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The wetting properties of multi-component liquids are crucial to numerous industrial applications. The mechanisms that determine the contact angles for such liquids remain poorly understood, with many intricacies arising due to complex physical phenomena, for example due to the presence of surfactants. Here, we consider two-component drops that consist of mixtures of vicinal alkane diols and water. These diols behave surfactant-like in water. However, the contact angles of such mixtures on solid substrates are surprisingly large. We experimentally reveal that the contact angle is determined by two separate mechanisms of completely different nature, namely Marangoni contraction (hydrodynamic) and autophobing (molecular). It turns out that the length of the alkyl tail of the alkane diol determines which mechanism is dominant, highlighting the intricate coupling between molecular physics and the macroscopic wetting of complex fluids.

The capillary traction of a liquid contact line causes highly localized deformations in soft solids, tremendously slowing down wetting and dewetting dynamics by viscoelastic braking. Enforcing nonetheless large velocities leads to the so-called stick-slip instability, during which the contact line periodically depins from its own wetting ridge. The mechanism of this periodic motion and, especially, the role of the dynamics in the fluid have remained elusive, partly because a theoretical description of the unsteady soft wetting problem is not available so far. Here we present the first numerical simulations of the full unsteady soft wetting problem, with a full coupling between the liquid and the solid dynamics. We observe three regimes of soft wetting dynamics: steady viscoelastic braking at slow speeds, stick-slip motion at intermediate speeds, followed by a region of viscoelastic braking where stick-slip is suppressed by liquid damping, which ultimately gives way to classical wetting dynamics, dominated by liquid dissipation., Comment: 6 pages 5 figures

SignificanceThe shape and dynamics of small sessile droplets are dictated by capillary forces. For liquid mixtures, evaporation adds spatio-temporal modulation to these forces that can either enhance or inhibit droplet spreading, depending on the direction of the resulting Marangoni flow. This work experimentally and numerically demonstrates the coexistence of two antagonistic Marangoni flows in a ternary mixture. Played against each other, they can choreograph a boomerang-like wetting motion: Droplets initially rapidly spread, then contract into a compact cap shape. While such a behavior has been impossible in wetting scenarios of simple liquids, it enables spread-retract-remove surface processing with the addition of a single small liquid volume, demonstrated here in a surface-cleaning experiment., Proceedings of the National Academy of Sciences of the United States of America, 119 (19), ISSN:0027-8424, ISSN:1091-6490

The interplay between phase separation and wetting of multicomponent mixtures is ubiquitous in nature and technology and recently gained significant attention across scientific disciplines, due to the discovery of biomolecular condensates. It is well understood that sessile droplets, undergoing phase separation in a static wetting configuration, exhibit microdroplet nucleation at their contact lines, forming an oil ring during later stages. However, very little is known about the dynamic counterpart, when phase separation occurs in a non-equilibrium wetting configuration, i.e., spreading droplets. Here we report that liquid-liquid phase separation strongly couples to the spreading motion of three-phase contact lines. Thus, the classical Cox-Voinov law is not applicable anymore, because phase separation adds an active spreading force beyond the capillary driving. Intriguingly, we observe that spreading starts well before any visible nucleation of microdroplets in the main droplet. Using high-speed ellipsometry, we further demonstrate that surface forces cause an even earlier nucleation in the wetting precursor film around the droplet, initiating the observed wetting transition. We expect our findings to enrich the fundamental understanding of phase separation processes that involve dynamical contact lines and/or surface forces, with implications in a wide range of applications, from oil recovery or inkjet printing to material synthesis and biomolecular condensates., 8 pages, 4 figures, 6 pages supplementary information

Geometry in materials is a key concept which can determine material behavior in ordering, frustration, and fragmentation. More specifically, the behavior of interacting degrees of freedom subject to arbitrary geometric constraints has the potential to be used for engineering materials with exotic phase behavior. While advances in lithography have allowed for an experimental exploration of geometry on ordering that has no precedent in nature, many of these methods are low throughput or the underlying dynamics remain difficult to observe directly. Here, we introduce an experimental system that enables the study of interacting many-body dynamics by exploiting the physics of multidroplet evaporation subject to two-dimensional spatial constraints. We find that a high-energy initial state of this system settles into frustrated, metastable states with relaxation on two timescales. We understand this process using a minimal dynamical model that simulates the overdamped dynamics of motile droplets by identifying the force exerted on a given droplet as being proportional to the two-dimensional vapor gradients established by its neighbors. Finally, we demonstrate the flexibility of this platform by presenting experimental realizations of droplet−lattice systems representing different spin degrees of freedom and lattice geometries. Our platform enables a rapid and low-cost means to directly visualize dynamics associated with complex many-body systems interacting via long-range interactions. More generally, this platform opens up the rich design space between geometry and interactions for rapid exploration with minimal resources.

The functionality of adhesives relies on their response under the application of a load. Yet, it has remained a challenge to quantitatively relate the macroscopic dynamics of peeling to the dissipative processes inside the adhesive layer. Here we investigate the peeling of a reversible adhesive made of a polymer gel, measuring the relationship between the peeling force, the peeling velocity, and the geometry of the interface at small-scale. Experiments are compared to a theory based on the linear viscoelastic response of the adhesive, augmented with an elastocapillary regularization approach. This theory, fully quantitative in the limit of small surface deformations, demonstrates the emergence of a "wetting" angle at the contact line and exhibits scaling laws for peeling which are in good agreement with the experimental results. Our findings provide a new strategy for design of reversible adhesives, by quantitatively combining wetting, geometry and dissipation.

The compression of soft elastic matter and biological tissue can lead to creasing, an instability where a surface folds sharply into periodic self-contacts. Intriguingly, the unfolding of the surface upon releasing the strain is usually not perfect: small scars remain that serve as nuclei for creases during repeated compressions. Here we present creasing experiments with sticky polymer surfaces, using confocal microscopy, which resolve the contact line region where folding and unfolding occurs. It is found that surface tension induces a second fold, at the edge of the self-contact, which leads to a singular elastic stress and self-similar crease morphologies. However, these profiles exhibit an intrinsic folding-unfolding asymmetry that is caused by contact line pinning, in a way that resembles wetting of liquids on imperfect solids. Contact line pinning is therefore a key element of creasing: it inhibits complete unfolding and gives soft surfaces a folding memory., Comment: 8 pages, 6 figures

The mechanical and chemical properties of soft solids are crucial to many applications in biology and surface science. Recent studies use wetting by liquid drops to probe the surface mechanics of reticulated polymer networks, leading to controversial interpretations. This controversy relates to the long-standing paradox of Young’s law for the liquid contact angle, which invokes only a horizontal force balance. Recent work shows that, for very soft materials, the solid’s surface tension plays a key role for the vertical force balance, involving a singular ridgelike deformation exactly at the point where the droplet pulls on the network. A hotly debated question is whether unexpected measurements on this singular deformation can be attributed to nonlinear bulk elasticity or whether these provide evidence for an intricate surface elasticity, known as the Shuttleworth effect. Here, we theoretically reveal the nature of the elastocapillary singularity on a hyperelastic substrate with various constitutive relations for the interfacial energy. First, we finely resolve the vicinity of the singularity using goal-adaptive finite-element simulations. This simulation confirms that bulk elasticity cannot affect the force balance at the contact line. Subsequently, we derive exact solutions of nonlinear elasticity that describe the singularity analytically. These solutions are in perfect agreement with numerics and show that both the angles and stretch at the contact line, as previously measured experimentally, consistently point to a strong Shuttleworth effect. Finally, using Noether’s theorem, we reveal the quantitative link between Young’s law, hysteresis, and the nature of the elastocapillary singularity. Our contribution closes the issue of the missing normal force at the contact line and opens up the development of modern techniques in polymer surface science. published

Elastohydrodynamic lubrication, or simply soft lubrication, refers to the motion of deformable objects near a boundary lubricated by a fluid, and is one of the key physical mechanisms to minimise friction and wear in natural and engineered systems. Hence it is of particular interest to relate the thickness of the lubricant layer to the entrainment (sliding/rolling) velocity, the mechanical loading exerted onto the contacting elements, and properties of the elastic boundary. In this work we provide an overview of the various regimes of soft lubrication for two-dimensional cylinders in lubricated contact with compliant walls. We discuss the limits of small and large entrainment velocity, which is equivalent to large and small elastic deformations, as the cylinder moves near thick or thin elastic layers. The analysis focusses on thin elastic coatings, both compressible and incompressible, for which analytical scaling laws are not yet available in the regime of large deformations. By analysing the elastohydrodynamic boundary layers that appear at the edge of the contact, we establish the missing scaling laws - including prefactors. As such, we offer a rather complete overview of physically relevant limits of soft lubrication., 21 pages, 8 figures

Flagella and cilia are cellular appendages that inherit essential functions of microbial life including sensing and navigating the environment. In order to propel a swimming microorganism they displace the surrounding fluid by means of periodic motions, while precisely timed modulations of their beating patterns enable the cell to steer towards or away from specific locations. Characterizing the dynamic forces, however, is challenging and typically relies on indirect experimental approaches. Here, we present direct in vivo measurements of the dynamic forces of motile Chlamydomonas reinhardtii cells in controlled environments. The experiments are based on partially aspirating a living microorganism at the tip of a micropipette force sensor and optically recording the micropipette’s position fluctuations with high temporal and sub-pixel spatial resolution. Spectral signal analysis allows for isolating the cell-generated dynamic forces caused by the periodic motion of the flagella from background noise. We provide an analytic, elasto-hydrodynamic model for the micropipette force sensor and describe how to obtain the micropipette’s full frequency response function from a dynamic force calibration. Using this approach, we measure the amplitude of the oscillatory forces during the swimming activity of individual Chlamydomonas reinhardtii cells of 26 ± 5 pN, resulting from the coordinated flagellar beating with a frequency of 49 ± 5 Hz. This dynamic micropipette force sensor technique generalizes the applicability of micropipettes as force sensors from static to dynamic force measurements, yielding a force sensitivity in the piconewton range. In addition to measurements in bulk liquid environment, we study the dynamic forces of the biflagellated microswimmer in the vicinity of a solid/liquid interface. As we gradually decrease the distance of the swimming microbe to the interface, we measure a significantly enhanced force transduction at distances larger than the maximum extent of the beating flagella, highlighting the importance of hydrodynamic interactions for scenarios in which flagellated microorganisms encounter surfaces.

Tracer particles are the workhorse of the fluid dynamicist for visualizing flow in transparent liquids. Thus a tracer becomes useless if its signal disappears, which frequently happens in practice, for instance due to bleaching. The opposite occurs in a recent work by Kim & Stone (J. Fluid Mech., vol. 850, 2018, pp. 769–783): the fading signal of a dissolving particle may reveal the local composition in a mixture. Such information is highly valuable in the study of evaporating droplets. In virtually all realistic cases, droplets consist of multiple components, ranging from trace impurities to engineered cocktails, which, for instance, generate a desired deposit pattern for a printing process. Different components typically evaporate at different rates, which causes inhomogeneities in droplet composition. Determining the latter is one of the main challenges in the field.

Flagella and cilia are cellular appendages that inherit essential functions of microbial life including sensing and navigating the environment. In order to propel a swimming microorganism they displace the surrounding fluid by means of periodic motions, while precisely-timed modulations of their beating patterns enable the cell to steer towards or away from specific locations. Characterizing the dynamic forces, however, is challenging and typically relies on indirect experimental approaches. Here, we present direct in vivo measurements of the dynamic forces of motile Chlamydomonas reinhardtii cells in controlled environments. The experiments are based on partially aspirating a living microorganism at the tip of a micropipette force sensor and optically recording the micropipette's position fluctuations with high temporal and sub-pixel spatial resolution. We provide an analytic elasto-hydrodynamic model for the micropipette force sensor and describe how to obtain the micropipette's full frequency response function from a dynamic force calibration. Using this approach, we find dynamic forces during the free swimming activity of individual Chlamydomonas reinhardtii cells of 23$\pm$5 pN resulting from the coordinated flagellar beating with a frequency of 51$\pm$6 Hz. In addition to measurements in bulk liquid environment, we study the dynamic forces of the biflagellated microswimmer in the vicinity of a solid/liquid interface. As we gradually decrease the distance of the swimming microbe to the interface, we measure a significantly enhanced force transduction at distances larger than the maximum extend of the beating flagella, highlighting the importance of hydrodynamic interactions for scenarios in which flagellated microorganisms encounter surfaces., 12 pages, 7 figures

The spreading of liquid drops on soft substrates is extremely slow, owing to strong viscoelastic dissipation inside the solid. A detailed understanding of the spreading dynamics has remained elusive, partly owing to the difficulty in quantifying the strong viscoelastic deformations below the contact line that determine the shape of moving wetting ridges. Here we present direct experimental visualisations of the dynamic wetting ridge, complemented with measurements of the liquid contact angle. It is observed that the wetting ridge exhibits a rotation that follows exactly the dynamic liquid contact angle -- as was previously hypothesized [Karpitschka \emph{et al.} Nature Communications \textbf{6}, 7891 (2015)]. This experimentally proves that, despite the contact line motion, the wetting ridge is still governed by Neumann's law. Furthermore, our experiments suggest that moving contact lines lead to a variable surface tension of the substrate. We therefore set up a new theory that incorporates the influence of surface strain, for the first time including the so-called Shuttleworth effect into the dynamical theory for soft wetting. It includes a detailed analysis of the boundary conditions at the contact line, complemented by a dissipation analysis, which shows, again, the validity of Neumann's balance., 23 pages, 12 figures

Evaporating salty droplets are ubiquitous in nature, in our home and in the laboratory. Interestingly, the transport processes in such apparently simple systems differ strongly from evaporating "freshwater" droplets since convection is partly inverted due to Marangoni stresses. Such an effect has crucial consequences to the salt crystallization process and to the deposits left behind. In this work we show unprecedented measurements that, not only confirm clearly the patterns of the flow inversion, but also elucidate their impact on the distribution of non-volatile solutes. Contrary to what has been often reported in the literature, such a flow reversal does not prevent the formation of ring-shaped stains: particles accumulate at the contact line driven solely by the interfacial flow. We can therefore conclude that the classical "coffee-stain effect" is not the only mechanism that can generate ring-shaped stains in evaporating droplets.

Solid particles floating at a liquid interface exhibit a long-ranged attraction mediated by surface tension. In the absence of bulk elasticity, this is the dominant lateral interaction of mechanical origin. Here, we show that an analogous long-range interaction occurs between adjacent droplets on solid substrates, which crucially relies on a combination of capillarity and bulk elasticity. We experimentally observe the interaction between droplets on soft gels and provide a theoretical framework that quantitatively predicts the interaction force between the droplets. Remarkably, we find that, although on thick substrates the interaction is purely attractive and leads to drop–drop coalescence, for relatively thin substrates a short-range repulsion occurs, which prevents the two drops from coming into direct contact. This versatile interaction is the liquid-on-solid analog of the “Cheerios effect.” The effect will strongly influence the condensation and coarsening of drops on soft polymer films, and has potential implications for colloidal assembly and mechanobiology. published

The elastic and adhesive properties of a solid surface can be quantified by indenting it with a rigid sphere. Indentation tests are classically described by the JKR-law when the solid is very stiff, while recent work highlights the importance of surface tension for exceedingly soft materials. Here we show that surface tension plays a crucial role even in stiff solids: Young's wetting angle emerges as a boundary condition and this regularizes the crack-like singularity at the edge of adhesive contacts. We find that the edge region exhibits a universal, self-similar structure that emerges from the balance of surface tension and elasticity. The similarity theory is solved analytically and provides a complete description of adhesive contacts, by which we reconcile global adhesion laws and local contact mechanics.

Wavelike patterns driving transport are ubiquitous in life. Peristaltic pumps are a paradigm of efficient mass transport by contraction driven flows—often limited by energetic constraints. We show that a cost-efficient increase in pumping performance can be achieved by modulating the phase difference between harmonics to increase occlusion. In experiments we find a phase difference shift in the living peristalsis model P. polycephalum as dynamic response to forced mass transport. Our findings provide a novel metric for wavelike patterns and demonstrate the crucial role of nonlinearities in life. published

The contact line of a liquid drop on a solid exerts a nanometrically sharp surface traction. This provides an unprecedented tool to study highly localised and dynamic surface deformations of soft polymer networks. One of the outstanding problems in this context is the stick-slip instability, observed above a critical velocity, during which the contact line periodically depins from its own wetting ridge. Time-resolved measurements of the solid deformation are challenging, and the mechanism of dynamical depinning has remained elusive. Here we present direct visualisations of the dynamic wetting ridge formed by water spreading on a PDMS gel. Unexpectedly, it is found that the opening angle of the wetting ridge increases with speed, which cannot be attributed to bulk rheology, but points to a dynamical increase of the solid's surface tensions. From this we derive the criterion for depinning that is confirmed experimentally. Our findings reveal a deep connection between stick-slip processes and newly identified dynamical surface effects., 5 pages, 4 figures

In Newtonian mechanics, an overdamped system at steady state is governed by a local balance of mechanical stress but also obeys a global balance between injected and dissipated energy. In the classical literature of purely viscous drop spreading, apparent differences in “dissipation” and “force” approaches have led to unnecessary debates, which ultimately could be traced back to different levels of mathematical approximation (1). In the context of wetting on a soft solid, Zhao et al. (2) interpret their experiments by a model based on viscoelastic dissipation inside the substrate. It is claimed that this global dissipation model is fundamentally different from the local mechanical model presented by Karpitschka et al. (3). The purpose of this letter is to demonstrate that ( i ) the models in refs. 2 and 3 are in fact strictly equivalent … [↵][1]1To whom correspondence should be addressed. Email: stefan.karpitschka{at}ds.mpg.de. [1]: #xref-corresp-1-1

We analyze the vertical composition profile during hydrodynamic-evaporative film thinning (spin casting) of mixtures of non-volatile solutes and volatile solvents. We present a generic approach based on ideal solution behavior. Our analysis complements more detailed (but more system specific) studies that are available in the literature. The hydrodynamic-evaporative film thinning is described analytically based on the solvent properties. We find a universal film thinning behavior as a function of the rotation speed, viscosity and evaporation rate. The thinning process is uniquely characterized by its transition height i.e., the film thickness where hydrodynamics and evaporation contribute equally to film thinning. The theoretically predicted film thinning is in agreement with experimental results. The evolution of the internal film composition is calculated numerically. The numerical description is tractable and offers quantitative insights into the influence of the experimental conditions on the evolution of the internal composition. A characteristic Sherwood Number is introduced as a fundamental process parameter. It characterizes the vertical solution profile and serves as a well-defined and experimentally accessible criterion for the regimes of quantitative validity of our analysis. We also present new power laws, which link the process control parameters to the composition evolution, process duration, and final solute coverage. Because the analysis is generic and tractable, it also yields valuable insights for solutions behaving non-ideally.

The surfaces of growing biological tissues, swelling gels, and compressed rubbers do not remain smooth, but frequently exhibit highly localized inward folds. We reveal the morphology of this surface folding in a novel experimental setup, which permits to deform the surface of a soft gel in a controlled fashion. The interface first forms a sharp furrow, whose tip size decreases rapidly with deformation. Above a critical deformation, the furrow bifurcates to an inward folded crease of vanishing tip size. We show experimentally and numerically that both creases and furrows exhibit a universal cusp-shape, whose width scales like $y^{3/2}$ at a distance $y$ from the tip. We provide a similarity theory that captures the singular profiles before and after the self-folding bifurcation, and derive the length of the fold from large deformation elasticity., 5 pages, 4 figures

Recent experiments have shown that liquid drops on highly deformable substrates exhibit mutual interactions. This is similar to the Cheerios effect, the capillary interaction of solid particles at a liquid interface, but now the roles of solid and liquid are reversed. Here we present a dynamical theory for this inverted Cheerios effect, taking into account elasticity, capillarity and the viscoelastic rheology of the substrate. We compute the velocity at which droplets attract, or repel, as a function of their separation. The theory is compared to a simplified model in which the viscoelastic dissipation is treated as a localized force at the contact line. It is found that the two models differ only at small separation between the droplets, and both of them accurately describe experimental observations., 11 pages, 8 figures

Motivated by the development of lubricant-infused slippery surfaces, we study a sessile drop of a nonvolatile (ionic) liquid which is embedded in a slowly evaporating lubricant film (n-decane) on a horizontal, planar solid substrate. Using laser scanning confocal microscopy we imaged the evolution of the shape of the liquid/liquid and liquid/air interfaces, including the angles between them. Results are compared to solutions of the generalized Laplace equations describing the drop profile and the annular wetting ridge. For all film thicknesses, experimental results agree quantitatively with the calculated drop and film shapes. With the verified theory we can predict height and volume of the wetting ridge. Two regimes can be distinguished: for macroscopically thick films (excess lubrication) the meniscus size is insensitive to changes in film thickness. Once the film is thin enough that surface forces between the lubricant/air and solid/lubricant interfaces become significant the meniscus changes significantly with varying film thickness (starved lubrication). The size of the meniscus is particularly relevant because it affects sliding angles of drops on lubricant-infused surfaces. published

The Marangoni contraction of sessile drops of a binary mixture of a volatile and a nonvolatile liquid has been investigated experimentally and theoretically. The origin of the contraction is the locally inhomogeneous evaporation rate of sessile drops. This leads to surface tension gradients and thus to a Marangoni flow. Simulations show that the interplay of Marangoni flow, capillary flow, diffusive transport, and evaporative losses can establish a quasistationary drop profile with an apparent nonzero contact angle even if both liquid components individually wet the substrate completely. Experiments with different solvents, initial mass fractions, and gaseous environments reveal a previously unknown universal power-law relation between the apparent contact angle and the relative undersaturation of the ambient atmosphere: θapp ∼ (RHeq – RH)1/3. This experimentally observed power law is in quantitative agreement with simulation results. The exponent can also be inferred from a scaling analysis of the hydrodynamic-evaporative evolution equations of a binary mixture of liquids with different volatilities. published

Due to capillarity, sessile droplets of identical liquids will instantaneously fuse when they come in contact at their three-phase lines. However, with drops of different, completely miscible liquids, instantaneous coalescence can be suppressed. Instead, the drops remain in a state of noncoalescence for some time, with the two drop bodies connected only by a thin neck. The reason for this noncoalescence is the surface tension difference, Δγ, between the liquids. If Δγ is sufficiently large, then it induces a sufficiently strong Marangoni flow, which keeps the main drop bodies temporarily separated. Studies with spreading drops have revealed that the boundary between instantaneous coalescence and noncoalescence is sharp (Karpitschka, S.; Riegler, H. J. Fluid. Mech. 2014, 743, R1). The boundary is a function of two parameters only: Δγ and Θ(a), the arithmetic mean of the contact angles in the moment of drop-drop contact. It appears plausible that surface forces (the disjoining pressure) could also influence the coalescence behavior. However, in experiments with spreading drops, surface forces always promote coalescence and their influence might be obscured. Therefore, we present here coalescence experiments with partially wetting liquids and compare the results to the spreading case. We adjust different equilibrium contact angles (i.e., different surface forces) with different substrate surface coatings. As for spreading drops, we observe a sharp boundary between regimes of coalescence and noncoalescence. The boundary follows the same power law relation for both partially and completely wetting cases. Therefore, we conclude that surface forces have no significant, explicit influence on the coalescence behavior of sessile drops from different miscible liquids.

We present experimental results on rare transitions between two states due to intrinsic noise between two states in a bistable surface reaction, namely the catalytic oxidation of CO on Pd(111) surfaces. The mean time scales involved are typically of order 104 s and the probability distribution shows two peaks over a large part of the bistable regime of this surface reaction. We use measurements of the resulting CO2 rate as well as photoelectron emission microscopy (PEEM) to characterize these rare transitions. From our dynamic data we can extract probability distributions for the CO2 rate. We use x – t plots from PEEM measurements to describe the transitions, which are–as we demonstrate–characterized by one wall moving through the field of view in PEEM measurements. The resulting probability distributions for the CO2 rate are shown to depend strongly on the value, Y, of the CO fraction in the reactant flux inside the bistable regime. We find that the probability distribution is strongly asymmetric indicating that the two basins of attraction are rather different in depth and width. This is also concluded from the PEEM measurements, which show in one case a rather sharp and narrow domain wall going one way, while it is rather wide and diffuse for the motion in the opposite direction. To have two basins of attraction in the bistable regime, which are rather different in nature is reminiscent of other bistable systems such as, for example, optical bistability, although the time scales involved in the present system are entirely different.

Lubrication flows appear in many applications in engineering, biophysics, and in nature. Separation of surfaces and minimisation of friction and wear is achieved when the lubrication fluid builds up a lift force. In this paper we analyse soft lubricated contacts by treating the solid walls as viscoelastic: soft materials are typically not purely elastic, but dissipate energy under dynamical loading conditions. We present a method for viscoelastic lubrication and focus on three canonical examples, namely Kelvin-Voigt-, Standard Linear-, and Power Law-rheology. It is shown how the solid viscoelasticity affects the lubrication process when the timescale of loading becomes comparable to the rheological timescale. We derive asymptotic relations between lift force and sliding velocity, which give scaling laws that inherit a signature of the rheology. In all cases the lift is found to decrease with respect to purely elastic systems., 14 pages, 3 figures

Liquid drops on soft solids generate strong deformations below the contact line, resulting from a balance of capillary and elastic forces. The movement of these drops may cause strong, potentially singular dissipation in the soft solid. Here we show that a drop on a soft substrate moves by surfing a ridge: the initially flat solid surface is deformed into a sharp ridge whose orientation angle depends on the contact line velocity. We measure this angle for water on a silicone gel and develop a theory based on the substrate rheology. We quantitatively recover the dynamic contact angle and provide a mechanism for stick-slip motion when a drop is forced strongly: the contact line depins and slides down the wetting ridge, forming a new one after a transient. We anticipate that our theory will have implications in problems such as self-organization of cell tissues or the design of capillarity-based microrheometers., 9 pages, 5 figures

International audience; Quantitative experiments on the evaporation from sessile droplets of aqueous saline (NaCl) solutions show a strong dependence on salt concentration and droplet shape. The experiments were performed with seven decades of initial NaCl concentrations, with various droplet sizes and with different contact angles. The evaporaton rate is significantly lower for high salt concentrations and small contact angles than what is expected from the well-accepted diffusion-controlled evaporation scenario for sessile drops, even if the change of the vapor pressure due to the salt is taken into account. Particle tracking velocimetry reveals that this modification of the evaporation behavior is caused by Marangoni flows that are induced by surface tension gradients originating from the local evaporative peripheral salt enrichment. In addition it is found that already very low salt concentrations lead to a pinning of the three phase contact line. Whereas drops with concentration ≥ 10-6M NaCl are pinned as soon as evaporation starts, drops with lower salt concentration do evaporate in a constant contact angle mode. Aside from new, fundamental insights the findings are also relevant for a better understanding of the widespread phenomenon of corrosion initiated by sessile drops.

The coalescence behavior of two sessile drops that contain different chemical reactants (cerium nitrate and oxalic acid) and its impact on the formation of the solid precipitate (cerium oxalate) are investigated. With different liquids, the surface tension difference in the moment of drop-drop contact can induce a Marangoni flow. This flow can strongly influence the drop-drop coalescence behavior and thus, with reacting liquids, also the reaction and its products (through the liquid mixing). In our study we find three distinctly different coalescence behaviors ("barrier", "intermediate", "noncoalescence"), in contrast to only two behaviors that were observed in the case of nonreacting liquids. The amount of liquid mixing and thus the precipitation rate are very different for the three cases. The "intermediate" case, which exhibits the strongest mixing, has been studied in more detail. For high oxalic acid concentrations, mainly needle-like aggregates, and for low concentrations, mainly flower-like precipitate morphologies are obtained. In a transition range of the oxalic acid concentration, both morphologies can be produced. With the applied coalescence conditions, the different aggregate particles are arranged and fixed in a precipitate raft in a regular, periodic line pattern. This confirms the drop-drop coalescence configuration as a convection-reaction-diffusion system, which can have stationary as well as oscillatory behavior depending on the system parameters.

Unexpectedly, under certain conditions, sessile drops from different but completely miscible liquids do not always coalesce instantaneously upon contact: the drop bodies remain separated in a temporary state of noncoalescence, connected through a thin liquid bridge. Here we investigate the transition between the states of instantaneous coalescence and temporary noncoalescence. Experiments reveal that it is barely influenced by viscosities and absolute surface tensions. The main system control parameters for the transition are the arithmetic means of the three-phase angles, $\overline{\Theta}_a$ and the surface tension differences $\Delta\gamma$ between both liquids. These relevant parameters can be combined into a single system parameter, a speciffic Marangoni number $\widetilde{M} = 3\Delta\gamma / (2\overline{\gamma}\overline{\Theta}_a^2)$. This $\widetilde{M}$ universally characterizes the coalescence respectively transition behavior as a function of both, the physicochemical liquid properties and the shape of the liquid body in the contact region. The transition occurs at a certain threshold value $\widetilde{M}_t$ and is sharp within the experimental resolution. The experimentally observed threshold value of $\widetilde{M}_t \approx 2$ agrees quantitatively with values obtained by simulations assuming authentic real space data. The simulations indicate that the absolute value of $\widetilde{M}_t$ very weakly depends on the molecular diffusivity., Comment: 9 pages, 6 figures

Individual surface nanobubbles are visualized with nonintrusive optical interference-enhanced reflection microscopy, demonstrating that their formation is not a consequence of the hitherto used intrusive atomic force microscopy technique. We then use this new and fast technique to demonstrate that surface nanobubbles form in less than a few seconds after ethanol-water exchange, which is the standard procedure for their preparation, and examine how they react to temperature variations.

Capillarity always favors drop fusion. Nevertheless sessile drops from different but completely miscible liquids often do not fuse instantaneously upon contact. Rather, intermediate non-coalescence is observed. Two separate drop bodies, connected by a thin liquid neck move over the substrate. Supported by new experimental data a thin film hydrodynamic analysis of this state is presented. Presumably advective and diffusive volume fluxes in the neck region establish a localized and temporarily stable surface tension gradient. This induces a local surface (Marangoni) flow that stabilizes a traveling wave i.e., the observed moving twin drop configuration. The theoretical predictions are in excellent agreement with the experimental findings., 5 pages, 5 figures

Mixing of droplets with a body of different liquids shows an interesting behavior for small contact angles at solid substrate. The droplets interact with each other, a liquid exchange appears between the approaching drops owing to surface tension gradients at the droplets interface. But the drops remain separated for some seconds (up to minutes), until the merging into a single drop occurs (Langmuir 24, 6395 (2008)). We investigate this phenomenon using lubrication approximation and phase field approach. For both methods, 2D quantitative computer simulations for delayed fusion of perfectly miscible thin liquid films/droplets with low contact angles are reported.

Quantitative experimental data on the coalescence behavior of sessile droplets with different but completely miscible liquids are presented. The liquids consist of various aqueous mixtures of different nonvolatile diols and carbon acids with surface tensions ranging from 33 to 68 mN/m, contact angles between 9 degrees and 20 degrees, and viscosities from 1 to 12 cP. Two distinctly different coalescence behaviors, a delayed and a fast regime, are found. The transition between the two behaviors is remarkably sharp. It is found that the coalescence mode depends predominantly on the differences in the surface tensions of the two droplets. If the surface tension difference exceeds approximately 3 mN/m, the coalescence is delayed. If it is less, droplet fusion occurs fast. Within the investigated parameter space, the transition seems independent from droplet size, absolute values of the surface tensions, and viscosity. Certain aspects of the experimental findings are explained with the simple hydrodynamic model presented in a recent publication.

In this work, we study a surface reaction on Pd(111) crystals under ultra-high-vacuum conditions that can be modeled by two coupled reaction-diffusion equations. In the bistable regime, the reaction exhibits travelling fronts that can be observed experimentally using photo electron emission microscopy. The spatial profile of the fronts reveals a coverage-dependent diffusivity for one of the species. We propose a method to solve the nonlinear eigenvalue problem and compute the direction and the speed of the fronts based on a geometrical construction in phase-space. This method successfully captures the dependence of the speed on control parameters and diffusivities.

Rate measurements of the reaction CO + O --CO(2) on palladium(111) single crystal surfaces have been performed by means of mass spectroscopy under ultrahigh vacuum conditions. The total flux Phi of the impinging reactants CO and O(2) was held constant at 1 ML s(-1), whereas its CO fraction Y was varied between 0 (pure O(2)) and 1 (pure CO). The measurements have been performed for surface temperatures between 370 and 510 K and with a wide range of sampling times, evaluating the system parameter range for bistable behavior. Long-time measurements lasting several days proved the bistable behavior to result from two stable states rather than from slow processes not visible on usual experimental time scales. Pulselike modulations of the feed gas composition revealed the mechanisms confining the experimentally observed bistable range: the high CO fraction border of the bistability is given by the equistability condition of both states, whereas the other border is found to be associated with a saddle-node bifurcation in the corresponding system of reaction diffusion equations.

The splashing of liquid drops onto a solid surface is important for a wide range of applications, including combustion and spray coating. As the drop hits the solid surface, the liquid is ejected into a thin horizontal sheet expanding radially over the substrate. Above a critical impact velocity, the liquid sheet is forced to separate from the solid surface by the ambient air, and breaks up into smaller droplets. Despite many applications involving complex fluids, their effects on splashing remain mostly unexplored. Here we show that the splashing of a nanoparticle dispersion can be suppressed at higher impact velocities by the interactions of the nanoparticles with the solid surface. Although the dispersion drop first shows the classical transition from deposition to splashing when increasing the impact velocity, no splashing is observed above a second higher critical impact velocity. This result goes against the commonly accepted understanding of splashing, that a higher impact velocity should lead to even more pronounced splashing. Our findings open new possibilities to deposit large amount of complex liquids at high speeds. This journal is