Solid/liquid interfaces control various processes of technological relevance in the process industry and many fundamental physicochemical phenomena. This work examines the link between the atomistic description of mass transfer at solid/liquid interfaces out of equilibrium and the constitutive mass transfer equations typically used to model these processes at the mesoscale. In our analysis, we discuss the microscopic inconsistencies apparent in simplified models of mass transfer whenever non-idealities dominate the liquid phase in the proximity of solid/liquid interfaces. Using CμMD - a molecular simulation technique to investigate out-of-equilibrium, concentration-driven processes with pseudo open-boundary conditions - we outline a strategy to capture and quantify non-idealities induced by specific interactions between the solid surface and molecules in the fluid phase. We demonstrate our approach by studying electrolyte solutions in technologically important, multi-component systems in which introducing a solid/liquid interface induces substantial deviations in the composition and electrochemical properties compared to the fluid phase bulk. To this aim, we analyse NaCl(aq) solutions in contact with i) the graphite basal surface and ii) {100} NaCl(s) crystalline surfaces. We uncover the tendency of the sodium cation to preferentially adsorb at the surfaces considered, which induces local violations of electroneutrality that leads to the emergence of an electric potential in the fluid phase at the solid/liquid interface.
Connecting the different length scales of characterization is an important, but often very tedious task for soft matter systems. Here we carry out such a procedure for the theoretical description of anisotropic uniaxial magnetic gels. The so-far undetermined material parameters in a symmetry-based macroscopic hydrodynamic-like description are determined starting from a simplified mesoscopic particle-resolved model. This mesoscopic approach considers chain-like aggregates of magnetic particles embedded in an elastic matrix. Our procedure provides an illustrative background to the formal symmetr…
Ferrogels and magnetic elastomers differentiate themselves from other materials by their unique capability of reversibly changing shape and mechanical properties under the influence of an external magnetic field. A crucial issue in the study of these outstanding materials is the interaction between the mesoscopic magnetic particles and the polymer matrix in which they are embedded. Here we analyze interactions between two such particles connected by a polymer chain, a situation representative for particle-crosslinked magnetic gels. To make a first step towards a scale-bridging description of t…
A simulation model is presented, comprising elastic spheres with a short range attraction. Besides conservative forces, radial- and shear friction, and radial noise are added. The model can be used to simulate colloids, granular solids and powders, and the parameters may be related to experimental systems via the range of attraction and the adhesion energy. The model shares the simplicity and speed of Dissipative Particle Dynamics (DPD), yet the predictions are rather non-trivial. We demonstrate that the model predicts the correct scaling relations for fracture of granular solids, and we prese…
Quantifying mechanical disorder in solids, either disordered crystals or glassy solids, and understanding its range of variability are of prime importance, e.g.~for discovering structure-properties relations. The bounds on the degree of mechanical fluctuations in disordered solids and how those depend on solids formation history remain unknown. Here, we study a broadly applicable quantifier of mesoscopic mechanical disorder $χ$, defined via the dimensionless fluctuations of the shear modulus, over a wide variety of disordered computer solids and upon varying different control parameters. $χ$ i…
We present a description of granular dynamics based on the idea of differentiation between fluid and solid components. First, we construct a model of completely fluidized phase. Then we discuss a shear surface motion on the boundary of the bulk solid phase, induced by a moving wall. Our results include the thickness dependence of the velocity of a developed avalanche, density and velocity profiles in granular Couette flow experiment.
Soft, amorphous solids such as tissues, foams, and emulsions are composed of deformable particles. However, the effect of single-particle deformability on the collective behavior of soft solids is still poorly understood. We perform numerical simulations of two-dimensional jammed packings of explicitly deformable particles to study the mechanical response of model soft solids. We find that jammed packings of deformable particles with excess shape degrees of freedom possess low-frequency quartic vibrational modes that stabilize the packings even though they possess fewer interparticle contacts …
We study a mesoscopic model for the flow of amorphous solids. The model is based on the key features identified at the microscopic level, namely peri- ods of elastic deformation interspersed with localised rearrangements of parti- cles that induce long-range elastic deformation. These long-range deformations are derived following a continuum mechanics approach, in the presence of solid boundaries, and are included in full in the model. Indeed, they mediate spatial cooperativity in the flow, whereby a localised rearrangement may lead a distant region to yield. In particular, we simulate a chann…
Clogging can occur whenever a suspension of particles flows through a confined system. The formation of clogs is often correlated to a reduction in the cross-section of the channel. In this study, we consider the clogging by bridging, i.e., through the formation of a stable arch of particles at a constriction that hinders the transport of particles downstream of the clog. To characterize the role of the volume fraction of the suspension on the clogging dynamics, we study the flow of particulate suspensions through 3D-printed millifluidic devices. We systematically characterize the bridging of …
We present a model based on the lattice Boltzmann equation that is suitable for the simulation of dynamic wetting. The model is capable of exhibiting fundamental interfacial phenomena such as weak adsorption of fluid on the solid substrate and the presence of a thin surface film within which a disjoining pressure acts. Dynamics in this surface film, tightly coupled with hydrodynamics in the fluid bulk, determine macroscopic properties of primary interest: the hydrodynamic slip; the equilibrium contact angle; and the static and dynamic hysteresis of the contact angles. The pseudo- potentials em…
By solving the Young Laplace equation of capillary hydrostatics one can accurately determine equilibrium shapes of droplets on relatively smooth solid surfaces. The solution, however of the Young Laplace equation becomes tricky when a droplet is sitting on a geometrically patterned surface and multiple, and unknown a priori, three phase contact lines have not been accounted for, since air pockets are trapped beneath the liquid droplet. In this work, we propose an augmented Young-Laplace equation, in which a unified formulation for the liquid/vapor and liquid/solid interfaces is adopted, incorp…
We present a thermodynamically consistent mesoscopic model of protein adsorption at liquid-solid interfaces. First describing the equilibrium state under varying protein concentration of the solution and binding conditions, we predict a non-trivial (non- monotonic) dependence of the experimentally observable properties of the adsorbed layer (such as the surface density and surface coverage) on these parameters. We subsequently proceed to develop a dynamical model consistent with the equilibrium description, which qualitatively reproduces known experimental phenomena and offers a promising way …
In this work we report studies of nitrogen adsorption and desorption onto solid surfaces using computer simulations of the three dimensional Ising model, for systems with complex porous structures at the mesoscopic and microscopic levels. A hysteresis cycle between the adsorption and desorption processes appears and we find that its characteristics are dependent on the geometry of the pore and on the strength of the surface fluid interaction. We obtained also an average adsorption isotherm, which represents a combination of differently shaped pores, and shows robust jumps at certain values of …
We show that a viscous liquid confined between two low thermal conductive surfaces (Al2O3) emit a thermal response upon applying a low frequency (Hz) shear excitation. Hot and cold thermal waves are observed in situ at atmospheric pressure and room temperature, in polypropylene glycol layers of various thicknesses ranging from 100 microns up to 340 microns, upon applying a mechanical oscillatory shear strain. The observed thermal effects, synchronous with the mechanical excitation, are inconsistent with a homogeneous viscous flow. It indicates that mesoscopic liquids are able to (partly) conve…
The contribution to the free energy for a film of liquid of thickness $h$ on a solid surface, due to the interactions between the solid-liquid and liquid-gas interfaces is given by the binding potential, $g(h)$. The precise form of $g(h)$ determines whether or not the liquid wets the surface. Note that differentiating $g(h)$ gives the Derjaguin or disjoining pressure. We develop a microscopic density functional theory (DFT) based method for calculating $g(h)$, allowing us to relate the form of $g(h)$ to the nature of the molecular interactions in the system. We present results based on using a…
Protein folding, peptide aggregation and crystallization, as well as adsorption of molecules on soft or solid substrates have an essential feature in common: In all these processes, structure formation is guided by a collective, cooperative behavior of the molecular subunits lining up to build chainlike macromolecules. Proteins experience conformational transitions related to thermodynamic phase transitions. For chains of finite length, an important difference of crossovers between conformational (pseudo)phases is, however, that these transitions are typically rather smooth processes, i.e., th…
The spontaneous spreading of non-volatile liquid droplets on solid substrates poses a classic problem in the context of wetting phenomena. It is well known that the spreading of a macroscopic droplet is in many cases accompanied by a thin film of macroscopic lateral extent, the so-called precursor film, which emanates from the three-phase contact line region and spreads ahead of the latter with a much higher speed. Such films have been usually associated with liquid-on-solid systems, but in the last decade similar films have been reported to occur in solid-on-solid systems. While the situation…
We review the recent literature on the simulation of the structure and deformation of amorphous glasses, including oxide and metallic glasses. We consider simulations at different length and time scales. At the nanometer scale, we review studies based on atomistic simulations, with a particular emphasis on the role of the potential energy landscape and of the temperature. At the micrometer scale, we present the different mesoscopic models of amorphous plasticity and show the relation between shear banding and the type of disorder and correlations (e.g. elastic) included in the models. At the m…
Friction in liquids arises from conservative forces between molecules and atoms. Although the hydrodynamics at the nanoscale is subject of intense research and despite the enormous interest in the non-Markovian dynamics of single molecules and solutes, the onset of friction from the atomistic scale so far could not be demonstrated. Here, we fill this gap based on frequency-resolved friction data from high-precision simulations of three prototypical liquids, including water. Combining with rigorous theoretical arguments, we show that friction in liquids emerges abruptly at a characteristic freq…
For a film of liquid on a solid surface, the binding potential $g(h)$ gives the free energy as a function of the film thickness $h$ and also the closely related structural disjoining pressure $Π= - \partial g / \partial h$. The wetting behaviour of the liquid is encoded in the binding potential and the equilibrium film thickness corresponds to the value at the minimum of $g(h)$. Here, the method we developed in [J. Chem. Phys. 142, 074702 (2015)], and applied with a simple discrete lattice-gas model, is used with continuum density functional theory (DFT) to calculate the binding potential for …
The ability to control wettability is important for a wide range of technological applications in which precise microfluidic handling is required. It is known that predesigned roughness at a micro- or nano- scale enhances the wetting properties of solid materials giving rise to super-hydrophobic or super-hydrophilic behavior. In this work, we study the dependence of the apparent wettability of a stripe-patterned solid surface on the stripe geometry, utilizing systems level analysis and mesoscopic Lattice-Boltzmann (LB) simulations. Through the computation of both stable and unstable states we …
Liquid water has anomalous liquid properties, such as its density maximum at 4\degree C. An attempt at theoretical explanation proposes a liquid-liquid phase transition line in the supercooled liquid state, with coexisting low-density (LDL) and high-density (HDL) liquid states. This line terminates at a critical point. It is assumed that the LDL state possesses mesoscopic tetrahedral structures that give it solid-like properties, while the HDL is a regular random liquid. But the short-lived nature of these solid-like structures make them difficult to detect directly. We take a thermodynamic ap…
