0000000000011772
AUTHOR
Sanjay Puri
Wetting and phase separation at surfaces
We study the problem ofsurfacedirected spinodal decomposition, viz., the dynamical interplay of wetting and phase separation at surfaces. In particular, we focus on the kinetics of wetting-layer growth in a semi-infinite geometry for arbitrary surface potentials and mixture compositions. We also present representative results for phase separation in confined geometries, e.g., cylindrical pores, thin films, etc.
Phase separation in thin films: Effect of temperature gradients
We study the phase-separation kinetics of a binary (AB) mixture confined in a thin film of thickness D with a temperature gradient. Starting from a Kawasaki-exchange kinetic Ising model, we use a master-equation approach to systematically derive an extension of the Cahn-Hilliard model for this system. We study the effect of temperature gradients perpendicular to the film with "neutral" (no preference for either A or B) surfaces. We highlight the rich phenomenology and pattern dynamics which arises from the interplay of phase separation and the temperature gradient.
Surface effects on spinodal decomposition in binary mixtures: The case with long-ranged surface fields
We present detailed numerical results for phase-separation kinetics of critical binary mixtures in the vicinity of a surface that exerts a long-ranged attractive force on one of the components of the mixture. We consider surface potentials of the form $V(Z)\ensuremath{\sim}{Z}^{\ensuremath{-}n}$, where $Z$ is the distance from the surface and $n=1,2,3$. In particular, we investigate the interplay of the surface wetting layer with the dynamics of domain growth. We find that the wetting layer at the surface exhibits power-law growth with an exponent that depends on $n$, in contrast to the case with a short-ranged surface potential, where the growth is presumably logarithmic. From correlation …
Asymptotic structure factor for the two-component Ginzburg-Landau equation
We derive an analytic form for the asymptotic time-dependent structure factor for the two-component Ginzburg-Landau equation in arbitrary dimensions. This form is in reasonable agreement with results from numerical simulations in two dimensions. A striking feature of our analytic form is the absence of Porod's law in the tail. This is a consequence of the continuous symmetry of the Hamiltonian, which inhibits the formation of sharp domain walls.
Formation of metastable structures by phase separation triggered by initial composition gradients in thin films.
Phase separation kinetics of a binary (A,B) mixture contained in a thin film of thickness D induced by a quench from the one-phase region into the miscibility gap is studied by simulations using a Cahn-Hilliard-Cook model. The initial randomly mixed state (50% A, 50% B) contains a concentration gradient perpendicular to the film, while the surfaces of the film are "neutral" (no preference for either A or B). In thermal equilibrium, a pattern of large A-rich and B-rich domains must result, separated by domain walls oriented perpendicularly to the external surfaces of the thin film. However, it is shown that for many choices of D and the strength of the initial gradient Ψ(g), instead a very l…
Surface-directed spinodal decomposition in a thin-film geometry: A computer simulation
The phase separation kinetics of a two-dimensional binary mixture at critical composition confined between (one-dimensional) straight walls which preferentially attract one component of the mixture is studied for a wide range of distancesD between the walls. Following earlier related work on semiinfinite systems, two choices of surface forces at the walls are considered, one corresponding to an incompletely wet state of the walls, the other to a completely wet state (forD→∞). The nonlinear Cahn-Hilliard-type equation, supplemented with appropriate boundary conditions which account for the presence of surfaces, is replaced by a discrete equivalent and integrated numerically. Starting from a …
Surface-directed spinodal decomposition: modelling and numerical simulations
We critically review the modelling and simulations of surface-directed spinodal decomposition, namely, the dynamics of phase separation of a critical or near-critical binary mixture in the presence of a surface with a preferential attraction for one of the components of the mixture.
Surface-directed spinodal decomposition: Phenomenology and numerical results.
We present a phenomenological theory for surface effects on spinodal decomposition in mixtures and related phenomena such as the dynamics of surface segregation. Numerical solutions of our equations show striking similarity to recent results from experiments on polymer mixtures with one component preferentially attracted to a wall.
Surface-directed phase separation with off-critical composition: Analytical and numerical results
We study the interplay of wetting and phase separation in an unstable binary mixture $(\mathrm{AB})$ with off-critical composition, placed in contact with a surface which prefers the component $A.$ We consider surface potentials $V(z)\ensuremath{\sim}{z}^{\ensuremath{-}n},$ where z is the distance from the surface, and present analytical arguments and detailed numerical results to elucidate wetting-layer kinetics for arbitrary mixture compositions. If the preferred component is the minority phase, the wetting-layer thickness exhibits a potential-specific behavior at early times $\ensuremath{\tau},$ ${R}_{1}\ensuremath{\sim}{\ensuremath{\tau}}^{1/(n+2)},$ before crossing over to the universa…
Spinodal decomposition in thin films: Molecular-dynamics simulations of a binary Lennard-Jones fluid mixture
We use molecular dynamics (MD) to simulate an unstable homogeneous mixture of binary fluids (AB), confined in a slit pore of width $D$. The pore walls are assumed to be flat and structureless, and attract one component of the mixture (A) with the same strength. The pair-wise interactions between the particles is modeled by the Lennard-Jones potential, with symmetric parameters that lead to a miscibility gap in the bulk. In the thin-film geometry, an interesting interplay occurs between surface enrichment and phase separation. We study the evolution of a mixture with equal amounts of A and B, which is rendered unstable by a temperature quench. We find that A-rich surface enrichment layers fo…
Kinetics of phase separation in thin films: simulations for the diffusive case.
We study the diffusion-driven kinetics of phase separation of a symmetric binary mixture (AB), confined in a thin-film geometry between two parallel walls. We consider cases where (a) both walls preferentially attract the same component (A), and (b) one wall attracts A and the other wall attracts B (with the same strength). We focus on the interplay of phase separation and wetting at the walls, which is referred to as {\it surface-directed spinodal decomposition} (SDSD). The formation of SDSD waves at the two surfaces, with wave-vectors oriented perpendicular to them, often results in a metastable layered state (also referred to as ``stratified morphology''). This state is reminiscent of th…
Phase separation of binary mixtures in thin films: Effects of an initial concentration gradient across the film.
We study the kinetics of phase separation of a binary (A,B) mixture confined in a thin film of thickness $D$ by numerical simulations of the corresponding Cahn-Hilliard-Cook (CHC) model. The initial state consisted of 50$%$ A:50$%$ B with a concentration gradient across the film, i.e., the average order parameter profile is ${\ensuremath{\Psi}}_{\mathrm{av}}(z,t=0)=(2z/D\ensuremath{-}1){\ensuremath{\Psi}}_{g},\phantom{\rule{0.28em}{0ex}}0\ensuremath{\leqslant}z\ensuremath{\leqslant}D$, for various choices of ${\ensuremath{\Psi}}_{g}$ and $D$. The equilibrium state (for time $t\ensuremath{\rightarrow}\ensuremath{\infty}$) consists of coexisting A-rich and B-rich domains separated by interfac…
Simulation of surface-controlled phase separation in slit pores: Diffusive Ginzburg-Landau kinetics versus Molecular Dynamics
The phase separation kinetics of binary fluids in constrained geometry is a challenge for computer simulation, since nontrivial structure formation occurs extending from the atomic scale up to mesoscopic scales, and a very large range of time needs to be considered. One line of attack to this problem is to try nevertheless standard Molecular Dynamics (MD), another approach is to coarse-grain the model to apply a time-dependent nonlinear Ginzburg–Landau equation that is numerically integrated. For a symmetric binary mixture confined between two parallel walls that prefer one species, both approaches are applied and compared to each other. There occurs a nontrivial interplay between the forma…
Molecular dynamics study of phase separation kinetics in thin films.
We use molecular dynamics to simulate experiments where a symmetric binary fluid mixture (AB), confined between walls that preferentially attract one component (A), is quenched from the one-phase region into the miscibility gap. Surface enrichment occurs during the early stages, yielding a B-rich mixture in the film center with well-defined A-rich droplets. The droplet size grows with time as l(t) proportional t(2/3) after a transient regime. The present atomistic model is also compared to mesoscopic coarse-grained models for this problem.
Asymptotic structure factor and power-law tails for phase ordering in systems with continuous symmetry.
We compute the asymptotic structure factor ${\mathit{S}}_{\mathbf{k}}$(t) [=L(t${)}^{\mathit{d}}$g(kL(t)), where L(t) is a time-dependent characteristic length scale and d is the dimensionality] for a system with a nonconserved n-component vector order parameter quenched into the ordered phase. The well-known Ohta-Jasnow-Kawasaki-Yalabik-Gunton result is recovered for n=1. The scaling function g(x) has the large-x behavior g(x)\ensuremath{\sim}${\mathit{x}}^{\mathrm{\ensuremath{-}}(\mathit{d}+\mathit{n})}$, which includes Porod's law (for n=1) as a special case.
Surface effects on spinodal decomposition in binary mixtures and the interplay with wetting phenomena.
The phase separation of binary mixtures in a semi-infinite geometry is investigated both by a phenomenological theory and by numerical calculations using a discrete equivalent of the descriptive equations. In the framework of ``model B'' (which describes solid binary mixtures), attention is paid to a proper treatment of the boundary conditions at the free surfaces. We confine ourselves to short-range surface forces and consider parameter values that correspond to both nonwet and wet surfaces in thermal equilibrium. During the initial stages of spinodal decomposition, after a quench from considering an initial condition that corresponds to a completely random concentration distribution, one …
Surface effects on kinetics of ordering
We study the effects of surfaces on the kinetics of phase changes in Ising-type systems. If the surface effects can be modelled by a field which couples linearly to the local order parameter, the growth of wetting or drying layers occurs. The numerical solution of the corresponding time-dependent Ginzburg-Landau equation yields a temporally logarithmic growth for the thickness of a wetting (drying) layer growing from an unstable dry (wet) state. On the other hand, if one starts off with a metastable state, the radius of a supercritical plug (wet or dry) grows linearly in time, in accordance with recent experimental results.
Power laws and crossovers in off-critical surface-directed spinodal decomposition.
We study the dynamics of phase separation in binary mixtures near a surface with a preferential attraction for one of the components of the mixture. We obtain detailed numerical results for a range of mixture compositions. In the case where the minority component is attracted to the surface, wetting layer growth is characterized by a crossover from a surface-potential-dependent growth law to a universal law. We formulate a simple phenomenological model to explain our numerical results.