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 long--ranged, power-like in the inverse distance but whose power sensitively depends on possible restrictions of the colloid degress of freedom. A nonzero line tension leads to changes in the magnitude but not in the functional form of the effective potential asymptotics.
A systematically designed study has been conducted to understand and clearly demarcate the degree of contribution by the constituting elements to the surface tension of nanocolloids. The effects of elements such as surfactants, particles and the combined effects of these on the interfacial tension of these complex fluids are studied employing pendant drop shape analysis method by fitting Young Laplace equation. Only particle has shown considerable increase in surface tension with particle concentration in a polar medium like DI water whereas only marginal effect particles on surface tension in…
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 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 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 …
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…
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…
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 re…
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）
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.
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.
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…
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 …
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 have developed a method to produce aqueous microdroplets in an oil phase, based on the periodic extraction of a pending droplet across the oil/air interface. This interface forms a capillary trap inside which a droplet can be captured and detached. This process is found to be capillary- based and quasi-static. The droplet size and emission rate are independently governed by the injected volume per cycle and the extraction frequency. We find that the minimum droplet diameter is close to the injection glass capillary diameter and that variations in surface tension moderately perturb the dropl…
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 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…
Thermally excited capillary waves at fluid interfaces in binary liquid mixtures exhibit simultaneously both density and composition fluctuations. Based on a density functional theory for inhomogeneous binary liquid mixtures we derive an effective wavelength dependent Hamiltonian for fluid interfaces in these systems beyond the standard capillary-wave model. Explicit expressions are obtained for the surface tension, the bending rigidities, and the coupling constants of compositional capillary waves in terms of the profiles of the two number densities characterizing the mixture. These results le…
Within the framework of a semi-microscopic interface displacement model we analyze the linear stability of sessile ridges and drops of a non-volatile liquid on a homogeneous, partially wet substrate, for both signs and arbitrary amplitudes of the three-phase contact line tension. Focusing on perturbations which correspond to deformations of the three-phase contact line, we find that drops are generally stable while ridges are subject only to the long-wavelength Rayleigh-Plateau instability leading to a breakup into droplets, in contrast to the predictions of capillary models which take line te…
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 …
The structure and the statistical fluctuations of interfaces between coexisting phases in the Asakura-Oosawa (AO) model for a colloid--polymer mixture are analyzed by extensive Monte Carlo simulations. We make use of a recently developed grand canonical cluster move with an additional constraint stabilizing the existence of two interfaces in the (rectangular) box that is simulated. Choosing very large systems, of size LxLxD with L=60 and D=120, measured in units of the colloid radius, the spectrum of capillary wave-type interfacial excitations is analyzed in detail. The local position of the i…
We consider the Asakura-Oosawa model of hard sphere colloids and ideal polymers in contact with a porous matrix modeled by immobilized configurations of hard spheres. For this ternary mixture a fundamental measure density functional theory is employed, where the matrix particles are quenched and the colloids and polymers are annealed, i.e. allowed to equilibrate. We study capillary condensation of the mixture in a tiny sample of matrix as well as demixing and the fluid-fluid interface inside a bulk matrix. Density profiles normal to the interface and surface tensions are calculated and compare…
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 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.
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…
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…
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…
We study the equilibrium shape of a liquid drop resting on top of a liquid surface, i.e., a floating lens. We consider the surface tension forces in non--wetting situations (negative spreading factor), as well as the effects of gravity. We obtain analytical expressions for the drop shape when gravity can be neglected. Perhaps surprisingly, when including gravity in the analysis, we find two different families of equilibrium solutions for the same set of physical parameters. These solutions correspond to drops whose center of mass is above or below the level of the external liquid surface. By m…
