Small-angle neutron scattering studies of different mixed micelles composed of dimeric and monomeric cationic surfactants

Measurements of small-angle neutron scattering (SANS) cross sections from different mixed micelles composed of CTAB and Br-, n-C16H33N+Me2-(CH2)(m)N+Me2-n-C16H33, Br- (16-m-16, 2Br(-), where m = 3, 5, and 10), in aqueous media (D2O) are reported. The data have been analyzed using the Hayter and Penfold model for macroion solution to compute the interparticle structure factor S(Q) taking into account the screened Coulomb interactions between the micelles. The aggregate composition matches with that predicted from an ideal mixing model. The SANS analysis further indicates that the extent of aggregate growth and the Variations of shapes of the mixed micelles could be modulated by the amount of dimeric surfactant present in these mixtures. With the spacer chain length m less than or equal to 4 in the dimeric surfactant, the propensity of micellar growth is particularly pronounced. The effect of the variation of the temperature for the mixed micellar system (23.1 mol % of 16-3-16, 2Br(-)) was also examined. The systemic microviscosities that the mixed micellar aggregates offer to a solubilized, extrinsic fluorescence probe, 1,6-diphenyl-1,3,5-hexatriene, were determined. The variation of the microviscosities of the mixed micelles as a function of percentages of the dimeric surfactants could be explained in terms of conformational variations and progressive looping of the spacer chain of dimeric surfactants in mixed micellar aggregates with increasing m values.

Solution of a hypersingular integral equation of the second kind

A straightforward analysis involving the complex function-theoretic method is employed to determine the closed-form solution of a special hypersingular integral equation of the second kind, and its known solution is recovered.

Studies on structural and electrical properties of barium strontium titanate thin films developed by metallo-organic decomposition

Thin films of barium strontium titanate (BST) including BaTiO3 and SrTiO3 end members were deposited using the metallo-organic decomposition (MOD) technique. Processing parameters such as nonstoichiometry, annealing temperature and time, film thickness and doping concentration were correlated with the structural and electrical properties of the films. A random polycrystalline structure was observed for all MOD films under the processing conditions in this study. The microstructures of the films showed multi-grains structure through the film thickness. A dielectric constant of 563 was observed for (Ba0.7Sr0.3)TiO3 films rapid thermal annealed at 750 degrees C for 60 s. The dielectric constant increased with annealing temperature and film thickness, while the dielectric constant could reach the bulk values for thicknesses as thin as similar to 0.3 mu m. Nonstoichiometry and doping in the films resulted in a lowering of the dielectric constant. For near-stoichiometric films, a small dielectric dispersion obeying the Curie-von Schweidler type dielectric response was observed. This behavior may be attributed to the presence of the high density of disordered grain boundaries. All MOD processed films showed trap-distributed space-charge limited conduction (SCLC) behavior with slope of similar to 7.5-10 regardless of the chemistry and processing parameter due to the presence of main boundaries through the film thickness. The grain boundaries masked the effect of donor-doping, so that all films showed distributed-trap SCLC behavior without discrete-traps. Donor-doping could significantly improve the time-dependent dielectric breakdown behavior of BST thin films, mostly likely due to the lower oxygen vacancy concentration resulted from donor-doping. From the results of charge storage density, leakage current and time-dependent dielectric breakdown behavior, BST thin films are found to be promising candidates for 64 and 256Mb ULSI DRAM applications. (C) 1997 Elsevier Science S.A.

Solution grafting of maleic anhydride onto polyethylene and compatibilization of polyetylene-nylon blends

Maleic anhydride (MAH) has been grafted onto high density polyethylene (HDPE) with benzoyl peroxide (BOP) initiator in toluene solution. Maximum degree of grafting (12%) without crosslinking has been obtained using MAH/HDPE and BOP/HDPE weight ratios of 1.0 and 0.15 respectively, at 110 degrees C. The HDPE-g-MAH compatibilizer is found to drastically reduce the dispersed phase size and also to produce homogeneous blends for relatively low concentrations of dispersed phase in HDPE/nylon blends. Addition of this compatibilizer results in increase of tensile strength and modulus with increasing nylon content of HDPE/nylon blends, while the opposite is found for the blends without any added compatibilizer.

Spectral, thermal and electrical properties of poly(o- and m-toluidine) PVC blends prepared by solution blending

Poly(o-toluidine) (POT) and poly(m-toluidine) (PMT) blends with polyvinylchloride (PVC) of five different compositions have been prepared by solution blending. The POT-PVC and PMT-PVC blends were prepared using THF as a solvent in which POT-HNO3, PMT-HNO3 bases and PVC are soluble. The blends have been characterized by spectral, thermal and electrical measurements. The results indicate the formation of blends at all the compositions presently studied. The thermal stability of the POT-PVC and PMT-PVC blends is higher than that of POT-HNO3 and PMT-HNO3 salts, respectively. Using the present method, POT/PMT can conveniently be blended with 30% wt/wt of PVC without significant loss in its conductivity. (C) 1998 Elsevier Science Ltd. All rights reserved.

EPR and photoluminescence studies of ZnO:Mn nanophosphors prepared by solution combustion route

Nanocrystalline ZnO:Mn (0.1 mol%) phosphors have been successfully prepared by self propagating, gas producing solution combustion method. The powder X-ray diffraction of as-formed ZnO:Mn sample shows, hexagonal wurtzite phase with particle size of similar to 40 nm. For Mn doped ZnO, the lattice parameters and volume of unit cell (a=3.23065 angstrom, c=5.27563 angstrom and V=47.684 (angstrom)(3)) are found to be greater than that of undoped ZnO (a=3.19993 angstrom, c=5.22546 angstrom and V=46.336 (angstrom)(3)). The SEM micrographs reveal that besides the spherical crystals, the powders also contained several voids and pores. The TEM photograph also shows the particles are approximately spherical in nature. The FTIR spectrum shows two peaks at similar to 3428 and 1598 cm(-1) which are attributed to O-H stretching and H-O-H bending vibration. The PL spectra of ZnO:Mn indicate a strong green emission peak at 526 nm and a weak red emission at 636 nm corresponding to T-4(1) -> (6)A(1) transition of Mn2+ ions. The EPR spectrum exhibits fine structure transition which will be split into six hyperfine components due to Mn-55 hyperfine coupling giving rise to all 30 allowed transitions. From EPR spectra the spin-Hamiltonian parameters have been evaluated and discussed. The magnitude of the hyperfine splitting (A) constant indicates that there exists a moderately covalent bonding between the Mn2+ ions and the surrounding ligands. The number of spins participating in resonance (N), its paramagnetic susceptibility (chi) have been evaluated. (C) 2011 Elsevier B.V. All rights reserved.

The Wiener-Hopf solution of a class of mixed boundary value problems arising in surface water wave phenomena

Two mixed boundary value problems associated with two-dimensional Laplace equation, arising in the study of scattering of surface waves in deep water (or interface waves in two superposed fluids) in the linearised set up, by discontinuities in the surface (or interface) boundary conditions, are handled for solution by the aid of the Weiner-Hopf technique applied to a slightly more general differential equation to be solved under general boundary conditions and passing on to the limit in a manner so as to finally give rise to the solutions of the original problems. The first problem involves one discontinuity while the second problem involves two discontinuities. The reflection coefficient is obtained in closed form for the first problem and approximately for the second. The behaviour of the reflection coefficient for both the problems involving deep water against the incident wave number is depicted in a number of figures. It is observed that while the reflection coefficient for the first problem steadily increases with the wave number, that for the second problem exhibits oscillatory behaviour and vanishes at some discrete values of the wave number. Thus, there exist incident wave numbers for which total transmission takes place for the second problem. (C) 1999 Elsevier Science B.V. All rights reserved.

Aryl monosulphides and symmetrical disulphides based second order nonlinear optical chromophores with transparency in the visible

A series of aryl monosulphides and disulphides have been synthesized and characterized. Their molecular hyperpolarizability (beta) has been measured in solution with the hyper-Rayleigh Scattering technique and also calculated by semiempirical AMI method. The trend in the observed and calculated values of first hyperpolarizability of these compounds has been found to be in good agreement. These compounds show moderate P values and excellent transparency in the visible region.

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.

Chiral Mitsunobu reactions with (1S)-(+)-ketopinic acid: kinetic resolutions of secondary alcohols

Several secondary alcohols undergo the Mitsunobu reaction with triphenylphosphine, diethyl azodicarboxylate and (1S)-(+)-ketopinic acid (0.5 equiv. each relative to alcohol) in CH2Cl2 solution at -23degreesC, to furnish the chiral secondary alcohol and its ketopinate ester (d.e. >95%,). Chromatographic separation of these and subsequent hydrolysis of the ketopinate ester (KOH EtOH/0degreesC) provides the chiral secondary alcohol in overall yields of similar to75% and e.e. of similar to80%. When the above Mitsunobu reaction is performed with 1 equiv. of all the reactants. an effective dynamic kinetic resolution of the alcohol is observed in two cases, the ketopinate esters being isolated in 63 and 75% yields and >95% d.e. (C) 2002 Elsevier Science Ltd. All rights reserved.

Conformation and orientation of alkyl chains in the layered organic-inorganic hybrids: (CnH2n+1NH3)(2)PbI4 (n=12,16,18)

Layered organic inorganic hybrids based on perovskite-derived alkylammonium lead halides have been demonstrated as important new materials in the construction of molecular electronic devices. Typical of this class of materials are the single-perovskite slab lead iodides of the general formula (CnH2n+1NH3)(2)PbI4. While for small n, these compounds are amenable to single-crystal structure determination, the increasing degree of disorder in the long chain (n = 12,14...) compounds makes such an analysis difficult. In this study, we use powder X-ray diffraction, and vibrational and C-13 NMR spectroscopies to establish the conformation, orientation and organization of hydrocarbon chains in the series of layered alkylammonium lead iodides (CnH2n+1NH3)(2)PbI4 (n = 12,16,18). We find that the alkyl chains adopt a tilted bilayer arrangement, while the structure of the inorganic layer remains invariant with respect to the value of n. Conformation-sensitive methylene stretching modes in the infrared and Raman spectra, as well as the C-13 NMR spectra indicate that bonds in the methylene chain are in trans configuration. The skeletal modes of the alkyl chain in the Raman spectra establish that there is a high degree of all-trans conformational registry for the values of n studied here. From the orientation dependence of the infrared spectra of crystals of (CnH2n+1NH3)(2)PbI4 ( n = 12,16), we find that the molecular axis of the all-trans alkyl chains are tilted away from the interlayer normal by an angle of 55degrees. This value of this tilt angle is consistent with the dependence of the c lattice expansion as a function of n, as determined from powder X-ray diffraction.

Continuous distribution kinetics for the thermal degradation of LDPE in solution

Polymer degradation in solution has several advantages over melt pyrolysis, The degradation of low-density polyethylene (LDPE) occurs at much lower temperatures in solution (280-360degreesC) than in conventional melt pyrolysis (400-450degreesC). The thermal degradation kinetics of LDPE in solution was investigated in this work. LDPE was dissolved in liquid paraffin and degraded for 3 h at various temperatures (280-360degreesC). Samples were taken at specific times and analyzed with high-pressure liquid chromatography/gel permeation chromatography for the molecular weight distribution (MWD), The time evolution of the MWD was modeled with continuous distribution kinetics. Data indicated that LDPE followed random-chain-scission degradation. The rapid initial drop in molecular weight, observed up to 45 min, was attributed to the presence of weak links in the polymer. The rate coefficients for the breakage of weak and strong links were determined, and the corresponding average activation energies were calculated to be 88 and 24 kJ/mol, respectively. (C) 2002 John Wiley Sons, Inc.

Crystal structure and thermal and electrical properties of the perovskite solid solution Nd1-xSrxFeO3-delta (0 <= x <= 0.4)

The crystal structure, thermal expansion and electrical conductivity of strontium-doped neodymium ferrite (Nd1-xSrxFeO3-delta where 0less than or equal toxless than or equal to0.4) were investigated. All compositions had the GdFeO3-type orthorhombic perovskite structure. The lattice parameters were determined at room temperature by X-ray powder diffraction. The orthorhombic distortion decreases with increasing Sr substitution. The pseudocubic lattice parameter shows a minimum at x=0.3. The thermal expansion curves for x=0.2-0.4 displayed rapid increase in slope at higher temperatures. The electrical conductivity increased with Sr content and temperature. The calculated activation energies for electrical conduction decreased with increasing x. The electrical conductivity can be described by the small polaron hopping mechanism. The charge compensation for divalent ion on the A-site is provided by the formation of Fe4+ ions on the B site and vacancies on the oxygen sublattice. The results indicate two defect domains: for low values of x, the predominant defect is Fe4+ ions, whereas for higher values of x, oxygen vacancies dominate. (C) 2002 Elsevier Science B.V. All rights reserved.