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At least 667 records · Page 37

Pronounced Size Dependence in Structure and Morphology of Gas-Phase Produced, Partially Oxidized Cobalt Nanoparticles under Catalytic Reaction Conditions

It is generally accepted that optimal particle sizes are key for efficient nanocatalysis. Much less attention is paid to the role of morphology and atomic arrangement during catalytic reactions. Here we unravel the structural, stoichiometric, and morphological evolution of gas-phase produced cobalt nanoparticles in a broad size range. Particles with diameters between 1.4 nm and 22nm generated in cluster sources are size selected and deposited on amorphous alumina (Al2O3) and ultrananocrystalline diamond (UNCD) films. A combination of different techniques is employed to monitor particle properties at the stages of production, exposure to ambient conditions, and catalytic reaction, in this case the oxidative dehydrogenation of cyclohexane at elevated temperatures. A pronounced size dependence is found, naturally classifying the particles into three size regimes. While small and intermediate clusters essentially retain their compact morphology, large particles transform into hollow spheres due to the nanoscale Kirkendall effect. Depending on the substrate an isotropic (Al2O3) or anisotropic (UNCD) Kirkendall effect is observed. The latter results in dramatic lateral size changes. Our results shed light on the interplay between chemical reactions and the catalyst's structure and provide an approach to tailor the cobalt oxide phase composition required for specific catalytic schemes.

cluster source↗

Catalytic Consequences of Particle Size and Chloride Promotion in the Ring-Opening of Cyclopentane on Pt/Al2O3

Ring-opening of cyclopentane on alumina-supported Pt particles was studied as a function of Pt particle size in the presence of different Cl contents. With catalysts prepared from a Cl-free precursor, measured turnover rates increased monotonically with increasing Pt particle size (1-15 nm). On catalysts derived from a Cl-containing precursor, the turnover rates fell into two separate trends with the change of Pt particle size, depending on the extent of Cl removal by increasing thermal treatment temperature. In both cases, catalytic activity increased with increasing particle size in the examined ranges of dispersions (D = 0.7-1.0 and 0-0.6) and for both series of catalysts, the apparent activation energies were higher on large Pt particles than on small ones, with only small differences in the reaction orders for H-2 and cyclopentane on particles of widely varying average sizes. Therefore, the effect of particle size on the turnover rates stems mainly from intrinsic rate constants, rather than from coverage effects. The relative adsorption coefficients of toluene and benzene indicated lower electron densities at the surface Pt atoms in the catalysts prepared from the Cl-containing precursor than in those from the Cl-free precursor. This subtle electron deficiency, which seems not to stem from the local Cl enrichment near Pt, affects both the concentration of chemisorbed hydrogen under reaction conditions and the barrier for C-C bond cleavage. The Cl postintroduced to the catalyst, in contrast, does not induce a similarly positive effect.

AROMATIC-HYDROCARBONS↗

Bilayer Thickness Mismatch Controls Domain Size in Model Membranes

The observation of lateral phase separation in lipid bilayers has received considerable attention, especially in connection to lipid raft phenomena in cells. It is widely accepted that rafts play a central role in cellular processes, notably signal transduction. While micrometer-sized domains are observed with some model membrane mixtures, rafts much smaller than 100 nm beyond the reach of optical microscopy are now thought to exist, both in vitro and in vivo. We have used small-angle neutron scattering, a probe free technique, to measure the size of nanoscopic membrane domains in unilamellar vesicles with unprecedented accuracy. These experiments were performed using a four-component model system containing fixed proportions of cholesterol and the saturated phospholipid 1,2-distearoyl-sn-glycero-3-phosphocholine (DSPC), mixed with varying amounts of the unsaturated phospholipids 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) and 1,2-dioleoylsn- glycero-3-phosphocholine (DOPC). We find that liquid domain size increases with the extent of acyl chain unsaturation (DOPC:POPC ratio). Furthermore, we find a direct correlation between domain size and the mismatch in bilayer thickness of the coexisting liquid-ordered and liquid-disordered phases, suggesting a dominant role for line tension in controlling domain size. While this result is expected from line tension theories, we provide the first experimental verification in free-floating bilayers. Importantly, we also find that changes in bilayer thickness, which accompany changes in the degree of lipid chain unsaturation, are entirely confined to the disordered phase. Together, these results suggest how the size of functional domains in homeothermic cells may be regulated through changes in lipid composition.

Heberle, Frederick A↗

Size and Temperature Dependence of Electron Transfer between CdSe Quantum Dots and a TiO 2 Nanobelt

Understanding charge transfer reactions between quantum dots (QD) and metal oxides is fundamental for improving photocatalytic, photovoltaic and electronic devices. The complexity of these processes makes it difficult to find an optimum QD size with rapid charge injection and low recombination. We combine time-domain density functional theory with nonadiabatic molecular dynamics to investigate the size and temperature dependence of the experimentally studied electron transfer and charge recombination at CdSe QD-TiO 2 nanobelt (NB) interfaces. The electron injection rate shows strong dependence on the QD size, increasing for small QDs. The rate exhibits Arrhenius temperature dependence, with the activation energy of the order of millielectronvolts. The charge recombination process occurs due to coupling of the electronic subsystem to vibrational modes of the TiO 2 NB. Inelastic electron-phonon scattering happens on a picosecond time scale, with strong dependence on the QD size. Our simulations demonstrate that the electron-hole recombination rate decreases significantly as the QD size increases, in excellent agreement with experiments. The temperature dependence of the charge recombination rates can be successfully modeled within the framework of the Marcus theory through optimization of the electronic coupling and the reorganization energy. Our simulations indicate that by varying the QD size, one can modulate the photoinduced charge separation and charge recombination, fundamental aspects of the design principles for high efficiency devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Observed and Bin Model Simulated Evolution of Drop Size Distributions in High-Based Cumulus Congestus Over the United Arab Emirates

This study examines microphysical processes in developing high-based cumulus congestus over the United Arab Emirates using aircraft observations and a large-eddy-simulation model with bin microphysics. A notable feature of this case is the lack of mm-sized drops despite having a liquid cloud layer >3.5 km deep, contrasting with copious large drops observed in maritime tropical cumulus congestus having a similar vertical extent. Modeled drop size distributions are similar to observations at various temperatures between 9.5 and –12°C, including the lack of mm-sized drops. Cloud dilution leads to low-to-moderate liquid water contents (~0.5–1.5 g m –3 ) in most of the cloud core, several times smaller than adiabatic values. Dilution is enhanced in the inflowing branch of the toroidal circulations associated with individual cloud thermals, which are favored regions for secondary droplet activation (activation above cloud base). Secondary activation in general contributes substantially to the droplet population. Turning it off leads to a sharp decrease in droplet concentration and increase in mean size aloft, but does little to increase rain drop production. Warm rain generation (or lack thereof) in this case is therefore determined more by the sub-cloud aerosol and the cloud base droplet size distribution (DSD) than DSD evolution aloft from secondary droplet activation. Decreasing the aerosol concentration by a factor of 10 greatly increases production of large drops via collision-coalescence. Thus, despite its high base (low temperatures) and substantial dilution, the simulated cloud is thermodynamically and dynamically capable of rapidly producing copious mm-sized drops from collision-coalescence under pristine aerosol conditions.

54 ENVIRONMENTAL SCIENCES↗

An Energetic Diagnostic of Tropical Cyclone Size in f –Plane Simulations

As a major feature of tropical cyclones (TCs), controlling factors of TC outer size or size scaling remains a fundamental scientific question. The Rossby deformation radius and a natural extent associated with potential intensity have been proposed as two scalings of TC size. But neither of them satisfactorily captures the sensitivity of TC size to sea surface temperature (SST) in idealized f-plane simulations. Inspired by the studies of the Hadley circulation, here we proposed a new TC scaling based on an energetic diagnostic scaling. TC size is primarily a ratio of the secondary circulation strength to subsidence velocity, further determined by the total atmospheric heating in the ascending area, the gross moist stability, the diabatic cooling, and the dry static stability. The former two is based on the moist energetic budget applied to the whole storm structure, while the latter two is based on the dry thermodynamic budget applied to the subsidence areas. The new scaling well captured the sensitivity of TC size to SST in idealized f-plane simulations, partly resulted from expanded ascending area, increased surface moisture deficit, and weakened subsidence with increased SST.

58 GEOSCIENCES↗

Optimal metal domain size for photocatalysis with hybrid semiconductor-metal nanorods

Semiconductor-metal hybrid nanostructures offer a highly controllable platform for light-induced charge separation, with direct relevance for their implementation in photocatalysis. Advances in the synthesis allow for control over the size, shape and morphology, providing tunability of the optical and electronic properties. A critical determining factor of the photocatalytic cycle is the metal domain characteristics and in particular its size, a subject that lacks deep understanding. Here, using a well-defined model system of cadmium sulfide-gold nanorods, we address the effect of the gold tip size on the photocatalytic function, including the charge transfer dynamics and hydrogen production efficiency. A combination of transient absorption, hydrogen evolution kinetics and theoretical modelling reveal a non-monotonic behaviour with size of the gold tip, leading to an optimal metal domain size for the most efficient photocatalysis. We show that this results from the size-dependent interplay of the metal domain charging, the relative band-alignments, and the resulting kinetics.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Continuously adjustable, molecular-sieving “gate” on 5A zeolite for distinguishing small organic molecules by size

Zeolites/molecular sieves with uniform, molecular-sized pores are important for many adsorption-based separation processes. Pore size gaps, however, exist in the current zeolite family. This leads to a great challenge of separating molecules with size differences at ~0.01 nm level. Here, we report a novel concept, pore misalignment, to form a continuously adjustable, molecular-sieving “gate” at the 5A zeolite pore entrance without sacrificing the internal capacity. Misalignment of the micropores of the alumina coating with the 5A zeolite pores was related with and facilely adjusted by the coating thickness. For the first time, organic molecules with sub-0.01 nm size differences were effectively distinguished via appropriate misalignment. Lastly, this novel concept may have great potential to fill the pore size gaps of the zeolite family and realize size-selective adsorption separation.

36 MATERIALS SCIENCE↗

Investigation into the crystal structure–dielectric property correlation in barium titanate nanocrystals of different sizes

For high capacitance multilayer ceramic capacitors, high dielectric constant and lead-free ceramic nanoparticles are highly desired. However, as the particle size decreases to a few tens of nanometers, their dielectric constant significantly decreases, and the underlying mechanism has yet to be fully elucidated. Herein, we report a systematic investigation into the crystal structure–dielectric property relationship of combustion-made BaTiO 3 (BTO) nanocrystals. When the nanocrystal size was 100 nm and below, a metastable paraelectric cubic phase was found in the as-received BTO (denoted as arBTO) nanocrystals based on an X-ray diffraction (XRD) study. A stable ferroelectric tetragonal phase was present when the nanocrystal size was above 200 nm. Notably, the cubic arBTO (particle size ≤100 nm) exhibited tetragonal fluctuations as revealed by Raman spectroscopy, whereas the tetragonal arBTO (particle size ≥200 nm) contained ~10% cubic fraction according to the Rietveld fitting of the XRD profiles. Thermal annealing of the multi-grain tetragonal arBTO at 950 °C yielded single crystals of annealed BTO (denoted as anBTO), whose dielectric constants were higher than those of arBTO. However, the single crystalline anBTO prevented the formation of 90° domains; therefore, they exhibited a low dielectric constant of ~300. Although X-ray photoelectron spectroscopy and high-resolution transmission electron microscopy could not identify the exact structural defects, our study revealed that surface and bulk defects formed during synthesis affect the final crystal structures and thus the dielectric properties of BTO nanocrystals with different sizes. Finally, the understanding obtained from this study will help us design high dielectric constant perovskite nanocrystals for next-generation multilayer ceramic capacitor applications.

36 MATERIALS SCIENCE↗

A thermal porosimetry method to estimate pore size distribution in highly porous insulating materials

Standard pore size determination methods such as mercury porosimetry, nitrogen sorption, microscopy, or x-ray tomography are not always applicable to highly porous, low density, and thus very fragile materials. For this kind of materials, a method based on thermal characterization is proposed. Indeed, the thermal conductivity of a highly porous and insulating medium is significantly dependent on the thermal conductivity of the interstitial gas that depends on both gas pressure and size of the considered pore (Knudsen effect). It is also possible to link the pore size with the thermal conductivity of the medium. Thermal conductivity measurements are realized on specimens placed in an enclosure where the air pressure is successively set to different values varying from 10{sup -1} to 10{sup 5} Pa. Knowing the global porosity ratio, an effective thermal conductivity model for a two-phase air-solid material based on a combined serial-parallel model is established. Pore size distribution can be identified by minimizing the sum of the quadratic differences between measured values and modeled ones. The results of the estimation process are the volume fractions of the chosen ranges of pore size. In order to validate the method, measurements done on insulating materials are presented. The results are discussed and show that pore size distribution estimated by the proposed method is coherent.

36 MATERIALS SCIENCE↗

Influence of core size on the upconversion luminescence properties of spherical Gd{sub 2}O{sub 3}:Yb{sup 3+}/Er{sup 3+}@SiO{sub 2} particles with core-shell structures

Spherical SiO{sub 2} particles with different sizes (30, 80, 120, and 180 nm) have been coated with Gd{sub 2}O{sub 3}:Yb{sup 3+}/Er{sup 3+} layers by a heterogeneous precipitation method, leading to the formation of core-shell structural Gd{sub 2}O{sub 3}:Yb{sup 3+}/Er{sup 3+}@SiO{sub 2} particles. The samples were characterized by using X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, upconversion (UC) emission spectra, and fluorescent dynamical analysis. The obtained core-shell particles have perfect spherical shape with narrow size distribution. Under the excitation of 980 nm diode laser, the core-shell samples showed size-dependent upconversion luminescence (UCL) properties. The inner SiO{sub 2} cores in core-shell samples were proved to have limited effect on the total UCL intensities of Er{sup 3+} ions. The UCL intensities of core-shell particles were demonstrated much higher than the values obtained in pure Gd{sub 2}O{sub 3}:Yb{sup 3+}/Er{sup 3+} with the same phosphor volume. The dependence of the specific area of a UCL shell on the size of its inner SiO{sub 2} particle was calculated and analyzed for the first time. It was confirmed that the surface effect came from the outer surfaces of emitting shells is dominant in influencing the UCL property in the core-shell samples. Three-photon UC processes for the green emissions were observed in the samples with small sizes of SiO{sub 2} cores. The results of dynamical analysis illustrated that more nonradiative relaxation occurred in the core-shell samples with smaller SiO{sub 2} core sizes.

36 MATERIALS SCIENCE↗

Effect of roll hot press temperature on crystallite size of PVDF film

Fabrication PVDF films have been made using Hot Roll Press. Preparation of samples carried out for nine different temperatures. This condition is carried out to see the effect of Roll Hot Press temperature on the size of the crystallite of PVDF films. To obtain the diffraction pattern of sample characterization is performed using X-Ray Diffraction. Furthermore, from the diffraction pattern is obtained, the calculation to determine the crystallite size of the sample by using the Scherrer equation. From the experimental results and the calculation of crystallite sizes obtained for the samples with temperature 130 °C up to 170 °C respectively increased from 7.2 nm up to 20.54 nm. These results show that increasing temperatures will also increase the size of the crystallite of the sample. This happens because with the increasing temperature causes the higher the degree of crystallization of PVDF film sample is formed, so that the crystallite size also increases. This condition indicates that the specific volume or size of the crystals depends on the magnitude of the temperature as it has been studied by Nakagawa.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Spot size dependence of laser accelerated protons in thin multi-ion foils

We present a numerical study of the effect of the laser spot size of a circularly polarized laser beam on the energy of quasi-monoenergetic protons in laser proton acceleration using a thin carbon-hydrogen foil. The used proton acceleration scheme is a combination of laser radiation pressure and shielded Coulomb repulsion due to the carbon ions. We observe that the spot size plays a crucial role in determining the net charge of the electron-shielded carbon ion foil and consequently the efficiency of proton acceleration. Using a laser pulse with fixed input energy and pulse length impinging on a carbon-hydrogen foil, a laser beam with smaller spot sizes can generate higher energy but fewer quasi-monoenergetic protons. We studied the scaling of the proton energy with respect to the laser spot size and obtained an optimal spot size for maximum proton energy flux. Using the optimal spot size, we can generate an 80 MeV quasi-monoenergetic proton beam containing more than 10{sup 8} protons using a laser beam with power 250 TW and energy 10 J and a target of thickness 0.15 wavelength and 49 critical density made of 90% carbon and 10% hydrogen.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Microfluidic sorting of protein nanocrystals by size for X-ray free-electron laser diffraction

The advent and application of the X-ray free-electron laser (XFEL) has uncovered the structures of proteins that could not previously be solved using traditional crystallography. While this new technology is powerful, optimization of the process is still needed to improve data quality and analysis efficiency. One area is sample heterogeneity, where variations in crystal size (among other factors) lead to the requirement of large data sets (and thus 10–100 mg of protein) for determining accurate structure factors. To decrease sample dispersity, we developed a high-throughput microfluidic sorter operating on the principle of dielectrophoresis, whereby polydisperse particles can be transported into various fluid streams for size fractionation. Using this microsorter, we isolated several milliliters of photosystem I nanocrystal fractions ranging from 200 to 600 nm in size as characterized by dynamic light scattering, nanoparticle tracking, and electron microscopy. Sorted nanocrystals were delivered in a liquid jet via the gas dynamic virtual nozzle into the path of the XFEL at the Linac Coherent Light Source. We obtained diffraction to ∼4 Å resolution, indicating that the small crystals were not damaged by the sorting process. We also observed the shape transforms of photosystem I nanocrystals, demonstrating that our device can optimize data collection for the shape transform-based phasing method. Using simulations, we show that narrow crystal size distributions can significantly improve merged data quality in serial crystallography. From this proof-of-concept work, we expect that the automated size-sorting of protein crystals will become an important step for sample production by reducing the amount of protein needed for a high quality final structure and the development of novel phasing methods that exploit inter-Bragg reflection intensities or use variations in beam intensity for radiation damage-induced phasing. This method will also permit an analysis of the dependence of crystal quality on crystal size.

36 MATERIALS SCIENCE↗

Accurate determination of electronic transport properties of silicon wafers by nonlinear photocarrier radiometry with multiple pump beam sizes

In this paper, photocarrier radiometry (PCR) technique with multiple pump beam sizes is employed to determine simultaneously the electronic transport parameters (the carrier lifetime, the carrier diffusion coefficient, and the front surface recombination velocity) of silicon wafers. By employing the multiple pump beam sizes, the influence of instrumental frequency response on the multi-parameter estimation is totally eliminated. A nonlinear PCR model is developed to interpret the PCR signal. Theoretical simulations are performed to investigate the uncertainties of the estimated parameter values by investigating the dependence of a mean square variance on the corresponding transport parameters and compared to that obtained by the conventional frequency-scan method, in which only the frequency dependences of the PCR amplitude and phase are recorded at single pump beam size. Simulation results show that the proposed multiple-pump-beam-size method can improve significantly the accuracy of the determination of the electronic transport parameters. Comparative experiments with a p-type silicon wafer with resistivity 0.1–0.2 Ω·cm are performed, and the electronic transport properties are determined simultaneously. The estimated uncertainties of the carrier lifetime, diffusion coefficient, and front surface recombination velocity are approximately ±10.7%, ±8.6%, and ±35.4% by the proposed multiple-pump-beam-size method, which is much improved than ±15.9%, ±29.1%, and >±50% by the conventional frequency-scan method. The transport parameters determined by the proposed multiple-pump-beam-size PCR method are in good agreement with that obtained by a steady-state PCR imaging technique.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Nature of size effects in compact models of field effect transistors

Investigations have shown that in the local approximation (for sizes L < 100 μm), AlGaN/GaN high electron mobility transistor (HEMT) structures satisfy to all properties of chaotic systems and can be described in the language of fractal geometry of fractional dimensions. For such objects, values of their electrophysical characteristics depend on the linear sizes of the examined regions, which explain the presence of the so-called size effects—dependences of the electrophysical and instrumental characteristics on the linear sizes of the active elements of semiconductor devices. In the present work, a relationship has been established for the linear model parameters of the equivalent circuit elements of internal transistors with fractal geometry of the heteroepitaxial structure manifested through a dependence of its relative electrophysical characteristics on the linear sizes of the examined surface areas. For the HEMTs, this implies dependences of their relative static (A/mm, mA/V/mm, Ω/mm, etc.) and microwave characteristics (W/mm) on the width d of the sink-source channel and on the number of sections n that leads to a nonlinear dependence of the retrieved parameter values of equivalent circuit elements of linear internal transistor models on n and d. Thus, it has been demonstrated that the size effects in semiconductors determined by the fractal geometry must be taken into account when investigating the properties of semiconductor objects on the levels less than the local approximation limit and designing and manufacturing field effect transistors. In general, the suggested approach allows a complex of problems to be solved on designing, optimizing, and retrieving the parameters of equivalent circuits of linear and nonlinear models of not only field effect transistors but also any arbitrary semiconductor devices with nonlinear instrumental characteristics.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Size dependent magnetic and electrical properties of Ba-doped nanocrystalline BiFeO{sub 3}

Improvement in magnetic and electrical properties of multiferroic BiFeO{sub 3} in conjunction with their dependence on particle size is crucial due to its potential applications in multifunctional miniaturized devices. In this investigation, we report a study on particle size dependent structural, magnetic and electrical properties of sol-gel derived Bi{sub 0.9}Ba{sub 0.1}FeO{sub 3} nanoparticles of different sizes ranging from ∼ 12 to 49 nm. The substitution of Bi by Ba significantly suppresses oxygen vacancies, reduces leakage current density and Fe{sup 2+} state. An improvement in both magnetic and electrical properties is observed for 10 % Ba-doped BiFeO{sub 3} nanoparticles compared to its undoped counterpart. The saturation magnetization of Bi{sub 0.9}Ba{sub 0.1}FeO{sub 3} nanoparticles increase with reducing particle size in contrast with a decreasing trend of ferroelectric polarization. Moreover, a first order metamagnetic transition is noticed for ∼ 49 nm Bi{sub 0.9}Ba{sub 0.1}FeO{sub 3} nanoparticles which disappeared with decreasing particle size. The observed strong size dependent multiferroic properties are attributed to the complex interaction between vacancy induced crystallographic defects, multiple valence states of Fe, uncompensated surface spins, crystallographic distortion and suppression of spiral spin cycloid of BiFeO{sub 3}.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Grain size constraints on twin expansion in hexagonal close packed crystals

Deformation twins are stress-induced transformed domains of lamellar shape that form when polycrystalline hexagonal close packed metals, like Mg, are strained. Several studies have reported that the propensity of deformation twinning reduces as grain size decreases. Here, we use a 3D crystal plasticity based micromechanics model to calculate the effect of grain size on the driving forces responsible for expanding twin lamellae. The calculations reveal that constraints from the neighboring grain where the grain boundary and twin lamella meet induce a stress reversal in the twin lamella. A pronounced grain size effect arises as reductions in grain size cause these stress-reversal fields from twin/grain boundary junctions to affect twin growth. We further show that the severity of this neighboring grain constraint depends on the crystallographic orientation and plastic response of the neighboring grain. We show that these stress-reversal fields from twin/grain boundary junctions will affect twin growth, below a critical parent grain size. Finally, these results reveal an unconventional yet influential role that grain size and grain neighbors can play on deformation twinning.

36 MATERIALS SCIENCE↗