In confined space, deviations from bulk structure and properties are expected due to additional thermodynamic variables. In particular, composition variations arising from surface interactions may lead to additional phases and altered phase transitions. Here, we introduce a non-invasive method for nanoscale composition mapping in confined liquids using the surface force balance (SFB). The method extends conventional SFB analysis from apex measurements to spatially resolved reconstruction of refractive index profiles within confined fluids. When multiple phases are present, the refractive index profiles provide direct access to the position and geometry of the nanoconfined fluid interfaces. We describe the interferogram analysis in detail and establish its range of validity through two model scenarios. First, measurements in air demonstrate the precision of the method and allow detection of a nanometric wetting capillary. Second, we analyse dynamic evaporation of a confined heptane droplet down to 0.1 pL volume. The method provides a time-resolved reconstruction of the meniscus geometry throughout the evaporation process. Although evaporation continuously drives the system out of equilibrium, the meniscus remains well described by a catenoidal geometry down to heights of approximately 80 nm. At smaller separations, systematic deviations from the catenoidal profile emerge, indicating a crossover from a surface tension-dominated regime to a confinement-dominated regime. Overall, we demonstrate composition profiling as a framework to analyse confinement-induced composition variations and to quantify interfacial thermodynamic effects at the nanoscale.
We probe the rheology of the model liquid octamethylcyclotetrasiloxane (OMCTS) confined into molecularly thin films, using a unique Surface Forces Apparatus allowing to explore a large range of shear rates and confinement. We thus show that OMCTS under increasing confinement exhibits the viscosity enhancement and the non-linear flow properties characteristic of a sheared supercooled liquid approaching its glass transition. Besides, we study the drainage of confined OMCTS via the propagation of "squeeze-out" fronts. The hydrodynamic model proposed by Becker and Mugele [Phys. Rev. Lett. {\bf 91}…
We investigate the effect of loading rate on drainage in molecularly thin films of a simple fluid made of quasi-spherical molecules (octamethylcyclotetrasiloxane, OMCTS). We find that (i) rapidly confined OMCTS retains its tendency to organize into layers parallel to the confining surfaces, and (ii) flow resistance in such layered films can be described by bulklike viscous forces if one accounts for the existence of one monolayer immobilized on each surfaces. The latter result is fully consistent with the recent work of Becker and Mugele, who reached a similar conclusion by analyzing the dynam…
Nanoconfinement can drastically change the behavior of liquids, puzzling us with counterintuitive properties. Moreover, it is relevant in applications, including decontamination and crystallization control. It still lacks a systematic analysis for fluids with different bulk properties. Here we fill this gap. We compare, by molecular dynamics simulations, three different liquids in a graphene slit pore: (A) A simple fluid, such as argon, described by a Lennard-Jones potential; (B) An anomalous fluid, such as a liquid metal, modeled with an isotropic core-softened potential; (C) Water, the proto…
We present Monte Carlo simulations of liquid-crystalline material confined to a nanoscopic slit-pore. The simulations are carried out under isothermal conditions in a specialized isostress ensemble in which N fluid molecules are exposed to a compressional stress acting on the fluid in directions parallel with the substrate planes. Fluid-fluid and fluid-substrate interactions are modelled as in our previous work [M. Greschek et al., Soft Matter, 2010, DOI:10.1039/B924417D). We study several anchoring mechanisms at the solid substrate by introducing an anchoring function (0<g(u)<1) that depends …
Spherical confinement can alter the properties of a dipolar fluid in several different ways. In an atomistic molecular dynamics simulation study of two different dipolar liquids (SPC/E water and a model Stockmayer fluid) confined to nanocavities of different radii ranging from Rc=1nm to 4nm, we find that the Kirkwood correlation factor remains surprisingly small in water, but not so in model Stockmayer liquid. This gives rise to an anomalous ultrafast relaxation of the total dipole moment time correlation function (DMTCF). The static dielectric constant of water under nanoconfinement (computed…
The flow of water confined to nanometer-sized pores is central to a wide range of subjects from biology to nanofluidic devices. Despite its importance, a clear picture about nanoscale fluid dynamics is yet to emerge. Here we measured dissipation in less than 20 nm thick water films and it was found to decrease for both wetting and non-wetting confining surfaces. The fitting of Carreau-Yasuda model of shear thinning to our measurements implies that flow is non-Newtonian and for wetting surfaces the no-slip boundary condition is valid. On the contrary, for non-wetting surfaces boundary slippage …
We analyse a binary mixture of colloidal parallel hard cylindrical particles with identical diameters but dissimilar lengths $L_1$ and $L_2$, with $s=L_2/L_1=3$, confined by two parallel hard walls in a planar slit-pore geometry, using a fundamental--measure density functional theory. This model presents nematic (N) and two types of smectic (S) phases, with first- and second-order N-S bulk transitions and S-S demixing, and surface behaviour at a single hard wall which includes complete wetting by the S phase mediated (or not) by an infinite number of surface-induced layering (SIL) transitions.…
Recent reports of surface forces across nanoconfined ionic liquids have revealed the existence of an anomalously long-ranged interaction apparently of electrostatic origin. Ionic liquids are viscous and therefore it is important to inspect rigorously whether the observed repulsive forces are indeed equilibrium forces or, rather, arise from the viscous force during drainage of the fluid between two confining surfaces. In this paper we present our direct measurements of surface forces between mica sheets approaching in the ionic liquid [C2C1Im][NTf2], exploring three orders of magnitude in appro…
The task of accurately locating fluid phase boundaries by means of computer simulation is hampered by problems associated with sampling both coexisting phases in a single simulation run. We explain the physical background to these problems and describe how they can be tackled using a synthesis of biased Monte Carlo sampling and histogram extrapolation methods, married to a standard fluid simulation algorithm. It is demonstrated that the combined approach provides a powerful method for tracing fluid phase boundaries.
We present here exact results for a one-dimensional gas, or fluid, of hard-sphere particles with attractive boundaries. The particles, which can exchange with a bulk reservoir, mediate an interaction between the boundaries. A two-dimensional lattice of such one-dimensional gas `columns' represents a discrete approximation of a three-dimensional gas of particles between two surfaces. The effective particle-mediated interaction potential of the boundaries, or surfaces, is calculated from the grand-canonical partition function of the one-dimensional gas of particles, which is an extension of the …
When a Coulombic fluid is confined between two parallel charged plates, an exact relation links the difference of ionic densities at contact with the plates, to the surface charges of these boundaries. It no longer applies when the boundaries are curved, and we work out how it generalizes when the fluid is confined between two concentric spheres (or cylinders), in two and in three space dimensions. The analysis is thus performed within the cell model picture. The generalized contact relation opens the possibility to derive new exact expressions, of particular interest in the regime of strong c…
Most biological fluids are viscoelastic, meaning that they have elastic properties in addition to the dissipative properties found in Newtonian fluids. Computational models can help us understand viscoelastic flow, but are often limited in how they deal with complex flow geometries and suspended particles. Here, we present a lattice Boltzmann solver for Oldroyd-B fluids that can handle arbitrarily-shaped fixed and moving boundary conditions, which makes it ideally suited for the simulation of confined colloidal suspensions. We validate our method using several standard rheological setups, and …
Using event-driven molecular dynamics simulations, we quantify how the self diffusivity of confined hard-sphere fluids depends on the nature of the confining boundaries. We explore systems with featureless confining boundaries that treat particle-boundary collisions in different ways and also various types of physically (i.e., geometrically) rough boundaries. We show that, for moderately dense fluids, the ratio of the self diffusivity of a rough wall system to that of an appropriate smooth-wall reference system is a linear function of the reciprocal wall separation, with the slope depending on…
Dynamically triangulated surface model is found to undergo a first-order crumpling transition between the smooth phase and a crumpled phase. Triangulated spheres are divided into compartmentalized domains, whose boundary bonds remain unflipped in the Monte Carlo simulations. The vertices can freely diffuse only inside the compartments, and they are prohibited from the free diffusion over the surface due to the domain boundaries. The violation of reparametrization invariance of the Hamiltonian is a reason for the existence of the long-range order in the fluid surface model.
We investigate the swim pressure exerted by non-chiral and chiral active particles on convex or concave circular boundaries. Active particles are modeled as non-interacting and non-aligning self-propelled Brownian particles. The convex and concave circular boundaries are used as models representing a fixed inclusion immersed in an active bath and a cavity (or container) enclosing the active particles, respectively. We first present a detailed analysis of the role of convex versus concave boundary curvature and of the chirality of active particles on their spatial distribution, chirality-induce…
In a recent letter, Buhot proposes that entropy driven phase-separation in hard-core binary mixtures is directly related to a bond-percolation transition. However, at least for binary hard-sphere mixtures, calculations based on an accurate approximation to g_{ll}(r) demonstrate that n_b varies widely along the phase-boundaries calculated directly by simulations, implying that bond-percolation is unrelated to the phase-separation in these systems.
Biological systems achieve precise control over ambient fluids through the self-organization of active protein structures including flagella, cilia, and cytoskeletal networks. In active structures individual proteins consume chemical energy to generate force and motion at molecular length scales. Self-organization of protein components enables the control and modulation of fluid flow fields on micron scales. The physical principles underlying the organization and control of active-matter driven fluid flows are poorly understood. Here, we apply an optically-controlled active-matter system compo…
The accumulation of small particles is analyzed in stationary flows through channels of variable width at small Reynolds number. The combined influence of pressure, viscous drag and thermal fluctuations is described by means of a Fokker-Planck equation for the particle density. It is shown that in the limit of vanishing particle size a uniform particle distribution is always approached in the long time limit. For extended spherical particles, conditions are specified that lead to inhomogeneous densities and consequently to particle accumulation and depletion. Hereby the boundary conditions for…
The active motion of phoretic colloids leads them to accumulate at boundaries and interfaces. Such an excess accumulation, with respect to their passive counterparts, makes the dynamics of phoretic colloids particularly sensitive to the presence of boundaries and pave new routes to externally control their single particle as well as collective behavior. Here we review some recent theoretical results about the dynamics of phoretic colloids close to and adsorbed at fluid interfaces in particular highlighting similarities and differences with respect to solid-fluid interfaces.
The classical Lorentz reciprocal theorem (LRT) was originally derived for slow viscous flows of incompressible Newtonian fluids under the isothermal condition. In the present work, we extend the LRT from simple to complex fluids with open or moving boundaries that maintain non-equilibrium stationary states. In complex fluids, the hydrodynamic flow is coupled with the evolution of internal degrees of freedom such as the solute concentration in two-phase binary fluids and the spin in micropolar fluids. The dynamics of complex fluids can be described by local conservation laws supplemented with l…
Boundary conditions dictate how fluids, including liquid crystals, flow when pumped through a channel. Can boundary conditions also be used to control internally driven active fluids that generate flows spontaneously? By using numerical simulations and stability analysis we explore how surface anchoring of active agents at the boundaries and substrate drag can be used to rectify coherent flow of an active polar fluid in a 2D channel. Upon increasing activity, a succession of dynamical states is obtained, from laminar flow to vortex arrays to eventual turbulence, that are controlled by the inte…
Thin fluid or elastic films and membranes are found in nature and technology, for instance, as confinements of living cells or in loudspeakers. When applying a net force, resulting flows in an unbounded two-dimensional incompressible low-Reynolds-number fluid or displacements in a two-dimensional linearly elastic solid seem to diverge logarithmically with the distance from the force center, which has led to some debate. Recently, we have demonstrated that such divergences cancel when the total (net) force vanishes. Here, we illustrate that, if a net force is present, the boundaries play a prom…
A wetting liquid is driven through a thin gap due to surface tension and when the gap boundaries are elastic, the liquid deforms the gap as it rises. But when the fluid boundaries are also permeable (or poroelastic), the liquid can permeate the boundaries as the fluid rises and change their properties, for example by swelling and softening, thereby altering the dynamics of the rise. In this paper, we study the dynamics of capillary rise between two poroelastic sheets to understand the effects of boundary permeability and softening. We find that if the bending rigidity of sheets is reduced, due…
Using computer simulations we explore how grain boundaries can be removed from three-dimensional colloidal crystals by doping with a small fraction of active colloids. We show that for sufficient self-propulsion, the system is driven into a crystal-fluid coexistence. In this phase separated regime, the active dopants become mobile and spontaneously gather at the grain boundaries. The resulting surface melting and recrystallization of domains result in the motion of the grain boundaries over time and lead to the formation of a large single crystal. However, when the self-propulsion is too low t…
Microorganisms are rarely found in Nature swimming freely in an unbounded fluid. Instead, they typically encounter other organisms, hard walls, or deformable boundaries such as free interfaces or membranes. Hydrodynamic interactions between the swimmer and nearby objects lead to many interesting phenomena, such as changes in swimming speed, tendencies to accumulate or turn, and coordinated flagellar beating. Inspired by this class of problems, we investigate locomotion of microorganisms near deformable boundaries. We calculate the speed of an infinitely long swimmer close to a flexible surface…
Confinement and wall effects are known to affect the kinematics and propulsive characteristics of swimming microorganisms. When a solid body is dragged through a viscous fluid at constant velocity, the presence of a wall increases fluid drag, and thus the net force required to maintain speed has to increase. In contrast, recent optical trapping experiments have revealed that the propulsive force generated by human spermatozoa is decreased by the presence of boundaries. Here, we use a series of simple models to analytically elucidate the propulsive effects of a solid boundary on passively actua…
We review recent dissipative particle dynamics (DPD) simulations of electrolyte flow in nanochannels. A method is presented by which the slip length $delta_B$ at the channel boundaries can be tuned systematically from negative to infinity by introducing suitably adjusted wall-fluid friction forces. Using this method, we study electroosmotic flow (EOF) in nanochannels for varying surface slip conditions and fluids of different ionic strength. Analytic expressions for the flow profiles are derived from the Stokes equation, which are in good agreement with the numerical results. Finally, we inves…
