Autoignition in a non-premixed medium: DNS studies on the effects of three-dimensional turbulence

Direct numerical simulation (DNS) results of autoignition in anon-premixed medium under an isotropic, homogeneous, and decaying turbulence are presented. The initial mixture consists of segregated fuel parcels randomly distributed within warm air, and the entire medium is subjected to a three-dimensional turbulence. Chemical kinetics is modeled by a four-step reduced reaction mechanism for autoignition of n-heptane/air mixture. Thus, this work overcomes the principal limitations of a previous contribution of the authors on two-dimensional DNS of autoignition with a one-step reaction model. Specific attention is focused on the differences in the effects of two- and three-dimensional turbulence on autoignition characteristics. The three-dimensional results show that ignition spots are most likely to originate at locations jointly corresponding to the most reactive mixture fraction and low scalar dissipation rate. Further, these ignition spots are found to originate at locations corresponding to the core of local vortical structures, and after ignition, the burning gases move toward the vortex periphery Such a movement is explained as caused by the cyclostrophic imbalance developed when the local gas density is variable. These results lead to the conclusion that the local ignition-zone structure does not conform to the classical stretched flamelet description. Parametric studies show that the ignition delay time decreases with an increase in turbulence intensity. Hence, these three-dimensional simulation results resolve the discrepancy between trends in experimental data and predictions from DNSs of two-dimensional turbulence. This qualitative difference between DNS results from three- and two-dimensional simulations is discussed and attributed to the effect of vortex stretching that is present in the former, but not in the latter.

Chemistry of dihydrogen complexes containing only phosphorus co-ligands

A series of new dicationic dihydrogen complexes of ruthenium of the type cis-[(dppm)(2)Ru(eta(2)-H-2)(L)][BF4](2) (dppm = Ph2PCH2PPh2; L = phosphite) have been prepared by protonating the precursor hydride complexes cis-[(dPPM)(2)Ru(H)(L)][BF4] using HBF4.Et2O. The precursor hydride complexes have been obtained from trans-[(dppm)(2)Ru(H)(L)][BF4][(L = phospfiite) via a rare acid-catalysed isomerization reaction in six coordinate species. The trans-[(dppm)(2)Ru(H)(L)][BF4] complexes (L = phosphine) upon protonation gave the isomerized derivatives, however, further addition of acid resulted in a five-coordinate species, [(dppm)(2)RuCl](+) presumably via an intermediate phosphine dihydrogen complex. The electronic as well as the steric properties of the co-ligands seem to strongly influence the structure-reactivity behaviour of this series of complexes.

Chemistry of tetrathiomolybdate: Applications in organic synthesis

The utility of tetrathiomolybdate in a variety of organic transformations is presented in this account. The sulfur transfer ability of tetrathiomolybdate is exploited in the synthesis of organic disulfides under mild reaction conditions. The induced internal redox reactions associated with tetrathiomolybdate have been thoroughly exploited in developing various methodologies, which include the reduction of organic azides, synthesis of diselenides, cyclic imines, thioamides, and thiolactams. In addition, novel deprotection strategies using tetrathiomolybdate have been developed to cleave the propargyl and propargyloxy carbonyl (POC) protecting groups. Tetrathiomolybdate mediated tandem sulfur transfer-reduction-Michael reactions have been applied to the synthesis of sulfur containing bicyclic systems. Furthermore, the reactions in the solid state and the reactions in water medium assisted by tetrathiomolybdate have greatly simplified the synthesis of organic disulfides.

Mechanical properties of Nylon-6/LDPE blends containing an epoxy resin compatibilizer

Binary and ternary blends of nylon-6/low density polyethylene (nylon-6/LDPE) and Nylon-6/LDPE/poly(ethylene-co-glycidyl methacrylate) were prepared by melt mixing. The blends exhibit two phase morphology with LDPE dispersed in the form of spherical domains in the nylon-6 matrix. The mechanical properties of the blends were measured by standard methods. It is shown that the use of the epoxy copolymer as a compatibilizer improves the impact strength of the blend as compared to nylon-6, which is attributed to better stress transfer across the interface due to the compatibilizer. The data for each mechanical property were also fitted into a best fit model equation and the method of steepest ascent was applied to arrive at the optimum composition of the blend for that property.

Synthesis and structure of La14V6CuO36.5: a transparent Cu(I) vanadate containing [OCuO](3-) sticks

The title compound, La14V6CuO36.5, was prepared from a stoichiometric mixture of La2O3,V2O5, and CuO at 1050-1080 degreesC. The compound forms transparent, pale green crystals and was characterized by wavelength dispersive spectroscopy and single crystal X-ray diffraction. The structure contains isolated VO43- tetrahedra and [OCuO](3-) sticks dispersed in a lanthanum oxide network. Films of La14V6CuO36.5 were grown on R-plane sapphire by using pulsed laser deposition. Rutherford backscattering spectroscopic and X-ray diffraction analyses of the films showed oriented growth of the title phase, a similar to5 eV optical band gap and n-type conductivity. The compound is an example of a transparent copper(I) oxide.

Synthesis of phospholipids with fatty acid chains containing aromatic units at various depths

A series of diacyl phosphatidylcholine lipid derivatives, which contain aromatic units at various depths of their fatty acid chains, have been synthesized. These lipids produced stable aqueous suspensions. Electron microscopy revealed the presence of vesicular aggregates in the suspensions of these newly synthesized lipids. These membranes were oxidatively stable and maintained fluid character at ambient temperature making them ideal candidates for membrane protein reconstitution studies.

The effect of mischmetal addition on the structure and mechanical properties of a cast Al-7Si-0.3Mg alloy containing excess iron (up to 0.6 Pct)

The effect of Fe content (0.2 to 0.6 pct) on the microstructure and mechanical properties of a cast Al-7Si-0.3Mg (LM 25/356) alloy has been investigated. Further, 1 pct mischmetal (MM) additions (a mixture of rare-earth (RE) elements) were made to these alloys, and their mechanical properties at room and at elevated temperatures (up to 200 degreesC) were evaluated. A structure-property correlation on this alloy was attempted using optical microstructure analysis, fractographs, X-ray diffraction, energy-dispersive analysis of X-rays (EDX), and quantitative metallography by image analysis. An increase in Fe content increased the volume percentage of Fe-bearing intermetallic compounds (beta and pi phases), contributing to the lower yield strength (YS), ultimate tensile strength (UTS), percentage elongation, and higher hardness. An addition of 1 pct MM to the alloys containing 0.2 and 0.6 pct Fe was found to refine the microstructure; modify the eutectic silicon and La, Ce, and Nd present in the MM; form different intermetallic compounds with Al, Si, Fe, and Mg; and improve the mechanical properties of the alloys both at room and elevated temperatures.

A layered chlorophosphate, Na-3[Cd4Cl3(HPO4)(2)(H2PO4)(4)], containing Na+ ions in the interlamellar space

Reaction between CdCl2.H2O and NaH2PO4.H2O Under hydrothermal conditions gives rise to a new cadmium chlorophosphate of the formula Na-3[Cd4Cl3(HPO4)(2)(H2PO4)(4)] I. This material crystallizes in the orthorhombic system with space group Fmm2(no. 42). I has macroanionic layers of [Cd4Cl3(HPO4)(2)(H2PO4)(4)](3-) with Na+ ions in the interlamellar space. The discovery of such compounds suggests that metathetic reactions carried out under hydrothermal conditions may provide a novel route for the synthesis of new open-framework structures.

Combustion synthesis and properties of Ce1-xPrxO2-delta red ceramic pigments

Praseodymium-doped ceria red pigments, Ce1−xPrxO2−δ, x=0–0.5 have been prepared by the thermal decomposition of the redox compound Ce1−xPrx(N2H3COO)3·3H2O as well as by the combustion of aqueous solutions containing cerous nitrate, praseodymium nitrate and oxalyl dihydrazide (ODH)/ammonium acetate. Formation of the pigment has been confirmed by its characteristic red colour and reflectance spectra which shows the reflection edge not, vert, similar690 nm corresponding to charge transfer from the ligand orbitals to the localised 4f1 of Pr4+. The particulate properties of praseodymium-doped ceria pigments obtained from the combustion of redox compounds and redox mixtures are compared.

Compressive behavior and fracture features of rubber bearing glass-epoxy composites exposed to aqueous media

Epoxy systems containing HTBN rubber material and reinforced with E-glass fibres, exposed to a fixed time duration in three separate media were subjected to compressive mode of deformation. The yield stress and fractographic features noted on the compression failed samples are reported in this work. The experiment reveals that the seawater exposed sample exhibits a drop in strength compared to dry (unexposed) sample. This kind of drop is maintained if the media is changed from seawater to distilled water. When HCl is included in seawater. the experiment shows a small rise in strength value. These changes have been attributed to various factors like medium ingress into samples assisting interface failure, the larger-sized Cl- influencing the extent of diffusion of medium into system and finally their participation in the deformation phenomena. The fractographic features reveal interface separations that show either scattered debris or a cleaner surface or display a whitish-coated matrix region depending on whether the tests are done on unexposed samples or on ones following the immersion in the media.

Scalable weak aligning medium for enantiodiscrimination of water soluble chiral molecules

The study reports the first indication of a lyotropic liquid crystalline phase of an aqueous solution of polysaccharide xanthan gum, as a physical parameter dependent scalable and reversible weak alignment medium, for enantiodiscrimination of water soluble chiral molecules.

An open-framework cobalt oxalato-squarate containing a ligated amine

A cobalt oxalato-squarate of the formula [Co-2(C4O4)(C2O4)(C3N2H4)(2)], containing a ligated amine has been synthesized hydrothermally and its structure determined by single crystal X-ray diffraction. The compound crystallizes in the orthorhombic space group P2(1)2(1)2 with a = 18.3845(8) Angstrom, b = 5.7884(3) Angstrom, c = 7.2598(4) Angstrom, V = 772.56(7)Angstrom(3) and Z = 4. It has a layered structure where two-dimensional sheets are formed by the connectivity of the squarate and the oxalate units with the cobalt centres, with the ligating amine molecules protruding out from the layers. (C) 2003 Editions scientifiques et medicales Elsevier SAS. All rights reserved.

Characterization of Ni-Pd alloy as anode for methanol oxidative fuel cell

Electrochemical deposition of Ni-Pd alloy films of various compositions from bath solution containing ethylenediamine (EDA) was carried out to use as anode material for methanol oxidative fuel cell in H2SO4 medium. Electronic absorption spectrum of bath solution containing Ni2+ Pd2+ ions and EDA indicated the formation of a four coordinate square planar metal-ligand complex of both the metal ions. X-ray diffraction (XRD) patterns of the deposited alloy films show an increase in Pd-Ni alloy lattice parameter with increase in Pd content, and indicate the substitution of Pd in the lattice. A nano/ultrafine kind of crystal growth was observed in the alloy film deposited at low current density (2.5 mA cm(-2)). X-ray photoelectron spectroscopic (XPS) studies on the successively sputtered films showed the presence of Ni and Pd in pure metallic states and the surface concentration ratio of Ni to Pd is less than bulk indicating the segregation of Pd on the surface. Electro-catalytic oxidation of methanol in H2SO4 medium is found to be promoted on Ni-Pd electrodeposits. The anodic peak current characteristics to oxidation reaction on Ni-Pd was found typically high when compared to pure nickel and the relative increase in surface area by alloying the Ni by Pd was found to be as much as 300 times. (C) 2003 Elsevier Science B.V. All rights reserved.

Segregation in the MgO–MgAl2O4 system processed from nitrate precursors

The occurrence of segregation and its influence on microstructural and phase evolution have been studied in MgO–MgAl2O4 powders synthesized by thermal decomposition of aqueous nitrate precursors. When the nitrate solutions of Mg and Al were spray-pyrolyzed on a substrate held at 673 or 573 K, homogeneous mixed oxides were produced. Spraying and drying the nitrate solutions at 473 K resulted in the formation of compositionally inhomogeneous, segregated oxide mixtures. It is suggested that segregation in the dried powders was caused by the difference in solubility of the individual nitrate salts in water which caused Mg-rich and Al-rich salts to precipitate during dehydration of the solutions. The occurrence of segregation in the powders sprayed at 473 K and not 573 or 673 K is ascribed to the sluggish rate at which the early stages of decomposition occurred during which the cations segregated. The phase evolution in segregated and segregation-free MgO–MgAl2O4 powders has been compared. The distinguishing feature of the segregated powders was the appearance of stoichiometric periclase grain dimensions in excess of 0.3 μm at temperatures as low as 973 K. By comparison, the segregation-free powders displayed broad diffraction peaks corresponding to fine-grained and nonstoichiometric periclase. The grain size was in the range 5–30 nm at temperatures up to 1173 K. The key to obtaining fine-grained periclase was the ability to synthesize (Mg Al)O solid solutions with the rock salt structure. In the temperature range 973–1173 K, spinel grain size varied from 5 to 40 nm irrespective of its composition and did not appear to be influenced by segregation.