Continuous distribution kinetics for ultrasonic degradation of poly(methyl methacrylate)

Ultrasonic degradation of poly(methyl methacrylate) (PMMA) was carried out in several solvents and some mixtures of solvents. The time evolution of molecular weight distribution (MWD), determined by gel permeation chromatography, is analysed by continuous distribution kinetics. The rate coefficients for polymer degradation are determined for each solvent. The variation of rate coefficients is correlated with the vapour pressure of the solvent, kinematic viscosity of the solution and solvent-polymer interaction parameters. The vapour pressure and the kinematic viscosity of the solution are found to be more critical than other parameters (such as the Huggins and Flory-Huggins constants) in determining the degradation rates. (C) 2001 Society of Chemical Industry.

A numerical model of a liquid-feed solid polymer electrolyte DMFC and its experimental validation

A one-dimensional, biphasic, multicomponent steady-state model based on phenomenological transport equations for the catalyst layer, diffusion layer, and polymeric electrolyte membrane has been developed for a liquid-feed solid polymer electrolyte direct methanol fuel cell (SPE- DMFC). The model employs three important requisites: (i) implementation of analytical treatment of nonlinear terms to obtain a faster numerical solution as also to render the iterative scheme easier to converge, (ii) an appropriate description of two-phase transport phenomena in the diffusive region of the cell to account for flooding and water condensation/evaporation effects, and (iii) treatment of polarization effects due to methanol crossover. An improved numerical solution has been achieved by coupling analytical integration of kinetics and transport equations in the reaction layer, which explicitly include the effect of concentration and pressure gradient on cell polarization within the bulk catalyst layer. In particular, the integrated kinetic treatment explicitly accounts for the nonhomogeneous porous structure of the catalyst layer and the diffusion of reactants within and between the pores in the cathode. At the anode, the analytical integration of electrode kinetics has been obtained within the assumption of macrohomogeneous electrode porous structure, because methanol transport in a liquid-feed SPE- DMFC is essentially a single-phase process because of the high miscibility of methanol with water and its higher concentration in relation to gaseous reactants. A simple empirical model accounts for the effect of capillary forces on liquid-phase saturation in the diffusion layer. Consequently, diffusive and convective flow equations, comprising Nernst-Plank relation for solutes, Darcy law for liquid water, and Stefan-Maxwell equation for gaseous species, have been modified to include the capillary flow contribution to transport. To understand fully the role of model parameters in simulating the performance of the DMCF, we have carried out its parametric study. An experimental validation of model has also been carried out. (C) 2003 The Electrochemical Society.

Kinetics of catalytic degradation of polycarbonate in benzene

The degradation kinetics of polycarbonate [poly(bisphenol A carbonate)] in benzene catalyzed by commercial (rutile) TiO2 (BET surface area = 11 m(2)/g), anatase TiO2 (156 m(2)/g), and 1 atom % Pt/TiO2 (111 m2/g), prepared by the solution combustion technique, was investigated at various temperatures (230-280 degreesC) and 50 atm. The time evolution of the molecular weight distribution (MWD) was determined by gel permeation chromatography (GPC) and modeled with continuous distribution kinetics to obtain the degradation rate coefficients. The rate coefficients for the catalytic degradation of polycarbonate increased by factors of 20, 3.5, and 1.3 compared to the rate coefficients for thermal degradation when catalyzed by nanosized TiO2 anatase, Pt/TiO2 anatase, and commercial TiO2, respectively, at 280 degreesC. The increased catalytic activity of combustion for synthesized TiO2 and 1% Pt/TiO2 might be due to the increased acidity and BET surface area. The activation energies, determined from the temperature dependencies of the rate coefficients, were 16.3, 21.5, and 39.1 kcal/mol for commercial TiO2, combustion-synthesized Pt/TiO2, and anatase TiO2, respectively.

Role of diffusion creep in a superplastic zirconia-alumina composite

The phenomenon of superplasticity has been demonstrated in several zirconia-alumina composites. However, the rate controlling mechanism has not yet been unambiguously identified, due to the limited data available on these materials in comparison with 3 mol% yttria stabilized tetragonal zirconia (3YTZ). The limited data on a zirconia-20 wt% alumina (3Y20A) composite suggest that the mechanical characteristics are similar to those of 3YTZ. The present experimental study on 3Y20A reveals the occurrence of diffusion creep. The experimental results are examined critically in terms of dislocation activity and diffusion creep, and their relevance to superplastic deformation.

Unsteady free convection flow over an infinite vertical porous plate due to the combined effects of thermal and mass diffusion, magnetic field and Hall currents

The unsteady free convection flow over an infinite vertical porous plate, which moves with time-dependent velocity in an ambient fluid, has been studied. The effects of the magnetic field and Hall current are included in the analysis. The buoyancy forces arise due to both the thermal and mass diffusion. The partial differential equations governing the flow have been solved numerically using both the implicit finite difference scheme and the difference-differential method. For the steady case, analytical solutions have also been obtained. The effect of time variation on the skin friction, heat transfer and mass transfer is very significant. Suction increases the skin friction coefficient in the primary flow, and also the Nusselt and Sherwood numbers, but the skin friction coefficient in the secondary flow is reduced. The effect of injection is opposite to that of suction. The buoyancy force, injection and the Hall parameter induce an overshoot in the velocity profiles in the primary flow which changes the velocity gradient from a negative to a positive value, but the magnetic field and suction reduce this velocity overshoot.

Reactive Diffusion Between Vanadium and Silicon

Interdiffusion study is conducted in the V-Si system to determine integrated diffusion coefficients of the phases. Activation energy values are calculated from the experiments conducted at different temperatures. The average values are found to be 208, 240 and 141 kJ/mol, respectively, for the V(3)Si, V(5)Si(3) and VSi(2) phases. The low activation energy for the VSi(2) phase indicates very high concentration of defects or the significant contribution from the grain boundary diffusion. The error in calculation of diffusion parameters from a very thin phase layer in a multiphase diffusion couple is discussed. Further the data available in the literature in this system is compared and the problems in the indirect methodology followed previously to calculate the diffusion parameters are discussed.

Dynamics of pulled desorption with effects of excluded-volume interaction: The p-Laplacian diffusion equation and its exact solution

We analyze the dynamics of desorption of a polymer molecule which is pulled at one of its ends with force f, trying to desorb it. We assume a monomer to desorb when the pulling force on it exceeds a critical value f(c). We formulate an equation for the average position of the n-th monomer, which takes into account excluded-volume interaction through the blob-picture of a polymer under external constraints. The approach leads to a diffusion equation with a p-Laplacian for the propagation of the stretching along the chain. This has to be solved subject to a moving boundary condition. Interestingly, within this approach, the problem can be solved exactly in the trumpet, stem-flower and stem regimes. In the trumpet regime, we get tau = tau(0)n(d)(2), where n(d) is the number of monomers that have desorbed at the time tau. tau(0) is known only numerically, but for f close to f(c), it is found to be tau(0) similar to f(c)/(f(2/3) - f(c)(2/3)) If one used simple Rouse dynamics, this result would change to tau similar to f(c)n(d)(2)/(f - f(c)). In the other regimes too, one can find exact solution, and interestingly, in all regimes tau similar to n(d)(2). Copyright (C) EPLA, 2011

Swam Intelligent Based Inverse Model for Laboratory Double Reservoir Diffusion Experiments

Theoretical approaches are of fundamental importance to predict the potential impact of waste disposal facilities on ground water contamination. Appropriate design parameters are, in general, estimated by fitting the theoretical models to a field monitoring or laboratory experimental data. Double-reservoir diffusion (Transient Through-Diffusion) experiments are generally conducted in the laboratory to estimate the mass transport parameters of the proposed barrier material. These design parameters are estimated by manual parameter adjusting techniques (also called eye-fitting) like Pollute. In this work an automated inverse model is developed to estimate the mass transport parameters from transient through-diffusion experimental data. The proposed inverse model uses particle swarm optimization (PSO) algorithm which is based on the social behaviour of animals for finding their food sources. Finite difference numerical solution of the transient through-diffusion mathematical model is integrated with the PSO algorithm to solve the inverse problem of parameter estimation.The working principle of the new solver is demonstrated by estimating mass transport parameters from the published transient through-diffusion experimental data. The estimated values are compared with the values obtained by existing procedure. The present technique is robust and efficient. The mass transport parameters are obtained with a very good precision in less time

Giant photoinduced optical bleaching at room and liquid helium temperatures in Sb/As(2)S(3) multilayered films

We report the observation of giant photo induced optical bleaching in Sb/As(2)S(3) multilayered film at room and liquid He temperatures, when irradiated with 532 nm laser at moderate intensities. The experimental results show a dramatic increase in transmittance near the band gap regime at both the temperatures; however the rates at which transmission change occurs are rather slow at low temperature. The huge change in transmission is due to the photo induced intermixing of As(2)S(3) layer with Sb. Our XPS measurements show that photo induced intermixing occurs through the wrong homopolar bonds, which under actinic light illumination are converted into energetically favored hetropolar bonds. (C) 2011 Elsevier B.V. All rights reserved.