Numerical method for calculation of the incompressible flow in general curvilinear co‐ordinates with double staggered grid

A solution methodology has been developed for incompressible flow in general curvilinear co‐ordinates. Two staggered grids are used to discretize the physical domain. The first grid is a MAC quadrilateral mesh with pressure arranged at the centre and the Cartesian velocity components located at the middle of the sides of the mesh. The second grid is so displaced that its corners correspond to the centre of the first grid. In the second grid the pressure is placed at the corner of the first grid. The discretized mass and momentum conservation equations are derived on a control volume. The two pressure grid functions are coupled explicitly through the boundary conditions and implicitly through the velocity of the field. The introduction of these two grid functions avoids an averaging of pressure and velocity components when calculating terms that are generated in general curvilinear co‐ordinates. The SIMPLE calculation procedure is extended to the present curvilinear co‐ordinates with double grids. Application of the methodology is illustrated by calculation of well‐known external and internal problems: viscous flow over a circular cylinder, with Reynolds numbers ranging from 10 to 40, and lid‐driven flow in a cavity with inclined walls are examined. The numerical results are in close agreement with experimental results and other numerical data. Copyright © 2003 John Wiley & Sons, Ltd.     

Collisional Relaxation of Luminescence Anisotropy in Rarefied Gases in the Condensed Phase

The orientational relaxation of optically induced anisotropy in rarefied gases and at a damped rotation has been investigated. It has been found that the anisotropy relaxation in rarefied gases is described by a reduced kinetic equation depending only on free rotation integrals. The behavior of the integral anisotropy of luminescence for free symmetric and asymmetric top molecules has been elucidated. The law of luminescence depolarization has been obtained for asymmetric top molecules in the Gordon J-diffusion model. It represents the sum of two Stern–Volmer-type dependences, whose relative contribution is determined by the orientation of the dipole moments of transitions with absorption and emission of light in the molecular coordinate system and by the principal moments of inertia of the molecular top. It has been established that in the limit of a strongly damped rotation, kinetic equations of the general form reduce to equations of rotational diffusion. A number of modified diffusion equations correctly describing the contribution of inertial effects to the orientational relaxation of anisotropy have been obtained.     

Kinetics and mechanism of polymerization of methyl methacrylate initiated by stibonium ylide

Homopolymerization of methyl methacrylate (MMA) was carried out in the presence of triphenylstibonium 1,2,3,4-tetraphenyl-cyclopentadienylide as an initiator in dioxane at 65°C±0·l°C. The system follows non-ideal radical kinetics (R _p ∝ [M]^1·4 [I]^0·44 @#@) due to primary radical termination as well as degradative chain-transfer reaction. The overall activation energy and average value ofk ₂ ^p /k _t were 64 kJmol⁻¹ and 0.173 × 10⁻³ 1 mol⁻¹ s⁻¹ respectively     

On the evaluation of the nonisothermal kinetic parameters of (GeS2)0.3(Sb2S3)0.7 crystallization using the IKP method

The isoconversional method suggested by Friedman and the invariant kinetic parameters method (IKP) were used in order to examine the kinetics of the nonisothermal crystallization of (GeS₂)_0.3(Sb₂S₃)_0.7. The objective of the paper is to show the usefulness of the IKP method both for determining the activation parameters as well as the model of the investigated process. It was shown that the kinetic triplet [(E, A, f(α), where E is the activation energy, A is the preexponential factor, and f(α) is the differential function of conversion], which results through the application of the IKP method, depends on the set of kinetic models considered. For different sets of kinetic models, proportional values of f(α) are obtained. A criterion for the selection of this set, the use of which lead to the true kinetic triplet corresponding to the analyzed process (E = 163.2 kJ mol^?1; A = 2.47 × 10¹² min^?1 and the Avrami‐Erofeev model, A_m, for m = 2.5–2.6 was suggested. © 2004 Wiley Periodicals, Inc. Int J Chem Kinet 36: 309–315, 2004     

Wave processes in media with hysteretic nonlinearity: Part 2

Nonlinear processes caused by the propagation of low-frequency and high-frequency acoustic pulses in an unbounded medium and the propagation of continuous waves in a ring resonator are theoretically studied on the basis of two hysteretic equations of state for media with imperfect elasticity. The profiles and parameters of pulses, the resonance curve and the Q factor of the resonator, and the ratio of the nonlinear resonance frequency shift to the nonlinear damping decrement are determined. For nonlinear wave processes in such media, the distinctive features that allow one to choose an appropriate hysteretic equation of state for analytically describing the experimental data are revealed.     

Dynamics of the surface layer in cyanobiphenyl-aerosil nanocomposites with a high silica density

Composites were prepared from an aerosil and 4-n-alkyl-4'cyanobiphenyls with five to eight carbon atoms in the alkyl chain. Their high silica density of ∼7 g aerosil in 1 cm³ of liquid crystal (LC) allows the observation of the behaviour of a thin cyanobiphenyl layer (having nearly a monolayer structure) on the silica particles. The systems are investigated by dielectric spectroscopy (10^-2-10⁹ Hz) in a large temperature range (220-370 K). All the composites show a (main) relaxation process at frequencies much lower than the processes observed for the bulk LC that was assigned to the dynamics of the molecules in the surface layer. The temperature dependence of its characteristic frequencies obeys the Vogel-Fulcher-Tammann law, which is found to be typical for glass-forming liquids. The quasi two-dimensional character of the glass transition in the surface layer is discussed for the first time. At the nematic-to-isotropic transition temperature of the bulk, the composites show a continuous decrease of the characteristic frequencies as a function of the alkyl chain length, while the bulk LCs show the well known odd-even behaviour. The magnitude and temperature dependence of the slow relaxation process in the composites (molecules on an outer surface) agree with those of the same molecules confined to the nanopores of molecular sieves (internal surface).     

Stability of Markovian structure observed in high frequency foreign exchange data

Contrary to the common sense in economics and financial engineering, price fluctuations at very fine level of motion exhibit various evidences against the efficient market hypothesis. We attempt to investigate this issue by studying extensive amount of foreign currency exchange data for over five years at the finest level of resolution. We specifically focus on the proposed stability in binomial conditional probabilities originally found in much smaller examples of financial time series. In order to handle very large data, we have written an efficient program in C that automatically generates those conditional probabilities. It is found that the stability is maintained for extremely large time duration that covers almost the entire period. Based on the length of conditions for which the conditional probabilities are distinguishable each other, we identify the length of memory being less than 3 movements.     

Click chemistry in materials synthesis. III. Metal‐adhesive polymers from Cu(I)‐catalyzed azide–alkyne cycloaddition

1,2,3‐Triazole‐based polymers generated from the Cu(I)‐catalyzed cycloaddition between multivalent azides and acetylenes are effective adhesive materials for metal surfaces. The adhesive capacities of candidate mixtures of azide and alkyne components were measured by a modified peel test, using a customized adhesive tester. A particularly effective tetravalent alkyne and trivalent azide combination was identified, giving exceptional strength that matches or exceeds the best commercial formulations. The addition of Cu catalyst was found to be important for the synthesis of stronger adhesive polymers when cured at room temperature. Heating also accelerated curing rates, but the maximum adhesive strengths achieved at both room temperature and high temperature were the same, suggesting that crosslinking reaches the same advanced point in all cases. Polytriazoles also form adhesives to aluminum, but copper is bound more effectively, presumably because active Cu(I) ions may be leached from the surface to promote crosslinking and adhesion. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5182–5189, 2007