Drops on Polymer Brushes: Advances in Thin-Film Modeling of Adaptive Substrates.

We briefly review recent advances in the hydrodynamic modeling of the dynamics of droplets on adaptive substrates, in particular, solids that are covered by polymer brushes. Thereby, the focus is on long-wave and full-curvature variants of mesoscopic hydrodynamic models in gradient dynamics form. After introducing the approach for films/drops of nonvolatile simple liquids on a rigid smooth solid substrate, it is first expanded to an arbitrary number of coupled degrees of freedom before considering the specific case of drops of volatile liquids on brush-covered solids. After presenting the model, its usage is illustrated by briefly considering the natural and forced spreading of drops of nonvolatile liquids on a horizontal brush-covered substrate, stick-slip motion of advancing contact lines as well as drops sliding down a brush-covered incline. Finally, volatile liquids are also considered.

Nonreciprocal Cahn-Hilliard Model Emerges as a Universal Amplitude Equation.

Oscillatory behavior is ubiquitous in out-of-equilibrium systems showing spatiotemporal pattern formation. Starting from a linear large-scale oscillatory instability-a conserved-Hopf instability-that naturally occurs in many active systems with two conservation laws, we derive a corresponding amplitude equation. It belongs to a hierarchy of such universal equations for the eight types of instabilities in homogeneous isotropic systems resulting from the combination of three features: large-scale vs small-scale instability, stationary vs oscillatory instability, and instability without and with conservation law(s). The derived universal equation generalizes a phenomenological model of considerable recent interest, namely, the nonreciprocal Cahn-Hilliard model, and may be of a similar relevance for the classification of pattern forming systems as the complex Ginzburg-Landau equation.

Stick-slip dynamics in the forced wetting of polymer brushes.

We study the static and dynamic wetting of adaptive substrates using a mesoscopic hydrodynamic model for a liquid droplet on a solid substrate covered by a polymer brush. First, we show that on the macroscale Young's law still holds for the equilibrium contact angle and that on the mesoscale a Neumann-type law governs the shape of the wetting ridge. Following an analytic and numeric assessment of the static profiles of droplet and wetting ridge, we examine the dynamics of the wetting ridge for a liquid meniscus that is advanced at constant mean speed. In other words, we consider an inverse Landau-Levich case where a brush-covered plate is introduced into (and not drawn from) a liquid bath. We find a characteristic stick-slip motion that emerges when the dynamic contact angle of the stationary moving meniscus decreases with increasing velocity, and relate the onset of slip to Gibbs' inequality and to a cross-over in relevant time scales.

Non-reciprocity induces resonances in a two-field Cahn-Hilliard model.

We consider a non-reciprocally coupled two-field Cahn-Hilliard system that has been shown to allow for oscillatory behaviour and suppression of coarsening. After introducing the model, we first review the linear stability of steady uniform states and show that all instability thresholds are identical to the ones for a corresponding two-species reaction-diffusion system. Next, we consider a specific interaction of linear modes-a 'Hopf-Turing' resonance-and derive the corresponding amplitude equations using a weakly nonlinear approach. We discuss the weakly nonlinear results and finally compare them with fully nonlinear simulations for a specific conserved amended FitzHugh-Nagumo system. We conclude with a discussion of the limitations of the employed weakly nonlinear approach. This article is part of the theme issue 'New trends in pattern formation and nonlinear dynamics of extended systems'.

Nonequilibrium configurations of swelling polymer brush layers induced by spreading drops of weakly volatile oil.

Polymer brush layers are responsive materials that swell in contact with good solvents and their vapors. We deposit drops of an almost completely wetting volatile oil onto an oleophilic polymer brush layer and follow the response of the system upon simultaneous exposure to both liquid and vapor. Interferometric imaging shows that a halo of partly swollen polymer brush layer forms ahead of the moving contact line. The swelling dynamics of this halo is controlled by a subtle balance of direct imbibition from the drop into the brush layer and vapor phase transport and can lead to very long-lived transient swelling profiles as well as nonequilibrium configurations involving thickness gradients in a stationary state. A gradient dynamics model based on a free energy functional with three coupled fields is developed and numerically solved. It describes experimental observations and reveals how local evaporation and condensation conspire to stabilize the inhomogeneous nonequilibrium stationary swelling profiles. A quantitative comparison of experiments and calculations provides access to the solvent diffusion coefficient within the brush layer. Overall, the results highlight the-presumably generally applicable-crucial role of vapor phase transport in dynamic wetting phenomena involving volatile liquids on swelling functional surfaces.

Symmetry-breaking, motion and bistability of active drops through polarization-surface coupling.

Cell crawling crucially depends on the collective dynamics of the acto-myosin cytoskeleton. However, it remains an open question to what extent cell polarization and persistent motion depend on continuous regulatory mechanisms and autonomous physical mechanisms. Experiments on cell fragments and theoretical considerations for active polar liquids have highlighted that physical mechanisms induce motility through splay and bend configurations in a nematic director field. Here, we employ a simple model, derived from basic thermodynamic principles, for active polar free-surface droplets to identify a different mechanism of motility. Namely, active stresses drive drop motion through spatial variations of polarization strength. This robustly induces parity-symmetry breaking and motility even for liquid ridges (2D drops) and adds to splay- and bend-driven pumping in 3D geometries. Intriguingly, then, stable polar moving and axisymmetric resting states may coexist, reminiscent of the interconversion of moving and resting keratocytes by external stimuli. The identified additional motility mode originates from a competition between the elastic bulk energy and the polarity control exerted by the drop surface. As it already breaks parity-symmetry for passive drops, the resulting back-forth asymmetry enables active stresses to effectively pump liquid and drop motion ensues.

Gradient-dynamics model for liquid drops on elastic substrates.

The wetting of soft elastic substrates exhibits many features that have no counterpart on rigid surfaces. Modelling the detailed elastocapillary interactions is challenging, and has so far been limited to single contact lines or single drops. Here we propose a reduced long-wave model that captures the main qualitative features of statics and dynamics of soft wetting, but which can be applied to ensembles of droplets. The model has the form of a gradient dynamics on an underlying free energy that reflects capillarity, wettability and compressional elasticity. With the model we first recover the double transition in the equilibrium contact angles that occurs when increasing substrate softness from ideally rigid towards very soft (i.e., liquid). Second, the spreading of single drops of partially and completely wetting liquids is considered showing that known dependencies of the dynamic contact angle on contact line velocity are well reproduced. Finally, we go beyond the single droplet picture and consider the coarsening for a two-drop system as well as for a large ensemble of drops. It is shown that the dominant coarsening mode changes with substrate softness in a nontrivial way.

Bifurcations of front motion in passive and active Allen-Cahn-type equations.

The well-known cubic Allen-Cahn (AC) equation is a simple gradient dynamics (or variational) model for a nonconserved order parameter field. After revising main literature results for the occurrence of different types of moving fronts, we employ path continuation to determine their bifurcation diagram in dependence of the external field strength or chemical potential. We then employ the same methodology to systematically analyze fronts for more involved AC-type models. In particular, we consider a cubic-quintic variational AC model and two different nonvariational generalizations. We determine and compare the bifurcation diagrams of front solutions in the four considered models.

Phase-field-crystal description of active crystallites: Elastic and inelastic collisions.

The active Phase-Field-Crystal (aPFC) model combines elements of the Toner-Tu theory for self-propelled particles and the classical Phase-Field-Crystal (PFC) model that describes the transition between liquid and crystalline phases. In the liquid-crystal coexistence region of the PFC model, crystalline clusters exist in the form of localized states that coexist with a homogeneous background. At sufficiently strong activity (related to self-propulsion strength), they start to travel. We employ numerical path continuation and direct time simulations to first investigate the existence regions of different types of localized states in one spatial dimension. The results are summarized in morphological phase diagrams in the parameter plane spanned by activity and mean density. Then we focus on the interaction of traveling localized states, studying their collision behavior. As a result, we distinguish "elastic" and "inelastic" collisions. In the former, localized states recover their properties after a collision, while in the latter, they may completely or partially annihilate, forming resting bound states or various traveling states.

Collective Cell Migration in Embryogenesis Follows the Laws of Wetting.

Collective cell migration is a fundamental process during embryogenesis and its initial occurrence, called epiboly, is an excellent in vivo model to study the physical processes involved in collective cell movements that are key to understanding organ formation, cancer invasion, and wound healing. In zebrafish, epiboly starts with a cluster of cells at one pole of the spherical embryo. These cells are actively spreading in a continuous movement toward its other pole until they fully cover the yolk. Inspired by the physics of wetting, we determine the contact angle between the cells and the yolk during epiboly. By choosing a wetting approach, the relevant scale for this investigation is the tissue level, which is in contrast to other recent work. Similar to the case of a liquid drop on a surface, one observes three interfaces that carry mechanical tension. Assuming that interfacial force balance holds during the quasi-static spreading process, we employ the physics of wetting to predict the temporal change of the contact angle. Although the experimental values vary dramatically, the model allows us to rescale all measured contact-angle dynamics onto a single master curve explaining the collective cell movement. Thus, we describe the fundamental and complex developmental mechanism at the onset of embryogenesis by only three main parameters: the offset tension strength, α, that gives the strength of interfacial tension compared to other force-generating mechanisms; the tension ratio, δ, between the different interfaces; and the rate of tension variation, λ, which determines the timescale of the whole process.

Equilibrium Contact Angle and Adsorption Layer Properties with Surfactants.

The three-phase contact line of a droplet on a smooth surface can be characterized by the Young equation. It relates the interfacial energies to the macroscopic contact angle θe. On the mesoscale, wettability is modeled by a film-height-dependent wetting energy f( h). Macro- and mesoscale descriptions are consistent if γ cos θe = γ + f( ha), where γ and ha are the liquid-gas interface energy and the thickness of the equilibrium liquid adsorption layer, respectively. Here, we derive a similar consistency condition for the case of a liquid covered by an insoluble surfactant. At equilibrium, the surfactant is spatially inhomogeneously distributed, implying a nontrivial dependence of θe on surfactant concentration. We derive macroscopic and mesoscopic descriptions of a contact line at equilibrium and show that they are consistent only if a particular dependence of the wetting energy on the surfactant concentration is imposed. This is illustrated by a simple example of dilute surfactants, for which we show excellent agreement between theory and time-dependent numerical simulations.

Connecting Monotonic and Oscillatory Motions of the Meniscus of a Volatile Polymer Solution to the Transport of Polymer Coils and Deposit Morphology.

We study the deposition mechanisms of polymer from a confined  meniscus of volatile liquid. In particular, we investigate the physical processes that are responsible for qualitative changes in the pattern deposition of polymer and the underlying interplay of the state of pattern deposition, motion of the meniscus, and the transport of polymer within the meniscus. As a model system we evaporate a solution of poly(methyl methacrylate) (PMMA) in toluene. Different deposition patterns are observed when varying the molecular mass,  the initial concentration of the solute, and temperature; these  are systematically presented in the form of morphological phase diagrams. The modi of deposition and meniscus motion are correlated. They vary with the ratio between the evaporation-driven convective flux and the diffusive flux of the polymer coils in the solution. In the case of a diffusion-dominated solute transport, the solution monotonically dewets the solid substrate by evaporation, supporting continuous contact line motion and continuous polymer deposition. However, a convection-dominated transport results in an oscillatory ratcheting dewetting-wetting motion of the contact line with more pronounced dewetting phases. The deposition process is then periodic and produces a stripe pattern. The oscillatory motion of the meniscus differs from the well documented stick-slip motion of the meniscus, observed as well, and is attributed to the opposing influences of evaporation and Marangoni stresses, which alternately dominate the deposition process.

Modelling of surfactant-driven front instabilities in spreading bacterial colonies.

The spreading of bacterial colonies at solid-air interfaces is determined by the physico-chemical properties of the involved interfaces. The production of surfactant molecules by bacteria is a widespread strategy that allows the colony to efficiently expand over the substrate. On the one hand, surfactant molecules lower the surface tension of the colony, effectively increasing the wettability of the substrate, which facilitates spreading. On the other hand, gradients in the surface concentration of surfactant molecules result in Marangoni flows that drive spreading. These flows may cause an instability of the circular colony shape and the subsequent formation of fingers. In this work, we study the effect of bacterial surfactant production and substrate wettability on colony growth and shape within the framework of a hydrodynamic thin film model. We show that variations in the wettability and surfactant production are sufficient to reproduce four different types of colony growth, which have been described in the literature, namely, arrested and continuous spreading of circular colonies, slightly modulated front lines and the formation of pronounced fingers.

Sliding Drops: Ensemble Statistics from Single Drop Bifurcations.

Ensembles of interacting drops that slide down an inclined plate show a dramatically different coarsening behavior as compared to drops on a horizontal plate: As drops of different size slide at different velocities, frequent collisions result in fast coalescence. However, above a certain size individual sliding drops are unstable and break up into smaller drops. Therefore, the long-time dynamics of a large drop ensemble is governed by a balance of merging and splitting. We employ a long-wave film height evolution equation and determine the dynamics of the drop size distribution towards a stationary state from direct numerical simulations on large domains. The main features of the distribution are then related to the bifurcation diagram of individual drops obtained by numerical path continuation. The gained knowledge allows us to develop a Smoluchowski-type statistical model for the ensemble dynamics that well compares to full direct simulations.

Continuous versus Arrested Spreading of Biofilms at Solid-Gas Interfaces: The Role of Surface Forces.

We introduce and analyze a model for osmotically spreading bacterial colonies at solid-air interfaces that includes wetting phenomena, i.e., surface forces. The model is based on a hydrodynamic description for liquid suspensions which is supplemented by bioactive processes. We show that surface forces determine whether a biofilm can expand laterally over a substrate and provide experimental evidence for the existence of a transition between continuous and arrested spreading for Bacillus subtilis biofilms. In the case of arrested spreading, the lateral expansion of the biofilm is confined, albeit the colony is biologically active. However, a small reduction in the surface tension of the biofilm is sufficient to induce spreading. The incorporation of surface forces into our hydrodynamic model allows us to capture this transition in biofilm spreading behavior.

Influence of the fluid structure on the binding potential: Comparing liquid drop profiles from density functional theory with results from mesoscopic theory.

For a film of liquid on a solid surface, the binding potential g(h) gives the free energy as a function of the film thickness h and also the closely related (structural) disjoining pressure Π=-∂g/∂h. The wetting behaviour of the liquid is encoded in the binding potential and the equilibrium film thickness corresponds to the value at the minimum of g(h). Here, the method we developed in the work of Hughes et al. [J. Chem. Phys. 142, 074702 (2015)], and applied with a simple discrete lattice-gas model, is used with continuum density functional theory (DFT) to calculate the binding potential for a Lennard-Jones fluid and other simple liquids. The DFT used is based on fundamental measure theory and so incorporates the influence of the layered packing of molecules at the surface and the corresponding oscillatory density profile. The binding potential is frequently input in mesoscale models from which liquid drop shapes and even dynamics can be calculated. Here we show that the equilibrium droplet profiles calculated using the mesoscale theory are in good agreement with the profiles calculated directly from the microscopic DFT. For liquids composed of particles where the range of the attraction is much less than the diameter of the particles, we find that at low temperatures g(h) decays in an oscillatory fashion with increasing h, leading to highly structured terraced liquid droplets.

Nudged elastic band calculation of the binding potential for liquids at interfaces.

The wetting behavior of a liquid on solid substrates is governed by the nature of the effective interaction between the liquid-gas and the solid-liquid interfaces, which is described by the binding or wetting potential g(h) which is an excess free energy per unit area that depends on the liquid film height h. Given a microscopic theory for the liquid, to determine g(h), one must calculate the free energy for liquid films of any given value of h, i.e., one needs to create and analyze out-of-equilibrium states, since at equilibrium there is a unique value of h, specified by the temperature and chemical potential of the surrounding gas. Here we introduce a Nudged Elastic Band (NEB) approach to calculate g(h) and illustrate the method by applying it in conjunction with a microscopic lattice density functional theory for the liquid. We also show that the NEB results are identical to those obtained with an established method based on using a fictitious additional potential to stabilize the non-equilibrium states. The advantages of the NEB approach are discussed.

Mode instabilities and dynamic patterns in a colony of self-propelled surfactant particles covering a thin liquid layer.

We consider a colony of point-like self-propelled surfactant particles (swimmers) without direct interactions that cover a thin liquid layer on a solid support. The particles predominantly swim normal to the free film surface with only a small component parallel to the film surface. The coupled dynamics of the swimmer density and film height profile is captured in a long-wave model allowing for diffusive and convective transport of the swimmers (including rotational diffusion). The dynamics of the film height profile is determined by i) the upward pushing force of the swimmers onto the liquid-gas interface, ii) the solutal Marangoni force due to gradients in the swimmer concentration, and iii) the rotational diffusion of the swimmers together with the in-plane active motion. After reviewing and extending the analysis of the linear stability of the uniform state, we analyse the fully nonlinear dynamic equations and show that point-like swimmers, which only interact via long-wave deformations of the liquid film, self-organise in highly regular (standing, travelling, and modulated waves) and various irregular patterns.

Instabilities of Layers of Deposited Molecules on Chemically Stripe Patterned Substrates: Ridges versus Drops.

A mesoscopic continuum model is employed to analyze the transport mechanisms and structure formation during the redistribution stage of deposition experiments where organic molecules are deposited on a solid substrate with periodic stripe-like wettability patterns. Transversally invariant ridges located on the more wettable stripes are identified as very important transient states and their linear stability is analyzed accompanied by direct numerical simulations of the fully nonlinear evolution equation for two-dimensional substrates. It is found that there exist two different instability modes that lead to different nonlinear evolutions that result (i) at large ridge volume in the formation of bulges that spill from the more wettable stripes onto the less wettable bare substrate and (ii) at small ridge volume in the formation of small droplets located on the more wettable stripes. In addition, the influence of different transport mechanisms during redistribution is investigated focusing on the cases of convective transport with no-slip at the substrate, transport via diffusion in the film bulk and via diffusion at the film surface. In particular, it is shown that the transport process does neither influence the linear stability thresholds nor the sequence of morphologies observed in the time simulation, but only the ratio of the time scales of the different process phases.

Bimodality and re-entrant behaviour in the hierarchical self-assembly of polymeric nanoparticles.

We show that a film of a suspension of polymer grafted nanoparticles on a liquid substrate can be employed to create two-dimensional nanostructures with a remarkable variation in the pattern length scales. The presented experiments also reveal the emergence of concentration-dependent bimodal patterns as well as re-entrant behaviour that involves length scales due to dewetting and compositional instabilities. The experimental observations are explained through a gradient dynamics model consisting of coupled evolution equations for the height of the suspension film and the concentration of polymer. Using a Flory-Huggins free energy functional for the polymer solution, we show in a linear stability analysis that the thin film undergoes dewetting and/or compositional instabilities depending on the concentration of the polymer in the solution. We argue that the formation via 'hierarchical self-assembly' of various functional nanostructures observed in different systems can be explained as resulting from such an interplay of instabilities.