Stability of non-parabolic flow in a flexible tube

Flows with velocity profiles very different from the parabolic velocity profile can occur in the entrance region of a tube as well as in tubes with converging/diverging cross-sections. In this paper, asymptotic and numerical studies are undertaken to analyse the temporal stability of such 'non-parabolic' flows in a flexible tube in the limit of high Reynolds numbers. Two specific cases are considered: (i) developing flow in a flexible tube; (ii) flow in a slightly converging flexible tube. Though the mean velocity profile contains both axial and radial components, the flow is assumed to be locally parallel in the stability analysis. The fluid is Newtonian and incompressible, while the flexible wall is modelled as a viscoelastic solid. A high Reynolds number asymptotic analysis shows that the non-parabolic velocity profiles can become unstable in the inviscid limit. This inviscid instability is qualitatively different from that observed in previous studies on the stability of parabolic flow in a flexible tube, and from the instability of developing flow in a rigid tube. The results of the asymptotic analysis are extended numerically to the moderate Reynolds number regime. The numerical results reveal that the developing flow could be unstable at much lower Reynolds numbers than the parabolic flow, and hence this instability can be important in destabilizing the fluid flow through flexible tubes at moderate and high Reynolds number. For flow in a slightly converging tube, even small deviations from the parabolic profile are found to be sufficient for the present instability mechanism to be operative. The dominant non-parallel effects are incorporated using an asymptotic analysis, and this indicates that non-parallel effects do not significantly affect the neutral stability curves. The viscosity of the wall medium is found to have a stabilizing effect on this instability.

Structure and stability of Li2F

The equilibrium geometries and fundamental vibration frequencies of the Li2F system were calculated by ab initio methods at the MP2 = full/6-311(+ +)G** and CCSD(T) levels. Two isomers were observed and are best described as salts of the Li-2(+) cation with F-. A linear isomer with an arrangement of atoms such as Li-Li-F and a bent C-2v structure are predicted. The stability of these structures are discussed in terms of charge resonance between Li and Li+. (C) 1999 Elsevier Science B.V. All rights reserved.

Catalytic oxidative polymerization of 1,1-diphenylethylene at ambient temperature and potential application of peroxide macroinitiator

The Co(II)TPP(Py) complex was used as an efficient dioxygen carrier for the radical polymerization of 1,1-diphenylethylene (DPE), which has a low ceiling temperature, at ambient temperature and low oxygen pressure. The mechanism of polymerization is discussed' on the basis of kinetic data, W-vis, ESR, and H-1 NMR studies. The rate of polymerization (RP) and number-average molecular weights (M) of poly(1,1-diphenylethylene peroxide) (PDPEP) are higher and the polydispersity is lower than in 2,2'-azobis(isobutyronitrile) (AIBN) initiated polymerization. PDPEP was further. used as a macroinitiator for the polymerization of MMA. The polymerization obeys classical kinetics. The K-2 value of the PDPEP has been determined from the slope of R-P(2) VS [M](2)[I], which reveals that it can also be used at higher temperature for the polymerization. An "active" PMMA was also synthesized, containing initiating segments in the polymer backbone.

Chromatographic methods for determination of nimesulide and for stability studies

Simple and rapid HPLC, GC, and TLC procedures have been developed for detection and determination of nimesulide, a non-pharmacopeial drug, in preformulation and dosage form. Use of these techniques has enabled separation of impurities and the precursor in the bulk material and in formulations. Isocratic reversed-phase HPLC was performed on a C-18 column with methanol-water-acetic acid, 67:32:1 (v/v), as mobile phase and UV detection at 230 nm. Calibration curves were linear over the concentration range 100-1000 mug mL(-1) with a good correlation coefficient (0.9993) and a coefficient of variation of 1.5%. Gas chromatography was performed on an OV-17 packed column with temperature programming and flame-ionization detection. The lower limit of determination by HPLC and GC was 4 ppm. Thin-layer chromatography of nimesulide was performed on silica gel G with toluene-ethyl acetate, 8:2, as mobile phase. Stability testing of the drug was performed under different temperature, humidity, and UV-radiation conditions.

Determination of the reactivity ratios for the oxidative copolymerizations of indene with methyl, ethyl and butyl acrylates

Full Paper: The copolyperoxides of various compositions of indene with methyl acrylate, ethyl acrylate and butyl acrylate have been synthesized by the free-radical-initiated oxidative copolymerization. The compositions of copolyperoxide obtained from H-1 and C-13 NMR spectra have been used to determine the reactivity ratios of the monomers. The copolyperoxides contain a greater proportion of the indene units in random placement. The NMR studies have shown irregularities in the copolyperoxide chain due to the cleavage reactions of the propagating peroxide radical. The thermal analysis by differential scanning calorimetry suggests alternating peroxide units in the copolyperoxide chain. From the activation energy for the thermal degradation, it was inferred that degradation occurs via the dissociation of the peroxide (O-O) bonds of the copolyperoxide chain. The flexibility of the polyperoxides in terms of glass transition temperature (T-g) has also been examined.

Examining the effects of species richness on community stability: an assembly model approach

We build dynamic models of community assembly by starting with one species in our model ecosystem and adding colonists. We find that the number of species present first increases, then fluctuates about some level. We ask: how large are these fluctuations and how can we characterize them statistically? As in Robert May's work, communities with weaker interspecific interactions permit a greater number of species to coexist on average. We find that as this average increases, however, the relative variation in the number of species and return times to mean community levels decreases. In addition, the relative frequency of large extinction events to small extinction events decreases as mean community size increases. While the model reproduces several of May's results, it also provides theoretical support for Charles Elton's idea that diverse communities such as those found in the tropics should be less variable than depauperate communities such as those found in arctic or agricultural settings.

Weakly non-linear stability of a hydrodynamic accretion disc

When the cold accretion disc coupling between neutral gas and a magnetic field is so weak that the magnetorotational instability is less effective or even stops working, it is of prime interest to investigate the pure hydrodynamic origin of turbulence and transport phenomena. As the Reynolds number increases, the relative importance of the non-linear term in the hydrodynamic equation increases. In an accretion disc where the molecular viscosity is too small, the Reynolds number is large enough for the non-linear term to have new effects. We investigate the scenario of the `weakly non-linear' evolution of the amplitude of the linear mode when the flow is bounded by two parallel walls. The unperturbed flow is similar to the plane Couette flow, but with the Coriolis force included in the hydrodynamic equation. Although there is no exponentially growing eigenmode, because of the self-interaction, the least stable eigenmode will grow in an intermediate phase. Later, this will lead to higher-order non-linearity and plausible turbulence. Although the non-linear term in the hydrodynamic equation is energy-conserving, within the weakly non-linear analysis it is possible to define a lower bound of the energy (alpha A(c)(2), where A(c) is the threshold amplitude) needed for the flow to transform to the turbulent phase. Such an unstable phase is possible only if the Reynolds number >= 10(3-4). The numerical difficulties in obtaining such a large Reynolds number might be the reason for the negative result of numerical simulations on a pure hydrodynamic Keplerian accretion disc.

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.

Reactivity ratios for the oxidative copolymerizations of indene with methyl methacrylate and methacrylonitrile

The copolyperoxides of indene with methyl methacrylate and methacrylonitrile have been synthesized by the free-radical-initiated oxidative copolymerization of indene and the monomers. The compositions of copolyperoxides, obtained from H-1 and C-13 NMR spectra, have been utilized to determine the reactivity ratios. The reactivity ratios indicate that the copolyperoxides contain a large proportion of the indene units in random placement. Thermal degradation studies of the copolyperoxides by differential scanning calorimetry and electron-impact mass spectroscopy support alternating peroxide units in the copolyperoxide chain. The energy of activation for thermal degradation suggests that the degradation is controlled by the dissociation of the peroxide (-O-O-) bonds in the copolyperoxide chain. The flexibility of copolyperoxide in terms of glass transition temperature (T-g) has also been examined. (C) 2002 Elsevier Science Ltd. All rights reserved.

Stability of fluid flow past a membrane

The stability of fluid flow past a membrane of infinitesimal thickness is analysed in the limit of zero Reynolds number using linear and weakly nonlinear analyses. The system consists of two Newtonian fluids of thickness R* and H R*, separated by an infinitesimally thick membrane, which is flat in the unperturbed state. The dynamics of the membrane is described by its normal displacement from the flat state, as well as a surface displacement field which provides the displacement of material points from their steady-state positions due to the tangential stress exerted by the fluid flow. The surface stress in the membrane (force per unit length) contains an elastic component proportional to the strain along the surface of the membrane, and a viscous component proportional to the strain rate. The linear analysis reveals that the fluctuations become unstable in the long-wave (alpha --> 0) limit when the non-dimensional strain rate in the fluid exceeds a critical value Lambda(t), and this critical value increases proportional to alpha(2) in this limit. Here, alpha is the dimensionless wavenumber of the perturbations scaled by the inverse of the fluid thickness R*(-1), and the dimensionless strain rate is given by Lambda(t) = ((gamma) over dot* R*eta*/Gamma*), where eta* is the fluid viscosity, Gamma* is the tension of the membrane and (gamma) over dot* is the strain rate in the fluid. The weakly nonlinear stability analysis shows that perturbations are supercritically stable in the alpha --> 0 limit.

Novel phenomenon of autoacceleration in the free radical oxidative polymerization of vinyl monomers: a thermochemical approach

A unique phenomenon of ‘autoacceleration’ was observed in a free radical polymerization of vinyl monomers and oxygen. Unlike the well known autoacceleration phenomenon in polymerization processes, this unusual phenomenon is not readily conceivable in terms of solution viscosity based reasoning. Surprisingly, we have observed manifestation of this new autoacceleration during free radical oxidative polymerization of some vinyl monomers at low conversions, where generally the polymerization reaction is zero order, the conversion–time plot are linear and viscosity effects are negligible. In the present paper, we interpret the mechanism of this new autoacceleration phenomenon on the basis of reactivity of the propagating radicals in terms of heat of formation data.

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.

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.