloidal self-assembly may lead to the development of a range of photonic materials that control the desirable properties of light. Thus, applications of ordered colloidal structures include not only ultrastructure ceramics, but also photonic crystals and photothermal nanosecond light-switching devices. Industries dealing with semiconductors, electro-optics, ceramics, and composites stand to benefit from such advancements.

Doherty, Michael P.↗

Colloidal State Machines as Smart Tracers for Chemical Reactor Analysis

A widely utilized tool in reactor analysis is passive tracers that report the residence time distribution, allowing estimation of the conversion and other properties of the system. Recently, advances in microrobotics have introduced powered and functional entities with sizes comparable to some traditional tracers. This has motivated the concept of Smart Tracers that could record the local chemical concentrations, temperature, or other conditions as they progress through reactors. Herein, the design constraints and advantages of Smart Tracers by simulating their operation in a laminar flow reactor model conducting chemical reactions of various orders are analyzed. It is noted that far fewer particles are necessary to completely map even the most complex concentration gradients compared with their conventional counterparts. Design criteria explored herein include sampling frequency, memory storage capacity, and ensemble number necessary to achieve the required accuracy to inform a reactor model. Cases of severe particle diffusion and sensor noise appear to bind the functional upper limit of such probes and require consideration for future design. The results of the study provide a starting framework for applying the new technology of microrobotics to the broad and impactful set of problems classified as chemical reactor analysis.

97 MATHEMATICS AND COMPUTING↗

Binary Colloidal Alloy Test-5: Aspheres

The Binary Colloidal Alloy Test - 5: Aspheres (BCAT-5-Aspheres) experiment photographs initially randomized colloidal samples (tiny nanoscale spheres suspended in liquid) in microgravity to determine their resulting structure over time. BCAT-5-Aspheres will study the properties of concentrated systems of small particles when they are identical, but not spherical in microgravity..

Chaikin, Paul M.↗

Collective behavior of “flexicles”

In recent years the functionality of synthetic active microparticles has edged even closer to that of their biological counterparts. However, we still lack the understanding needed to recreate at the microscale key features of autonomous behavior exhibited by microorganisms or swarms of macroscopic robots. In this study, we propose a model for a three-dimensional deformable cellular composite particle consisting of self-propelled rod-shaped colloids confined within a flexible vesicle—representing a superstructure we call a “flexicle” that couples particle deformation to the internal dynamics of the internal active components. Using molecular dynamics simulations, we investigate the collective behavior of dense systems composed of many flexicles. We show that individual flexicles exhibit shape changes upon collisions with other flexicles that lead to rearrangements of the internal active rods, which slows flexicle motion. This shape deformability gives rise to a diverse set of motility-induced phase separation phenomena and the spontaneous flow of flexicles reminiscent of the migration of cells in dense tissues. Our findings establish a foundation for designing responsive, cell-like active particles and developing strategies for controlling swarm migration and other autonomous swarm behaviors at cellular and colloidal scales.

Science & Technology - Other Topics↗

Fundamental Processes and Practical Considerations of Lead Chalcogenide Mesocrystals Formed via Self-Assembly and Directed Attachment of Nanocrystals at a Fluid Interface

Significant advances in the synthesis and processing of colloidal nanocrystals have given scientists and engineers access to a vast library of building blocks with precisely defined size, shape, and composition. These materials have inspired exciting prospects to enable bottom-up fabrication of programmable materials with properties by design. Successfully assembling and connecting the building blocks into superstructures in which constituent nanocrystals can purposefully interact requires robust understanding of and control over a complex interplay of dynamic physicochemical processes. Fluid interfaces provide an advantageous experimental workbench to both probe and control these processes. Despite the ostensible simplicity of fabricating nanocrystal assemblies at a fluid interface, sensitivity to processing conditions and limited reproducibility have underscored the complexity of this process. In situ studies have provided mechanistic insights into the competing dynamics of key subprocesses including solvent spreading and evaporation, superlattice formation, ligand detachment kinetics, and nanocrystal attachment. Understanding how these subprocesses influence the complex choreography of self-assembly, structure transformation, and oriented attachment processes presents a rich research challenge. In this context, we present a detailed methodology for self-assembly and attachment of lead chalcogenide nanocrystals at a liquid–gas interface as a model system for the fabrication of mono- and multilayer cubic connected superlattices. We discuss key experimental parameters such as the characteristics of the building blocks and processing conditions and detailed steps from colloidal nanocrystal injection to superlattice transfer. Furthermore, we hope that this Methods/Protocols paper will provide guidance for future advances in the exciting path toward bringing the prospect of nanocrystal-based programmable materials to fruition.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Water Contaminant Mitigation in Ionic Liquid Propellant

Appropriate system and operational requirements are needed in order to ensure mission success without unnecessary cost. Purity requirements applied to thruster propellants may flow down to materials and operations as well as the propellant preparation itself. Colloid electrospray thrusters function by applying a large potential to a room temperature liquid propellant (such as an ionic liquid), inducing formation of a Taylor cone. Ions and droplets are ejected from the Taylor cone and accelerated through a strong electric field. Electrospray thrusters are highly efficient, precise, scaleable, and demonstrate low thrust noise. Ionic liquid propellants have excellent properties for use as electrospray propellants, but can be hampered by impurities, owing to their solvent capabilities. Of foremost concern is the water content, which can result from exposure to atmosphere. Even hydrophobic ionic liquids have been shown to absorb water from the air. In order to mitigate the risks of bubble formation in feed systems caused by water content of the ionic liquid propellant, physical properties of the ionic liquid EMI-Im are analyzed. The effects of surface tension, material wetting, physisorption, and geometric details of the flow manifold and electrospray emitters are explored. Results are compared to laboratory test data.

Conroy, David↗