Design of polymeric stabilizers for size-controlled synthesis of monodisperse gold nanoparticles in water

A new methodology is described for the one-step aqueous preparation of highly monodisperse gold nanoparticles with diameters below 5 nm using thioether- and thiol-functionalized polymer ligands. The particle size and size distribution was controlled by subtle variation of the polymer structure. It was shown that poly(acrylic acid) (PAA) and poly(methacrylic acid) (PMAA) were the most effective stabilizing polymers in the group studied and that relatively low molar mass ligands (similar to 2500 g/mol) gave rise to the narrowest particle size distributions. Particle uniformity and colloidal stability to changes in ionic strength and pH were strongly affected by the hydrophobicity of the ligand end group. "Multidentate" thiol-terminated ligands were produced by employing dithiols and tetrathiols as chain-transfer agents, and these ligands gave rise to particles with unprecedented control over particle size and enhanced colloidal stability. It was found throughout that dynamic light scattering (DLS) is a very useful corroboratory technique for characterization of these gold nanoparticles in addition to optical spectroscopy and TEM.

Syntheses of Ag, PbSe, and PbTe nanocrystals and their binary self-assembly exploration at low size-ratio

Nanocrystals of Ag, PbSe, and PbTe were prepared via a high-temperature organic solution approach, respectively. Using a size-selection technique, the size-distribution of each set of nanocrystals could be fine-tuned and finally monodisperse products were achieved. Superlattice structure of binary self-assemblies in low size-ratio were also explored and characterized by transmission electron microscopy. It is realized that a success of achieving binary self-assembly pattern is greatly dependent on several key factors including particle size-distributions, relative concentrations of both components, as well as the size-ratios between Ag and PbSe (or PbTe) nanocrystals.

Influence of the size of ultrafine CaCO3 powder on PP crystallization

The effects of CaCO3 on the crystallization behavior of polypropylene (PP) were studied by means of DSC and WAXD. The average sizes of the CaCO3 powders used were 0.1 mum (UC) and 0.5 mum (GC), respectively. The PP/CaCO3 composites at compositions of 1 phr and 10 phr were investigated. The results showed that the addition of CaCO3 reduced the supercooling, the rate of nucleation and the overall rate of crystallization (except for the 10 phr UC/PP sample). The crystallinity of PP was increased and the size distribution of the crystallites of alpha -PP; was: broadened. On the other hand,the crystallization rate of 10 phr UC/PP is 1.5 times higher than that of neat PP. It has an overall rate of crystallization 2 times as much as that of the neat PP and has the maximum crystallinity. The sizes of crystallites and the unit cell parameters of alpha -PP were varied by the addition of CaCO3. beta -PP was formed by addition of Ge and was not detected by addition of UC. The differences of crystallization behaviors of PP might be attributed to the combined effects of the content and size of CaCO3 filled.

A novel method to synthesize amorphous silica-alumina materials with mesoporous distribution without using templates and pore-regulating agents

In this study, a novel sol-gel method is used to synthesize amorphous silica-alumina materials with a narrow mesoporous distribution and various Si/Al molar ratios without using any templates and pore-regulating agents. During the preparation procedure, only inexpensive inorganic salts were used as raw materials, instead of expensive and harmful alkoxides. The precursor sol was dried at room temperature in a vacuum box kept at 60 mmHg until it began to form the gel. The results of a nitrogen sorption experiment indicate that the synthesized materials with different Si/Al molar ratios have similar mesoporous distributions (within 2-12 nm). Moreover, it was found that the material's pore size distribution remains at a similar value during the heat treatment from room temperature to 550 degreesC. On the basis of the nitrogen sorption, TEM, and AFM characterization results, a formation mechanism of mesopores which accounts for the experimental data is also suggested. This suggested mechanism involves rearrangement of the primary particles during the drying process to form the precursors of the similarly sized mesopores. The synthesized materials were characterized by XRD, thermal analysis (TG/DTA), Al-27 and Si-29 MAS NMR spectroscopy, SEM, TEM, and AFM. The results of Al-27 and 29Si MAS NMR indicate that the distribution of silicon and aluminum in the synthesized materials is more uniform and homogeneous than that in the mixed oxides prepared via the traditional sol-gel method even at high alumina contents. The type and density of the acid sites were studied using pyridine adsorption-desorption FTIR spectroscopy. It was shown that the acidity of the synthesized materials is higher than that of the silica-alumina materials prepared by conventional methods.

Templateless synthesis of catalysts with narrow mesoporous distribution

In this study, amorphous silica-alumina nanomaterials with narrow mesoporous distribution can be obtained by two novel sol-gel processes, without the use of any templates. The results of our experiments show that the preparation method has a great influence on the precursor sol structure as well as the specific surface area and mesopore volume of the final product, but has no effect on the pore size distribution.

Ultrasonic synthesis of silica-alumina nanomaterials with controlled mesopore distribution without using surfactants

A novel sol-gel process has been developed for the synthesis of amorphous silica-aluminas with controlled mesopore distribution without the use of organic templating agents, e.g., surfactant molecules. Ultrasonic treatment during the synthesis enables production of precursor sols with narrow particle size distribution. Atomic force microscopy analysis shows that these sol particles are spherical in shape with a narrow size distribution (i.e., 13-25 nm) and their aggregation during the gelation creates clusters containing similar sized interparticle mesopores. A nitrogen physiadsorption study indicates that the mesoporous materials containing different Si/Al ratios prepared by the new synthesis method has a large specific surface area (i.e., 587-692 m(2)/g) and similar pore sizes of 2-11 nm. Solid-state Al-27 magic angle spinning (MAS) NMR shows that most of the aluminum is located in the tetrahedral position. A transmission electron microscopy (TEM) image shows that the mesoporous silica-alumina consists of 12-25 nm spheres. Additionally, high-resolution TEM and electron diffraction indicate that some nanoparticles are characteristic of a crystal, although X-ray diffraction and Si-29 MAS NMR analysis show an amorphous material.

Size-controllable synthesis of monodispersed SnO2 nanoparticles and application in electrocatalysts

Size-controllable tin oxide nanoparticles are prepared by heating ethylene glycol solutions containing SnCl2 at atmospheric pressure. The particles were characterized by means of transmission electron microscopic (TEM), X-ray diffraction (XRD) studies. TEM micrographs show that the obtained material are spherical nanoparticles, the size and size distribution of which depends on the initial experimental conditions of pH value, reaction time, water concentration, and tin precursor concentration. The XRD pattern result shows that the obtained powder is SnO2 with tetragonal crystalline structure. On the basis of UV/vis and FTIR characterization, the formation mechanism of SnO2 nanoparticles is deduced. Moreover, the SnO2 nanoparticles were employed to synthesize carbon-supported PtSnO2 catalyst, and it exhibits surprisingly high promoting catalytic activity for ethanol electrooxidation.

Ambient aerosol size distributions and number concentrations measured during the Pittsburgh Air Quality Study (PAQS)

Twelve months of aerosol size distributions from 3 to 560nm, measured using scanning mobility particle sizers are presented with an emphasis on average number, surface, and volume distributions, and seasonal and diurnal variation. The measurements were made at the main sampling site of the Pittsburgh Air Quality Study from July 2001 to June 2002. These are supplemented with 5 months of size distribution data from 0.5 to 2.5μm measured with a TSI aerosol particle sizer and 2 months of size distributions measured at an upwind rural sampling site. Measurements at the main site were made continuously under both low and ambient relative humidity. The average Pittsburgh number concentration (3-500nm) is 22,000cm-3 with an average mode size of 40nm. Strong diurnal patterns in number concentrations are evident as a direct effect of the sources of particles (atmospheric nucleation, traffic, and other combustion sources). New particle formation from homogeneous nucleation is significant on 30-50% of study days and over a wide area (at least a hundred kilometers). Rural number concentrations are a factor of 2-3 lower (on average) than the urban values. Average measured distributions are different from model literature urban and rural size distributions. © 2004 Elsevier Ltd. All rights reserved.

Hydrocarbon field size distributions: a case study in mixed integer nonlinear programming

Of key importance to oil and gas companies is the size distribution of fields in the areas that they are drilling. Recent arguments suggest that there are many more fields yet to be discovered in mature provinces than had previously been thought because the underlying distribution is monotonic not peaked. According to this view the peaked nature of the distribution for discovered fields reflects not the underlying distribution but the effect of economic truncation. This paper contributes to the discussion by analysing up-to-date exploration and discovery data for two mature provinces using the discovery-process model, based on sampling without replacement and implicitly including economic truncation effects. The maximum likelihood estimation involved generates a high-dimensional mixed-integer nonlinear optimization problem. A highly efficient solution strategy is tested, exploiting the separable structure and handling the integer constraints by treating the problem as a masked allocation problem in dynamic programming.

Pattern of benthic biomass size spectra from shallow waters in the East China Seas

Benthic biomass size spectra (BSS) and normalized biomass size spectra were constructed, and benthic secondary production was estimated by a size spectrum equation in the shallow waters in the East China Sea, ranging latitudinally from 40A degrees N to 29A degrees N. The BSS patterns were bimodal, two biomass peaks corresponding to meiofauna and macrofauna, respectively, separated by a trough of low biomass at 8-256 mu g individual dry weight which varied in position with median sediment particle size. The BSS also displayed bimodality within meiofauna size ranges, which in most stations was due to the relative proportions of nematodes and other meiofauna taxa. Re-analysis of data from sites in the UK, South Africa, and Antarctic showed a similar bimodality in the adult species body size distribution within the meiofauna size range. Macrofaunal production estimated by the size spectrum equation was very similar to the results of Brey90 empirical equation. However, these production values were much lower than those calculated by Brey01. Different individual dry-to-wet conversion ratios, temperature deviation, and macrofauna taxonomic composition might be responsible for the between-model differences. The macrofaunal P/B ratios calculated by this equation ranged from 0.3 to 3.4 which were in accordance with values from Northern Hemisphere mid-latitudes. Meiofaunal production estimates will need further empirical support.

Effect of batch size on mechanical properties of granules in high shear granulation

The flow patterns in a high shear granulator depend on the fill volume. For example, DEM simulations reported by Terashita et al. [1] show that fill volume affects the velocities and kinetic energies of the particles. It also influences the granule size distribution [2]. Here the effects on the properties of the granule are described. The total mass of the granulate material was varied without changing the other variables such as impeller speed, granulation time and liquid to solid ratio. The resulting mechanical properties, such as strength, yield stress and Young's modulus, of the granules were measured. For the materials studied in the current work, increasing the fill factor (batch size) increased the values of these material parameters. This could be explained by the relative increase in the number and intensity of collisions between the particles, when the size of a batch was increased, leading to smaller porosities. (c) 2010 Elsevier B.V. All rights reserved.

The effect of the binder size and viscosity on agglomerate growth in fluidised hot melt granulation

Fluidised hot melt granulation (FHMG) is a novel granulation technique for processing pharmaceutical powders. Several process and formulation parameters have been shown to significantly influence granulation characteristics within FHMG. In this study we have investigated the effect of the binder properties (binder particle size and binder viscosity) on agglomerate growth mechanisms within FHMG. Low-melting point co-polymers of polyoxyethylene–polyoxypropylene (Lutrol® F68 Poloxamer 188 and Lutrol® F127 Poloxamer 407) were used as meltable binders for FHMG, while standard ballotini beads were used as model fillers for this process. Standard sieve analysis was used to determine the size distribution of granules whereas we utilised fluorescence microscopy to investigate the distribution of binder within granules. This provided further insight into the growth mechanisms during FHMG. Binder particle size and viscosity were found to affect the onset time of granulation. Agglomerate growth achieved equilibrium within short time-scales and was shown to proceed by two competing processes, breakage of formed granules and re-agglomeration of fractured granules. Breakage was affected by the initial material properties (binder size and viscosity). When using binder with a small particle size (<250 µm), agglomerate growth via a distribution mechanism dominated. Increasing the binder particle size shifted the granulation mechanism such that agglomerates were formed predominantly via immersion. A critical ratio between binder diameter and filler has been calculated and this value may be useful for predicting or controlling granulation growth processes.

Effect of activated carbon xerogel pore size on the capacitance performance of ionic liquid electrolytes

The use of ionic liquid (IL) electrolytes promises to improve the energy density of electrochemical capacitors (ECs) by allowing for operation at higher voltages. Several studies have also shown that the pore size distribution of materials used to produce electrodes is an important factor in determining EC performance. In this research the capacitative, energy and power performance of ILs 1-ethyl-3- methylimidazolium tetrafluoroborate (EMImBF4), 1-ethyl-3-methylimidazolium dicyanamide (EMImN(CN)2), 1,2-dimethyl-3-propylimidazolium bis(trifluoromethylsulfonyl)imide (DMPImTFSI), and 1-butyl-3-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate (BMPyT(F5Et)PF3) were studied and compared with the commercially utilised organic electrolyte 1M tetraethylammonium tetrafluoroborate solution in anhydrous propylene carbonate (Et4NBF4–PC 1 M). To assess the effect of pore size on IL performance, controlled porosity carbons were produced from phenolic resins activated in CO2. The carbon samples were characterised by nitrogen adsorption– desorption at 77 K and the relevant electrochemical behaviour was characterised by cyclic voltammetry, galvanostatic charge–discharge and electrochemical impedance spectroscopy. The best capacitance performance was obtained for the activated carbon xerogel with average pore diameter 3.5 nm, whereas the optimum rate performance was obtained for the activated carbon xerogel with average pore diameter 6 nm. When combined in an EC with IL electrolyte EMImBF4 a specific capacitance of 210 F g1 was obtained for activated carbon sample with average pore diameter 3.5 nm at an operating voltage of 3 V. The activated carbon sample with average pore diameter 6 nm allowed for maximum capacitance retention of approximately 70% at 64 mA cm2.

Casualties distribution in human and natural hazards

Catastrophic events, such as wars and terrorist attacks, big tornadoes and hurricanes, huge earthquakes, tsunamis, floods, and landslides, are always accompanied by a large number of casualties. The size distribution of these casualties have separately been shown to follow approximate power law (PL) distributions. In this paper, we analyze the number of victims of catastrophic phenomena, in particular, terrorism, and find double PL behavior. This means that the data set is better approximated by two PLs instead of one. We have plotted the two PL parameters corresponding to all terrorist events occurred in every year, from 1980 to 2010. We observe an interesting pattern in the chart, where the lines, that connect each pair of points defining the double PLs, are roughly aligned to each other.

On the efficient evaluation of ruin probabilities for completely monotone claim size distributions

In this paper we propose a highly accurate approximation procedure for ruin probabilities in the classical collective risk model, which is based on a quadrature/rational approximation procedure proposed in [2]. For a certain class of claim size distributions (which contains the completely monotone distributions) we give a theoretical justification for the method. We also show that under weaker assumptions on the claim size distribution, the method may still perform reasonably well in some cases. This in particular provides an efficient alternative to a related method proposed in [3]. A number of numerical illustrations for the performance of this procedure is provided for both completely monotone and other types of random variables.