Influence of HZSM-5 catalyst on the thermal degradation of poly(vinyl chloride) in solution

The kinetics of thermal degradation of poly(vinyl chloride) (PVC) in solution was investigated at various temperatures (210-250degreesC). The degradation rate coefficients were determined from the time evolution of the molecular weight distribution (MWD). The energy of activation, determined from the temperature dependence of the rate coefficient, was 26.6 kcal/mol. The degradation of PVC was also studied in the presence of a catalyst (HZSM-5 zeolite). The results indicated that increase of the degradation rate of PVC is first order with the HZSM-5 concentration up to 50 g/L and zero order at higher concentrations. The thermal degradation kinetics of PVC in the presence of 50 g/L of the catalyst was studied at various temperatures. The temperature dependency of the rate coefficient was used to calculate the activation energy (21.5 kcal/mol). This is consistent with the observation that the presence of a catalyst generally decreases the activation energy and promotes degradation. (C) 2002 John Wiley Sons, Inc.

Kinetics of thermal degradation of vinyl polyperoxides in solution

The thermal degradation of vinyl polyperoxides, poly(styrene peroxide, (PSP), poly(alpha-methylstyrene peroxide) (PAMSP) and poly(alpha-phenylstyrene pet-oxide) (PAPSP), was carried out at different temperatures in toluene. The time evolution of molecular weight distributions (MWDs) was determined by gel permeation chromatography (GPC). A continuous distribution model was used to evaluate the random chain degradation rate coefficients. The activation energies, determined from the temperature dependence of the rate coefficients, suggest that thermal degradation of polyperoxides is controlled by the dissociation of the O-O bonds in the backbone of the polymer chain. Among the three polyperoxides investigated, the thermal stability is the highest for PAPSP and the lowest for PAMSP. (C) 2002 Elsevier Science Ltd. All rights reserved.

Rayleigh-Benard convection during solidification of an eutectic solution cooled from the top

The interaction between laminar Rayleigh-Benard convection and directional solidification is studied for the case of an eutectic solution kept in a rectangular cavity cooled from the top. Experiments and numerical simulations are carried out using an NH4Cl-H2O solution as the model fluid. The flow is visualized using a sheet of laser light scattered by neutrally buoyant, hollow-glass spheres seeded in the fluid. The numerical modeling is performed using a pressure-based finite-volume method according to the SIMPLER algorithm. The present configuration enables us to visualize flow vortices in the presence of a continuously evolving solid/liquid interface. Clear visualization of the Rayleigh-Benard convective cells and their interaction with the solidification front are obtained. It is observed that the convective cells are characterized by zones of up-flow and down-flow, resulting in the development of a nonplanar interface. Because of the continuous advancement of the solid/liquid interface, the effective liquid height of the cavity keeps decreasing. Once the height of the fluid layer falls below a critical value, the convective cells become weaker and eventually die out, leading to the growth of a planar solidification front. Results of flow visualization and temperature measurement are compared with those from the numerical simulation, and a good agreement is found.

Seismic bearing capacity factors for spread foundations

The effect of horizontal earthquake body forces on the bearing capacity of foundations has been examined computationally in a rigorous manner by employing the method of stress characteristics. The bearing capacity factors N-c, N-q and N-y, due to the components of soil cohesion, ground surcharge pressure and soil unit weight respectively, have been plotted as a function of earthquake acceleration coefficient (a(h)) for different values of soil friction angle (phi). The inclusion of earthquake body forces causes a considerable reduction in the bearing capacity factors. The bearing capacity factors N-c and N-q are seen to be approximately of the same magnitude as those reported in the literature on the basis of different solution methods. However, the obtained values of N-y are found to be significantly smaller than the available results. The nature of the pressure distribution along the footing base and the geometry of the observed failure patterns vary with the consideration of earthquake body forces.

Seismic passive earth pressure coefficients using the method of characteristics

The method of characteristics was used to generate passive earth pressure coefficients for an inclined wall retaining cohesionless backfill material in the presence of pseudostatic horizontal earthquake body forces. The variation of the passive earth pressure coefficients K-pq and K-pgamma with changes in horizontal earthquake acceleration coefficient due to the components of soil unit weight and surcharge pressure, respectively, has been obtained; a closed-form solution for K-pq is also provided. The passive earth resistance has been found to decrease sharply with an increase in the magnitude of horizontal earthquake acceleration. The computed passive earth pressure coefficients were found to be the lowest when compared to all of the previous solutions available in the literature.

Solid state structural and solution studies on the formation of a flexible cavity for anions by copper(I) and 1,2-bis(diphenylphosphino)ethane

Copper(l) complexes of 1,2-bis(diphenylphosphino)ethane (dppe) with a stoichiometry Cu-2(dppe)(3)(X)(2) [X- = CN- (1), SCN- (2), NO3- (3)] are obtained from direct reactions of CuX and dppe. The complexes are structurally and spectroscopically (NMR and IR) characterized. The structure of the [Cu-2(dPPe)(3)](2+) dication is similar to the structural motif observed in many other complexes with a chelating dppe and a bridging dppe connecting two copper centers. In complexes 1 -3, the anions are confined to the cavity formed by the phosphines which force a monodentate coordination mode despite the predominant bidentate/bridging character of the anions. The coordination angles rather than the thermochemical radii dictate the steric requirement of anions. While the solution behavior of 3, with nitrate, is similar to complexes studied earlier, complexes with pseudohalides exhibit new solution behavior. (C) 2002 Elsevier Science Ltd. All rights reserved.

Structural investigation of combustion synthesized Cu/CeO2 catalysts by EXAFS and other physical techniques: Formation of a Ce1-xCuxO2-delta solid solution

The structure and chemical environment of Cu in Cu/CeO2 catalysts synthesized by the solution combustion method have been investigated by X-ray diffraction (XRD), transmission electron microscopy (TEM), electron paramagnetic resonance (EPR) spectroscopy, X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV), and extended X-ray fine structure (EXAFS) spectroscopy. High-resolution XRD studies of 3 and 5 atom % Cu/CeO2 do not show CuO lines in their respective patterns. The structure could be refined for the composition Ce1-xCuxO2-delta (x = 0.03 and 0.05; delta similar to 0.13 and 0.16) in the fluorite structure with 5-8% oxide ion vacancy. High-resolution TEM did not show CuO particles in 5 atom % Cu/CeO2. EPR as well as XPS studies confirm the presence of Cu2+ species in the CeO2 matrix. Redox potentials of Cu species in the CeO2 matrix are lower than those in CuO. EXAFS investigations of these catalysts show an average coordination number of 3 around the Cu2+ ion in the first shell at a distance of 1.96 Angstrom, indicating the O2- ion vacancy around the Cu2+ ion. The Cu-O bond length also decreases compared to that in CuO. The second and third shell around the Cu2+ ion in the catalysts are attributed to -Cu2+-O2--Cu2+ - at 2.92 Angstrom and -Cu2+-O2--Ce4+- at the distance of 3.15 Angstrom, respectively. The present results provide direct evidence for the formation of a Ce1-xCuxO2-delta type of solid solution phase having -square-Cu2+-O-Ce4+- kind of linkages.

Synthesis of LiCo1-xNixO2 from a low temperature solution combustion route and characterization

Nickel substituted lithium-cobalt oxides, LiCo1-xNixO2 (0 < x < 0.4), have been synthesized in a very short time by a solution combustion method at 350 degreesC using diformyl hydrazine as a fuel. Pure phases with hexagonal lattice structure have been obtained. These compounds facilitate reversible insertion/extraction of Li+ ions with good discharge capacity between 3.0 and 4.4 V versus Li/Li+. Results of the studies by powder X-ray diffraction, scanning electron microscopy, cyclic voltammetry, galvanostatic charge-discharge cycling and ac impedance measurements are presented. (C) 2002 Elsevier Science B.V. All rights reserved.

Solution combustion synthesis of gamma(L)-Bi(2)MoO(6) and photocatalytic activity under solar radiation

The facile method of solution combustion was used to synthesize gamma(L)-Bi(2)MoO(6). The material was crystallized in a purely crystalline orthorhombic phase with sizes varying from 300 to 500 nm. Because the band gap was 2.51 eV, the degradation of wide variety of cationic and anionic dyes was investigated under solar radiation. Despite the low surface area (< 1 m(2)/g) of the synthesized material, gamma(L)-Bi(2)MoO(6) showed high photocatalytic activity under solar radiation due to its electronic and morphological properties. (C) 2011 Elsevier Ltd. All rights reserved.

Reliability Based Design Optimization for Internal Stability of Reinforced Soil Structures Using Pseudo‐Static Method

Seismic design of reinforced soil structures involves many uncertainties that arise from the backfill soil properties and tensile strength of the reinforcement which is not addressed in current design guidelines. This paper highlights the significance of variability in the internal stability assessment of reinforced soil structures. Reliability analysis is applied to estimate probability of failure and pseudo‐static approach has been used for the calculation of the tensile strength and length of the reinforcement needed to maintain the internal stability against tension and pullout failures. Logarithmic spiral failure surface has been considered in conjunction with the limit equilibrium method. Two modes of failure namely, tension failure and pullout failure have been considered. The influence of variations of the backfill soil friction angle, the tensile strength of reinforcement, horizontal seismic acceleration on the reliability index against tension failure and pullout failure of reinforced earth structure have been discussed.

On the solution of the problem of scattering of surface water waves by a sharp discontinuity in the surface boundary conditions

Closed-form analytical expressions are derived for the reflection and transmission coefficients for the problem of scattering of surface water waves by a sharp discontinuity in the surface-boundary-conditions, for the case of deep water. The method involves the use of the Havelock-type expansion of the velocity potential along with an analysis to solve a Carleman-type singular integral equation over a semi-infinite range. This method of solution is an alternative to the Wiener-Hopf technique used previously.

Effect of aging on swelling and swell-shrink behavior of a compacted expansive soil

Effect of aging on swelling and swell-shrink behavior of a compacted expansive soil is investigated in this paper. An expansive soil having a liquid limit of 100% is used for this purpose. Compacted specimens were prepared and aged for a predetermined number of days (7, 15, 30, and 90 days) to study their swelling and swell-shrink behavior. It has been shown that aging improves the resistance to compression of compacted specimens. The swelling potentials of specimens also decreased with aging. The dominant factors that influence the aging effects are the water content and degree of saturation at the beginning of the aging process. The changed behavior of aged specimens is attributed to particle rearrangements and formation of bonds, which affect the surface area absorbing water during swelling. The cyclic swell-shrink tests on aged specimens indicated that the differences in vertical displacement during the first swelling were eliminated in the subsequent cycles when specimens were shrunk more, but the aging effect was found to persist with cycles for specimens subjected to lower shrinkage magnitudes.

Identity, energetics, dynamics and environment of interfacial water molecules in a micellar solution

The structure and energetics of interfacial water molecules in the aqueous micelle of cesium perfluorooctanoate have been investigated, using large-scale atomistic molecular dynamics simulations, with the primary objective of classifying them. The simulations show that the water molecules at the interface fall into two broad classes: bound and free, present in a ratio of 9:1. The bound water molecules can be further categorized on the basis of the number of hydrogen bonds (one or two) that they form with the surfactant headgroups. The hydrogen bonds of the doubly hydrogen-bonded species are found to be, on the average, slightly weaker than those in the singly bonded species. The environment around interfacial water molecules is more ordered than that in the bulk. The surface water molecules have substantially lower potential energy, because of interaction with the micelle. In particular, both forms of bound water have energies that are lower by �2.5-4.0 kcal/ mol. Entropy is found to play an important role in determining the relative concentration of the species.