Dissolution and Deagglomeration of Silicon Nitride in Aqueous Medium

Silicon nitride undergoes hydrolysis and dissolution when subjected to an aqueous environment. Molecular dynamics simulations suggest that hydrolysis proceeds through nucleophilic attack of water with the formation of an intermediate molecular complex involving a pentacoordinated silicon. We found that the dissolution of an oxidized silicon nitride powder resembles that of silica; the dissolution rate could be described using a simple kinetic equation with a dissolution activation energy of 52 kJ·mol⁻¹. The deagglomeration of a fine silicon nitride powder under mild agitation was evaluated; we show that the peptization kinetics at room temperature is dominated by the breakup of particle–particle bonds due to hydrodynamic friction and cluster attrition. For breakup of hard agglomerates of small particles the dissolution of interparticle necks will play an important role.     

Mixing effects on particle formation in supercritical fluids

The process termed solution enhanced dispersion by supercritical fluids (SEDS™) is investigated. In the process particles are created in the rapid antisolvent process using a twin-fluid nozzle to co-introduce the SCF antisolvent and solution. Results of experimental and numerical studies are presented for two regions of pressure: above the mixture critical pressure where a single-phase exists for all solvent–antisolvent compositions, and below the mixture critical pressure where the two-phase region is observed. In experimental studies paracetamol (in the single-phase system) and nicotinic acid (in the two-phase system) were precipitated from ethanol solution using supercritical CO₂ as an antisolvent. To interpret the phenomena affecting creation of the supersaturation and to predict suprsaturation distribution, balances of momentum (flow), species (mixing), energy (heating and cooling) and population (droplet and crystal size distributions) are applied. The Favre averaged k–? model of the CFD code FLUENT is applied together with specific models for precipitation subprocesses and Peng–Robinson equation of state. This includes application of the PDF closure procedure for precipitation and the drop breakage kernel that is based on multifractal theory of turbulence for modelling drop dispersion. Thermodynamic effects of mixing and decompression are included as well. Predicted values not always agree with experimental data but anyhow simulations predict all trends observed in experiments.     

Nonignorable dropout models for longitudinal binary data with random effects: An application of Monte Carlo approximation through the Gibbs output

The analysis of longitudinal data with nonignorable dropout remains an active area in biostatistics research. Nonignorable dropout (ND) refers to the type of dropout when the probability of dropout depends on the missing observations at or after the time of dropout. Failure to account for such dependence may result in biased inference. Motivated by a methadone clinic data of longitudinal binary observations with dropouts, we propose a conditional first order autoregressive (AR1) logit model for the outcome measurements. The model is further extended to incorporate random effects in order to account for the population heterogeneity and intra-cluster correlation. The purposed models account for the dropout mechanism by a separate logit model in some covariates and missing outcomes for the binary dropout indicators. For model implementation, we proposed a likelihood approach through Monte Carlo approximation to the Gibbs output that evaluates the complicated likelihood function for the random effect ND model without tear. Finally simulation studies are performed to evaluate the biases on the parameter estimates of the outcome model for different dropout mechanisms.     

Preparation of a TiMEMO nanocomposite by the sol–gel method and its application in coloured thickness insensitive spectrally selective (TISS) coatings

An organic–inorganic nanocomposite was prepared via sol–gel processing from 3-(trimethoxysilyl)propyl methacrylate (MAPTMS) and titanium(IV) isopropoxide (TIP) precursors (TiMEMO) in the form of a viscous resin, and used as a binder for the preparation of coloured thickness insensitive spectrally selective (TISS) paints and corresponding solar absorber coatings. The spectral selectivity of TiMEMO-based TISS paints was optimized by varying the concentrations of binder and different pigments: black, coloured (red, green and blue) and aluminium flakes, the latter imparting low thermal emittance, which was correlated to the presence of titanium in the TiMEMO sol–gel host. The formation and the ensuing structure of the sol–gel TiMEMO hybrid was studied in detail and the nanocomposite structure of the TiMEMO binder formed was assessed from infrared and ²⁹Si NMR measurements, which confirmed the formation of Ti–O–Si linkages established after the hydrolysed precursors condensed into a compliant resinous material. XRD measurements provided additional information about the existence of small coherent domains of silsesquioxane units in the sol–gel host. The abrasion resistance of the non-pigmented TiMEMO binder deposited in thin film form on a PMMA substrate was assessed by the Taber test, and its hardness compared with other resin binders which have been used for making TISS paint coatings. The surface properties of the non-pigmented TiMEMO binder and the ensuing TISS paint coatings were determined from contact angle measurements. The results showed that the water contact angles of non-pigmented TiMEMO binder increased from 70° to 125–135° for the corresponding pigmented TISS paint coatings, inferring the influence of surface roughness on surface energy in the presence of pigments. SEM measurements revealed a striking similarity in the surface morphology of the TISS paint coatings with some other surfaces exhibiting the Lotus effect.     

Exploratory analysis of potential risk factors of a rare disease: Spatial distribution of adrenocortical carcinoma in Israel as a case study

The underlying assumption of the proposed exploratory approach is that, if the geographic patterns of different diseases are compared, the cases of a ‘subject’ disease should occur closer to cases of a disease with similar environmental risk factors (etiology) and farther away from cases of a disease with different etiology. In the present study, the performance of proposed approach is investigated by cross-examination of the spatial patterns of three widespread cancers — lung, larynx and colorectal (CRC) — with that of a rare malignant disease — Adrenocortical Carcinoma (ACC). As the analysis indicates, the spatial distribution of ACC is more likely to be related to hereditary factors than to environmental causes, in accordance with current knowledge about this rare disease.     

Textbook multigrid efficiency for the incompressible Navier–Stokes equations: high Reynolds number wakes and boundary layers

Textbook multigrid efficiencies for high Reynolds number simulations based on the incompressible Navier–Stokes equations are attained for a model problem of flow past a finite flat plate. Elements of the full approximation scheme multigrid algorithm, including distributed relaxation, defect correction, and boundary treatment, are presented for the three main physical aspects encountered: entering flow, wake flow, and boundary layer flow. Textbook efficiencies, i.e., reduction of algebraic errors below discretization errors in one full multigrid cycle, are attained for second order accurate simulations at a laminar Reynolds number of 10,000.     

Evaluating information in multiple horizon forecasts: The DOE's energy price forecasts

The United States Department of Energy's (DOE) quarterly price forecasts for energy commodities are examined to determine the incremental information provided at the one-through four-quarter forecast horizons. A direct test for determining information content at alternative forecast horizons, developed by Vuchelen and Gutierrez [Vuchelen, J. and Gutierrez, M.-I. “A Direct Test of the Information Content of the OECD Growth Forecasts.” International Journal of Forecasting. 21(2005):103–117.], is used. The results suggest that the DOE's price forecasts for crude oil, gasoline, and diesel fuel do indeed provide incremental information out to three-quarters ahead, while natural gas and electricity forecasts are informative out to the four-quarter horizon. In contrast, the DOE's coal price forecasts at two-, three-, and four-quarters ahead provide no incremental information beyond that provided for the one-quarter horizon. Recommendations of how to use these results for making forecast adjustments is also provided.