Interaction of lanthanide and actinide with BaHfO3 perovskite: A case study with cerium and uranium

Speciation of actinide (An) and lanthanide (Ln) in technologically important ceramics is very important from both fundamental as well as technological aspects. The intrinsic structural flexibility of perovskite containing AO₆ and BO₁₂ polyhedra makes them suitable and rich hosts for An and Ln. In this work, emphasis was given to deciphering information such as oxidation state, local dopant site, charge compensating defects, excited state kinetics, and so forth in BaHfO₃ (BHO) related to dopant uranium (BHO-U) and cerium (BHO-Ce). Several spectroscopic techniques namely, time-resolved photoluminescence (TRPL), positron annihilation lifetime spectra (PALS), and thermoluminescence (TL) spectroscopy coupled with density functional theory (DFT) were employed to probe the same. Ce and U though are distributed at both Ba and Hf sites, Ce prefers the former, while U prefers the latter site. Uranium on the other hand stabilizes as U⁶⁺ in the form of octahedral uranate ion giving green emission. PALS suggested the formation of defects in BHO-Ce and BHO-U with oxygen vacancies predominating in the former whereas BHO-U perovskites are loaded with cation vacancies and vacancy clusters. These cation vacancies are responsible for lower TL output in BHO-U. TL measurements also suggested cerium doping leads to a higher density of deeper traps in BHO-Ce compared to uranium doping in BHO-U which is in concurrence with DFT results and may have implications in designing afterglow phosphors based on perovskite. We believe this work would have a long-term impact on exploring the potential of perovskite for nuclear waste host and afterglow phosphors applications.     

Dependence of Silicon Carbide Product Morphology on the Degree of Mechanical Activation

Mechanical activation before carbothermic reduction can substantially enhance the formation of SiC from SiO₂and carbon mixtures. However, the morphology (e.g., particles or whiskers) of SiC formed from mechanically activated SiO₂and carbon mixtures is dependent of the degree of mechanical activation and the condition of the subsequent carbothermic reduction. These phenomena are investigated and rationalized based on the increased reactivity of the reactants and SiC formation mechanisms.     

Cholestane as a digestibility marker in the absorption of polyunsaturated fatty acid ethyl esters in Atlantic salmon

Salmonid fish require long-chain n−3 fatty acids in their diet. The digestibility of different chemical forms of fish oil fatty acids, fed as triacylglycerols, free fatty acids or ethyl esters, was examined in 300 g farmed Atlantic salmon (Salmo salar) using cholestane as an indicator of fat absorptionin lieu of the chromium oxide (Cr₂O₃) which is commonly used as a marker in digestibility studies. It was established that the two digestibility markers gave similar results. Conveniently, cholestane does not require a separate analysis if fatty acids are to be determined by appropriate gas-liquid chromatography. The long-chain polyunsaturated fatty acids were particularly well absorbed, the apparent digestibility being 90–98% when feeding triacylglycerols or free fatty acids. However, the digestibility of monounsaturated fatty acids (75–94%) was lower, and lower still for saturated fatty acids (50–80%). Ethyl esters of fatty acids were significantly less well absorbed (P<0.05) than were the corresponding fatty acids in free acid or triacylglycerol form. Irrespective of dietary fat type, only free fatty acids were identified in feces, indicating total hydrolysis of triacylglycerols and ethyl esters. Presented in part at the World Aquaculture Society meeting, June 10–14, 1990, Halifax, Canada.     

Modeling of the sheet‐molding process for poly(methyl methacrylate)

The sheet‐molding process for the production of poly(methyl methacrylate) (PMMA) involves an isothermal batch reactor followed by polymerization in a mold (the latter is referred to as a “sheet reactor”). The temperature at the outer walls of the mold varies with time. In addition, due to finite rates of heat transfer in the viscous reaction mass, spatial temperature gradients are present inside the mold. Further, the volume of the reaction mass also decreases with polymerization. These several physicochemical phenomena are incorporated into the model developed for this process. It was found that the monomer conversion attains high values of near‐unity in most of the inner region in the mold. This is because of the high temperatures there, since the heat generated due to the exothermicity of the polymerization cannot be removed fast enough. However, the temperature of the mold walls has to be increased in the later stages of polymerization so that the material near the outer edges can also attain high conversions of about 98%. This would give PMMA sheets having excellent mechanical strength. The effects of important operating (decision) variables were studied and it was observed that the heat‐transfer resistance in the mold influences the spatial distribution of the temperature, which, in turn, influences the various properties (e.g., monomer conversion, number‐average molecular weight, and polydispersity index) of the product significantly. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1951–1971, 2001     

Modeling of diffusional limitations in styrene acrylonitrile random bulk copolymerization

Diffusional limitations (the gel, glass, and cage effects) are manifested in several bulk free radical homopolymerizations as well as in random copolymerizations. These are associated with decreases of several orders of magnitude of the rate constants of termination, propagation, and initiation (the initiator efficiency), respectively. These phenomena have been modeled earlier using the free volume theory for the diffusivities of primary radicals, macro‐radicals, and monomer molecules, and have been applied to homopolymerizations. In this study, a similar model is developed for random bulk copolymerizations. The parameters of the model are fitted using isothermal data on styrene acrylonitrile random copolymerization carried out in small ampoules. Thereafter, best‐fit global correlations have been developed for this system. This enables the model to be used for studying non‐isothermal copolymerizations, as well as for carrying out optimization of industrial reactors, where non‐isothermal conditions are a norm. POLYM. ENG. SCI., 55:2098–2110, 2015. © 2014 Society of Plastics Engineers     

An in-Depth Analysis of the Swelling,Mechanical, Electrical,and Drug Release Properties of Agar–Gelatin Co-Hydrogels

Agar–gelatin-based co-hydrogels were prepared with different compositions of the agar and the gelatin fractions. The intermolecular hydrogen bonding was higher in the co-hydrogels as compared to the gelatin hydrogel. Swelling studies indicated diffusion-mediated swelling. The electrical stability of the co-hydrogels was higher as compared to the gelatin hydrogel. Though the firmness of the co-hydrogels was higher, Weichert model of viscoelasticity indicated that the inherent mechanical stability of the gelatin hydrogel was superior. The release of ciprofloxacin hydrochloride was predominately Fickian diffusion-mediated. In gist, the co-hydrogels can be tried as polymeric constructs for controlled drug delivery applications.     

Electrospinning of chitosan/PVA nanofibrous membrane at ultralow solvent concentration

In this work, chitin flakes were deacetylated with 50% (w/v) sodium hydroxide under nitrogen atmosphere at 120 °C for 80 min to obtain chitosan. The chitosan produced was characterized for degree of deacetylation (DD) and molecular weight. Chitosan with the DD of 78–80% was reproducibly obtained. Molecular weight showed an inverse relationship with concentration of NaOH. Chitosan nanofibrous membrane was prepared via the electrospinning of chitosan/polyvinyl alcohol (CH/PVA) aqueous solutions with varying blend compositions. The characteristics of CH/PVA nanofibrous membranes were studied as a function of viscosity of solution and applied voltage. A uniform nanofibrous membrane of average fibre diameter of 80–300 nm was obtained with blend of 2% (w/v) chitosan solution in 1% (v/v) acetic acid and 5% (w/v) PVA in distilled water in the electric field of 20–25 kV with varying proportion of CH/PVA. With the CH/PVA mass ratios; 40/60 to 10/90, electrospinning of nanofibres could be done. The electrospun nanofibrous membrane was analyzed by scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and Thermo gravimetric analysis (TGA). SEM images showed that the morphology and diameter of the nanofibres were mainly affected by the weight ratio of CH/PVA. XRD and FTIR confirmed the strong intermolecular hydrogen bonding between the molecules of Chitosan and PVA.     

The Dynamics of Particles with Translation–Rotational Coupling in the Stokes Flow Regime

Most naturally and industrially generated solid particles are irregular in shape. One type of particle commonly encountered can be identified as flakes and their aggregates. This class of particles exhibits translation-rotational coupling. Based on the principle of similarity, we have conducted an experimental investigation of the dynamics of flake-type particles, employing model particles settling in an oil tank. These model particles are about 1–2 cm in size. The particle Reynolds number is kept under 0.02 to simulate the motion of the flaky aerosols. By introducing factors representing the effects of configuration (e.g., finite thickness and rod diameter) and interaction, shape factors for the composite particles can be determined from the constituent disks. The translational configuration factor λ_t is found to depend mainly on the thickness-to-diameter ratio l _s/d _s and to satisfy λ_t = A + B(1 _s/d _s)^0.14. Furthermore, the ratio of the rotational and coupling configuration factors generally increases with the length of the rod connecting the disks. The wall effect depends linearly on the ratio d _s/D _T (where D _T is the tank diameter) for translational motion but is insignificant for rotational motion.     

Filtration of Chain Aggregate Aerosols by Model Screen Filter

A screen type diffusion battery was used as a model screen filter for studying the filtration of chain aggregate aerosols. The aerosols, with well-defined diameter and length, were generated with a system that included a flame aerosol generator and a differential mobility analyzer. Particle sizes were characterized using transmission electron microscopy and a digital image processing technique. The penetration efficiency of the aerosols through even stages of the diffusion battery at certain flow velocities were measured using a condensation nucleus counter (CNC). Quantitative data were obtained by operating the CNC in count mode simultaneously with a laser aerosol spectrometer. Results indicated that penetration efficiency decreased exponentially with the number of screens and increased with flow velocity. In addition, theoretical analysis of filtration mechanisms based on the fan model theory has been made and compared with the measurements of penetration efficiency. Results showed that the collection of chain aggregates on model screen niters was in the regime dominated by an interception mechanism. Average orientation angles of the aerosols with respect to the flow field were also estimated.