Synthesis and characterization of silica microcapsules using a sustainable solvent system template

We report direct encapsulation of a sustainable solvent system in silica microcapsules via a sol-gel reaction of silica precursor for potential application of thermoplastic self healing polymeric system. The silica microcapsules were realized by hydrolysis and condensation of tetraethyl orthosilicate (TEOS) using aqueous glycerol microemulsion as template. The pre-hydrolysis of TEOS was found to be useful to obtain isolated free flowing silica microcapsules. Furthermore, the effects of different parameters viz. temperature, rotor speed, the solvent/TEOS ratio on the synthesis of silica microcapsules are studied. A novel micro compression technique to study mechanical properties of the silica microcapsules is reported. The silica microcapsules reported were found to have better mechanical properties compared to incumbent Urea-Formaldehyde (UF) based organic microcapsules.     

Study of heterogeneously catalysed reactive distillation using the D+R tray—A novel type of laboratory equipment

Recently, novel equipment for heterogeneously catalysed reactive distillation, the D+R tray, has been introduced by Schmitt et al. (2009). The present work reports results of measurements of the separation capacity of D+R trays. Furthermore, results of reactive distillation experiments on two test systems are presented that show that the D+R tray can be used routinely for laboratory studies of heterogeneously catalysed reactive distillation. As test systems, the esterifications yielding butyl acetate and hexyl acetate were chosen. Reactive distillation using catalytic packings was studied previously in detail ( [Parada, 2008], [Schmitt et al., 2004] and [Schmitt et al., 2005]) with the same test system. The experiments of the present work are carried out so that a direct comparison is possible. For both test systems, the most important process parameters such as feed rate and mass of catalyst were systematically varied. High conversions of the reactants and high purities of the products were achieved. The reproducibility of the results is excellent. The study shows that the D+R tray is a novel laboratory equipment that facilitates fast and flexible investigations of heterogeneously catalysed reactive distillation processes and that it can be used for studying process designs of columns equipped with either catalytic packings or trays.     

Occupational exposure to hexabromocyclododecane at an industrial plant

Occupational exposure to hexabromocyclododecane (HBCD) among workers at an industrial plant producing expandable polystyrene (PS) added HBCD as flame retardant has been assessed in the present study. Airborne dust samples were collected near the breathing zone of 10 male workers during three 8-h work shifts. The HBCD concentrations in the airborne dust varied from 0.2 to 150 microg/m3 (mean 12.2 and median 2.1 microg/m3). Two serum samples were obtained from each of the workers. The mean serum concentration was 190 ng/g lipids; the median was 101 ng/g lipids (range 6 to 856 ng/g lipids). HBCD was not detected above 1 ng/g lipids (LOD) in any samples from persons in a reference group with no occupational exposure to HBCD. The contribution of gamma-HBCD to the total HBCD serum concentration was notably high (39%) compared to what has usually been observed in biological samples. There was no clear correlation of serum levels with average HBCD concentrations in the airborne dust samples collected near the subjects' breathing zone. The elevated exposure levels reported in this study compared to urban air and serum levels in general populations suggest that further and more detailed exposure assessment studies should be initiated in industries where HBCD is applied.     

Adsorption enhancement mechanisms of silica-titania nanocomposites for elemental mercury vapor removal

A novel nanocomposite that combines high-surface area silica with the photocatalytic properties of titania has been developed that allows for effective capture of elemental mercury vapor. The adsorption capability of the developed material has been found to improve after periods of photocatalytic oxidation. In this study, the mechanisms for adsorption enhancement were identified. BET nitrogen adsorption and mercury porosimetry were used to evaluate pore structure, and the results suggest that a decrease in contact angle was likely to be responsible for improved mercury capture over time. Contact angle measurements showed a significant change of more than 10 degrees, indicating greater attraction to mercury for the used pellets due to deposited mercuric oxide. ICP and TGA analyses showed that mercury was captured as both elemental mercury (Hg0) and mercuric oxide (HgO). In addition, it was shown that pellets used for nearly 500 h still showed greater than 90% removal efficiency and had an average capacity of 10 mg of Hg/g based on mass balance calculations, while some pellets had a capacity over 30 mg of Hg/g according to ICP and TGA analyses. Mercuric oxide doped pellets removed 100% of elemental mercury without pretreatment. The superior mercury removal efficiency combined with various advantages of the novel composite demonstrates its use as an effective alternative to conventional activated carbon injection technology.     

Composition and bioactive factor content of cowpea (Vigna unguiculata L. Walp) raw meal and protein concentrate

Analysis was done of the composition and bioactive factor content of whole meal, processed meal and protein concentrate from a cowpea cultivar (Vigna unguiculata L. Walp var. IT86D‐719) grown in Yucatan, Mexico and of changes in these parameters after soaking and dehulling. Both meals had a high protein content (247.53 and 257 g kg^?1 dry matter (DM) respectively). The protein concentrate was rich in protein (786 g kg^?1 DM) and lipids (58.47 g kg^?1 DM) and had an amino acid profile similar to that of the processed meal. The amino acid profiles of the meals almost covered human dietary requirements based on FAO/WHO/UNU‐suggested profiles but were deficient in sulphur amino acids. Trypsin inhibitor activity was high in both meals compared with levels found in previous studies. Trypsin inhibitor activity in the concentrate was not eliminated but was significantly reduced. Lectin activity, tannin levels, phytate levels and α‐amylase inhibitor activity were relatively low in the meals, and cyanogenic glucosides were not detected. Residual amounts of α‐amylase inhibitors, tannins and phytate were observed in the concentrate, and lectin activity was not detected. Results indicate that V. unguiculata L. Walp var. IT86D‐719 meals and protein concentrate are good potential foodstuffs in the Yucatan region. Copyright © 2006 Society of Chemical Industry     

Fossil fuel and wood combustion as recorded by carbon particles in Lake Erie sediments 1850-1998

Carbon particle analysis was performed on a dated sediment core from Lake Erie in order to explore the inputs of pollution from incomplete combustion of coal, oil, and wood. Carbon particles were isolated from the sediment by chemical digestion, and elemental carbon content was determined by CHN analysis. The type of carbon particle (from burning coal, oil, and wood) and particle size and relative abundance were determined using scanning electron microscopy on 100 particles from each core section. The elemental carbon content in the Lake Erie core ranges from 2.5 to 7.4 mg of carbon/g of sediment (1850-1998), and the maximum carbon content in the sediment occurs in the late 1960s to early 1970s. It is shown that particle mass is a better predictor than particle number of historical energy consumption records. This is especially clear for wood where variable particle volumes play a significant role in determining the record of elemental carbon mass from wood burning. Lake Erie core's content of total carbon and carbon particle type is in agreement with U.S. energy consumption records, except that a wood maximum occurs during 1905-1917, about 36 yr after the U.S. consumption maximum from 1870 to 1880.     

Different catalytic effects by copper and chromium on the formation and degradation of chlorinated aromatic compounds in fly ash

Fly ash from municipal solid waste incineration may catalytically enhance the formation and degradation of chlorinated aromatic compounds. The activities of three Deacon catalysts in this process were investigated in a statistically designed experiment. Chlorides of copper, chromium, and nickel were added to fly ash samples and the resulting samples heated at 300 degrees C for 2 h in an air atmosphere. The addition of copper increases the formation of all chlorinated aromatic compounds except the low chlorinated congeners of polychlorinated dibenzo-p-dioxins and dibenzofurans. The addition of chromium decreased the formation of most chlorinated aromatic compounds except the highest chlorinated species, where it was without effect. The addition of nickel did not show any significant effect. The outcome of the experiment can be interpreted as two competing processes: the chlorination of aromatic rings and the oxidation of carbon-carbon and carbon-oxygen bonds. The delicate balance between chlorination and oxidation could probably be further exploited to minimize both the emissions and the net production of chlorinated aromatic compounds from combustion.     

Is Ultra-Low Friction Needed to Prevent Wear of Diamond-Like Carbon (DLC)? An Alcohol Vapor Lubrication Study for Stainless Steel/DLC Interface

The effects of n-pentanol vapor on friction and wear of hydrogenated diamond-like carbon (DLC) films during sliding against a 440C stainless steel (SS) ball were investigated with a reciprocating pin-on-disc tribometer. Under dry sliding conditions, the friction coefficient is initially high (>0.2) for a so-called run-in period and then gradually subsequently decreases to an ultra-low value (<0.025). During the run-in period, a carbon transfer film is formed on the SS ball side, which seems to be the key for the ultra-low friction behavior. In n-pentanol vapor environments, the friction coefficient remained nearly constant at ~0.15 throughout the entire test cycles without any noticeable run-in period. Although the friction coefficient is high, there is no visible wear on rubbing surfaces when examined by optical microscopy, and the transfer film forming tendency on the SS ball side was much reduced. In humid environments, the wear prevention effect is not observed and transfer films do form on the ball side. These results imply that the n-pentanol layer adsorbed on DLC film from the vapor phase provides a molecularly thin lubrication layer which can prevent the substrate from wear.