Many textbooks dealing with surface tension favor the thermodynamic approach (minimization of some thermodynamic potential such as free energy) over the mechanical approach (balance of forces) to describe capillary phenomena, stating that the latter is flawed and misleading. Yet, mechanical approach is more intuitive for students than free energy minimization, and does not require any knowledge of thermodynamics. In this paper we show that capillary phenomena can be unmistakably described using the mechanical approach, as long as the system on which the forces act is properly defined. After reminding the microscopic origin of a tangential tensile force at the interface, we derive the Young-Dupr{é} equation, emphasizing that this relation should be interpreted as an interface condition at the contact line, rather than a force balance equation. This correct interpretation avoids misidentification of capillary forces acting on a given system. Moreover, we show that a reliable method to correctly identify the acting forces is to define a control volume that does not embed any contact line on its surface. Finally, as an illustration of this method, we apply the mechanical approach in a variety of ways on a classic example: the derivation of the equilibrium height of capillary rise (Jurin's law).
The surface free energy, or surface tension, of a liquid interface gives rise to a pressure jump when the interface is curved. Here we show that a similar capillary pressure arises at the interface of soft solids. We present experimental evidence that immersion of a thin elastomeric wire into a liquid induces a substantial elastic compression due to the solid capillary pressure at the bottom. We quantitatively determine the effective surface tension from the elastic displacement field, and find a value comparable to the liquid-vapor surface tension. Most importantly, these results also reveal …
The temperature dependence of surface tension γ(T) at liquid gallium is studied theoretically and experimentally using light scattering from capillary waves. The theoretical model based on the Gibbs thermodynamics relates the temperature derivative of γto the surface excess entropy -ΔS. Although capillary waves contribute to the surface entropy with a positive sign the effect of dipole layer on ΔS is negative. Experimental data collected at a free Ga surface in the temperature range from 30 to 160 C show that the temperature derivative of the tension changes sign near 100 C.
The effect of line tension on the axisymmetric nanoscale capillary bridge between two identical substrates with convex, concave and flat geometry at the liquid-vapor equilibrium is theoretically studied. The modified Young's equation for the contact angle, which takes into account the effect of line tension is derived on a general axisymmetric curved surface using the variational method. Even without the effect of line tension, the parameter space where the bridge can exist is limited simply by the geometry of substrates. The modified Young's equation further restricts the space where the brid…
We analyze the effective potential for nanoparticles trapped at a fluid interface within a simple model which incorporates surface and line tensions as well as a thermal average over interface fluctuations (capillary waves). For a single colloid, a reduced steepness of the potential well hindering movements out of the interface plane compared to rigid interface models is observed, and an instability of the capillary wave partition sum in case of negative line tensions is pointed out. For two colloids, averaging over the capillary waves leads to an effective Casimir--type interaction which is l…
In passive fluid-fluid phase separation, a single interfacial tension sets both the capillary fluctuations of the interface and the rate of Ostwald ripening. We show that these phenomena are governed by two different tensions in active systems, and compute the capillary tension $σ_{cw}$ which sets the relaxation rate of interfacial fluctuations in accordance with capillary wave theory. We discover that strong enough activity can cause negative $σ_{cw}$. In this regime, depending on the global composition, the system self-organizes, either into a microphase-separated state in which coalescence …
Our understanding of both structure and dynamics of adsorbed liquids heavily relies on the capillary wave Hamiltonian, but a thorough test of this model is still lacking. Here we study the capillary wave fluctuations of a liquid film with short range forces adsorbed on a solid exhibiting van der Waals interactions. We show for the first time that the measured capillary wave spectrum right above the first order wetting transition provides an interface potential consistent with independent calculations from thermodynamic integration. However, the surface tension exhibits an oscillatory film thic…
We study the interaction between capillary forces and deformation in the context of a deformable capillary adhesive: a clamped, tense membrane is adhered to a rigid substrate by the surface tension of a liquid droplet. We find that the equilibrium adhesive force for this elastocapillary adhesive is significantly enhanced in comparison to the capillary adhesion between rigid plates. In particular, the equilibrium adhesion force is orders of magnitude greater when the membrane is sufficiently deformed to contact the substrate. From a dynamic perspective, however, the formation of a fluid-filled …
We present a new finite deformation, dynamic finite element model that incorporates surface tension to capture elastocapillary effects on the electromechanical deformation of dielectric elastomers. We demonstrate the significant effect that surface tension can have on the deformation of dielectric elastomers through three numerical examples: (1) surface tension effects on the deformation of single finite elements with homogeneous and inhomogeneous boundary conditions; (2) surface tension effects on instabilities in constrained dielectric elastomer films, and (3) surface tension effects on burs…
In this paper we review simulation and experimental studies of thermal capillary wave fluctuations as an ideal means for probing the underlying disjoining pressure and surface tensions, and more generally, fine details of the Interfacial Hamiltonian Model. We discuss recent simulation results that reveal a film-height-dependent surface tension not accounted for in the classical Interfacial Hamiltonian Model. We show how this observation may be explained bottom-up from sound principles of statistical thermodynamics and discuss some of its implications.
Spontaneous currents determine capillary rise in active matter
Center for Soft Condensed Matter Physics and Interdisciplinary Research & School of Physical Science and Technology, Soochow University（苏州大学物理科学与技术学院软凝聚态物理与交叉研究中心）
The dependence of the surface tension on a nanodrop radius is important for the new-phase formation process. It is demonstrated that the famous Tolman formula is not unique and the size-dependence of the surface tension can distinct for different systems. The analysis is based on a relationship between the surface tension and disjoining pressure in nanodrops. It is shown that the van der Waals interactions do not affect the new-phase formation thermodynamics since the effect of the disjoining pressure and size-dependent component of the surface tension cancel each other.
An adhesively stressed thin film of a soft hydrogel confined between two rigid flat substrates auto-roughens with its dominant wavelength exhibiting pronounced dependence on the film thickness (H). A linear stability analysis confirmed that this long wavelength instability (~7H) is due to an elasto-capillary effect, the implementation of which required direct measurements of the surface tension and the elasticity of the gel. The surface tension of the gel was estimated from the fundamental spherical harmonic of a hemispherical cap of the gel that was excited by an external noise. The shear mod…
A continuum-space bead-spring model is used to study the phase behavior of binary blends of homopolymers and the structure of the interface between the two immiscible phases. The structure of the interface is investigated as a function of immiscibility, chain length, and system size. Capillary waves are observed and their measurement allows us to determine the surface tension $γ$. We propose a more universal method of measuring the interfacial width in terms of second moments of the different contributions to the first derivative of the interfacial profile. Predictions of this method are direc…
We present experiments to study the relaxation of a nano-scale cylindrical perturbation at one of the two interfaces of a thin viscous free-standing polymeric film. Driven by capillarity, the film flows and evolves towards equilibrium by first symmetrizing the perturbation between the two interfaces, and eventually broadening the perturbation. A full-Stokes hydrodynamic model is presented which accounts for both the vertical and lateral flows, and which highlights the symmetry in the system. The symmetrization time is found to depend on the membrane thickness, surface tension, and viscosity.
A paperclip can float on water. Drops of mercury refuse to spread on a surface. These capillary phenomena are macroscopic manifestations of molecular interactions, and can be explained in terms of surface tension. For students, the concept of surface tension is quite challenging since the microscopic intuition is often in conflict with the common macroscopic interpretations. In this paper we address a number of conceptual questions that are often encountered when teaching capillarity. By answering these questions we provide a perspective that reconciles the macroscopic viewpoints, from thermod…
We derive a non-linear one-dimensional (1d) strain gradient model predicting the necking of soft elastic cylinders driven by surface tension, starting from 3d finite-strain elasticity. It is asymptotically correct: the microscopic displacement is identified by an energy method. The 1d model can predict the bifurcations occurring in the solutions of the 3d elasticity problem when the surface tension is increased, leading to a localization phenomenon akin to phase separation. Comparisons with finite-element simulations reveal that the 1d model resolves the interface separating two phases accurat…
Capillary forces are involved in a variety of natural phenomena, ranging from droplet breakup to the physics of clouds. The forces from surface tension can also be exploited in industrial application provided the length scales involved are small enough. Recent experimental investigations showed how to take advantage of capillarity to fold planar structures into three-dimensional configurations by selectively melting polymeric hinges joining otherwise rigid shapes. In this paper we use theoretical calculations to quantify the role of geometry and fluid wetting on the final folded state. Conside…
Van der Waals-Zeeman Institute, Institute of Physics, University of Amsterdam（阿姆斯特丹大学范德瓦尔斯-泽曼研究所物理学院）；Department of Applied Mathematics and Theoretical Physics, University of Cambridge（剑桥大学应用数学与理论物理系）
Molecular dynamics simulations are used to study capillary adhesion from a nanometer scale liquid bridge between two parallel flat solid surfaces. The capillary force and the meniscus shape of the bridge are computed as the separation between the solid surfaces is varied. Macroscopic theory predicts the meniscus shape and the contribution of liquid/vapor interfacial tension to the capillary force quite accurately for separations as small as 2 or 3 molecular diameters (1-2nm). However the total capillary force differs in sign and magnitude from macroscopic theory for separations less than about…
We provide an extension to previous analysis of the localised beading instability of soft slender tubes under surface tension and axial stretching. The primary questions pondered here are: under what loading conditions, if any, can bifurcation into circumferential buckling modes occur, and do such solutions dominate localisation and periodic axial modes? Three distinct boundary conditions are considered; in case 1 the tube's curved surfaces are traction free and under surface tension, whilst in cases 2 and 3 the inner and outer surfaces (respectively) are fixed to prevent radial displacement a…
Recent studies of elasto-capillary phenomena have triggered interest in a basic variant of the classical Young-Laplace-Dupré (YLD) problem: The capillary interaction between a liquid drop and a thin solid sheet of low bending stiffness. Here, we consider a two-dimensional model where the sheet is subjected to an external tensile load and the drop is characterized by a well-defined Young's contact angle $θ_Y$. Using a combination of numerical, variational, and asymptotic techniques, we discuss wetting as a function of the applied tension. We find that, for wettable surfaces with $0<θ_Y<π/2$, co…
Condensate-mediated shape transformations of cellular membranes by capillary forces
University of Cologne（科隆大学）；Humboldt University of Berlin（柏林洪堡大学）；University of Warwick（华威大学）；Leibniz-Forschungsinstitut für Molekulare Pharmakologie（莱布尼兹分子药理学研究所）；Institute for Integrated Research, Institute of Science Tokyo（东京科学大学综合研究学院）；Graduate School and Faculty of Medicine, The University of Tokyo（东京大学医学部及研究生院）；Bilkent University（比尔肯特大学）
Molecular dynamics simulations are used to study the capillary adhesion from a nonvolatile liquid meniscus between a spherical tip and a flat substrate. The atomic structure of the tip, the tip radius, the contact angles of the liquid on the two surfaces, and the volume of the liquid bridge are varied. The capillary force between the tip and substrate is calculated as a function of their separation h. The force agrees with continuum predictions for h down to ~ 5 to 10nm. At smaller h, the force tends to be less attractive than predicted and has strong oscillations. This oscillatory component o…
In this paper we try to work out in detail the implications of a microscopic theory for capillary waves under the assumption that the density is given along lines normal to the interface. Our study provides interface Hamiltonians for adsorbed films in a variety of systems, and shows that the corrections to the classical capillary wave spectrum are of the same order as the surface tension. This implies that it is possible, at least in principle, to measure them in x-ray surface scattering experiments. Interestingly, our study also sheds some light on the nature of the liquid-vapor interface in …
We investigate the capillary force that applies on a tilted cylinder as a function of its dipping angle i, using a home-built tilting Atomic Force Microscope (AFM) with custom made probes. A micrometric-size rod is glued at the end of an AFM cantilever of known stiffness, whose deflection is measured when the cylindrical probe is dipped in and retracted from reference liquids. We show that a torque correction is necessary to understand the measured deflection. The results are compatible with a vertical capillary force varying as 1/ cos i, in agreement with a recent theoretical prediction. We a…
An essential element in the web-trap architecture, the capture silk spun by ecribellate orb spiders consists of glue droplets sitting astride a silk filament. Mechanically this thread presents a mixed solid-liquid behavior unknown to date. Under extension, capture silk behaves as a particularly stretchy solid, owing to its molecular nanosprings, but it totally switches behavior in compression to now become liquid-like: It shrinks with no apparent limit while exerting a constant tension. Here, we unravel the physics underpinning the unique behavior of this "liquid wire" and demonstrate that its…
Motivated by the still ongoing debate about the various possible meanings of the term surface tension of bilayer membranes, we present here a detailed discussion that explains the differences between the "intrinsic", "renormalized", and "mechanical" tensions. We use analytical considerations and computer simulations to show that the membrane spectrum of thermal fluctuations is governed by the mechanical and not the intrinsic tension. Our study highlights the fact that the commonly used quadratic approximation of Helfrich effective Hamiltonian is not rotationally invariant. We demonstrate that …
A numerical study of multi-phase granular materials based upon micro-mechanical modelling is proposed. Discrete element simulations are used to investigate capillary induced effects on the friction properties of a granular assembly in the pendular regime. Capillary forces are described at the local scale through the Young-Laplace equation and are superimposed to the standard dry particle interaction usually well simulated through an elastic-plastic relationship. Both effects of the pressure difference between liquid and gas phases and of the surface tension at the interface are integrated into…
Nematic liquid crystals at rough and fluctuating interfaces are analyzed within the Frank elastic theory and the Landau-de Gennes theory. We study specifically interfaces that locally favor planar anchoring. In the first part we reconsider the phenomenon of Berreman anchoring on fixed rough surfaces, and derive new simple expressions for the corresponding azimuthal anchoring energy. Surprisingly, we find that for strongly aligning surfaces, it depends only on the geometrical surface anisotropy and the bulk elastic constants, and not on the precise values of the chemical surface parameters. In …
We present a monolithic mechanical metamaterial comprising a periodic arrangement of snapping units with tunable tensile behavior. Under tension, the metamaterial undergoes a large extension caused by sequential snap-through instabilities, and exhibits a pattern switch from an undeformed wavy-shape to a diamond configuration. By means of experiments performed on 3D printed prototypes, numerical simulations and theoretical modeling, we demonstrate how the snapping architecture can be tuned to generate a range of nonlinear mechanical responses including monotonic, S-shaped, plateau and non-monot…
Surface tension-driven flow techniques have recently emerged as an efficient means of shedding light into the rheology of thin polymer films. Motivated by experimental and theoretical approaches in films bearing a varying surface topography, we present results on the capillary relaxation of a square pattern at the free surface of a viscoelastic polymer film, using molecular dynamics simulations of a coarse-grained polymer model. Height profiles are monitored as a function of time after heating the system above its glass-transition temperature and their time dependence is fitted to the theory o…
The effective capillary interaction potentials for small colloidal particles trapped at the surface of liquid droplets are calculated analytically. Pair potentials between capillary monopoles and dipoles, corresponding to particles floating on a droplet with a fixed center of mass and subjected to external forces and torques, respectively, exhibit a repulsion at large angular separations and an attraction at smaller separations, with the latter resembling the typical behavior for flat interfaces. This change of character is not observed for quadrupoles, corresponding to free particles on a mec…
Small scale contact between a soft, liquid-coated layer and a stiff surface is common in many situations, from synovial fluid on articular cartilage to adhesives in humid environments. Moreover, many model studies on soft adhesive contacts are conducted with soft silicone elastomers, which possess uncrosslinked liquid molecules (i.e. silicone oil) when the modulus is low. We investigate how the thickness of a silicone oil layer on a soft substrate relates to the indentation depth of glass microspheres in contact with crosslinked PDMS, which have a modulus of <10 kPa. The particles indent into …
I study how the contact area and the work of adhesion, between two elastic solids with randomly rough surfaces, depend on the relative humidity. The surfaces are assumed to be hydrophilic, and capillary bridges form at the interface between the solids. For elastically hard solids with relative smooth surfaces, the area of real contact and therefore also the sliding friction, are maximal when there is just enough liquid to fill out the interfacial space between the solids, which typically occurs for $d_{\rm K} \approx 3 h_{\rm rms}$, where $d_{\rm K}$ is the height of the capillary bridge and $…
In order to characterize very weak adhesive surfaces, we have developed a quantitative test inspired by the Johnson, Kendall, and Roberts adhesion test for soft adhesives, which relies on the formation and then the rupture of a capillary bridge between the surface to be tested and a liquid bath. Both the shape and the kinetics of breakage of the capillary bridge for various coatings put into contact with liquids of various viscosities and surface tensions have been studied. Several pull off regimes can be distinguished. For low pull off velocities, a quasi-static regime is observed, well descr…
This work reports an innovative humidity driven actuation concept based on Bangham effect using simple nanoporous sol-gel silica thin films as humidity responsive materials. Bilayer shaped actuators, consisting on a humidity-sensitive active nanostructured silica film deposited on a polymeric substrate (Kapton) were demonstrated as an original mean to convert water molecule adsorption and capillary condensation in useable mechanical work. Reversible silica surface energy modifications by water adsorption and the energy produced by the rigid silica film contraction, induced by water capillary c…
One of the most noticeable collective motion of non-cohesive granular matter is clustering under certain conditions. In particular, when a quasi-two-dimensional monolayer of mono-disperse non-cohesive particles is vertically vibrated, a solid-liquid-like transition occurs when the driving amplitude exceeds a critical value. Here, the physical mechanism underlying particle clustering relies on the strong interactions mediated by grain collisions, rather than on grain-grain cohesive forces. In average, the solid cluster resembles a drop, with a striking circular shape. We experimentally investig…
Attempts to extend the capillary-wave theory of fluid interfacial fluctuations to microscopic wavelengths, by introducing an effective wave-vector ($q$) dependent surface tension $σ_\text{eff}(q)$, have encountered difficulties. There is no consensus as to even the shape of $σ_\text{eff}(q)$. By analysing a simple density functional model of the liquid-gas interface, we identify different schemes for separating microscopic observables into background and interfacial contributions. In order for the backgrounds of the density-density correlation function and local structure factor to have a cons…
The mechanical properties of collagen fibrils depend on the amount and the distribution of water molecules within the fibrils. Here, we use atomic force microscopy (AFM) to study the effect of hydration on the viscoelastic properties of reconstituted type I collagen fibrils in air with controlled relative humidity. With the same AFM tip, we investigate the same area of a collagen fibril with two different force spectroscopy methods: force-distance (FD) and amplitude-phase-distance (APD) measurements. This allows us to separate the contributions of the fibril's viscoelastic response and the cap…
A droplet of surfactant spreading on an ultrasoft ($E \lesssim 100$ Pa) gel substrate will produce capillary fractures at the gel surface; these fractures originate at the contact-line and propagate outwards in a starburst pattern. There is an inherent variability in both the number of fractures formed and the time delay before fractures form. In the regime where single fractures form, we observe a Weibull-like distribution of delay times, consistent with a thermally-activated process. The shape parameter is close to 1 for softer gels (a Poisson process), and larger for stiffer gels (indicativ…
Deformation of a fluid interface caused by the presence of objects at the interface can lead to large lateral forces between the objects. We explore these fluid-mediated attractive force between partially submerged vertical cylinders. Forces are experimentally measured by slowly separating cylinder pairs and cylinder triplets after capillary rise is initially established for cylinders in contact. For cylinder pairs, numerical computations and a theoretical model are found to be in good agreement with measurements. The model provides insight into the relative importance of the contributions to …
This work introduces a methodology for the statistical mechanical analysis of polymeric chains under tension controlled by optical or magnetic tweezers at thermal equilibrium with an embedding fluid medium. The response of single bonds between monomers or of entire groups of monomers to tension is governed by the activation of statistically interacting particles representing quanta of extension or contraction. This method of analysis is capable of describing thermal unbending of the freely jointed or wormlike chain kind, linear or nonlinear contour elasticity, and structural transformations in…
