Transient absorption studies on 3,6-dibromo polyvinylcarbazole and its model compounds

3,6-Dibromo-N-ethylcarbazole (DBNEC) and its polymeric analogue poly-3,6-dibromovinylcarbazole (PDBVCz) were studied by transient absorption spectroscopy. The transient absorption spectrum of the 3,6-dibromo-N-ethylcarbazole radical cation and decay rate constants of radical cations of 3,6-dibromo-N-ethylcarbazole and its polymeric analogue are presented. In the case of unsubstituted carbazole, the ratio of the yield of radical cation of monomer to polymer is 2.0, whereas in the case of PDBVCz, under the same experimental conditions, the yield of the radical cation is an order of magnitude less in comparison with the monomer model compound DBNEC. This drastic difference in yield has been correlated to the difference in the conformational structure of the polymer as evidenced by nuclear magnetic resonance spectroscopy. (C) 1997 Elsevier Science S.A.

Transient analysis of mammalian cell growth in hollow fibre bioreactor

A mathematical model describing the dynamics of mammalian cell growth in hollow fibre bioreactor operated in closed shell mode is developed. Mammalian cells are assumed to grow as an expanding biofilm in the extra-capillary space surrounding the fibre. Diffusion is assumed to be the dominant process in the radial direction while axial convection dominates in the lumen of the bioreactor. The transient simulation results show that steep gradients in the cell number are possible under the condition of substrate limitation. The precise conditions which result in nonuniform growth of cells along the length of the bioreactor are delineated. The effect of various operating conditions, such as substrate feed rate, length of the bioreactor and diffusivity of substrate in different regions of the bioreactor, on the bioreactor performance are evaluated in terms of time required to attain the steady-state. The rime of growth is introduced as a measure of effectiveness factor for the bioreactor and is found to be dependent on two parameters, a modified Peclet number and a Thiele modulus. Diffusion, reaction and/or convection control regimes are identified based on these two parameters. The model is further extended to include dual substrate growth limitations, and the relative growth limiting characteristics of two substrates are evaluated. (C) 1997 Elsevier Science Ltd.

Irreversibility-to-reversibility crossover in transient response of an optically trapped particle

We study the transient response of a colloidal bead which is released from different heights and allowed to relax in the potential well of an optical trap. Depending on the initial potential energy, the system's time evolution shows dramatically different behaviors. Starting from the short-time reversible to long-time irreversible transition, a stationary reversible state with zero net dissipation can be achieved as the release point energy is decreased. If the system starts with even lower energy, it progressively extracts useful work from thermal noise and exhibits an anomalous irreversibility. In addition, we have verified the Transient Fluctuation Theorem and the Integrated Transient Fluctuation Theorem even for the non-ergodic descriptions of our system. Copyright (C) EPLA, 2011

Modeling and control of unified power flow controller for transient stability

FACTS controllers are emerging as viable and economic solutions to the problems of large interconnected ne networks, which can endanger the system security. These devices are characterized by their fast response, absence of inertia, and minimum maintenance requirements. Thyristor controlled equipment like Thyristor Controlled Series Capacitor (TCSC), Static Var Compensator (SVC), Thyristor Controlled Phase angle Regulator (TCPR) etc. which involve passive elements result in devices of large sizes with substantial cost and significant labour for installation. An all solid-state device using GTOs leads to reduction in equipment size and has improved performance. The Unified Power Flow Controller (UPFC) is a versatile controller which can be used to control the active and reactive power in the Line independently. The concept of UPFC makes it possible to handle practically all power flow control and transmission line compensation problems, using solid-state controllers, which provide functional flexibility, generally not attainable by conventional thyristor controlled systems. In this paper, we present the development of a control scheme for the series injected voltage of the UPFC to damp the power oscillations and improve transient stability in a power system. (C) 1998 Elsevier Science Ltd. All rights reserved.

Process-kinetics in facing targets sputtering of multi-component oxide thin films

The kinetics of the processes in facing targets sputtering of multicomponent oxide films is presented. The novel configuration of the process exhibits an enhanced ionization efficiency. Discharge diagnostics performed using optical emission spectroscopy revealed strong dependence of plasma parameters on process conditions. Numerical simulation based on thermalization and diffusion of sputtered atoms has been performed to estimate the transport efficiency in off-axis mode. Composition, structure and epitaxial quality of YBa2Cu3O7-x films prepared was found to be strongly dependent on atomic flux ratios (of Cu/Y and Ba/Y) arriving at the substrate, resputtering effect and phase stability of YBa2Cu3O7-x These studies have been shown to be useful in understanding the complex processes that occur in sputtering of multicomponent films. (C) 1999 Elsevier Science S.A. All rights reserved.

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.

Control of transient thermal response during sequential open-die forging: A trajectory optimization approach

A trajectory optimization approach is applied to the design of a sequence of open-die forging operations in order to control the transient thermal response of a large titanium alloy billet. The amount of time tire billet is soaked in furnace prior to each successive forging operation is optimized to minimize the total process time while simultaneously satisfying constraints on the maximum and minimum values of the billet's temperature distribution to avoid microstructural defects during forging. The results indicate that a "differential" heating profile is the most effective at meeting these design goals.

Critical stress intensity factors for cracked hollow pipes under transient thermal loads

Finite element analyses of a long hollow cylinder having an axisymmetric circumferential internal edge crack, subjected to convective cooling on the inner surface are performed. The transient thermal stress intensity factor is estimated using a domain version of the J-integral method. The effect of the thickness of the cylinder, crack length, and heat transfer coefficient on the stress intensity factor history are studied. The variations of critical normalized stress intensity factor with crack length-to-thickness ratio for different parameters are presented. The results show that if a small inner surface crack begins to grow, its stress intensity factor will increase with increase in crack length, reach a maximum, and then begin to drop. Based on the results, a fracture-based design methodology for cracked hollow pipes under transient thermal loads is discussed.

High-pressure kinetics of oxidative copolymerization of styrene with alpha-methyl styrene

This is the first report on the study carried out on high-pressure free-radical initiated oxidated copolymerization of styrene (STY) with alpha-methylstyrene (AMS) at various temperatures (45-65degreesC) at constant pressure (100 psi) and then at various pressures (50-300 psi) keeping the temperature (50degreesC) constant. The compositions of the copolyperoxides obtained from the H-1 NMT spectra were utilized to determine the reactivity ratios of the monomers. The reactivity ratios indicate that STY forms an ideal copolyperoxide with AMS and the copolyperoxide is richer in AMS. The effect of temperature and oxygen pressure in the reactivity ratios of the monomers was studied. The rates of copolymerization (R-p) were used to determine the overall activation energies (E-a) and activation volume (DeltaV(#)) of copolymerization. The unusually higher values of the DeltaV(#) may be due to the pressurizing fluid oxygen which itself is a reactant in the copolymerization, the side reactions, and the chain-transfer reactions occuring during copolymerizations.

Kinetics of hydrogen evolution on submicron size Co, Ni, Pd and CoNi alloy powder electrodes by d.c. polarization and a.c. impedance studies

Submicron size Co, Ni and Co-Ni alloy powders have been synthesized by the polyol method using the corresponding metal malonates and Pd powder by reduction of PdOx in methanol. The kinetics of the hydrogen evolution reaction ( HER) in 6 M KOH electrolyte have been studied on electrodes made from the pressed powders. The d.c. polarization measurements have resulted in a value close to 120 mV decade(-1) for the Tafel slope, suggesting that the HER follows the Volmer-Heyrovsky mechanism. The values of exchange current density (i(o)) are in the range 1-10 mA cm(-2) for electrodes fabricated in the study. The a.c. impedance spectra measured at several potentials in the HER region showed a single semicircle in the Nyquist plots. Exchange current density (i(o)) and energy transfer coefficient (alpha) have been calculated by employing a nonlinear least square-fitting program.

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.

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.

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.