Permeation of CO₂ and N₂ through glassy poly(dimethyl phenylene) oxide under steady- and presteady-state conditions

Glassy polymers are often used for gas separations because of their high selectivity. Although the dual‐mode permeation model correctly fits their sorption and permeation isotherms, its physical interpretation is disputed, and it does not describe permeation far from steady state, a condition expected when separations involve intermittent renewable energy sources. To develop a more comprehensive permeation model, we combine experiment, molecular dynamics, and multiscale reaction–diffusion modeling to characterize the time‐dependent permeation of N₂ and CO₂ through a glassy poly(dimethyl phenylene oxide) membrane, a model system. Simulations of experimental time‐dependent permeation data for both gases in the presteady‐state and steady‐state regimes show that both single‐ and dual‐mode reaction–diffusion models reproduce the experimental observations, and that sorbed gas concentrations lag the external pressure rise. The results point to environment‐sensitive diffusion coefficients as a vital characteristic of transport in glassy polymers

Complex Patterns in Reaction-Diffusion Systems: A Tale of Two Front Instabilities

Two front instabilities in a reaction-diffusion system are shown to lead to the formation of complex patterns. The first is an instability to transverse modulations that drives the formation of labyrinthine patterns. The second is a Nonequilibrium Ising-Bloch (NIB) bifurcation that renders a stationary planar front unstable and gives rise to a pair of counterpropagating fronts. Near the NIB bifurcation the relation of the front velocity to curvature is highly nonlinear and transitions between counterpropagating fronts become feasible. Nonuniformly curved fronts may undergo local front transitions that nucleate spiral-vortex pairs. These nucleation events provide the ingredient needed to initiate spot splitting and spiral turbulence. Similar spatio-temporal processes have been observed recently in the ferrocyanide-iodate-sulfite reaction.Comment: Text: 14 pages compressed Postscript (90kb) Figures: 9 pages compressed Postscript (368kb

Propagation Failure in Excitable Media

We study a mechanism of pulse propagation failure in excitable media where stable traveling pulse solutions appear via a subcritical pitchfork bifurcation. The bifurcation plays a key role in that mechanism. Small perturbations, externally applied or from internal instabilities, may cause pulse propagation failure (wave breakup) provided the system is close enough to the bifurcation point. We derive relations showing how the pitchfork bifurcation is unfolded by weak curvature or advective field perturbations and use them to demonstrate wave breakup. We suggest that the recent observations of wave breakup in the Belousov-Zhabotinsky reaction induced either by an electric field or a transverse instability are manifestations of this mechanism.Comment: 8 pages. Aric Hagberg: http://cnls.lanl.gov/~aric; Ehud Meron:http://www.bgu.ac.il/BIDR/research/staff/meron.htm

A Phase Front Instability in Periodically Forced Oscillatory Systems

Multiplicity of phase states within frequency locked bands in periodically forced oscillatory systems may give rise to front structures separating states with different phases. A new front instability is found within bands where $\omega_{forcing}/\omega_{system}=2n$ ($n>1$). Stationary fronts shifting the oscillation phase by $\pi$ lose stability below a critical forcing strength and decompose into $n$ traveling fronts each shifting the phase by $\pi/n$. The instability designates a transition from stationary two-phase patterns to traveling $n$-phase patterns

Multi-Phase Patterns in Periodically Forced Oscillatory Systems

Periodic forcing of an oscillatory system produces frequency locking bands within which the system frequency is rationally related to the forcing frequency. We study extended oscillatory systems that respond to uniform periodic forcing at one quarter of the forcing frequency (the 4:1 resonance). These systems possess four coexisting stable states, corresponding to uniform oscillations with successive phase shifts of $\pi/2$. Using an amplitude equation approach near a Hopf bifurcation to uniform oscillations, we study front solutions connecting different phase states. These solutions divide into two groups: $\pi$-fronts separating states with a phase shift of $\pi$ and $\pi/2$-fronts separating states with a phase shift of $\pi/2$. We find a new type of front instability where a stationary $\pi$-front ``decomposes'' into a pair of traveling $\pi/2$-fronts as the forcing strength is decreased. The instability is degenerate for an amplitude equation with cubic nonlinearities. At the instability point a continuous family of pair solutions exists, consisting of $\pi/2$-fronts separated by distances ranging from zero to infinity. Quintic nonlinearities lift the degeneracy at the instability point but do not change the basic nature of the instability. We conjecture the existence of similar instabilities in higher 2n:1 resonances (n=3,4,..) where stationary $\pi$-fronts decompose into n traveling $\pi/n$-fronts. The instabilities designate transitions from stationary two-phase patterns to traveling 2n-phase patterns. As an example, we demonstrate with a numerical solution the collapse of a four-phase spiral wave into a stationary two-phase pattern as the forcing strength within the 4:1 resonance is increased

Breathing Spots in a Reaction-Diffusion System

A quasi-2-dimensional stationary spot in a disk-shaped chemical reactor is observed to bifurcate to an oscillating spot when a control parameter is increased beyond a critical value. Further increase of the control parameter leads to the collapse and disappearance of the spot. Analysis of a bistable activator-inhibitor model indicates that the observed behavior is a consequence of interaction of the front with the boundary near a parity breaking front bifurcation.Comment: 4 pages RevTeX, see also http://chaos.ph.utexas.edu/ and http://t7.lanl.gov/People/Aric

Domain Walls in Non-Equilibrium Systems and the Emergence of Persistent Patterns

Domain walls in equilibrium phase transitions propagate in a preferred direction so as to minimize the free energy of the system. As a result, initial spatio-temporal patterns ultimately decay toward uniform states. The absence of a variational principle far from equilibrium allows the coexistence of domain walls propagating in any direction. As a consequence, *persistent* patterns may emerge. We study this mechanism of pattern formation using a non-variational extension of Landau's model for second order phase transitions. PACS numbers: 05.70.Fh, 42.65.Pc, 47.20.Ky, 82.20MjComment: 12 pages LaTeX, 5 postscript figures To appear in Phys. Rev.

Phase Transitions in a Forest-Fire Model

We investigate a forest-fire model with the density of empty sites as control parameter. The model exhibits three phases, separated by one first-order phase transition and one 'mixed' phase transition which shows critical behavior on only one side and hysteresis. The critical behavior is found to be that of the self-organized critical forest-fire model [B. Drossel and F. Schwabl, Phys. Rev. Lett. 69, 1629 (1992)], whereas in the adjacent phase one finds the spiral waves of the Bak et al. forest-fire model [P. Bak, K. Chen and C. Tang, Phys. Lett. A 147, 297 (1990)]. In the third phase one observes clustering of trees with the fire burning at the edges of the clusters. The relation between the density distribution in the spiral state and the percolation threshold is explained and the implications for stationary states with spiral waves in arbitrary excitable systems are discussed. Furthermore, we comment on the possibility of mapping self-organized critical systems onto 'ordinary' critical systems.Comment: 30 pages RevTeX, 9 PostScript figures (Figs. 1,2,4 are of reduced quality), to appear in Phys. Rev.

Streamer Propagation as a Pattern Formation Problem: Planar Fronts

Streamers often constitute the first stage of dielectric breakdown in strong electric fields: a nonlinear ionization wave transforms a non-ionized medium into a weakly ionized nonequilibrium plasma. New understanding of this old phenomenon can be gained through modern concepts of (interfacial) pattern formation. As a first step towards an effective interface description, we determine the front width, solve the selection problem for planar fronts and calculate their properties. Our results are in good agreement with many features of recent three-dimensional numerical simulations.Comment: 4 pages, revtex, 3 ps file