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At least 865 records · Page 48

Transparent bulk-size nanocomposites with high inorganic loading

With relatively high nanoparticle loading in polymer matrices, hybrid nanocomposites made by colloidal dispersion routes suffer from severe inhomogeneous agglomeration, a phenomenon that deteriorates light transmission even when the refractive indices of the inorganic and organic phases are closely matched. The dispersion of particles in a matrix is of paramount importance to obtain composites of high optical quality. Here, we describe an innovative, yet straightforward method to fabricate monolithic transparent hybrid nanocomposites with very high particle loading and high refractive index mismatch tolerance between the inorganic and organic constituents. We demonstrate 77% transmission at 800 nm in a 2 mm-thick acrylate polymer nanocomposite containing 61 vol. % CaF{sub 2} nanoparticles. Modeling shows that similar performance could easily be obtained with various inorganic phases relevant to a number of photonic applications.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Application of a new coordination compound for the preparation of AgI nanoparticles

Graphical abstract: Silver iodide nanoparticles have been sonochemically synthesized by using silver salicylate complex, [Ag(HSal)], as silver precursor. A series of control experiments were carried out to investigate the effects of solvent, surfactant concentration, sonication time and temperature on the morphology of AgI nanostructures. - Highlights: • Silver salicylate as a new precursor was applied to fabricate γ-AgI nanoparticles. • To further decrease the particle size of AgI, SDS was used as surfactant. • The effect of preparation parameters on the particle size of AgI was investigated. - Abstract: AgI nanoparticles have been sonochemically synthesized by using silver salicylate, [Ag(HSal)], as silver precursor. To investigate the effects of solvent, surfactant concentration, sonication time and temperature on the morphology of AgI nanostructures, several experiments were carried out. The products were characterized by SEM, TEM, XRD, TGA/DTA, UV–vis, and FT-IR. Based on the experimental findings in this research, it was found that the size of AgI nanoparticles was dramatically dependent on the silver precursor, sonochemical irradiation, and surfactant concentration. Sodium dodecyl sulfate (SDS) was applied as surfactant. When the concentration of SDS was 0.055 mM, very uniform sphere-like AgI nanoparticles with grain size of about 25–30 nm were obtained. These results indicated that the high concentration of SDS could prevent the aggregation between colloidal nanoparticles due to its steric hindrance effect.

36 MATERIALS SCIENCE↗

Dynamics of hard sphere colloidal dispersions

Our objective is to perform on homogeneous, fully equilibrated dispersions the full set of experiments characterizing the transition from fluid to solid and the properties of the crystalline and glassy solid. These include measurements quantifying the nucleation and growth of crystallites, the structure of the initial fluid and the fully crystalline solid, and Brownian motion of particles within the crystal, and the elasticity of the crystal and the glass. Experiments are being built and tested for ideal microgravity environment. Here we describe the ground based effort, which exploits a fluidized bed to create a homogeneous, steady dispersion for the studies. The differences between the microgravity environment and the fluidized bed is gauged by the Peclet number Pe, which measures the rate of convection/sedimentation relative to Brownian motion. We have designed our experiment to accomplish three types of measurements on hard sphere suspensions in a fluidized bed: the static scattering intensity as a function of angle to determine the structure factor, the temporal autocorrelation function at all scattering angles to probe the dynamics, and the amplitude of the response to an oscillatory forcing to deduce the low frequency viscoelasticity. Thus the scattering instrument and the colloidal dispersion were chosen such as that the important features of each physical property lie within the detectable range for each measurement.

Zhu, J. X.↗

Mechanistic insights into the colloidal assembly of mesoporous silica using in-operando cross-scale X-ray scattering and spectroscopic measurements

Advancing a mechanistic understanding of the colloidal to solid-phase transformations of silica allows us to tune these meso-scale structures. In this study, we probe the structural transformations associated with the formation of mesoporous silica particles, SBA-15 using in-operando Small Angle X-ray Scattering (SAXS) and Grazing Incidence-Small Angle X-ray Scattering (GI-SAXS). The chemical transformations associated with the hydrolysis and condensation of silica particles is investigated using Attenuated Total Reflection – Fourier Transform Infrared Spectroscopy (ATR-FTIR) measurements. Fast polymerization of Si-O-Si species to form mesoporous silica is noted when SBA-15 is synthesized in the presence of nitrate salts, due to the “salting-in” effect or enhanced solubility of polymers. However, aging the silica particles resulted in plate-like morphologies in the absence of the nitrate salt and spherical morphologies in the presence of nitrate salt. Early onset of nucleation of silica particles in the presence of nitrate salts was captured using GI-SAXS measurements. These studies show that the rational basis for developing new synthesis routes for accelerated kinetics or specific meso-scale structures can be informed by detailed characterization of the evolution in chemistry and meso-scale structure of these materials.

36 MATERIALS SCIENCE↗

Dynamics of a Supercooled Disordered Sphere-Forming Diblock Copolymer as Determined by X-ray Photon Correlation and Dynamic Mechanical Spectroscopies

Here, we report the dynamic behavior of a sphere-forming poly(styrene)-block-poly(1,4-butadiene) (PS–PB) diblock copolymer comprising 20 vol % PB below the order–disorder transition temperature ( T ODT = 153 °C) using dynamic mechanical spectroscopy (DMS) and X-ray photon correlation spectroscopy (XPCS). A time–temperature transformation diagram was constructed by monitoring the elasticity of the sample as a function of time following rapid quenches of the disordered melt to various temperatures T < T ODT . Isothermal frequency spectra acquired prior to nucleation of the ordered BCC phase were time–temperature superposed, and the shift factors were fit using the Williams–Landel–Ferry (WLF) equation. For comparison, XPCS measurements were used to extract relaxation times from the supercooled liquid as a function of the quench temperature. Alignment of the temperature dependence of the XPCS-based relaxation times with that of the WLF shift factors in the range T = 125–140 °C indicates that both techniques probe the fluctuating mesomorphic micelle dynamics mediated by the relaxation modes of individual chains, including interparticle chain exchange. For deeper quench temperatures, T ODT – T ≥ 28 °C, departure of the XPCS time constant from WLF behavior is consistent with a jamming transition, analogous to that encountered in concentrated colloidal systems. We postulate that the dominant relaxation mode in the supercooled disordered liquid transitions from ergodic dynamics governed by chain exchange to a nonergodic regime dominated by local rearrangement of micellar particles at T ≈ T erg , where T erg denotes the ergodicity temperature.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Shape-directed rotation of homogeneous micromotors via catalytic self-electrophoresis

The pursuit of chemically-powered colloidal machines requires individual components that perform different motions within a common environment. Such motions can be tailored by controlling the shape and/or composition of catalytic microparticles; however, the ability to design particle motions remains limited by incomplete understanding of the relevant propulsion mechanism(s). Here, we demonstrate that platinum microparticles move spontaneously in solutions of hydrogen peroxide and that their motions can be rationally designed by controlling particle shape. Nanofabricated particles with n-fold rotational symmetry rotate steadily with speed and direction specified by the type and extent of shape asymmetry. The observed relationships between particle shape and motion provide evidence for a self-electrophoretic propulsion mechanism, whereby anodic oxidation and cathodic reduction occur at different rates at different locations on the particle surface. We develop a mathematical model that explains how particle shape impacts the relevant electrocatalytic reactions and the resulting electrokinetic flows that drive particle motion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Colloidal quasicrystals engineered with DNA

In principle, designing and synthesizing almost any class of colloidal crystal is possible. Nonetheless, the deliberate and rational formation of colloidal quasicrystals has been difficult to achieve. Here we describe the assembly of colloidal quasicrystals by exploiting the geometry of nanoscale decahedra and the programmable bonding characteristics of DNA immobilized on their facets. Further, this process is enthalpy-driven, works over a range of particle sizes and DNA lengths, and is made possible by the energetic preference of the system to maximize DNA duplex formation and favour facet alignment, generating local five- and six-coordinated motifs. This class of axial structures is defined by a square–triangle tiling with rhombus defects and successive on-average quasiperiodic layers exhibiting stacking disorder which provides the entropy necessary for thermodynamic stability. Taken together, these results establish an engineering milestone in the deliberate design of programmable matter.

36 MATERIALS SCIENCE↗

Structural characterization of electric-field assisted dip-coating of gold nanoparticles on silicon

We report the effect of applying an electric field on the surface coverage of 40nm gold colloidal nanoparticles on silicon wafer using dip-coating and electrochemical cell set up. By applying electric field during the dip-coating of silicon wafer in a solution of gold nano particles (GNP) the surface coverage increased by 10% when the electric field varied from 5V/cm to 25V/cm at fixed deposition time of 90s. Ultra High Resolution Scanning Electron Microscopy (HRSEM) images shows that the particle agglomeration becomes more noticeable at higher electric field and as the deposition time increases from 90 s to 20 min a thin film of gold is achieved. Moreover, the results are discussed in terms of chemical bonding, electrostatic force and electrophoretic mobility of Au nano particles during the electric field enhanced deposition on the Si surface. Applied voltage, time of dipping, concentration of the aqueous solution, and particles zeta potential are all can be controlled to enhance the uniformity and particles profile on the silicon surface.

36 MATERIALS SCIENCE↗

Improved Optics For Quasi-Elastic Light Scattering

Improved optical train devised for use in light-scattering measurements of quasi-elastic light scattering (QELS) and laser spectroscopy. Measurements performed on solutions, microemulsions, micellular solutions, and colloidal dispersions. Simultaneous measurements of total intensity and fluctuations in total intensity of light scattered from sample at various angles provides data used, in conjunction with diffusion coefficients, to compute sizes of particles in sample.

Cheung, Harry Michael↗

Memory in aging colloidal gels with time-varying attraction

Here, we report a combined rheology, x-ray photon correlation spectroscopy, and modeling study of gel formation and aging in suspensions of nanocolloidal spheres with volume fractions of 0.20 and 0.43 and with a short-range attraction whose strength is tuned by changing temperature. Following a quench from high temperature, where the colloids are essentially hard spheres, to a temperature below the gel point, the suspensions form gels that undergo aging characterized by a steadily increasing elastic shear modulus and slowing, increasingly constrained microscopic dynamics. The aging proceeds at a faster rate for stronger attraction strength. When the attraction strength is suddenly lowered during aging, the gel properties evolve non-monotonically in a manner resembling the Kovacs effect in glasses, in which the modulus decreases and the microscopic dynamics become less constrained for a period before more conventional aging resumes. Eventually, the properties of the gel following the decrease in attraction strength converge to those of a gel that has undergone aging at the lower attraction strength throughout. The time scale of this convergence increases as a power law with the age at which the attraction strength is decreased and decreases exponentially with the magnitude of the change in attraction. A model for gel aging in which particles attach and detach from the gel at rates that depend on their contact number reproduces these trends and reveals that the non-monotonic behavior results from the dispersion in the rates that the populations of particles with different contact number adjust to the new attraction strength.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Observing structural reorientations at solvent–nanoparticle interfaces by X-ray diffraction – putting water in the spotlight

Nanoparticles are attractive in a wide range of research genres due to their size-dependent properties, which can be in contrast to those of micrometre-sized colloids or bulk materials. This may be attributed, in part, to their large surface-to-volume ratio and quantum confinement effects. There is a growing awareness that stress and strain at the particle surface contribute to their behaviour and this has been included in the structural models of nanoparticles for some time. One significant oversight in this field, however, has been the fact that the particle surface affects its surroundings in an equally important manner. It should be emphasized here that the surface areas involved are huge and, therefore, a significant proportion of solvent molecules are affected. Experimental evidence of this is emerging, where suitable techniques to probe the structural correlations of liquids at nanoparticle surfaces have only recently been developed. The recent validation of solvation shells around nanoparticles has been a significant milestone in advancing this concept. Restructured ordering of solvent molecules at the surfaces of nanoparticles has an influence on the entire panoply of solvent–particle interactions during, for example, particle formation and growth, adhesion forces in industrial filtration, and activities of nanoparticle–enzyme complexes. This article gives an overview of the advances made in solvent–nanoparticle interface research in recent years: from description of the structure of bulk solids and liquids via macroscopic planar surfaces, to the detection of nanoscopic restructuring effects. Water–nanoparticle interfaces are given specific attention to illustrate and highlight their similarity to biological systems.

36 MATERIALS SCIENCE↗

Structural behavior and dynamics of an anomalous fluid between attractive and repulsive walls: Templating, molding, and superdiffusion

Confinement can modify the dynamics, the thermodynamics, and the structural properties of liquid water, the prototypical anomalous liquid. By considering a generic model for anomalous liquids, suitable for describing solutions of globular proteins, colloids, or liquid metals, we study by molecular dynamics simulations the effect that an attractive wall with structure and a repulsive wall without structure have on the phases, the crystal nucleation, and the dynamics of the fluid. We find that at low temperatures the large density of the attractive wall induces a high-density, high-energy structure in the first layer (“templating” effect). In turn, the first layer induces a “molding” effect on the second layer determining a structure with reduced energy and density, closer to the average density of the system. This low-density, low-energy structure propagates further through the layers by templating effect and can involve all the existing layers at the lowest temperatures investigated. Therefore, although the high-density, high-energy structure does not self-reproduce further than the first layer, the structured wall can have a long-range influence thanks to a sequence of templating, molding, and templating effects through the layers. We find that the walls also have an influence on the dynamics of the liquid, with a stronger effect near the attractive wall. In particular, we observe that the dynamics is largely heterogeneous (i) among the layers, as a consequence of the sequence of structures caused by the walls presence, and (ii) within the same layer, due to superdiffusive liquid veins within a frozen matrix of particles near the walls at low temperature and high density. Hence, the partial freezing of the first layer does not correspond necessarily to an effective reduction of the channel's section in terms of transport properties, as suggested by other authors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Sensitive Detection: Photoacoustics, Thermography, and Optical Radiation Pressure

Research during the granting period has been carried out in several areas concerned with sensitive detection. An infrared pyrometer based on the photoacoustic effect has been developed. The sensitivity of this instrument to temperature differentials has been shown to be 50 mK. An investigation of transients that accompany photoacoustic waves generated by pulsed lasers has been carried out. Experiments have shown the existence of the transients, and a theory based on rapid heat diffusion has been developed. The photoacoustic effect in one dimension is known to increase without bound (in the linear acoustics regime) when an optical beam moves in a fluid at the sound speed. A solution to the wave equation for pressure has been found that describes the photoacoustic effect in a cell where an infrared optical grating moves at the sound speed. It was shown that the amplification effect exists along with a cavity resonance that can be used to great advantage in trace gas detection. The theory of the photoacoustic effect in a structure where the acoustic properties periodically vary in a one-dimensional based has been formulated based on solutions to a Mathieu equation. It was found that it is possible to excite photoacoustic waves within the band gaps to produce large amplitude acoustic waves. The idea of self-oscillation in a photoacoustic cell using a continuous laser has been investigated. A theory has been completed showing that in a compressive wave, the absorption increases as a result of the density increase leading to further absorption and hence an increased amplitude photoacoustic effect with the result that in a resonator, self-oscillation can place. Experiments have been carried out where irradiation of a suspension of absorbing carbon particles with a high power laser has been shown to result in cavitation luminescence. That is, following generation of CO and H 2 from the carbon particles through the carbon-steam reaction, an expanding gas bubble is produced, which during the phase where the bubble collapses, a sonoluminescent flash is produced. Work on the voltage generated by a spherical, colloidal object irradiated with an acoustic wave has been determined. The theory of X-ray imaging using a grating to generate a spatially heterodyned image has been formulated. The properties of X-ray images taken with a grating placed before the object and the resulting image Fourier transformed and filtered has been determined. The method essentially heterodynes the spatial component of the object in the image which can be used to eliminate scatter that degrades contrast. Another area of investigation is the motion of the components in a separation method known as thermal diffusion, or the Soret effect. By exploring the mathematics of the effect, it was found that the underlying mechanism of the separation is propagation of a shock whose features are masked typically by the effects of viscosity.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Stereo Imaging Velocimetry Technique Using Standard Off-the-Shelf CCD Cameras

Stereo imaging velocimetry is a fluid physics technique for measuring three-dimensional (3D) velocities at a plurality of points. This technique provides full-field 3D analysis of any optically clear fluid or gas experiment seeded with tracer particles. Unlike current 3D particle imaging velocimetry systems that rely primarily on laser-based systems, stereo imaging velocimetry uses standard off-the-shelf charge-coupled device (CCD) cameras to provide accurate and reproducible 3D velocity profiles for experiments that require 3D analysis. Using two cameras aligned orthogonally, we present a closed mathematical solution resulting in an accurate 3D approximation of the observation volume. The stereo imaging velocimetry technique is divided into four phases: 3D camera calibration, particle overlap decomposition, particle tracking, and stereo matching. Each phase is explained in detail. In addition to being utilized for space shuttle experiments, stereo imaging velocimetry has been applied to the fields of fluid physics, bioscience, and colloidal microscopy.

McDowell, Mark↗

Entropic colloidal crystallization pathways via fluid–fluid transitions and multidimensional prenucleation motifs

Complex crystallization pathways are common in protein crystallization, tetrahedrally coordinated systems, and biomineralization, where single or multiple precursors temporarily appear before the formation of the crystal. The emergence of precursors is often explained by a unique property of the system, such as short-range attraction, directional bonding, or ion association. But, structural characteristics of the prenucleation phases found in multistep crystallization remain unclear, and models are needed for testing and expanding the understanding of fluid-to-solid ordering pathways. Here, we report 3 instances of 2-step crystallization of hard-particle fluids. Crystallization in these systems proceeds via a high-density precursor fluid phase with prenucleation motifs in the form of clusters, fibers and layers, and networks, respectively. The density and diffusivity change across the fluid–fluid phase transition increases with motif dimension. We observe crystal nucleation to be catalyzed by the interface between the 2 fluid phases. The crystals that form are complex, including, notably, a crystal with 432 particles in the cubic unit cell. Finally, our results establish the existence of complex crystallization pathways in entropic systems and reveal prenucleation motifs of various dimensions.

2-step crystallization↗