Investigation of the selective catalytic reduction of NO by NH3 on Fe-ZSM5 monolith catalysts

Photocatalytic nitric oxide (NO) decomposition and reduction reactions, using carbon monoxide (CO) as a reducing gas, have been investigated over Degussa P25 titanium dioxide photocatalysts, using a continuous flow reactor. The effects of thermal pretreatment temperature and reaction gas composition on the activity and selectivity of the decomposition and reduction reactions have been evaluated. Prepared materials were characterised by X-ray diffraction (XRD), N₂ physisorption, transmission electron microscopy (TEM) and differential scanning calorimetry (DSC) and findings from these techniques were used to explain the observed photocatalytic properties. XRD and TEM results indicated that for the pretreatment temperatures used (70, 120, 200, 450 and 600 °C) there was no appreciable change in the phase composition and the original composition of ca. 77 vol.% anatase and 23 vol.% rutile was maintained even after treatment at 600 °C. It was found that the photocatalytic activity for both the decomposition and reduction reactions decreased with increasing pretreatment temperature. This was attributed to the removal of surface hydroxyl species that act as active sites for reaction. For the decomposition reactions the only products observed were nitrogen and nitrous oxide and the selectivity for nitrogen formation remained constant (ca. 23%) regardless of the pretreatment temperature. The presence of CO in the reaction gas had a dramatic effect on the selectivity of the reactions with nitrogen selectivities as high as 65% being observed. It was found that as the CO/NO ratio increased the selectivity for nitrogen formation increased.     

On the application of matrix generalized inverses to the design of observers for time-varying and time-invariant linear systems

A method for the design of Luenberger observers is developed utilizing the simplest generalized inverse of matrices. The method can be applied to time-invariant and to time-varying systems.     

Synthesis, characterization, thermolysis and performance evaluation studies on alkali metal salts of TABA and NTO

The lithium (Li) and potassium (K) salts of 3-nitro-1,2,4-triazol-5-one (NTO) and 2,4,6-trinitroanilino benzoic acid (TABA) were prepared and characterized during this work. The synthesis was carried out by addition of a solution of lithium/potassium hydroxide to the aqueous solution of NTO and TABA, respectively. The products were characterized by elemental analysis, metal content determination and Fourier Transform Infrared (FTIR) Spectrum. Differential scanning calorimetry (DSC) profile indicated that Li and K salts of NTO and TABA undergo exothermic decomposition in the temperature range of 257-360 degrees C suggesting their energetic nature. The thermo gravimetric (TG) weight loss pattern revealed loss of water for Li/K salts of NTO and TABA in the temperature range of 115-155 degrees C. Sensitivity results revealed that the compounds are insensitive to impact and friction (impact sensitivity--height of 50% explosion>170 cm and friction insensitivity up to 36 kg) stimuli despite even the parent molecule of NTO salts (NTO) being HEM in the hazard category of 1.1. The FTIR spectra of the gaseous products evolved during TGA of NTO and TABA salts indicated the release of NO2. The formation of products such as LiNCO and KNCO was also observed in case of NTO salts, whereas that of CO2 and NH containing products was indicated in case of TABA salts during this study. In order to assess the performance as energetic ballistic modifiers (EBMs), NTO and TABA salts were incorporated in the ammonium perchlorate-hydroxyl terminated polybutadiene (AP-HTPB) composite propellants. The potassium salts enhanced the burning rate of the propellant. The best catalytic effect was obtained with K-TABA salt, which increased the burning rate to the extent of approximately 81% as well as brought down the n-value to 0.15 (pressure 2-9 MPa).     

Quantum chemical, ballistic and explosivity calculations on 2,4,6,8-tetranitro-1,3,5,7-tetraaza cyclooctatetraene: a new high energy molecule

Ab initio molecular orbital calculations have been carried out on 2,4,6,8-tetranitro-1,3,5,7-tetraazacyclooctatetraene, the tetramer of the series (NO(2)CN)(n) where n=1-4, using the Hartree-Fock theory with the 6-31 G(d) basis set. These calculations yield three conformers for the tetramer with D(4h), C(4h) and C(2) symmetries. The nonplanar conformer with the C(2) symmetry turns out to be 99.0 and 164.4kJmol(-1), respectively, lower in energy than the C(4h) and D(4h) conformers. The electron density topography - the density at the bond critical point - has been used as a measure of the CNO(2) strengths. Based on these bond strengths, heats of formation [obtained from the parametric model 3 (PM3) method] and specific decomposition energies, it may be concluded that (NO(2)CN)(4) is a promising candidate in the class of high energy molecules. Theoretically computed explosive (velocity of detonation, detonation pressure, etc.) and ballistic (characteristic velocity, specific impulse, etc.) parameters support these conclusions.     

Low-Temperature Fine-Grained Alumina–Aluminum Titanate Composites Produced from a Titania-Coated Alumina Precursor

A method for the preparation of alumina–aluminum titanate (AT) composites, which can be sintered to high density with a fine-grained microstructure at <1450°C, is reported. The composite precursor is alumina particles coated by sol–gel-derived titania, which reacts during sintering to form AT in situ at temperature as low as 1300°C. The composite can be sintered at 1350°C to 98% density with 1.5–2.0 μm grain size. Other composites containing 5–50 wt% AT are also investigated.     

Environmentally compatible next generation green energetic materials (GEMs)

This paper briefly reviews the literature work reported on the environmentally compatible green energetic materials (GEMs) for defence and space applications. Currently, great emphasis is laid in the field of high-energy materials (HEMs) to increase the environmental stewardship along with the deliverance of improved performance. This emphasis is especially strong in the areas of energetic materials, weapon development, processing, and disposal operations. Therefore, efforts are on to develop energetic materials systems under the broad concept of green energetic materials (GEMs) in different schools all over the globe. The GEMs program initiated globally by different schools addresses these challenges and establishes the framework for advances in energetic materials processing and production that promote compliance with environmental regulations. This review also briefs the principles of green chemistry pertaining to HEMs, followed by the work carried out globally on environmentally compatible green energetic materials and allied ingredients.     

Rheokinetic modeling of HTPB–TDI and HTPB–DOA–TDI systems

A study of the effect of temperature on a mixture of polymer and curative in the processing of rocket propellants is reported. Experimental viscosity of a hydroxyl‐terminated polybutadiene–toluene diisocyanate (HTPB–TDI) system was measured using a Brookfield viscometer model DV III. Viscosity showed dependence on temperature as well as time. The viscosity data of the HTPB–TDI system showed a linear relationship with temperature, with a change in slope at 45°C. The time dependence model showed a fourth‐order curve fit, which gave better results over the exponential model fit. The activation energy required for flow of the HTPB–TDI system was found to be 15.5 kJ/mol. Experimental viscosity measurements at various temperatures was also carried out on a hydroxyl‐terminated polybutadiene–dioctyl adipate –toluene diisocyanate (HTPB–DOA–TDI) system. The temperature dependence showed a decrease in viscosity with an increase in temperature up to 60 min, beyond which the viscosity increased. Viscosity showed a linear relation with temperature, with a change in the slope at 50°C instead of at 45°C for HTPB–TDI system. Beyond 50°C the data followed a polynomial model similar to that of the HTPB–TDI system, and the results matched well with the experimental data. The activation energy of the HTPB–DOA–TDI system increased with an increase in the binder weight ratio. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1331–1335, 2003     

Role of PCBM in the Suppression of Hysteresis in Perovskite Solar Cells

The power conversion efficiency of inorganic–organic hybrid lead halide perovskite solar cells (PSCs) is approaching that of those made from single crystalline silicon; however, they still experience problems such as hysteresis and photo/electrical‐field‐induced degradation. Evidences consistently show that ionic migration is critical for these detrimental behaviors, but direct in‐situ studies are still lacking to elucidate the respective kinetics. Three different PSCs incorporating phenyl‐C61‐butyric acid methyl ester (PCBM) and a polymerized form (PPCBM) is fabricated to clarify the function of fullerenes towards ionic migration in perovskites: 1) single perovskite layer, 2) perovskite/PCBM bilayer, 3) perovskite/PPCBM bilayer, where the fullerene molecules are covalently linked to a polymer backbone impeding fullerene inter‐diffusion. By employing wide‐field photoluminescence imaging microscopy, the migration of iodine ions/vacancies under an external electrical field is studied. The polymerized PPCBM layer barely suppresses ionic migration, whereas PCBM readily does. Temperature‐dependent chronoamperometric measurements demonstrate the reduction of activation energy with the aid of PCBM and X‐ray photoemission spectroscopy (XPS) measurements show that PCBM molecules are viable to diffuse into the perovskite layer and passivate iodine related defects. This passivation significantly reduces iodine ions/vacancies, leading to a reduction of built‐in field modulation and interfacial barriers.