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At least 55 records · Page 3

Size-tunable silver nanoparticle synthesis in glycerol driven by a low-pressure nonthermal plasma

Silver nanoparticles (NPs) are extensively used in electronic components, chemical sensors, and disinfection applications, in which many of their properties depend on particle size. However, control over silver NP size and morphology still remains a challenge for many synthesis techniques. Here, in this work, we demonstrate the surfactant-free synthesis of silver NPs using a low-pressure inductively coupled nonthermal argon plasma. Continuously forming droplets of silver nitrate (AgNO 3 ) precursor dissolved in glycerol are exposed to the plasma, with the droplet residence time being determined by the precursor flow rate. Glycerol has rarely been studied in plasma-liquid interactions but shows favorable properties for controlled NP synthesis at low pressure. We show that the droplet residence time and plasma power have strong influence on NP properties, and that improved size control and particle monodispersity can be achieved by pulsed power operation. Silver NPs had mean diameters of 20 nm with geometric standard deviations of 1.6 under continuous wave operation, which decreased to 6 nm mean and 1.3 geometric standard deviation for pulsed power operation at 100 Hz and 20% duty cycle. We propose that solvated electrons from the plasma and vacuum ultraviolet (VUV) radiation induced electrons produced in glycerol are the main reducing agents of Ag + , the precursor for NPs, while no significant change of chemical composition of the glycerol solvent was detected.

36 MATERIALS SCIENCE↗

Optimization of the parameters for a rotating, mixed-phase reactor

The motion of small, monodisperse particles in fluid was studied in a horizontal, cylindrical container rotating about its axis. One instigation for the study was the common requirement for mixed-phase, chemical or biological reactors to maintain particles in suspension for extended periods. A cylindrical, rotating reactor can allow long-term particle suspension without particle collisions and resulting agglomeration. The purpose of this study was to verify parametric effects and optimize the time of particle suspension. The theoretical and experimental results were obtained for inert, constant-diameter particles of nearly neutral buoyancy. The centrifugal buoyancy and gravitation terms were both included in the equations of motion. Laser illumination, photography and computer imaging were used to measure experimental particle concentration.

Cleland, J. G.↗

Engineering of Novel Biocolloid Suspensions

Colloidal suspensions are materials with a variety of uses from cleaners and lubricants to food, cosmetics, and coatings. In addition, they can be used as a tool for testing the fundamental tenets of statistical physics. Colloidal suspensions can be synthesized from a wide variety of materials, and in the form of monodisperse particles, which can self-assemble into highly ordered colloidal crystal structures. As such they can also be used as templates for the construction of highly ordered materials. Materials design of colloids has, to date, relied on entropic self-assembly, where crystals form as result of lower free energy due to a transition to order. Here, our goal is to develop a completely new method for materials fabrication using colloidal precursors, in which the self-assembly of the ordered colloidal structures is driven by a highly controllable, attractive interaction. This will greatly increase the range of potential structures that can be fabricated with colloidal particles. In this work, we demonstrate that colloidal suspensions can be crosslinked through highly specific biological crosslinking reactions. In particular, the molecules we use are protein-carbohydrate interactions derived from the immune system. This different driving force for self-assembly will yield different and novel suspensions structures. Because the biological interactions are heterotypic (A binding to B), this chemical system can be used to make binary alloys in which the two colloid subpopulations vary in some property - size, density, volume fraction, magnetic susceptibility, etc. An additional feature of these molecules which is unique - even within the realm of biological recognition - is that the molecules bind reversibly on reasonable time-scales, which will enable the suspension to sample different configurations, and allow us to manipulate and measure the size of the suspension dynamically. Because of the wide variety of structures that can be made from these novel colloids, and because the suspension structure can be altered dynamically, we believe this biocolloid system will yield a novel set of materials with many technological applications, including sensors (both biological and non-biological), optical filters and separation media.

Hammer, D. A.↗

Fine-tuning of process conditions to improve product uniformity of polystyrene particles used for wind tunnel velocimetry

Monodisperse polymer particles (having uniform diameter) were used for the last two decades in physical, biological, and chemical sciences. In NASA Langley Research Center monodisperse polystyrene particles are used in wind tunnel laser velocimeters. These polystyrene (PS) particles in latex form were formulated at the Engineering Laboratory of FENGD using emulsion-free emulsion polymerization. Monodisperse PS latices particles having different particle diameters were formulated and useful experimental data involving effects of process conditions on particle size were accumulated. However, similar process conditions and chemical recipes for polymerization of styrene monomer have often yielded monodisperse particles having varying diameters. The purpose was to improve the PS latex product uniformity by fine-tuning the process parameters based on the knowledge of suspension and emulsion polymerization.

Ray, Asit K.↗

Monodisperse Latex Reactor (MLR): A materials processing space shuttle mid-deck payload

The monodisperse latex reactor experiment has flown five times on the space shuttle, with three more flights currently planned. The objectives of this project is to manufacture, in the microgravity environment of space, large particle-size monodisperse polystyrene latexes in particle sizes larger and more uniform than can be manufactured on Earth. Historically it has been extremely difficult, if not impossible to manufacture in quantity very high quality monodisperse latexes on Earth in particle sizes much above several micrometers in diameter due to buoyancy and sedimentation problems during the polymerization reaction. However the MLR project has succeeded in manufacturing in microgravity monodisperse latex particles as large as 30 micrometers in diameter with a standard deviation of 1.4 percent. It is expected that 100 micrometer particles will have been produced by the completion of the the three remaining flights. These tiny, highly uniform latex microspheres have become the first material to be commercially marketed that was manufactured in space.

Kornfeld, D. M.↗

Real-time measurement of sodium chloride in individual aerosol particles by mass spectrometry

The method of particle analysis by mass spectrometry has been applied to the quantitative measurement of sodium chloride in individual particles on a real-time basis. Particles of known masses are individually introduced, in the form of a beam, into a miniature Knudsen cell oven (1600 K). The oven is fabricated from rhenium metal sheet (0.018 mm thick) and is situated in the ion source of a quadrupole mass spectrometer. A particle once inside the oven is trapped and completely volatilized; this overcomes the problem of partial volatilization due to particles bouncing from the filament surface. Individual particles are thermally volatilized and ionized inside the rhenium oven, and produce discrete sodium ion pulses whose intensities are measured with the quadrupole mass spectrometer. An ion pulse width of several milliseconds (4-12 ms) is found for particles in the mass range 1.3 x 10 to the -13th to 5.4 x 10 to the -11th g. The sodium ion intensity is found to be proportional to the particle mass to the 0.86-power. The intensity distribution for monodisperse aerosol particles possesses a geometric standard deviation of 1.09, showing that the method can be used for the determination of the mass distribution function with good resolution in a polydisperse aerosol.

Sinha, M. P.↗

Formation of Aerosol Nanoparticles by Gas-Phase Hydrolysis Reaction of Uranium Hexafluoride

The aerosol physics of uranyl particle formation has been addressed in this research using advanced aerosol instrumentation and an aerosol dynamics model. Based on the research works, we conclude that the formation and growth of aerosol particles by gas-phase UF6 hydrolysis strongly depends on the availability of water molecules in our reactor conditions. The total number concentration of the UO 2 F 2 particulate material that could be produced in the hydrolysis reaction is also regulated primarily by the availability of water molecule concentration. The higher the water molecule concentration, the higher the number and the larger the size of UO 2 F 2 aerosol particles that could be produced in a reactor custom-built at ORNL. Although the aerosol reactor was enabling the study of particle formation kinetics, the instrumentation was still insufficient in characterizing the chemical composition of the produced particles as well as the time-dependent evolution of the particulate species. The temporal evolution could impact the eventual fate of the particles upon release to the environment (i.e., the physio-chemical transformation, transport, and removal). On uranyl particle formation kinetics, we found that the growth rates of aerosol particles appeared to approach a single number in the range of 0.05 ± 0.03 - 0.08 ± 0.04 nm/s, statistically, as the ω value becomes smaller than 1. The size of primary particles from the UF6 hydrolysis at water-deprived condition was estimated to be 3.6 ± 0.4 nm; the higher the availability of water molecules, the larger the primary particles. The ability to precisely control the availability of water molecules in the reaction could lead to the production of nearly monodispersed aerosol particles. In other words, the result suggests that one can precisely manipulate the size of UO 2 F 2 aerosol particles by controlling the water vapor availability and interaction of water molecules with U F6 in the reaction. This finding has significant implications in the engineering manufacturing of fuel powder materials and possibly to future development and deployment of an environmental sampling apparatus.

74 ATOMIC AND MOLECULAR PHYSICS↗

Experimental and computational study of particle formation kinetics in UF6 hydrolysis

The formation and growth of UO 2 F 2 particles by gas-phase UF 6 hydrolysis remains of interest to actinide chemistry researchers. The total number concentration of the UO 2 F 2 aerosol particles that can be produced in the reaction is regulated primarily by the availability of water molecules under our reactor conditions. An increase in water molecule concentration corresponds with a higher amount and larger size of UO 2 F 2 aerosol particles produced. The growth rates of aerosol particles appear to approach a single number in the range of [0.05 ± 0.03–0.08 ± 0.04] (nm s -1 ), as the molar ratio of water to UF 6 decreases below 1. The size of primary particles produced from the UF 6 hydrolysis under water-deprived conditions was estimated to be 3.6 ± 0.4 nm. As the molar ratio became greater than 1.7, the size of primary particles increased with increased availability of water molecules. The primary particle model developed in this work predicted a size range for the UO 2 F 2 primary particles similar to that estimated based on the data from gas-phase UF 6 hydrolysis experiments. This result suggests that the volume-driven coalescence process assumption used in the derivation of the primary particle model was reasonable. The ability to precisely control the availability of water molecules and reaction time could lead to the production of nearly monodispersed aerosol particles. This finding has significant implications in the engineering and manufacturing of fuel powder materials and possibly the future development and deployment of environmental sampling apparatus.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Spectral Radiative Properties of Polydispersed SiO 2 Particle Beds

The focus of this work is on the measurement and analysis of the radiative properties of polycrystalline SiO 2 particle beds with various layer thicknesses. The particles are polydispersed with average diameters of 222, 150, and 40 μm . The spectral, directional–hemispherical reflectance and transmittance of the particle bed are measured at wavelengths from 0.4 to 1.8 μm using a monochromator, and the reflectance measurement is extended to 15 μm using a Fourier-transform infrared spectrometer. Particles are closely packed between two transparent windows for measuring the radiative properties. In the visible and near-infrared region up to 1.8 μm, the inverse adding–doubling method yields the effective absorption and scattering coefficients. The results suggest that short wavelength absorption needs to be included in modeling the behavior of particle beds due to multiple scattering. A discrete-scale Monte Carlo ray-tracing method is developed to model the radiative properties by assuming monodispersed spherical particles, and the simulated results compare well with measurements. The effective absorption and scattering coefficients of the particle beds obtained from the independent scattering theory are compared to those from the inverse method. As a result, the impact of dependent scattering on the packed beds is observed for smaller-sized particles.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Thermal conductivity modeling of monodispersed microspheres using discrete element method

Particle beds are widely used in various systems and processes, such as particle heat exchangers, granular flow reactors, and additive manufacturing. Accurate modeling of the thermal conductivity of particle beds and understanding of their heat transfer mechanisms are important. However, previous models were based on simple cubic packing of particles, which could not accurately represent the actual heat transfer processes under certain conditions. Here, we examine the effect of the packing structure on the thermal conductivity of particle beds. We use monodispersed silica microspheres with average particle sizes ranging from 23 to 330 μm as a model material. We employ a transient hot-wire technique to measure the thermal conductivity of the particle beds with packing density of 43%–57% within a temperature range of room temperature to 500 °C and under N2 gaseous pressures of 20–760 Torr. We then use a discrete element method (DEM) to obtain the realistic packing structure of the particles, which is then fed into a finite-element model (FEM) to calculate the thermal conductivity, with the consideration of solid conduction, gas conduction, and radiation heat transfer. Our results show that the thermal conductivity model based on the more realistic random packing structure derived from the DEM shows better agreement with the experimental data compared to that based on the simple cubic-packing structure. The combined DEM and FEM methodology can serve as a useful tool to predict the effective thermal conductivity of particle beds and to quantify different heat transfer mechanisms under various conditions.

14 SOLAR ENERGY↗

Aerosol size distributions obtained by inversion of spectral optical depth measurements

Columnar aerosol size distributions have been inferred by numerically inverting particulate optical depth measurements as a function of wavelength. An inversion formula which explicitly includes the magnitude of the measurement variances is derived and applied to optical depth measurements obtained in Tucson with a solar radiometer. It is found that the individual size distributions of the aerosol particles (assumed spherical), at least for radii greater than or approximately equal to 0.1 micron, fall into one of three distinctly different categories. Approximately 50% of all distributions examined thus far can best be represented as a composite of a Junge distribution plus a distribution of relatively monodispersed larger particles centered at a radius of about 0.5 micron. Scarcely 20% of the distributions yielded Junge size distributions, while 30% yielded relatively monodispersed distributions of the log-normal or gamma distribution types. A representative selection of each of these types will be presented and discussed. The sensitivity of spectral attenuation measurements to the radii limits and refractive index assumed in the numerical inversion will also be addressed.

King, M. D.↗

Development and characterization of an aerosol-generated multi-method analytical particle test material

Ceria (CeO 2 ) particles with low to ultra-low loading of nickel dopant were produced using an aerosol-based, droplet-to-particle synthesis via an in-line calcination technique. This aerosol-based synthesis method enables the production of particles with a monodisperse size distribution. These produced and well-characterized, multi-element, ceria-based particles demonstrate a material exemplar for multi-method analytical testing. They were prepared from a cerium nitrate feedstock where low loading nickel dopant was added at target Ni/(Ni + Ce) atomic percents of 1 %, 0.1 %, and 0.01 %, using a nickel nitrate spike. This methodology proved to produce ceria particles doped with a dynamic range of low to ultra-low loadings of nickel over a 24-h period, with consistent size distribution, morphology, and composition. The successful incorporation of nickel was demonstrated with bulk and single particle inductively coupled plasma mass spectroscopy and revealed notable particle-to-particle elemental homogeneity. X-ray photoelectron spectroscopy demonstrated the presence of a high concentration of nickel dopant incorporated preferentially toward the surface of the particles, and that this dopant aided oxidation of surface Ce(III) atoms to Ce(IV). These particle test materials were then validated through X-ray absorption near edge spectroscopy, comparing the ultra-low 0.01 % Ni and low 1 % Ni-doped ceria samples. This revealed a more-reduced oxidation state of the nickel with an increase in dopant concentration. Finally, this work demonstrates a synthesis and systematic characterization scheme to produce multi-method analytical test particulates.

36 MATERIALS SCIENCE↗

Performance of a focused cavity aerosol spectrometer for measurements in the stratosphere of particle size in the 0.06-2.0-micrometer-diameter range

A focused cavity aerosol spectrometer aboard a NASA ER-2 high-altitude aircraft provided high-resolution measurements of the size of the stratospheric particles in the 0.06-2.0-micrometer-diameter range in flights following the eruption of Mount Pinatubo in 1991. Effects of anisokinetic sampling and evaporation in the sampling system were accounted for by means adapted and specifically developed for this instrument. Calibrations with monodisperse aerosol particles provided the instrument's response matrix, which upon inversion during data reduction yielded the particle size distributions. The resultant dataset is internally consistent and generally shows agreement to within a factor of 2 with comparable measurements simultaneously obtained by a condensation nuclei counter, a forward-scattering spectrometer probe, and aerosol particle impactors, as well as with nearby extinction profiles obtained by satellite measurements and with lidar measurements of backscatter.

Jonsson, H. H.↗

The Features of Self-Assembling Organic Bilayers Important to the Formation of Anisotropic Inorganic Materials in Microgravity Conditions

There is a growing need for inorganic anisotropic particles in a variety of materials science applications. Structural, optical, and electrical properties can be greatly augmented by the fabrication of composite materials with anisotropic microstructures or with anisotropic particles uniformly dispersed in an isotropic matrix. Examples include structural composites, magnetic and optical recording media, photographic film, certain metal and ceramic alloys, and display technologies including flat panel displays. While considerable progress has been made toward developing an understanding of the synthesis of powders composed of monodispersed, spherical particles, these efforts have not been transferred to the synthesis of anisotropic nanoparticles. The major objective of the program is to develop a fundamental understanding of the growth of anisotropic particles at organic templates, with emphasis on the chemical and structural aspects of layered organic assemblies that contribute to the formation of anisotropic inorganic particles.

Talham, Daniel R.↗

Comprehensive defect suppression in perovskite nanocrystals for high-efficiency light-emitting diodes

Electroluminescence efficiencies of metal halide perovskite nanocrystals (PNCs) are limited by a lack of material strategies that can both suppress the formation of defects and enhance the charge carrier confinement. Here we report a one-dopant alloying strategy that generates smaller, monodisperse colloidal particles (confining electrons and holes, and boosting radiative recombination) with fewer surface defects (reducing non-radiative recombination). Doping of guanidinium into formamidinium lead bromide PNCs yields limited bulk solubility while creating an entropy-stabilized phase in the PNCs and leading to smaller PNCs with more carrier confinement. Further, the extra guanidinium segregates to the surface and stabilizes the undercoordinated sites. Furthermore, a surface-stabilizing 1,3,5-tris(bromomethyl)-2,4,6-triethylbenzene was applied as a bromide vacancy healing agent. The result is highly efficient PNC-based light-emitting diodes that have current efficiency of 108 cd A –1 (external quantum efficiency of 23.4%), which rises to 205 cd A –1 (external quantum efficiency of 45.5%) with a hemispherical lens.

36 MATERIALS SCIENCE↗

Synthesis and disassembly of an organometallic polymer comprising redox-active Co 4 S 4 clusters and Janus biscarbene linkers

Here, we show for the first time that main-chain organometallic polymers (MCOPs) can be prepared from Janus N-heterocyclic carbene (NHC) linkers and polynuclear cluster nodes. The crosslinked framework Co 4 S 4 -MCOP is synthesized via ligand displacement reactions and undergoes reversible electron transfer in the solid state. Discrete molecular cluster species can be excised from the framework by digesting the solid in solutions of excess monocarbene. Lastly, we demonstrate a synthetic route to monodisperse framework particles via coordination modulation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Bidisperse supension balance model

The suspension balance model (SBM) for viscous Stokes flow has been well studied for the case of identical, monodisperse spherical particles in a channel, however, more work remains to be done to explore the bidisperse and polydisperse SBM. Here, we present a simple extension of the SBM that allows for modeling of suspensions of particles of bidisperse size. The comparison with avaiable experiments and direct simulations is found to be good. Additionally, we present a range of simulations to justify the assumptions made in the polydisperse suspension balance model for non-Brownian, neutrally buoyant particles that vary in size with a bidisperse distribution. The aim is to study the effects of moderate size variation on the rheology of the suspension and the distribution of the particles across the flow, especially in the near-wall regions. It is shown that, at the size ratios considered, bidispersity in the particle size does not significantly affect rheological parameters including the particle volume fraction and relative viscosity in the bulk of a Couette flow. The particle phase stresses are distributed between small and large particles in proportion to the relative volume fractions of each species. In bidisperse suspensions, the large particles in the wall layer develop a spatial structure and form chains in the streamwise direction.

97 MATHEMATICS AND COMPUTING↗