Calcium sulphide formation in fluidized bed boilers

Analyses of samples of bed ash from a stationary fluidized bed boiler show the presence of calcium sulphide. In some samples, half of the total sulphur was present as sulphide. The samples containing CaS were obtained under unstaged conditions and with a high excess air ratio, 1.3 to 1.4. The samples were taken after a stop in the limestone addition, i.e. at high SO₂ emissions of about 1000 mL/m³ (ppm). No CaS was found during limestone addition when the SO₂ emission was 300–400 mL/m³. This indicates that formation of large amounts of CaS may be initiated as the SO₂ concentration exceeds some critical level.     

Comprehensive wellbore stability analysis utilizing Quantitative Risk Assessment

A comprehensive geomechanical approach to wellbore stability requires knowledge of rock strength, pore pressure and the magnitude and orientation of the three principal stresses. These parameters are often uncertain, making confidence in deterministic predictions of the risks associated with instabilities during drilling and production difficult to assess. This paper demonstrates the use of Quantitative Risk Assessment (QRA) to formally account for the uncertainty in each input parameter to assess the probability of achieving a desired degree of wellbore stability at a given mud weight. We also utilize QRA to assess how the uncertainty in each parameter affects the mud weight calculated to maintain stability. In one case study, we illustrate how this approach allows us to compute optimal mud weight windows and casing set points at a deep-water site. In another case study, we demonstrate how to assess the feasibility of underbalanced drilling and open-hole completion of horizontal wells utilizing a comprehensive stability analysis that includes application of QRA.     

Capillary Electrophoretic Analysis Reveals Subcellular Binding between Individual Mitochondria and Cytoskeleton

Interactions between the cytoskeleton and mitochondria are essential for normal cellular function. An assessment of such interactions is commonly based on bulk analysis of mitochondrial and cytoskeletal markers present in a given sample, which assumes complete binding between these two organelle types. Such measurements are biased because they rarely account for nonbound "free" subcellular species. Here we report on the use of capillary electrophoresis with dual laser induced fluorescence detection (CE-LIF) to identify, classify, count, and quantify properties of individual binding events of the mitochondria and cytoskeleton. Mitochondria were fluorescently labeled with DsRed2 while F-actin, a major cytoskeletal component, was fluorescently labeled with Alexa488-phalloidin. In a typical subcellular fraction of L6 myoblasts, 79% of mitochondrial events did not have detectable levels of F-actin, while the rest had on average ～2 zmol of F-actin, which theoretically represents a ～2.5 μm long network of actin filaments per event. Trypsin treatment of L6 subcellular fractions prior to analysis decreased the fraction of mitochondrial events with detectable levels of F-actin, which is expected from digestion of cytoskeletal proteins on the surface of mitochondria. The electrophoretic mobility distributions of the individual events were also used to further distinguish between cytoskeleton-bound from cytoskeleton-free mitochondrial events. The CE-LIF approach described here could be further developed to explore cytoskeleton interactions with other subcellular structures, the effects of cytoskeleton destabilizing drugs, and the progression of viral infections.     

Dielectric response and structure of amorphous hydrogenated carbon films with nitrogen admixture

The optical properties and structure of a-C:H films were modified by addition of nitrogen into the CH₄/H₂ deposition mixture. Three films prepared in capacitively coupled rf discharge were compared: (a) hydrogenated diamond like carbon film with hydrogen content of 34% and indentation hardness of 21.7 GPa, (b) hard a-C:H:N film with nitrogen content of 13% and indentation hardness of 18.5 GPa and (c) soft a-C:H:N film with nitrogen content of 10% and indentation hardness of 6.7 GPa. It is shown how the parametrized density of states model describing dielectric response of electronic interband transitions can be applied to modified a-C:H:N and how it can be combined with correct treatment of transmittance measured in infrared range using additional Gaussian peaks in joint density of phonon states. This analysis resulted in determination of film dielectric function in wide spectral range (0.045-30 eV) and provided also information about the density of states of valence and conduction bands and lattice vibrations.     

Effect of thiourea on thiuram-accelerated sulfur vulcanization and its significance for vulcanization mechanism

Tetramethylthiuram disulfide-accelerated sulfur vulcanization of natural rubber has been investigated at temperatures from 100°C to 140°C. Continuous measurements in a Vuremo curemeter were used to estimate the extent of crosslinking, which was plotted against cure time. The linearized forms of the cure curves clearly show that at lower cure temperatures, the course of vulcanization differs significantly from the first-order rate law. These digressions were removed by the addition of thiourea, which simultaneously speeds up the course of vulcanization and diminishes its activation energy on the one hand but, on the other hand, diminishes the ultimate extent of crosslinking. On the basis of the above results, the mechanism of thiuram-accelerated sulfur vulcanization, in which ionic and radical reactions take place, is discussed.     

Effect of zinc oxide concentration on the course of thiuram-accelerated sulfur vulcanization

Tetramethylthiuram disulfide-accelerated sulfur vulcanization of natural rubber has been investigated. Continuous measurements in a Vuremo curemeter at 145°C were used to estimate the effects of zinc oxide concentration on the induction periods, on the first-order rate constants, and on the ultimate extents of crosslinking, on the extents of degradation reaction (reversion), and on the extents of relaxation of vulcanizates at the cure temperature. The concentration of zinc oxide has practically no influence on the rate of thiuram-accelerated sulfur cure. The values of the ultimate extents of crosslinking increase with increasing the zinc oxide content in the rubber compound up to a certain limit corresponding to the theoretical amount of zinc oxide which is necessary for the formation of zinc dimethyldithiocarbamate from tetramethylthiuram disulfide and zinc oxide during the vulcanization reaction. From the point of view of the reversion, however, this limit value of zinc oxide concentration is not sufficient. The relaxation measurements provide the same results. On the basis of these, for thiuram-accelerated sulfur vulcanizations, the optimum zinc oxide content in the rubber mix of 2.5 phr has been calculated. This value is in very good agreement with the optimum value of zinc oxide concentration found for both sulfenamides and thiazoles-accelerated sulfur cures.     

Long-time sulfenamide-accelerated sulfur vulcanization of natural rubber/chlorobutyl rubber compounds

Sulfenamide-accelerated sulfur vulcanization of natural rubber/chlorobutyl rubber compounds has been investigated at temperatures from 155 to 175°C over 0.1 to 400 min. Continuous measurements in a Cone Rheometer were used to estimate the extent of crosslinking, which was plotted against cure time. On the basis of a kinetic analysis, two first-order vulcanization reactions, crosslinking and degradation, have been evaluated. Over the temperature range studied, there is no significant difference between the values of activation energy for these reactions. The rate of the degradation is slower by a factor of 20 than the rate of crosslinking. The degradation reaction can be limited by increasing the “efficiency” of the vulcanizing system.     

Thermovulcanization of polychloroprene rubber and its blends with poly(vinyl chloride)

Heat and mechanical stressing at higher temperatures effect changes in polychloroprene rubber leading to network formation. During thermovulcanization of polychloroprene rubber in the temperature range of 150–200°C, two reactions have been observed and their kinetic parameters determined. When the rubber is stressed by shearing forces, the rate of degradation crosslinking is fairly high even at relatively low temperatures (90–150°C). Thermovulcanization of polychloroprene rubber/poly(vinyl chloride) blends has been investigated in the entire concentration range at 180°C. Maxima have been observed on the dependences of some kinetic parameters of the thermovulcanization reaction on polymer blend composition.