The non-Fickian diffusion of deterrents into a nitrocellulose-based propellant

The diffusion of solutions of ethyl centralite (EC), dibutylphthalate (DBP), and dinitrotoluene (DNT) into a nitrocellulose (NC) propellant is investigated. DBP and EC penetrate the propellant in a way consistent with Case II diffusion. The diffusion of DNT solutions is Fickian. The apparent activation energy for Case II diffusion is 62 kJ/mol for DBP and 66 kJ/mol for EC. Changes to coating solvent polarity have little effect on DNT and DBP penetration and merely alter the rate, not the mechanism, of EC diffusion into the propellant.     

Effect of catalyst on regioselectivity and vinyl/H exchange on silicon in the hydrosilylation of vinyl-siloxanes by T8 hydrogen silsesquioxane

We have recently reported the synthesis of octopus molecules of defined shape and size with molecular weights well into the thousands. These octopus molecules were made by placing eight pendant groups symmetrically about a central silsesquioxane core via the H₂PtCl₆ catalyzed hydrosilylation of 1-alkenes as well as vinyl- and allyl-siloxanes by T₈ hydrogen silsesquioxane, (HSiO₃₂)₈. The chemistry of addition was studied and it was found that while the addition of the 1-alkenes to T₈ was regioprecise with only -addition being observed, both - and -addition occurred with vinyl-siloxane. In addition, H-vinyl exchange on silicon was observed to occur with addition of vinyl-siloxane to T₈. In the current studies, the effect of the hydrosilylation catalyst. homogeneous and heterogeneous, on the regioselectivity of addition and on the extent of exchange on silicon was evaluated. It was found that the heterogeneous catalysts Pt–C, sulfided Pt–C, and Rh–C required higher temperature and longer times to get complete reaction than the homogeneous catalysts. H₂PtCl₆ and the tetramethyldivinyldisiloxane complex of Pt. Pd supported catalysts were not effective catalysts for this hydrosilylation. The extent of exchange on silicon and the degree of the second mode of addition occurring were higher with the heterogenous catalysts and may be a result of the higher reaction temperatures.     

Carbonization and liquid-crystal (mesophase) development. 12. Mechanisms of the co-carbonization of coals with organic additives

In industrial situations, coals interact with solvents or additives to produce liquid fuels, solvent-refined coal, coal extract and metallurgical coke. In these processes there occurs a wide variation in effects or modifications of the coal by these additives. This paper describes the modifications which can occur, using a wide range of rank of coal, when these coals interact and are co-carbonized with a wide range of additives of different chemical properties. The optical texture of the resultant cokes is given special attention. The objective of the paper is to summarize the current state of knowledge of the mechanisms of these interactions. Possible mechanisms of interactions are summarized, kinetic and chemical structural aspects of reactions are outlined, the importance is mentioned of the formation of liquid phases enabling anisotropic optical textures in modified cokes to be created, and the industrial relevance of its possible development is discussed.     

Analysis of Indentation Crack as a Wedge-Loaded Half-Penny Crack

Surface cracks produced by indentation with a Vickers indenter were modeled as half-penny cracks extended by symmetric disk-shaped wedges. The wedge diameter was assumed to be equal to the hemispherical plastic zone size, and the wedge thickness was calculated by equating the wedge volume to the hardness-impression volume. The resulting equilibrium relation between the indentation load and the radius of the half-penny crack is in good quantitative agreement with similar relations obtained from fracture toughness calibration.     

2,2′-oxo-1,1′-azobenzene: microbial transformation of rye (Secale cereale L.) allelochemical in field soils byAcinetobacter calcoaceticus: III

Acinetobacter calcoaceticus, a gram-negative bacterium isolated from field soil, was found to be responsible for the biotransformation of 2(3H)-benzoxazolinone (BOA) to 2,2-oxo-1,1-azobenzene (AZOB). Experiments were conducted to evaluate the transformation of BOA to AZOB by this microbe in sterile and nonsterile soil. Transformation studies with soils inoculated withA. calcoaceticus indicated that the production of AZOB increased linearly with the concentration of BOA in sterile soil and showed a quadratic trend in nonsterile soils. This also indicated that all soil types studied for the transformation experiments might containA. calcoaceticus capable of the conversion of benzoxazolinones.     

Measurement of the size, shape and orientation of convex bodies

Different types of solid bodies (particles) with specific shape and size are needed for industrial processes. For spherical particles, ‘sizer’ measurements are usually reported as sphere diameters. For non-spherical particles, particle shape and especially orientation must be taken into account. Particles of a specific shape will present different views when looked at from different directions.We have employed a Camsizer^® instrument to measure the distribution of projected area under different physical conditions for solid cylindrical particles:

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Under ‘ideal’ conditions, corresponding to a uniform distribution of particle orientation, measurements agreed with predictions. The celebrated theorem of Cauchy applies only to this case.

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For two other situations, measured and predicted results differed. However, from the experimental data it was possible to infer the particle orientations and hence theoretically predict the projected area distribution. Excellent agreement between theory and practice was then restored.

     

Carbonization and liquid-crystal (mesophase) development. 8. The co-carbonization of coals with acenaphthylene and decacyclene

Several coals of different rank have been carbonized singly and also co-carbonized with acenaphthylene and decacyclene. The resultant cokes were mounted in resin and polished surfaces were examined for optical texture using a polarized-light optical microscope fitted with a half-wave retarder plate. The optical texture can be assessed qualitatively (visually) or quantitatively by a point-counting technique in terms of size and shape of constituent isochromatic anisotropic units. Some cokes from coals were Isotropic. Acenaphthylene was only able to exert a smaller influence than decacyclene on the optical texture of the resultant cokes from co-carbonizations. Decacyclene was able to modify the optical texture for both the low-rank non-fusible and the caking coals. The effects of changing the proportions of coal to additive were examined. Results are interpreted in terms of ‘depolymerization’ of the coal by the action of the additive (as solvent) and also by the action of the additive in modifying the processes of formation of semi-coke via nematic liquid crystals.     

Influence of alginite on the reflectance of vitrinite from Joadja,NSW, and some other coals and oil shales containing alginite

Reflectance data for vitrinite occurring in torbanites indicate that the mean maximum reflectance and the range of reflectance values are significantly lowered by the presence of alginite. This is the probable cause of apparently anomalous rank gradients in some deep oil exploration wells. Intermaceral effects need to be considered in assessing rank or maturity from vitrinite reflectance, and by inference, in most other methods. The interpretation of the cause of the effect is open to further study but the findings are highly significant in relation to coal utilization, oil and gas exploration, and studies of oil shales.     

Synthetic hydrogels 3. Solvent effects on poly(2-hydroxyethyl methacrylate) networks

Poly(2-hydroxyethyl methacrylate) networks were synthesized in aqueous solutions of propylene glycol, ethylene glycol, ethylene glycol monomethyl ether, or ethylene glycol dimethyl ether and the influences of solvent on phase separation during the polymerization process studied. Results from conversion-phase diagrams, turbidity measurements, swelling studies, and viscosity measurements show that the phase separation process is dependent upon the solubility parameter of the organic solvent, the instantaneous monomer concentration at each stage of the gel formation process, and the crosslinker content of the reaction mixture.