Adsorption of cadmium on anatase nanoparticles-effect of crystal size and pH

The adsorption and desorption of Cd(2+) to large and nanometer-scale anatase crystals have been studied to determine the relationship between heavy metal adsorption properties and anatase particle size. A solvothermal method was used to synthesize very fine anatase nanocrystals with average grain sizes ranging from 8 to 20 nm. On a surface area basis, it was found that large and nanometer-scale anatase particles had similar maximum Cd(2+) adsorption capacities, while their adsorption slopes differed by more than 1 order of magnitude. The particle-size effect on adsorption is constant over a pH range of 4-7.5. The desorption of Cd(2+) from both particle sizes is completely reversible. The adsorption data have been modeled by the Basic Stern model using three monodentate surface complexes. It is proposed that intraparticle electrostatic repulsion may reduce the adsorption free energy significantly for nanometer-sized particles.     

Controlling submicron-particle template morphology: effect of solvent chemistry

Porous solids were obtained from self-assembled deposits of silica particles used as templates to form 3-D porous membranes. The effect of the solvent chemistry on the morphology of the deposits was investigated. The parameters of interest are surface tension and ionic strength of the solvent, as they impact electrostatic and capillary interactions. Deposits of particles of different sizes were obtained from a variety of conditions. The deposits were imaged by SEM and showed distinctive structures for each of the solvent chemistries. The phenomenon is qualitatively consistent with DLVO theory and calculations of capillary interaction energy as developed by Kralchevsky and co-workers.     

A model for plasticity kinetics and its role in simulating the dynamic behavior of Fe at high strain rates

The recent diagnostic capability of the Omega laser to study solid-solid phase transitions at pressures greater than 10 GPa and at strain rates exceeding 10⁷ s⁻¹ has also provided valuable information on the dynamic elastic-plastic behavior of materials. We have found, for example, that plasticity kinetics modifies the effective loading and thermodynamic paths of the material. In this paper we derive a kinetics equation for the time-dependent plastic response of the material to dynamic loading, and describe the model’s implementation in a radiation-hydrodynamics computer code. This model for plasticity kinetics incorporates the Gilman model for dislocation multiplication and saturation. We discuss the application of this model to the simulation of experimental velocity interferometry data for experiments on Omega in which Fe was shock compressed to pressures beyond the α-to-ε phase transition pressure. The kinetics model is shown to fit the data reasonably well in this high strain rate regime and further allows quantification of the relative contributions of dislocation multiplication and drag. The sensitivity of the observed signatures to the kinetics model parameters is presented.     

Direct observation of the alpha-epsilon transition in shock-compressed iron via nanosecond x-ray diffraction

In situ x-ray diffraction studies of iron under shock conditions confirm unambiguously a phase change from the bcc (alpha) to hcp (epsilon) structure. Previous identification of this transition in shock-loaded iron has been inferred from the correlation between shock-wave-profile analyses and static high-pressure x-ray measurements. This correlation is intrinsically limited because dynamic loading can markedly affect the structural modifications of solids. The in situ measurements are consistent with a uniaxial collapse along the [001] direction and shuffling of alternate (110) planes of atoms, and are in good agreement with large-scale nonequilibrium molecular dynamics simulations.     

Direct observation of terahertz surface modes in nanometer-sized liquid water pools

The far-infrared absorption spectrum of nanometer-sized water pools at the core of AOT micelles exhibits a pronounced resonance which is absent in bulk water. The amplitude and spectral position of this resonance are sensitive to the size of the confined water core. This resonance results from size-dependent modifications in the vibrational density of states, and thus has far-reaching implications for chemical processes which involve water sequestered within small cavities. These data represent the first study of the terahertz dielectric properties of confined liquids.     

Synthesis,Properties, and Crystal Structure of Silyl Nitronates (Silyl Esters of aci-Nitroalkanes): Towards the SN2 Reaction Path with Retention of Configuration at Silicon

An efficient and flexible method for the preparation of silyl nitronates is described (see 1–10 ). NMR. spectral investigations indicate a rapid 1,3-silyl migration process, with an activation energy of about 10 kcal mol^?1. X-ray crystallographic studies on the silyl nitronates 3 and 8 show structures that lean towards an S_N2 retention pathway at silicon.     

Coupling (launching) efficiency for a light-emitting diode,optical fibre termination

A ray tracing technique is used for calculating coupling efficiency between a light-emitting diode (LED) and an optical fibre. With an air interface, efficiency is estimated as a function of separation, waveguide diameter and source diameter, estimates are obtained using numerical methods. Initially the treatment considers a uniform source and is subsequently extended to Lambertian and weighted Lambertian distributions. The effect of numerical aperture on coupling coefficients is described.     

Modeling and Anomalous Cluster Detection for Point Processes Using Process Convolutions

We present a model using process convolutions, which describes spatial and temporal variations of the intensity of events that occur at random geographical locations. An inhomogeneous Poisson process is used to model the intensity over a spatial region with multiplicative spatial and temporal covariate effects. Temporal variation in the structure of the intensity is obtained by employing a time-varying process for the convolution. Use of a compactly supported kernel in the convolution improves the computational efficiency. Additionally, anomalous cluster detection in the event rates is developed based on exceedance probabilities. The methods are demonstrated on data of major crimes in Cincinnati during 2006. Supplementary materials for this article are available online.