Synthesis and characterization of electrically conducting copolymer of aniline and o‐bromoaniline using methane sulfonic acid as dopant

Polyaniline (PAN), poly(o‐bromoaniline) (POBA), and poly(aniline‐co‐o‐bromoaniline) (PABA) were synthesized by oxidative coupling. These polymers are protonated by 10–20% methane sulfonic acid (MSA) and 1M HCl. The new polymer bases have greater solubility than that of PAN in common polar organic solvents; PAN–MSA was observed to be the most thermally stable of these polymers. POBA is associated with residual quinoid diimine units as illustrated in the IR and UV‐vis spectra, after reduction with hydrazine dihydrochloride. Both the doping agents cause a downward shift of the quinoid absorption in the IR spectra. MSA‐ and HCl‐doped PAN and PABA polymers exhibit a coil‐like conformation in DMSO, whereas only MSA‐doped PAN and PABA show an “expanded coil‐like” conformation in m‐cresol with a “free carrier tail” above 800 nm in their electronic spectra. XPS spectra indicated the presence of covalent bromine in the POBA and PABA polymers. Bromine retention was greater in the homopolymer as evidenced by the IR studies after aging at 350°C. Compared to HCl, MSA is found to be a more effective dopant, enhancing the conductivity of the copolymers by 10²–10³ times in magnitude. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2662–2669, 2002     

Rotating fluidized bed with a static geometry: Guidelines for design and operating conditions

Computational fluid dynamics (CFD) simulations of the hydrodynamic behavior of rotating fluidized beds in static geometry (RFB-SG) are carried out for gas–solid flows. The rotating motion of the reactor bed is induced by the tangential injection of the gas along the circumference of the fluidization chamber. Steep gradients in the gas velocity fields both in radial and tangential direction generate turbulence. The radial and tangential drag forces fluidize the particle bed in both radial and tangential direction.An Eulerian two-fluid model is used. Gas phase turbulence is accounted for by a k–ε model adapted for rotational flows. The RFB-SG simulations provide guidelines for a design and operation with a high efficiency in gas–solid momentum transfer, excellent gas–solid separation and limited solids losses. Hydrodynamic variables like the centrifugal force, the injection pressure, the radial and tangential slip velocities, solids hold-up are calculated for both polymer particles (300 μm, 950 kg/m³, Geldart Group B) and glass beads (70 μm, 2500 kg/m³, Geldart Group A) to allow for a comparison among different fluidization chamber designs. Unstable bed behavior, like slugging and channeling, is also numerically predicted.     

Preferential oxidation of linolenic acid compared to linoleic acid in the liver of catfish (Heteropneustes fossilis andClarias batrachus)

The fate of [1-¹⁴C] linoleic acid and [1-¹⁴C] linolenic acid in the liver slices and also in the liver tissues of live carnivorous catfish,Heteropneustes fossilis andClarias batrachus, was studied. Incorporation of the fatty acids into different lipid classes in the live fish differed greatly from the tissue slices, indicating certain physiological control operative in vivo. The extent of desaturation and chain elongation of linoleic and linolenic acids into long-chain polyunsaturated fatty acids was low. Linolenic acid was oxidized (thus labeling the saturated fatty acid with liberated¹⁴C-acetyl-CoA) in preference to linoleic acid, and this oxidation also seemed to be under physiological control since both of the fatty acids were poorly oxidized in the tissue slices and in the killed fish. These fish can therefore recognize the difference in the acyl chain structures of linoleate and linolenate. The higher oxidation of liolenic acid and poor capacity for its conversion to longer chain, highly unsaturated derivatives indicates a higher demand for the dietary supply of these essential fatty acids in these two species.     

Acid-base equilibria of sulfonephthalein dyes in aqueous polymer-surfactant media

The acid-base equilibria of three anionic sulfonephthalein dyes, viz., bromothymol blue (BTB), thymol blue (TB), and cresol red (CR), were studied spectroscopically in aqueous media containing the water-soluble noninonic polymers polyvinyl alcohol (PVA) and polyethylene glycol (PEG) in the presence of an anionic surfactant, sodium dodecyl sulfate (SDS). A partition equilibrium method was used to determine the equilibrium constant of partition of the dyes between the micellar pseudo phase and aqueous phase in the presence of PVA and PEG. The critical aggregation concentrations (CAC) of the surfactants in buffered aqueous systems containing the neutral polymers were also determined. The CAC of the polymer-surfactant systems were found to be lower than the critical micelle concentration of such systems in the absence of polymer, in otherwise identical conditions. The pH-dependent association constants, K _ass, of the sulfonephthalein dyes with the SDS-PVA system increased with the increase in molecular weight of the polymer. The interactions of the dyes with the buffered aqueous SDS-PVA and SDS-PEG systems were found to be endothermic and entropy oriented. In the polymer domain, the head group region of the micelles was more exposed at lower concentrations of the polymer, but under excess polymer concentration they were increasingly shielded, which impaired their electrostatic interaction with the dyes.     

Nonlinear analysis of nuclear coupled density wave instability in time domain for a boiling water reactor core undergoing core-wide and regional modes of oscillations

The objective of the paper is to develop a nuclear coupled thermal-hydraulic model in order to simulate core-wide (in-phase) and regional (out-of-phase) stability analysis in time domain within the limitation of desktop research facility for a boiling water reactor subjected to operational transients. The integrated numerical tool, which is a combination of thermal-hydraulic, neutronic and fuel heat conduction models, is used to analyze a complete boiling water reactor core taking into account the strong nonlinear coupling between the core neutron dynamics and primary circuit thermal-hydraulics via the void-temperature reactivity feedback effects. The integrated model is validated against standard benchmark and published results. Finally, the model is used for various parametric studies and a number of numerical simulations are carried out to investigate core-wide and regional instabilities of the boiling water reactor core with and without the neutronic feedback effects. Results show that the inclusion of neutronic feedback effects has an adverse effect on boiling water reactor core by augmenting the instability at lower power for same inlet subcooling during core-wide mode of oscillations, whereas the instability is being suppressed during regional mode of oscillations in presence of the neutronic feedback. Dominance of core-wide instability over regional mode of oscillations is established for the present case of simulations which indicates that the preclusion of the former will automatically prevent the latter at the existing working condition.     

Isolation and identification of phosphate‐solubilizing microorganisms and distribution of orthophosphate in different seasons from sewage‐fed East Kolkata Wetland

This study focused on isolation and identification of possible phosphate‐solubilizing bacteria (PSB ) from the sewage‐fed East Kolkata Wetland (EKWL ), a prospective water resource for pisciculture. In addition, different limnological parameters have been correlated with orthophosphate and seasonal variations. PSB have been isolated in Pikovskaya medium and identified morphologically and biochemically and finally analysed by 16S rDNA gene sequence. Limnological studies involving temperature (potentiometric), pH (potentiometric), dissolved oxygen (iodometric), ammonia‐nitrogen (spectrophotometric) and orthophosphate (spectrophotometric) concentrations were conducted. The results of this study established the presence of Bacillus megaterium , a potential PSB in EKWL . The activity of B. megaterium is also supported by the seasonal orthophosphate variations. The changes in concentration of other limnological parameters were also prominent. The water quality parameters of temperature (r  = 0.886), dissolved oxygen (r  = 0.729) and ammonia‐nitrogen (r  = 0.396) concentrations exhibited a positive correlation with orthophosphate and a negative correlation with pH (r  = ?0.699). The B. megaterium obtained in this study, exhibited a significant alteration in regard to orthophosphate content and relationships with other factors. Further experiment on the soluble phosphorus solubilization potential of B. megaterium revealed the biological availability of phosphorus was increased by threefold after 120 hr of incubation, with the decreasing pH value, although the phytase activity was 0.419 U/ml. PSB have a vital function in plant nutrition in supplying phosphate, essential nutrients and its uptake results in appropriate functioning and metabolism of different aquatic plants and organisms. PSB are competent biofertilizer to amplify aquaculture production for sustainable development.     

Epitaxial nucleation model for chiral-selective growth of single-walled carbon nanotubes on bimetallic catalyst surfaces

An epitaxial nucleation model for single-walled carbon nanotube (SWCNT) growth on bimetallic catalysts surfaces is reported in support of experimental observations of chiral enrichment. We model the bimetallic catalyst surfaces as a 2D (1 1 1) surface consisting of Ni or a combination of Ni and Fe atoms, with varying average bond length between nearest neighbor atoms which corresponds to the crystal structure of the alloys. The energies associated with nanotube cap formation on these various surfaces are calculated using density functional theory (DFT). We find that certain cap chiralities, such as (8, 4), are more stably bound to a surface that resembles a Ni_0.27Fe_0.73 bimetallic catalyst, whereas other chiralities, such as (9, 4), are more stable on a pure Ni surface. These results help explain the predominance of certain chiralities on specific bimetallic catalysts and provide a potential route to controlling the chirality of as-grown SWCNTs.     

Synthesis and characterization of solid-phase super acid catalysts and their application for isomerization of n-alkanes

In the present work, first, the reference catalyst super acidic nanostructured sulfated zirconia (SZ) and super acidic nanostructured aluminum chloride impregnated sulfated zirconium oxides in mole ratios of Zr⁴⁺:Al³⁺ as 2:1 (ACSZ-1), 1:1 (ACSZ-2), and 1:2 (ACSZ-3) were synthesized by a simple precipitation method. The catalytic performance of these four catalysts were evaluated during the isomerization of n-hexane, n-heptane, and n-octane to their corresponding branched chain isomers at low temperature and pressure conditions. ACSZ-2 shows high activity toward isomerization of n-hexane, n-heptane, and n-octane into their corresponding branched chain isomers. The reference catalyst SZ was proved to be less effective compare to the other three synthesized ACSZ catalysts. Ammonia-temperature-programmed desorption of these two materials ensures that the super acidity of ACSZ-2 is higher than that of SZ. Atomic force microscopic and scanning electron microscopic pictures predict the nature of the surface of the catalysts. Transmission electron micrographic analysis indicates the presence of particle-bulks having average size 12–20?nm, presenting an amorphous nature and having no definite surface morphology of ACSZ-2. Fourier transform infrared provides an outline regarding different linkages and bond connectivities between atoms and groups in ACSZ-2 and SZ. After catalyst evaluation and characterization a probable reaction mechanism has been proposed theoretically. The reactivity and selectivity of ACSZ-2 and SZ as well as the order and activation energy of the isomerization reactions in presence of ACSZ-2 have been calculated. The use of ACSZ-2 is beneficial from the point of cost efficiency as well as its use is energy saving.     

Template-free synthesis of flower-shaped zero-valent iron nanoparticle: Role of hydroxyl group in controlling morphology and nitrate reduction

Well-dispersed single phasic flower-like zero valent iron nanoparticles have been synthesized under aerobic conditions using a facile approach without the addition of any additives or templates. The role of hydroxyl groups of polyhydroxy alcohols in controlling surface morphology of nanoparticles has been thoroughly investigated. The obtained nanoparticles have been characterized by TEM, FE-SEM, XRD and BET surface area analyzer. Electron microscopy analyses reveal that the solvent plays a pivotal role in determining the morphology of the particles. With increase in viscosity of the solvent, formations of ‘petal-like’ structures, which are joined at the center are formed. The nitrate removal efficiency of the iron nanoparticles synthesized in different solvents has been studied and it is seen that the “flower-like” iron nanoparticles were most active in the removal of nitrate. Experiments have been done by varying (i) nitrate concentrations, (ii) nanoparticle dose, and (iii) type of nanoparticles. The results conclude that highest removal efficiency (～100%) was achieved when the nanoparticle dose was 2.88 g/L, even for high nitrate concentrations up to 400 mg/L. The major highlight of this work is the fact that even though the nanoparticles synthesized in glycerol-water mixture have larger size in comparison to the other nanoparticles, still they remove the nitrates with highest efficiency.”     

Progressive cutting tool wear detection from machined surface images using Voronoi tessellation method

Tool condition monitoring by machine vision approach has been gaining popularity day by day since it is a low cost and flexible method. In this paper, a tool condition monitoring technique by analysing turned surface images has been presented. The aim of this work is to apply an image texture analysis technique on turned surface images for quantitative assessment of cutting tool flank wear, progressively. A novel method by the concept of Voronoi tessellation has been applied in this study to analyse the surface texture of machined surface after the creation of Voronoi diagram. Two texture features, namely, number of polygons with zero cross moment and total void area of Voronoi diagram of machined surface images have been extracted. A correlation study between measured flank wear and extracted texture features has been done for depicting the tool flank wear. It has been found that number of polygons with zero cross moment has better linear relationship with tool flank wear than that of total void area.