Heterogeneous permanganate oxidation of 1,5-dienes: a novel synthesis of 5-substituted butanolides

In the presence of a catalytic amount of water, 1,5-dienes undergo novel and unusual oxidation with potassium permanganate�copper sulfate in dichloromethane to give substituted butanolides in good yields under very mild conditions.

Hybridization of carbon-glass epoxy composites: An approach to achieve low coefficient of thermal expansion at cryogenic temperatures

The paper is based on a study to develop carbon-glass epoxy hybrid composites with desirable thermal properties for applications at cryogenic temperatures. It analyzes the coefficient of thermal expansion of carbon-epoxy and glass-epoxy composite materials and compares it with the properties of carbon-glass epoxy hybrid composites in the temperature range 300 K to 125K. Urethane modified epoxy matrix system is used to make the composite specimens suitable for use even for temperatures as low as 20K. It is noted that the lay-up with 80% of carbon fibers in the total volume fraction of fibers oriented at 30 degrees and 20% of glass fibers oriented at 0 degrees yields near to zero coefficient of thermal expansion as the temperature is lowered from ambient to 125 K. (c) 2010 Elsevier Ltd. All rights reserved.

Combustion synthesis of oxide materials for nuclear waste immobilization

Oxide materials like perovskite, zirconolite, hollandite, pyrochlore, NASICON and sphene which are used for nuclear waste immobilization have been prepared by a solution combustion process. The process involves the combustion of stoichiometric amount of corresponding metal nitrates and carbohydrazide/tetraformyl trisazine/diformyl hydrazide at 450 degrees C. The combustion products have been characterized using powder X-ray diffraction, infrared spectroscopy, and Si-29 MAS-NMR. The fine particle nature of the combustion derived powders has been studied using density, particle size, BET surface area measurements and scanning electron microscopy. Sintering of combustion derived powder yields 85-95% dense ceramics in the temperature range 1000 degrees-1300 degrees C.

High Yield Room Temperature Synthesis And Spectral Studies Of Tri(Amino)Silanes: (R2n)3SIH

Tri(amino)silanes were prepared by the condensation of trichlorosilane with secondary amines in 1:6 molar ratio. Reactions of trichlorosilane with pyrrolidine, piperidine, hexamethyleneimine, morpholine, N-methylpiperazine and diethylamine afford the tri(amino)silanes in nearly quantitative yields. Their physical and spectroscopic properties are discussed. All these compounds are highly sensitive to moisture and hydrolyse to silica and the respective amine with the evolution of hydrogen. The compounds have been characterised by IR, 1H NMR, [1H]29Si NMR spectroscopic methods and CHN elemental analysis.

Dynamics of I-asterisk(P-2(1/2)) production inthe ultraviolet photodissociation of alkyn iodides

The relative quantum yields, phi*, for the production of I*(P-2(1/2)) at 266, 280, and similar to 305 nm are reported for a series of primary alkyl iodides using the technique of two-photon laser-induced fluorescence for the detection of I(P-2(3/2)) and I*(P-2(1/2)) atoms. Results are analyzed by invoking the impulsive energy disposal model, which summarizes the dynamics of dissociation as a single parameter. Comparison of our data with those calculated by a more sophisticated time-dependent quantum mechanical model is also made. Near the red edge of the alkyl iodide A band, absorption contribution from the (3)Q(1) state is important and the dynamics near the (3)Q(0)-(1)Q(1) curve-crossing region seem to be influenced by the kinematics of the dissociation process

Metastable extension of the fluorite phase field in Y2O3---ZrO2 and its effect on grain growth

Pure Y2O3 and Y2O3---ZrO2 solid solutions have been prepared by melt atomization and by pyrolysis of nitrate solutions. Extended solubility is readily achieved in both techniques for the entire composition range investigated: melts with 0–30% ZrO2 and precursors with 0–50% ZrO2. However, solidification of under cooled droplets yields almost exclusively single phase powders with the structure of cubic yttria (D53). In contrast, the pyrolysis route leads to a sequence of metastable microstructures beginning with a nanocrystalline disordered fluorite-based (C1) solid solution. Further heating leads to the evolution of much larger (micron size) flake crystals with a {001} texture, concurrent with partial ordering of the oxygen ions to the sites occupied in the D53 structure. The driving force for ordering and the rate of grain growth decrease with increasing ZrO2 addition. Abrupt heating to high temperatures or electron irradiation can induce ordering without substantial grain growth. There is no significant reduction in porosity during the recrystallization, which with the other observations suggests that grain growth is driven by the free energy available for the ordering transformation from fluorite to the yttria structure. This route offers opportunities for single crystal thin film development at relatively low processing temperatures.

Highly selective sulfur transfer reaction in the solid state

Benzyltriethylammonium tetrathiomolybdate 1 reacts readily with benzyl halides, alkyl iodides and acyl halides in the solid state to give the corresponding disulfides in good yields and with remarkable selectivity.

Improved velocity method for the determination of coefficient of consolidation

Parkin (1978) suggested the velocity method based on the observation that the theoretical rate of consolidation and time factor plot on a log-log scale yields an initial slope of 1:2 up to 50% consolidation. A new method is proposed that is an improvement over Parkin's velocity method because it minimizes the problems encountered in using that method. The results obtained agree with the other methods in use.

Investigations of carbon nanotubes

Experiments have been carried out to optimize the yields of carbon nanotubes obtained by the arc-evaporation of graphite. Other types of carbon particles such as nanocrystalline graphite usually present along with the nanotubes are readily removed by heating the material in oxygen around 763 K. Clean nanotubes so obtained have been characterized by X-ray diffraction. The clean tubes are thermally more stable than graphite or fullerenes. The tips of carbon nanotubes are opened by reaction with oxygen, but more interestingly, when the oxygen produced by the decomposition of a metal oxide is used to open the tube tips, the metal formed in the process enters the nanotube. Electrical resistance of pressed pellets of clean tubes is not unlike that of graphite. Tunnelling conductance measurements on isolated tubes characterized by means of scanning tunnelling microscopy however show that the conductance gap increases with decreasing tube diameter.

Iron, cobalt and nickel nanoparticles encapsulated in carbon obtained by the arc evaporation of graphite with the metals

Are evaporation of graphite with Fe, Co and Ni yields two distinct types of metal nanoparticles, wrapped in graphitic layers and highly resistant to oxidation. Electron microscopy shows that the metal particles (10-40 nm) in the stub region are encapsulated in carbon onions, the particles in the soot being considerably smaller (2-15 nm). The metal particles in the soot are either ferromagnetic with lowered Curie temperatures or superparamagnetic.

Metastable extension of the fluorite phase field in Y2O3---ZrO2 and its effect on grain growth

Pure Y2O3 and Y2O3-ZrO2 solid solutions have been prepared by melt atomization and by pyrolysis of nitrate solutions. Extended solubility is readily achieved in both techniques for the entire composition range investigated: melts with 0-30% ZrO2 and precursors with 0-50% ZrO2. However, solidification of under cooled droplets yields almost exclusively single phase powders with the structure of cubic yttria (D5(3)). In contrast, the pyrolysis route leads to a sequence of metastable microstructures beginning with a nanocrystalline disordered fluorite-based (C1) solid solution. Further heating leads to the evolution of much larger (micron size) flake crystals with a {001} texture, concurrent with partial ordering of the oxygen ions to the sites occupied in the D5(3) structure. The driving force for ordering and the rate of grain growth decrease with increasing ZrO2 addition. Abrupt heating to high temperatures or electron irradiation can induce ordering without substantial grain growth. There is no significant reduction in porosity during the recrystallization, which with the other observations suggests that grain growth is driven by the free energy available for the ordering transformation from fluorite to the yttria structure. This route offers opportunities for single crystal thin film development at relatively low processing temperatures.

Pressure-induced band gap reduction, orientational ordering and reversible amorphization in single crystals of C70: Photoluminescence and Raman studies

Photoluminescence and Raman scattering experiments have been carried out on single crystals of C70 up to 31 GPa to investigate the effect of pressure on the optical band gap, vibrational modes and stability of the molecule. The photoluminescence band shifts to lower energies and the pressure dependence of the band maxima yields the hydrostatic deformation potential to be 2.15 eV. The slope changes in the pressure dependence of peak positions and linewidths of the Raman modes associated with the intramolecular vibrations at 1 GPa mark the known face-centred cubic-->rhombohedral orientational ordering transition. The reversible amorphization in C70 at P > 20 GPa has been compared with the irreversible amorphization in C60 at P > 22 GPa in terms of carbon-carbon distance between the neighbouring molecules at the threshold transition pressures, in conjunction with the interplay between the intermolecular and intramolecular interactions.

Soft chemical synthesis of new layered and three-dimensional oxide hydrates, hxVxW1-xO3×yH2O, related to WO3×2 H2O and WO3. times.1/3 H2O

Two new vanadium-tungsten oxide hydrates of the formulas, H0.125V0.125W0.875O3.1.5H2O (I) and Ho.33V0.33W0.67O3.1/3H2O (II), have been synthesized by acid-leaching of LiVWO6 with aqueous HNO3/HCl. While phase I obtained by treatment of LiVWO6 with dilute HNO3/HCl possesses an orthorhombic structure (a = 7.77(3), b = 13.87(6), c = 7.44(3) angstrom) related to WO3.2H2O, phase II, prepared by refluxing LiVWO6 with concentrated HNO3, is isostructural with WO3.1/3H2O. Dehydration of II around 330-degrees-C yields a hexagonal phase (III, a = 7.25(4), c = 7.74(3) angstrom) isotypic with hexagonal WO3. Both land III exhibit redox and acid-base intercalation reactivity characteristic of layered and tunnel structures.

Sonochemical reaction engineering

Ultrasound has been widely used by chemists to enhance yields as well as rates of homogeneous as well as heterogeneous chemical reactions. The effect of ultrasound on the course of chemical reactions is mediated through cavitation bubbles it generates. High temperatures and pressures are attained inside the cavitating bubbles when they collapse. The extreme conditions so generated lead to the formation of reactive intermediates, e.g., free radiacls, inside the bubbles, which cause chemical reactions to occur when they enter the surrounding liquid. This is the mechanism through which ultrasound influences the path of homogeneous reactions. The cavitation bubbles collapse asymmetrically in the vicinity of solids, e.g., catalyst particles. Asymmetric collapse lead to formation of high speed microjets. The microjets can enhance transport rates, the increase surface area through pitting as well as particle fragmentation through collisions. Both can alter the rates of heterogeneous reaction rates. It however appears that these effects do not exhaust the scope of the influence of ultrasound on heterogeneous reactions. Modelling and quantitative prediction of the effect of ultrasound on chemical reactions is however at a stage of infancy as the phenomena are complex. Only a few examples of modelling exist in literature. Apart from this, reactor design and scaleup pose significant problems. Thus sonochemical reaction engineering offers large scope for research and development efforts.

Studies on pyridinium hexafluorostannate and its derivatives

Pyridinium hexafluorostannate, (C5H5NH)2SnF6, has been prepared by the reaction of stannous chloride or tin metal with pyridinium poly(hydrogen fluoride), PPHF, and identified by chemical analysis, IR and NMR (H-1, F-19, C-13). Making use of (C5H5NH)2SnF6 as a precursor, the following important hexafluorostannate salts have been synthesized in high yields at room temperature by ionic exchange: M2SnF6 (M = NH4, Na, K, Rb, Cs) and BaSnF6. These salts have been characterised by chemical analysis and infrared spectroscopy. Indexed powder X-ray diffraction data for Na2SnF6, Rb2SnF6 and Cs2SnF6 have been reported.