Experimental studies of pattern formation in a reaction-advection-diffusion system

Experiments are presented on pattern formation in the Belousov-Zhabotinsky (BZ) reaction in a blinking vortex flow. Mixing in this flow is chaotic, with nearby tracers separating exponentially with time. The patterns that form in this flow with the BZ reaction mimic chaotic mixing structures seen in passive transport. The behavior is analyzed in terms of a mixing time taum and a characteristic decorrelation time TBZ for the BZ system. Flows with taum comparable to or smaller than TBZ generate large-scale patterns whose features are captured by simulations of mixing fields for the flow.     

Experimental and numerical studies of noise-induced coherent patterns in a subexcitable system

A subexcitable medium of Belousov-Zhabotinsky (BZ) reaction subjected to external Gaussian white noise is studied in experiments and numerical simulations. We observe that at an optimal level of noise the wave sources of excited traveling waves become synchronous, as though there exists a long distance spatial correlation. The synchronous behavior fades if the noise level becomes larger or smaller. Numerical simulations confirm the experimental findings, and point out that the best synchronous behavior takes place when the signal-to-noise ratio of waves becomes largest.     

External forcing of spiral waves

The effect of an external rhythm on rotating spiral waves in excitable media is investigated. Parameters of the unperturbed medium were chosen, such that the organizing spiral tip describes meandering (hypocyclic) trajectories, which are the most general shape for the experimentally observed systems. Periodical modulation of excitability in a model of the Belousov-Zhabotinsky (BZ) reaction forces meandering spiral tips to describe trajectories that are not found at corresponding stationary conditions. For different modulation periods, two types of resonance drift, phase-locked tip motion, a spectrum of hypocyclic trajectories, and complex multifrequency patterns were computed. The computational results are complemented by experimental data obtained for periodically changing illumination of the photosensitive BZ reaction. The observed drastic deformation of the tip trajectory is considered as an efficient means to study and to control wave processes in excitable media.     

Pattern formation in a reaction-diffusion-advection system with wave instability

In this paper, we show by means of numerical simulations how new patterns can emerge in a system with wave instability when a unidirectional advective flow (plug flow) is added to the system. First, we introduce a three variable model with one activator and two inhibitors with similar kinetics to those of the Oregonator model of the Belousov-Zhabotinsky reaction. For this model, we explore the type of patterns that can be obtained without advection, and then explore the effect of different velocities of the advective flow for different patterns. We observe standing waves, and with flow there is a transition from out of phase oscillations between neighboring units to in-phase oscillations with a doubling in frequency. Also mixed and clustered states are generated at higher velocities of the advective flow. There is also a regime of "waving Turing patterns" (quasi-stationary structures that come close and separate periodically), where low advective flow is able to stabilize the stationary Turing pattern. At higher velocities, superposition and interaction of patterns are observed. For both types of patterns, at high velocities of the advective field, the known flow distributed oscillations are observed.     

Beating polymer gels coupled with a nonlinear chemical reaction

We report on a beating polymer gel that exhibits periodical volume changes (swelling and deswelling) in a closed solution without external stimuli, like autonomous heartbeat. The mechanical oscillation is driven by the chemical energy of the oscillatory Belousov-Zhabotinsky (BZ) reaction. The gel is a copolymer gel of N-isopropylacrylamide (NIPAAm) in which ruthenium tris(2,2(')-bipyridine) [Ru(bpy)(3)], known as a catalyst of the BZ reaction, is covalently bonded to the polymer chain. The poly[NIPAAm-co-Ru(bpy)(3)] gel provides an open system where the BZ reaction proceeds, when immersed in an aqueous solution containing the reactants of the BZ reaction (with the exception of a catalyst). The chemical oscillation in the BZ reaction generates the periodical changes of the charge of Ru(bpy)(3) in the gel network between reduced [Ru(II)] and oxidized [Ru(III)] states. The gel swells at the oxidized state because the hydrophilicity of the polymer chains increases, while at the reduced state the gel deswells. Thus, the chemical energy is transduced into the mechanical energy to drive the polymer gel oscillation with a period of about 5 min, depending on the composition of the surrounding solution. The oscillation mode of the gel depends on its size scaled by the wavelength of the BZ pattern. Sufficiently small bead-like gels demonstrate isotropic beating. A large rectangular gel shows mechanical oscillation with a peristaltic motion coupled with the propagating chemical waves. The dynamic behavior of the chemical and mechanical oscillations have been analyzed with a model simulation. (c) 1999 American Institute of Physics.     

Prediction of flow stress and textures of AZ31 magnesium alloy at elevated temperature

The viscoplastic behaviour of magnesium alloys at high temperatures leads to highly temperature-dependent mechanical properties. While at high strain rates a notable strain hardening response is observed, at low strain rates the material shows a smooth plastic response with negligible amount of hardening. This complicated behaviour is due to different deformation mechanisms that are active at different strain rate regimes, resulting in different strain rate sensitivity parameters. In this study we show, by utilizing both numerical simulations and experiments, that this behaviour can be predicted by a model that combines two deformation mechanisms, grain boundary sliding mechanism and dislocation glide mechanism. We discuss the importance of each deformation mechanism at different strain rate regimes based on the findings of modelling and experimental results for AZ3 magnesium alloy. By developing a model that includes the above-mentioned two deformation mechanism, the prediction of flow properties is expanded to a wide range of strain rate regimes compared to previous study. The obtained numerical findings for the stress–strain behaviour as well as texture evolution show good agreement with the experimental results.     

Imaging of Flow Patterns with Fluorescent Molecular Rotors

Molecular rotors are a group of fluorescent molecules that form twisted intramolecular charge transfer states (TICT) upon photoexcitation. Some classes of molecular rotors, among them those that are built on the benzylidene malononitrile motif, return to the ground state either by nonradiative intramolecular rotation or by fluorescence emission. In low-viscosity solvents, intramolecular rotation dominates, and the fluorescence quantum yield is low. Higher solvent viscosities reduce the intramolecular rotation rate, thus increasing the quantum yield. We recently described a different mechanism whereby the fluorescence quantum yield of the molecular rotor also depends on the shear stress of the solvent. In this study, we examined a possible application for shear-sensitive molecular rotors for imaging flow patterns in fluidic chambers. Flow chambers with different geometries were constructed from polycarbonate or acrylic. Solutions of molecular rotors in ethylene glycol were injected into the chamber under controlled flow rates. LED-induced fluorescence (LIF) images of the flow chambers were taken with a digital camera, and the intensity difference between flow and no-flow images was visualized and compared to computed fluid dynamics (CFD) simulations. Intensity differences were detectable with average flow rates as low as 0.1 mm/s, and an exponential association between flow rate and intensity increase was found. Furthermore, a good qualitative match to computed fluid dynamics simulations was seen. On the other hand, prolonged exposure to light reduced the emission intensity. With its high sensitivity and high spatial and temporal resolution, imaging of flow patterns with molecular rotors may become a useful tool in microfluidics, flow measurement, and control.     

Features of Motion of Soliton Transported Bio-energy in Aperiodic α-Helix Protein Molecules with Three Channels

The structure aperiodicities can influence seriously the features of motion of soliton excited in the α-helix protein molecules with three channels. We study the influence of structure aperiodicities on the features of the soliton in the improved model by numerical simulation and Runge-Kulta method. The results obtained show that the new soliton is very robust against the structure aperiodieities including large disorder in the sequence of mass of the amino acids and fluctuations of spring constant, coupling constant, dipole-dipole interactional constant, ground state energy and chain-chain interaction. However, very strong structure aperiodieities can also destroy the stability of the soliton in the α-helix protein molecules.     

Constructing self-organized structures on silicon and sapphire surfaces

We investigated methods to fabricate distinctive structures on silicon and sapphire substrates to grow a carbon nanotube (CNT) network using a solution from the Belousov-Zhabotinsky (BZ) reaction. The BZ reaction is a chemical system where chemical reactions and material diffusion coexist in a nonequilibrium state and generate spatiotemporal patterns in a petri dish. Precipitates from the reaction should also produce distinctive structures after being piled on the substrates. The structures have metal particles that act as catalysts for growing CNTs or quantum dots of nanodot devices. Therefore, such structures should be suitable to fabricate three-dimensional CNT networks or nanodot devices. To confirm this, we investigated the fabrication of distinctive structure using a BZ reaction solution. Results indicated that the BZ reaction solution produced interesting structures on the substrates. Moreover, we confirmed that the shape of the structure changed when the substrate used was changed. We believe that the developed methods are suitable to fabricate nanodevices, especially CNT network devices.     

On the behavior of suspension of drops on an inclined surface

The flow of drops suspended on an inclined surface, are studied by numerical simulations at finite Reynolds numbers. The flow is driven by the acceleration due to gravity, and there is no pressure gradient in the flow direction. The effect of the Reynolds number, the Capillary number and density ratio on the distribution of drops and the fluctuation energy across the channel are investigated. It is found that drops tend to stay away from the channel floor, which is consistent with the behavior observed in the granular flow regime. Drops that are less deformable will stay further away from the channel floor. Also, drops appear at a larger distance from the floor as the Reynolds number increases. Simulations at large density ratios show that results are more compatible with computer simulations of granular flows. The behavior observed here resembles more the granular flow regime when the restitution coefficient is low.     

Structure of a tethered polymer under flow using molecular dynamics and hybrid molecular-continuum simulations

We analyse the structure of a single polymer tethered to a solid surface undergoing a Couette flow. We study the problem using molecular dynamics (MD) and hybrid MD-continuum simulations, wherein the polymer and the surrounding solvent are treated via standard MD, and the solvent flow farther away from the polymer is solved by continuum fluid dynamics (CFD). The polymer represents a freely jointed chain (FJC) and is modelled by Lennard-Jones (LJ) beads interacting through the FENE potential. The solvent (modelled as a LJ fluid) and a weakly attractive wall are treated at the molecular level. At large shear rates the polymer becomes more elongated than predicted by existing theoretical scaling laws. Also, along the normal-to-wall direction the structure observed for the FJC is, surprisingly, very similar to that predicted for a semiflexible chain. Comparison with previous Brownian dynamics simulations (which exclude both solvent and wall potential) indicates that these effects are due to the polymer–solvent and polymer–wall interactions. The hybrid simulations are in perfect agreement with the MD simulations, showing no trace of finite size effects. Importantly, the extra cost required to couple the MD and CFD domains is negligible.     

Numerical study of dynamo action at low magnetic Prandtl numbers

We present a three-pronged numerical approach to the dynamo problem at low magnetic Prandtl numbers P(M). The difficulty of resolving a large range of scales is circumvented by combining direct numerical simulations, a Lagrangian-averaged model and large-eddy simulations. The flow is generated by the Taylor-Green forcing; it combines a well defined structure at large scales and turbulent fluctuations at small scales. Our main findings are (i) dynamos are observed from P(M)=1 down to P(M)=10(-2), (ii) the critical magnetic Reynolds number increases sharply with P(M)(-1) as turbulence sets in and then it saturates, and (iii) in the linear growth phase, unstable magnetic modes move to smaller scales as P(M) is decreased. Then the dynamo grows at large scales and modifies the turbulent velocity fluctuations.     

Molecular origin of shear thickening in transient polymer networks: A molecular dynamics study

This paper proposes a simple model of transient networks of telechelic associating polymers for molecular simulations and reports the main results obtained by molecular dynamics on the rheological properties of the transient networks. The steady shear viscosity obtained by the non-equilibrium molecular dynamics simulation exhibits shear thickening at moderate shear rates and shear thinning at larger shear rates. The behavior is similar to that observed in experiments of telechelic associating polymers. By analyzing the distribution function of the end-to-end vector of bridge chains as a function of the shear rate, we find that shear thickening is mainly caused by the stress from the bridge chains highly stretched by shear flow. We also find that fracture of the transient network occurs in the shear-thinning regime at high shear rates.     

Water vapour pressure influence on the kinetics of the superconducting YBCO thin films epitaxic growth by the TFA–MOD method

We have found two different regimes in the kinetics of the YBCO formation depending on the water partial pressure at a constant temperature and total flow rate of the carrier gas. The first regime at low partial water pressure shows continual kinetics curves until the end of YBCO growth and the reaction is controlled chemically. The second regime at high partial water pressure shows irreproducible steps in the kinetics curves during the thin films YBCO growth. In this work we suggest that there is formation of a boundary layer of water (Nernst layer) when the partial water pressure is higher than 20 hPa at 795 °C for a total gas flow rate lower than 2.4 × 10⁻² m s⁻¹. These irreproducible steps dues probably to a water boundary layer formation can be eliminated by increasing the stirring rate of the carrier gas. The reaction order of YBa₂Cu₃O_7−x formation respect to the water pressure is n = 0.5 when the water boundary layer is not formed, but the apparent reaction order respect to the partial water pressure is zero or negative when the gas flow rate of the carrier gas is not big enough for the elimination of this water layer. This work also evidences that there is an intermediate step in the kinetics curves before the formation of YBCO. This step, which starts at low temperature during the heating ramp (400 °C) is attributed to the partial elimination of F from the BaF₂ precursor to form oxyfluoride compounds. So, at low total flow gas rates and low partial water pressures, the reaction is controlled by diffusion mechanism due to the formation of a HF boundary layer (Nernst layer), because the apparent order of YBCO formation is one respect to the stirring rate. Nevertheless, at high flow gas rates and low partial water pressures, the YBCO formation is controlled chemically, then the apparent order respect to the stirring rate is zero and the HF Nernst layer is eliminated. The apparent E_a for the oxyfluoride formation at low temperatures is only 18 Kj/mol indicating that this intermediate reaction is controlled by diffusion mechanism even at high stirring rate and relatively low partial water pressure. The apparent E_a for the YBCO formation at partial water pressures higher than 20 hPa for a total flow rate of 2.4 × 10⁻² m s⁻¹ is only 32 Kj/mol, indicating that the reaction control is mainly diffusive or mixed (diffusive and chemist).     

Molecular dynamics study of reaction kinetics in viscous media

Predicted by stochastic models and observed experimentally in a number of isomerization reactions, viscosity-induced solvent effects manifest themselves in a significant departure of the reaction rates from the values expected on the basis of transition state theory. These effects are well understood within the framework of stochastic models; however, the predictive power of such models is limited by the fact that their parameters are not readily available. Experiment and molecular dynamics (MD) simulations can provide such information and can serve as the testing grounds for various stochastic models. In real solvents, a change in viscosity is inevitably associated with variation of at least one of the three factors – temperature, pressure, or solvent identity, resulting in different solvent–solvent and solvent–solute interactions. A model is proposed in which solvent viscosity is manipulated through mass scaling, which allows one to maintain other factors constant for a series of viscosities. This approach was tested on MD simulations of the kinetics of two model isomerization reactions in Lennard–Jones solvents, whose viscosity was varied over three orders of magnitude. The results reproduce the Kramers turnover and a strong negative viscosity dependence of the reaction rates in the high viscosity limit, somewhat weaker than η ^?1.     

Numerical Simulation for Falling Film Flow Characteristics of Refrigerant on the Smooth and Structured Surfaces

Flow characteristics of a liquid film flowing over a smooth surface and structured surface with the Reynolds number range from 10 to 1121 are studied. The mixture of R21 and R114 refrigerants is used as the test liquid. The 3D transient simulations are taken to capture the liquid film’s dynamic characteristics and spatial distribution. Effects of the inlet dimension, inlet flow rates, surface tension, and surface structuring on the wettability, average velocity, and film thickness are studied systematically. The obtained results show that surface tension is essential for an accurate simulation, while inlet width has no effect on the liquid film parameters in the steady-state flow regime. For low flow rates, wetting area and film thickness both are small, and a suggested range of Reynolds number is chosen to simulate further heat transfer in order to balance the film thickness and dry spots generation. It is shown that a ripple surface structure hinders the liquid film movement, reflected in a lower velocity and a larger film thickness compared to the smooth surface. Lateral movement of a liquid film can also be observed at the structured surface.     

Synthesis,spectroscopic, and computational studies of charge‐transfer complexation between benzidine with 2,3‐dichloro‐5,6‐dicyano‐p‐benzoquinone and chloronil

The solid charge transfer (CT) complexes that have been formed from the reactions of donor benzidine (BZ) and the π‐acceptors such as 2,3‐dichloro‐5,6‐dicyano‐p‐benzoquinone (DDQ) and chloronil (CHL) have been studied and characterized experimentally and theoretically. The experimental work which includes the use of UV‐visible spectroscopy to identify the CT band of the CT‐complex. The composition of the complexes has been investigated successfully by using spectrophotometric titration and Job method of continuous variation to be 1:1. Furthermore, to calculate the formation constant and molar extinction coefficient, we have used the Benesi‐Hildebrand equation. Infrared and proton nuclear magnetic resonance spectral studies were used to characterize and confirm the formation of CT‐complex. The experimental studies were well supported by quantum chemical simulations by using density functional theory. The computational analysis of molecular geometry, Mulliken charges, and molecular electrostatic potential surfaces of reactants and complexes is very much helpful in assigning the CT route. The C═O bond length of DDQ and CHL increased upon complexation with BZ. We have also observed that the substantial amount of charge has been transferred from BZ to DDQ and CHL in the process of complexation. An excellent consistency has been achieved between experimental and theoretical results.     

Shear localization in a model glass

Using molecular dynamics simulations, we show that a simple model of a glassy material exhibits the shear localization phenomenon observed in many complex fluids. At low shear rates, the system separates into a fluidized shear band and an unsheared part. The two bands are characterized by a very different dynamics probed by a local intermediate scattering function. Furthermore, a stick-slip motion is observed at very small shear rates. Our results, which open the possibility of exploring complex rheological behavior using simulations, are compared to recent experiments on various soft glasses.     

Monte Carlo simulation of temperature programmed reaction and surface explosion during CO oxidation on a Pt catalyst

A Monte Carlo model of CO oxidation on a Pt(111) surface that includes finite rates of adsorption-desorption and reaction and the effect of the catalyst temperature is presented. The results show that, as expected from the reaction-adsorption probabilities, the surface coverage changes from being almost completely covered by CO at low temperature (60°C), to being completely covered by oxygen at high temperature (160°C). Furthermore, it was found that an unstable state occurs when cooling down the oxygen covered surface from 160°C to 60°C. It is shown that if a site for CO adsorption is created under this metastable state, a surface explosion that propagates spatially occurs. Thus the MC simulations provide a method to describe a catalytic reaction on surfaces with strongly non-linear spatio-temporal dynamics.     

Modification of the spectra of correlated charm-anticharm quark pairs in the quark-gluon plasma

Heavy quarks play an important role in probing the properties of strongly interacting quark-gluon plasma(QGP)created in ultra-relativistic heavy-ion collisions.We study the interactions of single heavy(charm)quarks and correlated charm and anticharm(ccˉ)quark pairs with the medium constituents of QGP by performing fireball+Langevin simulations of the pertinent Brownian motion with elastic collisions.Besides studying the traditional observables,the nuclear modification factor and the elliptic flow of single heavy quarks in QGP for different thermal relaxation rates,we also study the broadening of the azimuthal correlations of charm and anticharm quark pairs in the QGP medium for different relaxation rates and transverse momenta classes.We quantified the smearing of ccˉpair azimuthal correlations with an increasing thermal relaxation rate:while the(nearly)back-to-back correlations among ccˉpairs are almost completely washed out at low transverse momentum(pT),these correlations at high pT largely survive the pair diffusion.This provides a novel observable for diagnosing the properties of QGP.