Exploring bifurcations in Bose-Einstein condensates via phase field crystal models.

To facilitate the analysis of pattern formation and the related phase transitions in Bose-Einstein condensates, we present an explicit approximate mapping from the nonlocal Gross-Pitaevskii equation with cubic nonlinearity to a phase field crystal (PFC) model. This approximation is valid close to the superfluid-supersolid phase transition boundary. The simplified PFC model permits the exploration of bifurcations and phase transitions via numerical path continuation employing standard software. While revealing the detailed structure of the bifurcations present in the system, we demonstrate the existence of localized states in the PFC approximation. Finally, we discuss how higher-order nonlinearities change the structure of the bifurcation diagram representing the transitions found in the system.

Soft wetting with (a)symmetric Shuttleworth effect.

The wetting of soft polymer substrates brings in multiple complexities when compared with the wetting on rigid substrates. The contact angle of the liquid is no longer governed by Young's Law, but is affected by the substrate's bulk and surface deformations. On top of that, elastic interfaces exhibit a surface energy that depends on how much they are stretched-a feature known as the Shuttleworth effect (or as surface-elasticity). Here, we present two models through which we explore the wetting of drops in the presence of a strong Shuttleworth effect. The first model is macroscopic in character and consistently accounts for large deformations via a neo-Hookean elasticity. The second model is based on a mesoscopic description of wetting, using a reduced description of the substrate's elasticity. While the second model is more empirical in terms of the elasticity, it enables a gradient dynamics formulation for soft wetting dynamics. We provide a detailed comparison between the equilibrium states predicted by the two models, from which we deduce robust features of soft wetting in the presence of a strong Shuttleworth effect. Specifically, we show that the (a)symmetry of the Shuttleworth effect between the 'dry' and 'wet' states governs horizontal deformations in the substrate. Our results are discussed in the light of recent experiments on the wettability of stretched substrates.

Solidification in soft-core fluids: Disordered solids from fast solidification fronts.

Using dynamical density functional theory we calculate the speed of solidification fronts advancing into a quenched two-dimensional model fluid of soft-core particles. We find that solidification fronts can advance via two different mechanisms, depending on the depth of the quench. For shallow quenches, the front propagation is via a nonlinear mechanism. For deep quenches, front propagation is governed by a linear mechanism and in this regime we are able to determine the front speed via a marginal stability analysis. We find that the density modulations generated behind the advancing front have a characteristic scale that differs from the wavelength of the density modulation in thermodynamic equilibrium, i.e., the spacing between the crystal planes in an equilibrium crystal. This leads to the subsequent development of disorder in the solids that are formed. In a one-component fluid, the particles are able to rearrange to form a well-ordered crystal, with few defects. However, solidification fronts in a binary mixture exhibiting crystalline phases with square and hexagonal ordering generate solids that are unable to rearrange after the passage of the solidification front and a significant amount of disorder remains in the system.

Continuous and discontinuous dynamic unbinding transitions in drawn film flow.

When a plate is withdrawn from a liquid bath a coating layer is deposited whose thickness and homogeneity depend on the velocity and the wetting properties of the plate. Using a long-wave mesoscopic hydrodynamic description that incorporates wettability via a Derjaguin (disjoining) pressure we identify four qualitatively different dynamic transitions between microscopic and macroscopic coatings that are out-of-equilibrium equivalents of known equilibrium unbinding transitions. Namely, these are continuous and discontinuous dynamic wetting and emptying transitions. Several of their features have no equivalent at equilibrium.

Collapsed heteroclinic snaking near a heteroclinic chain in dragged meniscus problems.

A liquid film is studied that is deposited onto a flat plate that is inclined at a constant angle to the horizontal and is extracted from a liquid bath at a constant speed. We analyse steady-state solutions of a long-wave evolution equation for the film thickness. Using centre manifold theory, we first obtain an asymptotic expansion of solutions in the bath region. The presence of an additional temperature gradient along the plate that induces a Marangoni shear stress significantly changes these expansions and leads to the presence of logarithmic terms that are absent otherwise. Next, we numerically obtain steady solutions and analyse their behaviour as the plate velocity is changed. We observe that the bifurcation curve exhibits collapsed (or exponential) heteroclinic snaking when the plate inclination angle is above a certain critical value. Otherwise, the bifurcation curve is monotonic. The steady profiles along these curves are characterised by a foot-like structure that is formed close to the meniscus and is preceded by a thin precursor film further up the plate. The length of the foot increases along the bifurcation curve. Finally, we prove with a Shilnikov-type method that the snaking behaviour of the bifurcation curves is caused by the existence of an infinite number of heteroclinic orbits close to a heteroclinic chain that connects in an appropriate three-dimensional phase space the fixed point corresponding to the precursor film with the fixed point corresponding to the foot and then with the fixed point corresponding to the bath.

Solidification fronts in supercooled liquids: how rapid fronts can lead to disordered glassy solids.

We determine the speed of a crystallization (or, more generally, a solidification) front as it advances into the uniform liquid phase after the system has been quenched into the crystalline region of the phase diagram. We calculate the front speed by assuming a dynamical density functional theory (DDFT) model for the system and applying a marginal stability criterion. Our results also apply to phase field crystal (PFC) models of solidification. As the solidification front advances into the unstable liquid phase, the density profile behind the advancing front develops density modulations and the wavelength of these modulations is a dynamically chosen quantity. For shallow quenches, the selected wavelength is precisely that of the crystalline phase and so well-ordered crystalline states are formed. However, when the system is deeply quenched, we find that this wavelength can be quite different from that of the crystal, so the solidification front naturally generates disorder in the system. Significant rearrangement and aging must subsequently occur for the system to form the regular well-ordered crystal that corresponds to the free energy minimum. Additional disorder is introduced whenever a front develops from random initial conditions. We illustrate these findings with simulation results obtained using the PFC model.

Modeling the structure of liquids and crystals using one- and two-component modified phase-field crystal models.

A modified phase-field crystal model in which the free energy may be minimized by an order parameter profile having isolated bumps is investigated. The phase diagram is calculated in one and two dimensions and we locate the regions where modulated and uniform phases are formed and also regions where localized states are formed. We investigate the effectiveness of the phase-field crystal model for describing fluids and crystals with defects. We further consider a two-component model and elucidate how the structure transforms from hexagonal crystalline ordering to square ordering as the concentration changes. Our conclusion contains a discussion of possible interpretations of the order parameter field.

Modelling the evaporation of thin films of colloidal suspensions using dynamical density functional theory.

Recent experiments have shown that various structures may be formed during the evaporative dewetting of thin films of colloidal suspensions. Nanoparticle deposits of strongly branched 'flower-like', labyrinthine and network structures are observed. They are caused by the different transport processes and the rich phase behaviour of the system. We develop a model for the system, based on a dynamical density functional theory, which reproduces these structures. The model is employed to determine the influences of the solvent evaporation and of the diffusion of the colloidal particles and of the liquid over the surface. Finally, we investigate the conditions needed for 'liquid-particle' phase separation to occur and discuss its effect on the self-organized nanostructures.

Dynamical density functional theory for the dewetting of evaporating thin films of nanoparticle suspensions exhibiting pattern formation.

Recent experiments have shown that the striking structure formation in dewetting films of evaporating colloidal nanoparticle suspensions occurs in an ultrathin "postcursor" layer that is left behind by a mesoscopic dewetting front. Various phase change and transport processes occur in the postcursor layer that may lead to nanoparticle deposits in the form of labyrinthine, network, or strongly branched "finger" structures. We develop a versatile dynamical density functional theory to model this system which captures all these structures and may be employed to investigate the influence of evaporation or condensation, nanoparticle transport, and solute transport in a differentiated way. We highlight, in particular, the influence of the subtle interplay of decomposition in the layer and contact line motion on the observed particle-induced transverse instability of the dewetting front.

Thin film evolution equations from (evaporating) dewetting liquid layers to epitaxial growth.

In the present contribution we review basic mathematical results for three physical systems involving self-organizing solid or liquid films at solid surfaces. The films may undergo a structuring process by dewetting, evaporation/condensation or epitaxial growth, respectively. We highlight similarities and differences of the three systems based on the observation that in certain limits all of them may be described using models of similar form, i.e. time evolution equations for the film thickness profile. Those equations represent gradient dynamics characterized by mobility functions and an underlying energy functional. Two basic steps of mathematical analysis are used to compare the different systems. First, we discuss the linear stability of homogeneous steady states, i.e. flat films, and second the systematics of non-trivial steady states, i.e. drop/hole states for dewetting films and quantum-dot states in epitaxial growth, respectively. Our aim is to illustrate that the underlying solution structure might be very complex as in the case of epitaxial growth but can be better understood when comparing the much simpler results for the dewetting liquid film. We furthermore show that the numerical continuation techniques employed can shed some light on this structure in a more convenient way than time-stepping methods. Finally we discuss that the usage of the employed general formulation does not only relate seemingly unrelated physical systems mathematically, but does allow as well for discussing model extensions in a more unified way.

Modelling approaches to the dewetting of evaporating thin films of nanoparticle suspensions.

We review recent experiments on dewetting thin films of evaporating colloidal nanoparticle suspensions (nanofluids) and discuss several theoretical approaches to describe the ongoing processes including coupled transport and phase changes. These approaches range from microscopic discrete stochastic theories to mesoscopic continuous deterministic descriptions. In particular, we describe (i) a microscopic kinetic Monte Carlo model, (ii) a dynamical density functional theory and (iii) a hydrodynamic thin film model. Models (i) and (ii) are employed to discuss the formation of polygonal networks, spinodal and branched structures resulting from the dewetting of an ultrathin 'postcursor film' that remains behind a mesoscopic dewetting front. We highlight, in particular, the presence of a transverse instability in the evaporative dewetting front, which results in highly branched fingering structures. The subtle interplay of decomposition in the film and contact line motion is discussed. Finally, we discuss a simple thin film model (iii) of the hydrodynamics on the mesoscale. We employ coupled evolution equations for the film thickness profile and mean particle concentration. The model is used to discuss the self-pinning and depinning of a contact line related to the 'coffee-stain' effect. In the course of the review we discuss the advantages and limitations of the different theories, as well as possible future developments and extensions.

Front instabilities in evaporatively dewetting nanofluids.

Various experimental settings that involve drying solutions or suspensions of nanoparticles-often called nanofluids-have recently been used to produce structured nanoparticle layers. In addition to the formation of polygonal networks and spinodal-like patterns, the occurrence of branched structures has been reported. After reviewing the experimental results we use a modified version of the Monte Carlo model first introduced by Rabani [Nature 426, 271 (2003)] to study structure formation in evaporating films of nanoparticle solutions for the case that all structuring is driven by the interplay of evaporating solvent and diffusing nanoparticles. After introducing the model and its general behavior we focus on receding dewetting fronts which are initially straight but develop a transverse fingering instability. We analyze the dependence of the characteristics of the resulting branching patterns on the driving effective chemical potential, the mobility and concentration of the nanoparticles, and the interaction strength between liquid and nanoparticles. This allows us to understand the underlying instability mechanism.

Fingering instabilities in dewetting nanofluids.

The growth of fingering patterns in dewetting nanofluids (colloidal solutions of thiol-passivated gold nanoparticles) has been followed in real time using contrast-enhanced video microscopy. The fingering instability on which we focus here arises from evaporatively driven nucleation and growth in a nanoscopically thin precursor solvent film behind the macroscopic contact line. We find that well-developed isotropic fingering structures only form for a narrow range of experimental parameters. Numerical simulations, based on a modification of the Monte Carlo approach introduced by Rabani et al. [Nature (London) 426, 271 (2003)10.1038/nature02087], reproduce the patterns we observe experimentally.

Self-propelled running droplets on solid substrates driven by chemical reactions.

We study chemically driven running droplets on a partially wetting solid substrate by means of coupled evolution equations for the thickness profile of the droplets and the density profile of an adsorbate layer. Two models are introduced corresponding to two qualitatively different types of experiments described in the literature. In both cases an adsorption or desorption reaction underneath the droplets induces a wettability gradient on the substrate and provides the driving force for droplet motion. The difference lies in the behavior of the substrate behind the droplet. In case I the substrate is irreversibly changed whereas in case II it recovers allowing for a periodic droplet movement (as long as the overall system stays far away from equilibrium). Both models allow for a non-saturated and a saturated regime of droplet movement depending on the ratio of the viscous and reactive time scales. In contrast to model I, model II allows for sitting drops at high reaction rate and zero diffusion along the substrate. The transition from running to sitting drops in model II occurs via a super- or subcritical drift-pitchfork bifurcation and may be strongly hysteretic implying a coexistence region of running and sitting drops.

Dynamic domain formation in membranes: thickness-modulation-induced phase separation.

A simple model investigates the amplification of fluctuations on membranes constituted of two lipids having different lengths. Van der Waals and electrostatic interactions across the lipid bilayer result in a destabilization favoring thickness variations of the membrane. Close to spontaneous demixing of the two components, the additional gain in free energy due to thickness undulations shifts the stability boundary which promotes phase separation into domains. Interestingly, this effect can be induced by an applied electric field or membrane potential. In biological systems, the dynamic model presented here indicates that electric fields might be important for controlling phase separation and the formation of domains called "rafts".

Open questions and promising new fields in dewetting.

This contribution summarizes the present understanding of dewetting focusing on three points that are either controversial or open. The first issue concerns the initial formation of holes, i.e. the film rupture. The second point concerns the unstable growth of holes, i.e. the transversal instability of the receding contact line. Finally, recent extensions towards dewetting on heterogeneous substrates are examined. In passing the long time evolution in dewetting and the coupling of dewetting with other effects are discussed.

Modelling thin-film dewetting on structured substrates and templates: bifurcation analysis and numerical simulations.

We study the dewetting process of a thin liquid film on a chemically patterned solid substrate (template) by means of a thin-film evolution equation incorporating a space-dependent disjoining pressure. Dewetting of a thin film on a homogeneous substrate leads to fluid patterns with a typical length scale, that increases monotonously in time (coarsening). Conditions are identified for the amplitude and periodicity of the heterogeneity that allow to transfer the template pattern onto the liquid structure ("pinning") emerging from the dewetting process. A bifurcation and stability analysis of the possible liquid ridge solutions on a periodically striped substrate reveal parameter ranges where pinning or coarsening ultimately prevail. We obtain an extended parameter range of multistability of the pinning and coarsening morphologies. In this regime, the selected pattern depends sensitively on the initial conditions and potential finite perturbations (noise) in the system as we illustrate with numerical integrations in time. Finally, we discuss the instability to transversal modes leading to a decay of the ridges into rows of drops and show that it may diminish the size of the parameter range where the pinning of the thin film to the template is successful.

Sliding drops in the diffuse interface model coupled to hydrodynamics.

Using a film thickness evolution equation derived recently combining long-wave approximation and diffuse interface theory [L. M. Pismen and Y. Pomeau, Phys. Rev. E 62, 2480 (2000)] we study one-dimensional surface profiles for a thin film on an inclined plane. We discuss stationary flat film and periodic solutions including their linear stability. Flat sliding drops are identified as universal profiles, whose main properties do not depend on mean film thickness. The flat drops are analyzed in detail, especially how their velocity, advancing and receding dynamic contact angles and plateau thicknesses depend on the inclination of the plane. A study of nonuniversal drops shows the existence of a dynamical wetting transition with hysteresis between droplike solutions and a flat film with small amplitude nonlinear waves.

Film rupture in the diffuse interface model coupled to hydrodynamics.

The process of dewetting of a thin liquid film is usually described using a long-wave approximation yielding a single evolution equation for the film thickness. This equation incorporates an additional pressure term-the disjoining pressure-accounting for the molecular forces. Recently a disjoining pressure was derived coupling hydrodynamics to the diffuse interface model [L. M. Pismen and Y. Pomeau, Phys. Rev. E 62, 2480 (2000)]. Using the resulting evolution equation as a generic example for the evolution of unstable thin films, we examine the thickness ranges for linear instability and metastability for flat films, the families of stationary periodic and localized solutions, and their linear stability. The results are compared to simulations of the nonlinear time evolution. From this we conclude that, within the linearly unstable thickness range, there exists a well defined subrange where finite perturbations are crucial for the time evolution and the resulting structures. In the remainder of the linearly unstable thickness range the resulting structures are controlled by the fastest flat film mode assumed up to now for the entire linearly unstable thickness range. Finally, the implications for other forms of disjoining pressure in dewetting and for spinodal decomposition are discussed.