Thin-film dewetting is classically governed by an adhesion-mediated spinodal instability in which curvature-driven diffusion controls post-rupture coarsening. We show that internal activity fundamentally restructures this instability. Using a minimal microscopic model of an active liquid film on a solid substrate, we identify a competition between active stresses and film-substrate adhesion that produces two independently regulated dynamical length scales: vertical liquid accumulation and lateral rupture propagation. While passive films exhibit universal diffusion-limited growth, $\ell_z(t)\sim t^{1/3}$, activity converts transport from curvature-controlled diffusion to persistence-driven motion, yielding a continuous increase of the coarsening exponent from $\approx 0.33$ to $\approx 0.6$. The growth law analysis shows that persistent self-propulsion introduces an advective flux that competes with curvature-induced chemical potential gradients, enhancing growth when the persistence length becomes comparable to the evolving domain size. Simultaneously, the rupture front transitions from dissipative spreading to strongly accelerated propagation approaching ballistic scaling. This decoupling shows that activity does not simply renormalize effective surface forces but generates a distinct nonequilibrium interfacial instability governed by the balance between persistence length and adhesion. The results provide a minimal physical mechanism linking classical thin-film dewetting to dewetting-like rupture observed in active and biological materials.
We study numerically the effect of thermal fluctuations and of variable fluid-substrate interactions on the spontaneous dewetting of thin liquid films. To this aim, we use a recently developed lattice Boltzmann method for thin liquid film flows, equipped with a properly devised stochastic term. While it is known that thermal fluctuations yield shorter rupture times, we show that this is a general feature of hydrophilic substrates, irrespective of the contact angle. The ratio between deterministic and stochastic rupture times, though, decreases with $θ$. Finally, we discuss the case of fluctuat…
Numerical simulations of spontaneous dewetting of non-slipping, variable viscosity unstable thin liquid films on homogeneous substrates reveal the existence of sub-spinodal lengthscales through formation of satellite holes, a marker of nucleated dewetting and/or heterogeneous substrates, in the late stages of dewetting if the liquid viscosity decreases continually with decreasing film thickness. These films also show established signatures of slipping films such as faster rupture and flatter morphologies in the early stages even without invoking any slippage.
Stability of thin lubricating fluid coated slippery surfaces depends on the surface energy of the underlying solid surface. High energy solid surfaces, coated with thin lubricating oil, lead to the dewetting of the oil films upon depositing aqueous drops on it. The total surface energy, which is due to the long range and short range interactions, also predict the instability of thin lubricating films under the given condition. In this article, we present experimental study of dewetting of thin lubricating oil films sandwiched between hydrophilic solid surface and aqueous drops. Fluorescence im…
Ultrathin polymer films on non-wettable substrates display dynamic features which have been attributed to either viscoelastic or slip effects. Here we show that in the weak and strong slip regime effects of viscoelastic relaxation are either absent or not distinguishable from slip effects. Strong-slip modifies the fastest unstable mode in a rupturing thin film, which questions the standard approach to reconstruct the effective interface potential from dewetting experiments.
The stability of thin liquid coatings is of fundamental interest in every- day life. Homogeneous and non-volatile liquid coatings may dewet either by heterogeneous nucleation, thermal nucleation, or spinodal dewetting. Wetting and dewetting is explained on a fundamental level, including a discussion of relevant interactions. The article will also address the various dewetting scenarios and explain how the effective interface potential governs the behavior obtained for various stratified substrates and film thicknesses.
The stability of thin liquid films on a surface depends on the excess free energy of the system involving various short-range and long-range interactions. In an unstable condition, thin liquid films may dewet into multiple small-sized droplets via spinodal, homogeneous, or heterogeneous nucleation process. However, if the total excess free energy of the system can be manipulated using an external stimulus, one can control the stability of thin liquid films on demand. Here, we study the reversible dewetting process of thin lubricating films underneath aqueous drops on slippery surfaces using an…
We discuss a recent effort in the modelling of binary component thin films, which yielded the same conclusions and stability limits as earlier work, despite a different method of incorporating constraints into the gradient dynamics description of the system.
We study dewetting of thin polymer films with built-in topographical fluctuations produced by rubbing the film surface with a rayon cloth. By varying the density of imposed surface defects, we unambiguously distinguish spinodal dewetting, which dominates in liquid films thinner than a characteristic thickness = 13.3 nm, from heterogeneous nucleation in the thicker films. Invariance of this characteristic thickness upon more than a decade change in the defect density makes kinetic effect an unseemly origin. A crossover of the spinodal line provides a consistent picture. This interpretation, how…
Dewetting of thin polystyrene films deposited onto silicone wafers at temperatures close to the glass transition exhibits unusual dynamics and front morphologies. Here, we present a new theoretical approach of these phenomena taking into account both the viscoelastic properties of the film and the non-zero velocity of the film at the interface with the substrate (due to slippage). We then show how these two ingredients lead to : (a) A very asymmetric shape of the rim as the film dewetts, (b) A decrease of the dewetting velocity with time like $t^{-{1/2}}$ for times shorter than the reptation t…
We study a model for a thin liquid film dewetting from a periodic heterogeneous substrate (template). The amplitude and periodicity of a striped template heterogeneity necessary to obtain a stable periodic stripe pattern, i.e. pinning, are computed. This requires a stabilization of the longitudinal and transversal modes driving the typical coarsening dynamics during dewetting of a thin film on a homogeneous substrate. If the heterogeneity has a larger spatial period than the critical dewetting mode, weak heterogeneities are sufficient for pinning. A large region of coexistence between coarseni…
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 evapor…
We study the dewetting of liquid films capped by a thin elastomeric layer. When the tension in the elastomer is isotropic, circular holes grow at a rate which decreases with increasing tension. The morphology of holes and rim stability can be controlled by changing the boundary conditions and tension in the capping film. When the capping film is prepared with a biaxial tension, holes form with a non-circular shape elongated along the high tension axis. With suitable choice of elastic boundary conditions, samples can even be designed such that square holes appear.
A gradient dynamics model based on an extended interface Hamiltonian is presented that is able to describe the dynamics of structuring processes in thin films of liquid mixtures, solutions and suspensions on solid substrates including coupled dewetting and decomposition. After discussing known limiting cases the model is employed to investigate the dewetting of thin films of liquid mixtures and suspensions under the influence of effective long-range van der Waals forces that depend on solute concentration. The occurring fluxes are discussed and it is shown that spinodal dewetting may be trigge…
Experiments on dewetting thin polymer films confirm the theoretical prediction that thermal noise can strongly influence characteristic time-scales of fluid flow and cause coarsening of typical length scales. Comparing the experiments with deterministic simulations, we show that the Navier-Stokes equation has to be extended by a conserved bulk noise term to accomplish the observed spectrum of capillary waves. Due to thermal fluctuations the spectrum changes from an exponential to a power law decay for large wavevectors. Also the time evolution of the typical wavevector of unstable perturbation…
We consider two stacked ultra-thin layers of different liquids on a solid substrate. Using long-wave theory, we derive coupled evolution equations for the free liquid-liquid and liquid-gas interfaces. Linear and non-linear analyses show that depending on the long-range van-der-Waals forces and the ratio of the layer thicknesses, the system follows different pathways of dewetting. The instability may be driven by varicose or zigzag modes and leads to film rupture either at the liquid-gas interface or at the substrate.
In this paper we present a theoretical model for the dewetting of ultra-thin polymer films. Assumming that the shear-thinning properties of these films can be described by a Cross-type constitutive equation, we analyze the front morphology of the dewetting film, and characterize the time evolution of the dry region radius, and of the rim height. Different regimes of growth are expected, depending on the initial film thickness, and on the power-law index involved in the constitutive equation. In the thin-films regime, the dry radius and the rim height obey power-law time dependences. We then co…
Sub-100 nm polymeric spherical plano-convex nano-lens arrays are fabricated using short electron beam exposures to selectively modify the ultrathin (< 30 nm) polymer films, followed by their intensified self-organized dewetting under an aqueous-organic mixture. A short exposure to e-beam locally modifies the polymer chains to effectively change the viscosity of the film in small domains, thus bringing in the dynamical dewetting contrast in the film that produces aligned and ordered dewetted nanostructures. Both negative and positive e-beam tone polymers are thus used to produce array of nano-l…
The study of the dewetting of very thin polymer films has recently revealed many unexpected features (e.g. unusual rim morphologies and front velocities) which have been the focus of several theoretical models. Surprisingly, the most striking feature of all, that is a decrease of the rim width with time, have not yet been explained. In the present letter, we show how the combined effects of a non-linear friction between the film and the substrate, and the presence of residual stresses within the film, result in the presence of a maximum in the time evolution of the rim width. In addition, we s…
Dewetting of ultra-thin polymer films near the glass transition exhibits unexpected front morphologies [G. Reiter, Phys. Rev. Lett., 87, 186101 (2001)]. We present here the first theoretical attempt to understand these features, focusing on the shear-thinning behaviour of these films. We analyse the profile of the dewetting film, and characterize the time evolution of the dry region radius, $R_{d}(t)$, and of the rim height, $h_{m}(t)$. After a transient time depending on the initial thickness, $h_{m}(t)$ grows like $\sqrt{t}$ while $R_{d}(t)$ increases like $\exp{(\sqrt{t})}$. Different regim…
Ultrathin polymer films that are produced e.g. by spin-coating are believed to be stressed since polymers are 'frozen in' into out-of-equilibrium configurations during this process. In the framework of a viscoelastic thin film model, we study the effects of lateral residual stresses on the dewetting dynamics of the film. The temporal evolution of the height profiles and the velocity profiles inside the film as well as the dissipation mechanisms are investigated in detail. Both the shape of the profiles and the importance of frictional dissipation vs. viscous dissipation inside the film are fou…
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, …
The dewetting dynamics of ultrathin polymer films, e.g. in the model system of polystyrene on a polydimethylsiloxane-covered substrate, exhibits interesting behavior like a fast decay of the dewetting velocity and a maximum in the width of the built-up rim in the course of time. These features have been recently ascribed to the relaxation of residual stresses in the film that stem from the nonequilibrium preparation of the samples. Recent experiments by Coppee et al. on PS with low molecular weight, where such stresses could not be evidenced, showed however similar behavior. By scaling argumen…
Slippage of Newtonian liquids in the presence of a solid substrate is a newly found phenomenon the origin of which is still under debate. In this paper, we present a new analysis method to extract the slip length. Enhancing the slip of liquids is an important issue for microfluidic devices that demand for high throughput at low pumping power. We study the velocity of short-chained liquid polystyrene (PS) films dewetting from non-wettable solid substrates. We show how the dynamics of dewetting is influenced by slippage and we compare the results of two types of substrates that give rise to diff…
We compare the dispersion relations for spinodally dewetting thin liquid films for increasing magnitude of interfacial slip length in the lubrication limit. While the shape of the dispersion relation, in particular the position of the maximum, are equal for no-slip up to moderate slip lengths, the position of the maximum shifts to much larger wavelengths for large slip lengths. Here, we discuss the implications of this fact for recently developed methods to assess the disjoining pressure in spinodally unstable thin films by measuring the shape of the roughness power spectrum. For PS films on O…
This study reveals the influence of the surface energy and solid/liquid boundary condition on the breakup mechanism of dewetting ultra-thin polymer films. Using silane self-assembled monolayers, SiO$_2$ substrates are rendered hydrophobic and provide a strong slip rather than a no-slip solid/liquid boundary condition. On undergoing these changes, the thin-film breakup morphology changes dramatically -- from a spinodal mechanism to a breakup which is governed by nucleation and growth. The experiments reveal a dependence of the hole density on film thickness and temperature. The combination of l…
An experimental investigation is reported on the effect of shear on the bursting of molten ultra-thin polymer films embedded in an immiscible matrix. By using an optical microscope coupled with a shearing hotstage, the dewetting dynamics, i.e. the growth of dewetting holes is monitored over time at various shear rates. It is observed that their circularity is modified by shear and that for all temperatures and thicknesses studied, the growth speed of the formed holes rapidly increases with increasing shear rate. A model balancing capillary forces and viscous dissipation while taking into accou…
The spontaneous formation of droplets via dewetting of a thin fluid film from a solid substrate allows for materials nanostructuring, under appropriate experimental control. While thermal fluctuations are expected to play a role in this process, their relevance has remained poorly understood, particularly during the nonlinear stages of evolution. Within a stochastic lubrication framework, we show that thermal noise speeds up and substantially influences the formation and evolution of the droplet arrangement. As compared with their deterministic counterparts, for a fixed spatial domain, stochas…
Dewetting of thin liquid films is monitored in situ by atomic force microscopy, results are compared with simulations. The experimental setting is mimicked as close as possible using the experimental parameters including the effective interface potential. Numerics for the thin film equation are based on recently developed schemes which are up to now the only methods convergent in all relevant space dimensions. Temporal evolution and morphology of experiment and simulation are compared quantitatively. Our results explain the origin of complex generic patterns that evolve upon dewetting.
Hypothesis: Although wetting agents have been developed to limit tear film dewetting over contact lenses, systematic analyses correlating wetting agents properties to mechanisms of the tear film destabilization are not readily available. Clarifying destabilization characteristics across key physio-chemical variables will provide a rational basis for identifying optimal wetting agents. Experiments: We employ an in-house, in vitro platform to comprehensively evaluate drainage and dewetting dynamics of five wetting agents across seventeen different formulations and two model tear film solutions: …
Dynamics and morphology of hole growth in a film of power hardening viscoplastic solid (yield stress ~ [strain-rate]^n) is investigated. At short-times the growth is exponential and depends on the initial hole size. At long-times, for n > 1/3, the growth is exponential with a different exponent. However, for n < 1/3, the hole growth slows; the hole radius approaches an asymptotic value as time tends to infinity. The rim shape is highly asymmetric, the height of which has a power law dependence on the hole radius (exponent close to unity for 0.25 < n < 0.4). The above results explain recent int…
Here, we report experimental results on the rupture of flat colloidal films over a large range of volume fractions, 0.00 $\le ϕ\le$ 0.47. The films are formed using a constant fluid volume, ruptured with a needle, and recorded using a high-speed camera. We show that colloidal films rupture in a manner quantitatively similar to Newtonian fluids, even well into the shear thinning regime. These results are consistent with the well-known mechanism of the rupture of Newtonian films, where the rupture rim rolls outward collecting more fluid and thus film rupture is a shear-free process. However, in …
Field-induced self-organized patterning in ultrathin (< 100 nm) polymer films produces resolutions of the order of 10 μm or more because of the high energy penalty for the surface deformations on small scales. We propose here a very simple but versatile method to fabricate sub-micron (~100 nm) ordered and tunable polymeric structures by self-organized room temperature dewetting of ultrathin polystyrene films by minimizing the surface tension limitation. We illustrate this technique by fabricating sub-micron lens arrays of tunable curvature. This is achieved by switching to controlled room temp…
Dewetting of ultrathin (< 100 nm) polymer films, by heating above the glass transition, produces droplets of sizes of the order of microns and mean separations between droplets of the order of tens of microns. These relatively large length scales are because of the weak destabilizing van der Waals forces and the high surface energy penalty required for deformations on small scales. We show a simple, one-step versatile method to fabricate sub-micron (>~100 nm) droplets and their ordered arrays by room temperature dewetting of ultrathin polystyrene (PS) films by minimizing these limitations. Thi…
The influence of wall slip on the instability of a non-wetting liquid film placed on a solid substrate is analyzed in the limit of negligible inertia. In particular, we focus on the stability properties of the film, comparing the performance of the three lubrication models available in the literature, namely the weak, intermediate and strong slip models, with the Stokes equations. Since none of the aforementioned leading-order lubrication models is shown to be able to predict the growth rate of perturbations for the whole range of slipping lengths, we develop a parabolic model able to accurate…
The instability, dynamics and morphological transitions of patterns in thin liquid films on periodic striped surfaces (consisting of alternating less and more wettable stripes) are investigated based on 3-D nonlinear simulations that account for the inter-site hydrodynamic and surface-energetic interactions. The film breakup is suppressed on some potentially destabilizing nonwettable sites when their spacing is below a characteristic lengthscale of the instability, the upper bound for which is close to the spinodal lengthscale. The thin film pattern replicates the substrate surface energy patt…
We consider a porous solid covered with a water film (or with a drop) in situations where the liquid is pumped in, either spontaneously (if the porous medium is hydrophilic) or mechanically (by an external pump). The dynamics of dewetting is then strongly modified. We analyse a few major examples: a) horizontal films, which break at a certain critical thickness, b) the "modified Landau-Levich problem" where a porous plate moves up from a bath and carries a film: aspiration towards the plate limits the height H reached by the film, c) certain situation where the hysteresis of contact angles is …
Partially wetting nematic liquid crystal (NLC) films on substrates are unstable to dewetting-type instabilities due to destablizing solid/NLC interaction forces. These instabilities are modified by the nematic nature of the films, which influences the effective solid/NLC interaction. In this work, we focus on the influence of imposed substrate anchoring on the instability development. The analysis is carried out within a long-wave formulation based on the Leslie-Ericksen description of NLC films. Linear stability analysis of the resulting equations shows that some features of the instability, …
This paper presents the first MD simulations of a model, which we have designed for understanding the development of electro-induced instability of a thin toluene emulsion film in contact with saline aqueous phase. This study demonstrates the charge accumulation role in toluene film rupture when a DC electric field is applied. The critical value of the external field at which film ruptures, thin film charge distribution, capacitance, number densities and film structure have been obtained in simulating the system within NVT and NPT ensembles. A mechanism of thin film rupture driven by the elect…
For one-component fluids, we predict a pre-dewetting phase transition between a thin and thick low-density layer in liquid on a wall repelling the fluid. This is the case of a hydrophobic wall for water. A pre-dewetting line starts from the coexistence curve and ends at a surface critical point in the phase diagram. We calculate this line numerically using the van der Waals model and analytically using the free energy expansion up to the quartic order. We also examine the pre-dewetting dynamics of a layer created on a hydrophobic spot on a heterogeneous wall. It is from a thin to thick layer d…
We examine the profile of a liquid front of a film that is dewetting a solid substrate. Since volume is conserved, the material that once covered the substrate is accumulated in a rim close to the three phase contact line. Theoretically, such a profile of a Newtonian liquid resembles an exponentially decaying harmonic oscillation that relaxes into the prepared film thickness. For the first time, we were able to observe this behavior experimentally. A non-Newtonian liquid - a polymer melt - however, behaves differently. Here, viscoelastic properties come into play. We will demonstrate that by a…
We investigate the effect of short chains on slip of highly entangled polystyrenes (PS) during thin film dewetting from non-wetting fluorinated surfaces. Binary and ternary mixtures were prepared from monodisperse PS with weight average molecular weights $5 < M_\textrm{w} < 490$ kg/mol. Flow dynamics and rim morphology of dewetting holes were captured using optical and atomic force microscopy. Slip properties are assessed in the framework of hydrodynamic models describing the rim height profile of dewetting holes. We show that short chains with $M_\textrm{w}$ below the polymer critical molecul…
We have studied the breakup and subsequent fluid flow in very thin films of partially wetting liquid on solid substrates, using molecular dynamics simulations. The liquid is made of short chain molecules interacting with Lennard-Jones interactions, and the solid is modeled as a clean crystal lattice whose atoms have thermal oscillations. Films below a critical thickness are found to exhibit a spontaneous spinodal-like instability leading to dry patches, as predicted theoretically and observed in some experiments. Liquid withdrawing from a dry patch collects in a moving rim whose fluid dynamics…
It is shown that the intrinsic stress in solvent cast polymer coatings plays a key role in the nucleation of holes in the film. Nucleation is important because it is meanwhile clear that heterogeneous nucleation is the only relevant rupture mechanism for the technologically relevant thickness regime well above 100 nm. The most striking feature is that in contrast to what has been widely believed, the number density of holes scales not algebraically, but exponentially with the film thickness.
Theory and numerical simulations of the Navier-Stokes equations are used to unravel the inertia-driven dewetting dynamics of an ultrathin film of Newtonian liquid deposited on a solid substrate. A classification of the film thinning regimes at finite Ohnersorge numbers is provided, unifying previous findings. We reveal that, for Ohnesorge numbers smaller than one, the final approach to the rupture singularity close to the molecular scales is controlled by a balance between liquid inertia and van der Waals forces leading to a self-similar asymptotic regime with $h_{\text{min}} \propto τ^{2/5}$,…
Although soap films are prone to evaporate due to their large surface to volume ratio, the effect of evaporation on macroscopic film features has often been disregarded in the literature. In this work, we investigate experimentally the influence of environmental humidity on soap film stability. An original experiment allows to measure both the maximum length of a film pulled at constant velocity and its thinning dynamics in a controlled atmosphere for various values of the relative humidity $\RH$. At first order, the environmental humidity seems to have almost no impact on most of the film thi…
Understanding evaporation or drying in granular media still remains complex despite recent advancements. Evaporation depends on liquid transport across a connected film network from the bulk to the surface. In this study, we investigate the stability of film networks as a function of granular packing. Using a controlled experimental approach, we vary the granular packing geometry and show the changes in the height of the liquid film network during evaporation as packing shifts from a loose-packed to a close-packed arrangement. This height can be calculated from an equilibrium between hydrostat…
Hydrodynamic slip of Newtonian liquids is a new phenomenon, the origin of which is not yet clarified. There are various direct and indirect techniques to measure slippage. Here we describe a method to characterize the influence of slippage on the shape of rims surrounding growing holes in thin polymer films. Atomic force microscopy is used to study the shape of the rim; by analyzing its profile and applying an appropriate lubrication model we are able to determine the slip length for polystyrene films. In the experiments we study polymer films below the entanglement length that dewet from hydr…
For partially wetting fluids, previous results suggest that the thickness and the dewetting velocity of gravity driven films are uniquely determined by the triple line dynamics. In contrast, when flushing aqueous liquids through polymer tubes, our measurements show that the dewetting velocity and thickness can be selected. The control parameter is pressure, i.e. the macroscopic curvature of the meniscus. Our results demonstrate directly the major role played by the macroscopic geometry in the stability of the triple line in a dynamic meniscus as predicted by Eggers (Phys. Rev. Lett. 93, 094502…
We revisit the fundamental problem of liquid-liquid dewetting and perform a detailed comparison of theoretical predictions based on thin-film models with experimental measurements obtained by atomic force microscopy (AFM). Specifically, we consider the dewetting of a liquid polystyrene (PS) layer from a liquid polymethyl methacrylate (PMMA) layer, where the thicknesses and the viscosities of PS and PMMA layers are similar. The excellent agreement of experiment and theory reveals that dewetting rates for such systems follow no universal power law, in contrast to dewetting scenarios on solid sub…
Suppressed Rupture of Thin Metal Films via van der Waals Epitaxy
Peking University（北京大学）；Beijing University of Technology（北京工业大学）；National Center for Nanoscience and Technology（国家纳米科学中心）；Univ. Bordeaux, CNRS, LOMA, UMR 5798（波尔多大学，法国国家科学研究中心，LOMA实验室）
