Chemical gradients are ubiquitous in porous media flows, from tidal salt gradients in aquifers to irrigation-driven gradients in soils and ionic gradients from metabolic activity in tissues. Although chemical gradients are known to drive diffusiophoretic migration of colloids, these nonequilibrium forces have largely been ignored in porous media flows. Under typical subsurface conditions, flow velocities within preferential pathways exceed phoretic velocities by orders of magnitude, suggesting that diffusiophoresis would be limited to stagnant pockets. Here, using microfluidic experiments, numerical simulations, and theoretical modeling, we show that even moderate solute gradients, typical of natural mixing, can markedly alter colloid transport. We uncover a previously overlooked effect: cross-streamline phoretic migration within preferential flow pathways, which changes macroscopic dispersion by orders of magnitude and suppresses the impact of geometric disorder on transport. Our findings challenge classical models of colloid transport, highlighting the broad implications of solute gradients for technological, biomedical, and environmental applications.
Diffusiophoretic transport of colloids in pressure-driven channel flow is commonly analysed in two limits: an early-time regime in which the solute field is fully two-dimensional, and a late-time macrotransport regime in which cross-sectional homogenization leaves only a weak axial bias on the particles. For colloids, however, many experiments operate in the broad intermediate window a^2/D_s≪ t≪ a^2/D_p: the solute has entered the Taylor-dispersion regime, but the particles remain effectively non-diffusive across the gap. We show that the Taylor-dispersed solute retains a residual transverse gradient that is Péclet-enhanced relative to the axial gradient and decays only as t^-1/2. This gradient is small in the solute concentration but large enough in ∇ln c to drive cross-streamline migration of colloids. Attractive fronts (c_f>c_i) move particles toward faster centreline streamlines, sharpening the leading edge and accelerating removal; repulsive fronts (c_f<c_i) move particles toward slower near-wall streamlines, broadening the trailing edge and delaying removal. Direct simulations and microfluidic experiments confirm these front-sharpening and front-broadening dynamics. An asymptotic Taylor-regime solute field, combined with a non-diffusive trajectory model, captures the observed front geometries, density profiles, and removal dynamics. The results show that Taylor-dispersed solute fields can remain dynamically two-dimensional for particles, even when their concentration is nearly cross-sectionally uniform.
Predicting and controlling the transport of colloids in porous media is essential for applications ranging from contaminant remediation to drug delivery. In these complex environments, solute gradients are ubiquitous and could drive diffusiophoretic particle migration, yet their impact on macroscopic colloid dispersion remains poorly understood. Here we combine experiments and simulations to quantify how diffusiophoresis alters the spreading of a colloidal blob in a 2D ordered/disordered porous medium. A joint blob of colloids and salt at high concentration is introduced into a medium filled with salt at low concentration and advected by a background flow. Intuition suggests that when colloids are attracted toward or repelled from the solute-rich blob, dispersion should be suppressed or enhanced, respectively. Instead, we observe the opposite trend: longitudinal dispersion is enhanced in the attractive case, whereas dispersion is suppressed in the repulsive case. Numerical simulations reveal that this striking reversal arises from diffusiophoretic exchange of particles between slow and fast streamlines, which we capture using a minimal two-layer model of coupled fast and slow plug flows. Finally, we probe how geometric disorder in the medium modulates this mechanism. Our results demonstrate that diffusiophoresis can strongly modulate macroscopic dispersion of colloids in porous media with implications for transport in subsurface and biological environments.
Predicting and controlling the transport of colloids in porous media is essential for applications ranging from contaminant remediation to drug delivery. In these complex environments, solute gradients are ubiquitous and could drive diffusiophoretic particle migration, yet their impact on macroscopic colloid dispersion remains poorly understood. Here we combine experiments and simulations to quantify how diffusiophoresis alters the spreading of a colloidal blob in a two-dimensional ordered/disordered porous medium. A joint blob of colloids and salt at high concentration is introduced into a medium filled with salt at low concentration and advected by a background flow. Intuition suggests that when colloids are attracted towards or repelled from the solute-rich blob, dispersion should be suppressed or enhanced, respectively. Instead, we observe the opposite trend: longitudinal dispersion is enhanced in the attractive case, whereas dispersion is suppressed in the repulsive case. Numerical simulations reveal that this striking reversal arises from diffusiophoretic exchange of particles between slow and fast streamlines, which we capture using a minimal two-layer model of coupled fast and slow plug flows. Finally, we probe how geometric disorder in the medium modulates this mechanism. Our results demonstrate that diffusiophoresis can strongly modulate macroscopic dispersion of colloids in porous media with implications for transport in subsurface and biological environments.
Hysterons provide a minimal description of memory in driven matter: bistable elements with distinct switching thresholds whose interactions generate hysteresis, avalanches, and return point memory or its violation. Experimental realizations have so far been dominated by solid state mechanical systems, where bistability is usually encoded structurally through buckling, snap through, or geometric incompatibility. Here we realize hysteron physics through a hydrodynamic route. A single elastic fiber anchored in a microfluidic channel becomes bistable through nonlinear elastohydrodynamic feedback: viscous loading deforms the fiber, deformation reshapes hydraulic resistance, and flow redistribution modifies the loading. This feedback produces a fluidic hysteron whose onset is organized by a cusp catastrophe in geometric control parameters. A parallel bypass channel acts as a geometric load line that reshapes, and can even eliminate, bistability while simultaneously mediating long ranged hydraulic interactions between fibers. In arrays, varying a single geometric parameter drives a transition from a non interacting Preisach regime with return point memory to an interacting regime with avalanche like switching and return point memory violation. These results establish a passive hydrodynamic route to hysteron networks, in which memory emerges from flow structure feedback and global hydraulic constraints rather than solid state multistability or external control.
Biofilms are structured communities of microorganisms embedded in an extracellular polymeric substance (EPS) matrix whose dense, polymer-rich architecture strongly hinders the transport of antimicrobial agents and nanoparticle carriers. Diffusiophoresis, the motion of colloidal particles along solute concentration gradients, can enhance penetration into viscoelastic matrices. However, how the changes in biofilm microstructure and density modulate diffusiophoretic delivery of particles is not yet understood. Here, we investigate how biofilm density as characterized by the transmitted light intensity index, Ĩ, modulates diffusiophoretic particle penetration by systematically varying biofilm culture time and particle size and by comparing motile and nonmotile Escherichia coli (E. coli) strains. We find that increasing Ĩ systematically reduces the effective early-time diffusiophoretic mobility, identifying a biofilm-accumulation regime beyond which gradient-enhanced delivery becomes strongly suppressed. Over the range examined here, larger particles penetrate more deeply than smaller ones, indicating that their mobility advantage outweighs the geometric advantage of smaller size. We further observe later-stage reverse particle motion and propose that it results from the combined effects of weakening diffusiophoretic penetration, transient biofilm deformation under the imposed solute gradient, and possible shear-assisted removal of expanded biofilm material near the pore entrance. Together, these results provide a quantitative framework for identifying the range of biofilm accumulation states in which diffusiophoresis can effectively enhance colloidal delivery into biofilms and the denser regime in which biofilm structure suppresses that enhancement.
Chemical gradients are ubiquitous in porous and crowded environments, including soils, filters, fabrics, tissues, hydrogels, biofilms and living cells. They arise from displacement fronts, dissolution and precipitation, ion exchange, metabolism, root exudation, evaporation, gas dissolution, freeze–thaw cycles and externally imposed chemical treatments. These gradients can drive colloids, macromolecules and emulsion droplets by diffusiophoresis, while simultaneously driving diffusioosmotic flows along confining surfaces. Classical models of colloid transport in porous media emphasize hydrodynamic dispersion, surface interactions, straining, deposition, detachment and filtration. This chapter places diffusiophoresis within that broader transport framework and reviews how porous media generate, stretch, disperse and sustain the solute gradients that drive phoretic motion. We first discuss sources of chemical gradients and the distinction between spreading and mixing, then summarize classical colloid transport, the minimal physicochemical model for diffusiophoresis and diffusioosmosis, and the experimental platforms used to study these effects. Particular emphasis is placed on recent results showing that diffuse solute fronts can enhance phoretic removal from dead-end pores by prolonging the duration of forcing, and that cross-streamline migration within flowing pathways can change macroscopic breakthrough and dispersion by orders of magnitude. We close by discussing emulsion droplets, multiphase flows, confined and living media, and open problems, including the transition from algebraic mixing in two-dimensional micromodels to chaotic mixing in three-dimensional porous media.
Active wetting extends classical wetting physics to living systems, in which cells and tissues spread by generating internal forces rather than relying solely on passive interfacial tensions. Unlike passive systems, which evolve toward thermodynamic and mechanical equilibrium by minimizing free energy, active systems remain far from equilibrium due to continuous energy input and dissipation. Their dynamics are sustained, adaptive, and responsive to chemical and mechanical cues in ways that depart fundamentally from passive behavior. In addition, active systems lack a unified energetic or variational principle to describe their evolution. What insights can be drawn from passive models, and how these models might be generalized to account for activity, remain open questions. Studying active wetting may thus reveal new principles of nonequilibrium dynamics at soft and living interfaces, and offer deeper understanding of key biological processes such as wound healing, cancer invasion, and biofilm growth.
We present a phase-field model to study two-phase displacement with moving contact lines in a capillary tube. We construct a diffuse-interface formulation of solid-liquid surface energy by enforcing a consistent structure of the fluid-fluid interface between the bulk fluid and the solid surface. We first show, via simulation of equilibrium liquid slugs in a capillary tube, that this formulation allows prescribing arbitrary static contact angles and leads to the correct capillary pressure. We then propose a formulation to account for out-of-equilibrium dynamics near the contact line and demonstrate the ability of this generalized formulation to simulate spontaneous imbibition as well as viscously unstable, constant-rate displacements in a capillary tube. We show that our phase-field model captures the imbibition dynamics described by a theoretical model that combines classic Lucas-Washburn theory with Cox's law of dynamic contact angle. It also predicts wetting transition, thin-film formation, and interface pinch-off that quantitatively agree with recent experiments.
Solute gradients next to an interface drive a diffusioosmotic flow, the origin of which lies in the intermolecular interactions between the solute and the interface. These flows on the surface of colloids introduce an effective slip velocity, driving their diffusiophoretic migration. In confined environments, the interplay between diffusiophoresis and diffusioosmosis governs the motion of colloids. Previous studies have indeed demonstrated the quantitative modulation of phoretic migration by the osmotic flows. Here, we show that diffusioosmotic flows can lead to qualitatively distinct outcomes, reversing the direction of colloidal focusing expected from diffusiophoresis alone. Using microfluidic experiments in a T-junction, numerical simulations, and theoretical modeling, we explain our observations to be due to an interplay between diffusiophoretic migration of colloids toward the walls and their entrainment in a diffusioosmotic vortex. We show this focusing to be persistent for a range of salt types, salt gradients, and flow rates, and establish a criterion for its emergence. Our work sheds light on how boundaries modulate the solute-mediated transport of colloids in confined environments and how the colloidal trajectories can be utilized to infer the surface properties.
Particle-mediated multiphase flow in confined geometries is common in natural processes and industrial applications. Here, we study air-suspension interfacial patterns under the impact of particle dynamics through a combination of experiments and theory in a lifting Hele-Shaw cell where the suspension is undergoing stretching deformation. We observe a transition of interfacial morphology from wavy pattern with noticeable wiggles, to blobby fingering featured by blunt tips, and eventually to dendritic fingering pattern characterized by densely spaced side branching. Three particle effects are identified in the pattern formation, including rheological modification, nonuniform spatial distribution, and particle perturbations. Notably, the emergence of dendritic fingering is rarely observed in pure fluids under comparable conditions. To explain this phenomenon, we quantify the particle-induced perturbations using linear stability theory. The particle-induced perturbations correspond to higher wave-number modes than cell roughness-induced perturbation. Once their amplitudes become comparable, tip splitting is continuously triggered and evolves into side branching during finger propagation, ultimately leading to the formation of dendritic morphology. On this basis, we propose a perturbation amplitude-based criterion to predict the emergence of dendritic pattern, and further establish a regime diagram of interfacial patterns in the parameter space of capillary number and aspect ratio. The proposed criterion and the phase diagram are in good agreement with our experiments. This study elucidates the crucial role of particle dynamics in shaping the interface morphologies of suspensions, offering insights into controlling interfacial instability in relevant engineering applications.
Fluid instabilities can be harnessed for facile self-assembly of patterned structures on the nano- and microscale. Evaporative self-assembly from drops is one simple technique that enables a range of patterning behaviors due to the multitude of fluid instabilities that arise due to the simultaneous existence of temperature and solutal gradients. However, the method suffers from limited controllability over patterns that can arise and their morphology. Here, we demonstrate that a range of distinct crystalline patterns including hexagonal arrays, branches, and sawtooth structures emerge from evaporation of water drops containing calcium sulfate on hydrophilic and superhydrophilic substrates. Different pattern regimes emerge as a function of contact line dynamics and evaporation rates, which dictate which fluid instabilities are most likely to emerge. The underlying physical mechanisms behind instability for controlled self-assembly involve Marangoni flows and forced wetting/dewetting. We also demonstrate that these patterns composed of water-soluble inorganic crystals can serve as sustainable and easily removable masks for applications in microscale fabrication.
Bacteria are one of the oldest life forms on Earth, dating back to more than 3.5 billion years ago. They control the global cycling of carbon, nitrogen, and oxygen. They provide plants, fungi and other organisms with the necessary nutrients and elements. They help us digest our food, protect us against pathogens, and even affect our behavior. Microplastics, however, have disrupted the bacterial ecosystems across the globe, from the soil to the oceans. Microplastics are tiny plastic particles formed as a result of the breakdown of the consumer products and plastic waste. Due to their stability and persistence, they can travel long distances in the soil and subsurface environments, ultimately making their way to the water resources, rivers, and oceans. In this journey, they interact with bacteria and other micro/macro-organisms, become ingested or colonized, and act as carriers for contaminants and pathogens. How and whether bacteria adapt to these new microplastic-rich ecosystems are open questions with far-reaching implications for the health of our planet and us. Therefore, there is an urgent need for improving our fundamental understanding of bacterial interactions with the microplastics in complex environments. In this commentary, we focus on the nexus of bacteria, biofilms, and microplastics, also known as the “plastisphere”, and discuss the challenges and opportunities.
We investigate interfacial instability in a lifting Hele-Shaw cell by experiments and theory. We characterize the unexplored transition from stable to unstable patterns under a wide range of controlling parameters. Surprisingly, we find that the perturbation growth rate-based criterion for the onset of instability from linear stability theory is too strict by over 3 orders of magnitude. To reconcile this striking discrepancy, we propose a new criterion based on perturbation amplitude, which is in excellent agreement with the experimental results. We further show that the fingering pattern evolves to produce a hierarchical fluid structure and derive a theoretical equation to predict the fingering evolution.
The fluid-fluid interface is a complex environment for a floating object where the statics and dynamics may be governed by capillarity, gravity, inertia, and other external body forces. Yet, the alignment of these forces in intricate ways might result in beautiful pattern formation and self-assembly of these objects, as in the case of bubble rafts or colloidal particles. While interfacial self-assembly has been explored widely, controlled manipulation of floating objects, e.g. drops, at the fluid-fluid interface still remains a challenge largely unexplored. In this work, we reveal the self-assembly and manipulation of water drops floating at an oil-air interface. We show that the assembly occurs due to electrostatic interactions between the drops and their environment. We highlight the role of the boundary surrounding the system by showing that even drops with a net zero electric charge can self-assemble under certain conditions. Using experiments and theory, we show that the depth of the oil bath plays an important role in setting the distance between the self-assembled drops. Furthermore, we demonstrate ways to manipulate the drops actively and passively at the interface.
Solute gradients next to an interface drive a diffusioosmotic flow, the origin of which lies in the intermolecular interactions between the solute and the interface. These flows on the surface of colloids introduce an effective slip velocity, driving their diffusiophoretic migration. In confined environments, we expect the interplay between diffusiophoretic migration and diffusioosmotic flows near the walls to govern the motion of colloids. These near-wall osmotic flows are, however, often considered weak and neglected. Here, using microfluidic experiments in a T-junction, numerical simulations, and theoretical modeling, we show that the interplay between osmotic and phoretic effects leads to unexpected outcomes: forming a colloidal vortex in the absence of inertial effects, and demixing and focusing of the colloids in the direction opposite to what is commonly expected from diffusiophoresis alone. We show these colloidal vortices to be persistent for a range of salt types, salt gradients, and flow rates, and establish a criterion for their emergence. Our work sheds light on how boundaries modulate the solute-mediated transport of colloids in confined environments.
Droplets of alcohol-based formulations are common in applications from sanitizing sprays to printing inks. However, our understanding of the drying dynamics of these droplets on surfaces and the influence of ambient humidity is still very limited. Here, we report the drying dynamics of picoliter droplets of isopropyl alcohol deposited on a surface under controlled humidity. Condensation of water vapor in the ambient environment onto alcohol droplets leads to unexpectedly complex drying behavior. As relative humidity (RH) increases, we observed a variety of phenomena including enhanced spreading, nonmonotonic changes in the drying time, the formation of pancake-like shapes that suppress the coffee-ring effect, and the formation of water rich films around an alcohol-rich drop. We developed a lubrication model that accounts for the coupling between the flow field within the drop, the shape of the drop, and the vapor concentration field. The model reproduces many of the experimentally observed morphological and dynamic features, revealing the presence of unusually large spatial compositional gradients within the evaporating droplet and surface-tension-gradient driven flows arising from water condensation/evaporation at the surface of the droplet. One unexpected feature from the simulation is that water can evaporate and condense concurrently in different parts of the drop, providing fundamental insights that simpler models based on average fluxes lack. We further observed rim instabilities at higher RH that are well-described by a model based on the Rayleigh-Plateau instability. Our findings have implications for the testing and use of alcohol-based disinfectant sprays and printing inks.
The shapes of highly volatile oil-on-water droplets become strongly asymmetric when they are out of equilibrium. The unsaturated organic vapor atmosphere causes evaporation and leads to a strong Marangoni flow in the bath, unlike that previously seen in the literature. Inspecting these shapes experimentally on millisecond and submillimeter time and length scales and theoretically by scaling arguments, we confirm that Marangoni-driven convection in the subphase mechanically stresses the droplet edges to an extent that increases for organic droplets of smaller contact angle and accordingly smaller thickness. The viscous stress generated by the subphase overcomes the thermodynamic Laplace pressure. The oil droplets develop copious regularly spaced fingers, and these fingers develop spike-shaped and branched treelike structures. Unlike this behavior for single-component (surfactant-free) oil droplets, droplets composed of two miscible (surfactant-free) organic liquids develop a rim of the less volatile component along the droplet perimeter, from which jets of monodisperse smaller droplets eject periodically due to the Rayleigh-Plateau instability. When evaporation shrinks droplets to μm size, their shapes fluctuate chaotically, and ellipsoidal shapes rupture into smaller daughter droplets when subphase convection flow pulls them in opposite directions. The shape of the evaporating oil droplets is kneaded and sculpted by vigorous flow in the water subphase.
A collection of the data and scripts used to produce figures and derive conclusions for: "Aerodynamic interactions of drops on parallel fibers." The DOI number for this paper is 10.1038/s41567-023-02159-4. It is available at the following URL: https://www.nature.com/articles/s41567-023-02159-4. Please see Repo_Contents.pdf for details.