Solvent Quality and Aggregation State of Asphaltenes on Interfacial Mechanics and Jamming Behavior at the Oil/Water Interface.

The formation of highly stable water-in-oil emulsions results in complications in both upstream and downstream processing. Emulsion stability in these systems has been connected to the adsorption of surface-active asphaltenes that are assumed to form a rigidified film at the oil/water (o/w) interface. Full characterization of this behavior is needed to allow for engineered solutions for enhanced oil recovery. Interfacial properties, such as surface pressure and interfacial elasticity, are implicated in the stabilizing mechanism for these observed films. Asphaltenes are known to be interfacially active in both good solvents (aromatics) and poor solvents (high ratio of aliphatic to aromatic). However, due to inherent complexities present in asphaltene studies, the details of the mechanical properties of the interface remain poorly understood. Despite the widely accepted perception that asphaltenes form persistent rigid films at fluid-fluid interfaces, the connection between bulk solution properties and interfacial mechanics has not been resolved. Here, the effects of solvent quality on the interfacial properties of asphaltene dispersions are determined by using a well-defined asphaltene/solvent system. Interfacial rigidity is observed only under poor solvent conditions, while the good solvent system remains fluid-like. The interfacial rheology under good and poor solvent conditions is measured simultaneously with surface pressure measurements to track interfacial development. It is shown that surface pressure and dilatational modulus measurements are not indicators of whether an interface demonstrates rigid behavior under large compressions. Finally, conditions required for asphaltene-coated interfaces to exhibit the mechanical behavior associated with a rigidified interface are defined. This work provides a framework for quantifying the impact of the aggregation state of asphaltenes on the stability and mechanics at the o/w interface.

Vacuole dynamics and popping-based motility in liquid droplets of DNA.

Liquid droplets of biomolecules play key roles in organizing cellular behavior, and are also technologically relevant, yet physical studies of dynamic processes of such droplets have generally been lacking. Here, we investigate and quantify the dynamics of formation of dilute internal inclusions, i.e., vacuoles, within a model system consisting of liquid droplets of DNA 'nanostar' particles. When acted upon by DNA-cleaving restriction enzymes, these DNA droplets exhibit cycles of appearance, growth, and bursting of internal vacuoles. Analysis of vacuole growth shows their radius increases linearly in time. Further, vacuoles pop upon reaching the droplet interface, leading to droplet motion driven by the osmotic pressure of restriction fragments captured in the vacuole. We develop a model that accounts for the linear nature of vacuole growth, and the pressures associated with motility, by describing the dynamics of diffusing restriction fragments. The results illustrate the complex non-equilibrium dynamics possible in biomolecular condensates.

Curvature and shape relaxation in surface-viscous domains.

The mechanics of curved, heterogeneous, surfactant-laden surfaces and interfaces are important to a variety of engineering and biological applications. To date, most models of rheologically complex interfaces have focused on homogeneous systems of planar or fixed curvature. In this study, we investigate a simple, dynamical model of a two-phase surface fluid on a curved interface: a condensed, surface-viscous domain embedded within a surface-inviscid, spherical interface of time-varying radius of curvature. Our aim is to understand how changes in surface curvature generate two-dimensional Stokes flows inside the domain, thereby resisting curvature deformation and distorting the domain shape. We model the surface stress within the domain using the classical Boussinesq-Scriven constitutive equation, simplified for a near-spherical cap undergoing a small-amplitude curvature deformation. We then analyze the frequency-dependent dynamics of the surface stress and curvature within the domain when the pressure difference across the surface is sinusoidally oscillated. We find that the curvature relaxes diffusively, and thus define a Peclet number (Pe) relating the rate of diffusion to the oscillation frequency. At small enough Pe, the surface deforms quasi-statically, whereas at high Pe, the curvature varies sharply within a thin boundary layer adjacent to the domain border. Consequently, the curvature of the domain appears discontinuous from the rest of the surface under rapid oscillation. We then examine the linear stability of the domain shape to small, non-axisymmetric perturbations when the surface is steadily compressed (i.e., the pressure difference across it is increased). While the line tension at the domain border tends to maintain circular symmetry, surface-viscous stresses generated by surface compression tend to destabilize the perimeter. A shape instability arises above a critical surface capillary number (Ca) relating surface-viscous stresses to line tension. Moreover, we show that the mechanism of instability is distinct from that of the famous Saffman-Taylor fingering instability. Various extensions of our model are discussed, including materials with finite dilatational surface viscosity, linear and nonlinear (visco)elasticity, and large-amplitude deformations.

A two-phase model that unifies and extends the classical models of membrane transport.

Two models describe solvent transport through swollen, nonporous membranes. The pore-flow model, based on fluid mechanics, works for porous membranes, whereas the solution-diffusion model invokes molecular diffusion to treat nonporous membranes. Both approaches make valid arguments for swollen polymer membranes, but they disagree in their predictions of intramembrane pressure and concentration profiles. Using a fluid-solid model that treats the solvent and membrane matrix as separate phases, we show both classical models to be valid, to represent complementary approaches to the same phenomenon, and to make identical predictions. The fluid-solid model clarifies recent reverse osmosis measurements; provides a predictive and mechanistic basis for empirical high-pressure limiting flux phenomena, in quantitative agreement with classic measurements; and gives a framework to treat nonporous but mechanically heterogeneous membrane materials.

Temperature dependence of diffusiophoresis via a novel microfluidic approach.

The temperature dependence of the diffusiophoretic mobility (DDP) is investigated experimentally and compared with theoretical predictions. These systematic measurements were made possible by a new microfluidic approach that enables truly steady state gradients to be imposed, and direct and repeatable measurements of diffusiophoretic migration to be made over hours-long time scales. Diffusiophoretic mobilities were measured for fluorescent, negatively charged polystyrene particles under NaCl gradients, at temperatures ranging from 20 °C to 70 °C. Measured DDP values were found to increase monotonically with temperature, and to agree, both qualitatively and relatively quantitatively, with theoretical predictions based on electrophoretically-measured zeta potentials. These results provide confidence that existing diffusiophoresis theories can accurately predict DP mobilities over a range of temperatures. More broadly, we anticipate our new microfluidic approach will facilitate and enable new tests of diffusiophoretic phenomena under a wide range of physical and chemical conditions.

Room-level ventilation in schools and universities.

Ventilation is of primary concern for maintaining healthy indoor air quality and reducing the spread of airborne infectious disease, including COVID-19. In addition to building-level guidelines, increased attention is being placed on room-level ventilation. However, for many universities and schools, ventilation data on a room-by-room basis are not available for classrooms and other key spaces. We present an overview of approaches for measuring ventilation along with their advantages and disadvantages. We also present data from recent case studies for a variety of institutions across the United States, with various building ages, types, locations, and climates, highlighting their commonalities and differences, and examples of the use of this data to support decision making.

Curvature-Mediated Forces on Elastic Inclusions in Fluid Interfaces.

Heterogeneous fluid interfaces often include two-dimensional solid domains that mechanically respond to changes in interfacial curvature. While this response is well-characterized for rigid inclusions, the influence of solid-like elasticity remains essentially unexplored. Here, we show that an initially flat, elastic inclusion embedded in a curved, fluid interface will exhibit qualitatively distinct behavior depending on its size and stiffness. Small, stiff inclusions are limited by bending and experience forces directed up gradients of Gaussian curvature, in keeping with prior findings for rigid discoids. By contrast, larger and softer inclusions are driven down gradients of squared Gaussian curvature in order to minimize the elastic penalty for stretching. Our calculations of the force on a solid inclusion are shown to collapse onto a universal curve spanning the bending- and stretching-limited regimes. From these results, we make predictions for the curvature-directed motion of deformable solids embedded within a model interface of variable Gaussian curvature.

A two-step strategy for delivering particles to targets hidden within microfabricated porous media.

The delivery of small particles into porous environments remains highly challenging because of the low permeability to the fluids that carry these colloids. Even more challenging is that the specific location of targets in the porous environment usually is not known and cannot be determined from the outside. Here, we demonstrate a two-step strategy to deliver suspended colloids to targets that are "hidden" within closed porous media. The first step serves to automatically convert any hidden targets into soluto-inertial "beacons," capable of sustaining long-lived solute outfluxes. The second step introduces the deliverable objects, which are designed to autonomously migrate against the solute fluxes emitted by the targets, thereby following chemical trails that lead to the target. Experimental and theoretical demonstrations of the strategy lay out the design elements required for the solute and the deliverable objects, suggesting routes to delivering colloidal objects to hidden targets in various environments and technologies.

Hydrogen Bonding Strength Determines Water Diffusivity in Polymer Ionogels.

Polymeric ionogels, cross-linked gels swollen by ionic liquids (ILs), are useful vehicles for the release and storage of molecular solutes in separation, delivery, and other applications. Although rapid solute diffusion is often critical for performance, it remains challenging to predict diffusivities across multidimensional composition spaces. Recently, we showed that water (a neutral solute) diffuses through alkyl-methylimidazolium halide ILs by hopping between hydrogen bonding sites on relatively immobile cations. Here, we expand on this activated hopping mechanism in two significant ways. First, we demonstrate that water diffuses through poly(ethylene glycol)diacrylate ionogels via the same mechanism at a reduced rate. Second, we hypothesize that the activation energy barrier can be determined from relatively simple 1H NMR chemical shift measurements of the proton responsible for H-bonding. This relationship enables water's diffusivity in ionogels of this class to be predicted quantitatively, requiring only (1) the composition-dependent diffusivity and Arrhenius behavior of a single IL and (2) 1H NMR spectra of the ionogels of interest. High-throughput microfluidic Fabry-Perot interferometry measurements verify prediction accuracy across a broad formulation space (four ILs, 0 ≤ xH2O ≤ 0.7, 0 ≤ ϕPEGDA ≤ 0.66). The predictive model may expedite IL-material screening; moreover, it intimates a powerful connection between solute mobility and hydrogen bonding and suggests targets for rational design.

Capillary force on an 'inert' colloid: a physical analogy to dielectrophoresis.

"Inert" colloids are µm-scale particles that create no distortion when trapped at a planar fluid-fluid interface. When placed in a curved interface, however, such colloids can create interfacial distortions of quadrupolar symmetry - so-called "induced capillary quadrupoles." The present work explores the analogy between capillary quadrupoles and electric dipoles, and the forces exerted on them by a symmetry-breaking gradient. In doing so, we weigh in on an outstanding debate as to whether a curvature gradient can induce a capillary force on an inert colloid. We argue that this force exists, for the opposite would imply that all dielectrophoretic forces vanish in two dimensions (2D). We justify our claim by solving 2D Laplace problems of electrostatics and capillary statics involving a single particle placed within a large circular shell with an imposed gradient. We show that the static boundary condition on the outer shell must be considered when applying the principle of virtual work to compute the force on the particle, as verified by a direct calculation of this force through integration of the particle stresses. Our investigation highlights some of the subtleties that emerge in virtual work calculations of capillary statics and electrostatics, thereby clarifying and extending previous results in the field. The broader implication of our results is that inert particles - including particles with planar, pinned contact lines and equilibrium contact angles - interact through interparticle capillary forces that scale quadratically with the deviatoric curvature of the host interface, contrary to recent claims made in the literature.

Surfactant dynamics: hidden variables controlling fluid flows.

Surfactants - molecules and particles that preferentially adsorb to fluid interfaces - play a ubiquitous role in the fluids of industry, of nature, and of life. Since most surfactants cannot be seen directly, their behavior must be inferred from their impact on observed flows, like the buoyant rise of a bubble, or the thickness of a coating film. In so doing, however, a difficulty arises: physically distinct surfactant processes can affect measurable flows in qualitatively identical ways, raising the specter of confusion or even misinterpretation. This Perspective describes, in one coherent piece, both the equilibrium properties and dynamic processes of surfactants, to better enable the fluid mechanics community to understand, interpret, and design surfactant/fluid systems. Specifically, §2 treats the equilibrium thermodynamics of surfactants at interfaces, including surface pressure, isotherms of soluble and insoluble surfactants, and surface dilatational moduli (Gibbs and Marangoni). §3 describes surfactant dynamics in fluid systems, including surfactant transport and interfacial stress boundary conditions, the competition between surface diffusion, advection, and adsorption/desorption, Marangoni stresses and flows, and surface excess rheology. §4 discusses paradigmatic problems from fluid mechanics that are impacted by surfactants, including translating drops and bubbles, surfactant adsorption to clean and oscillating interfaces; capillary wave damping, thin film dynamics, foam drainage, and the dynamics of particles and probes at surfactant-laden interfaces. Finally, §5 discusses the additional richness and complexity that frequently arise in 'real' surfactants, including phase transitions, phase coexistence, and polycrystalline phases within surfactant monolayers, and their impact on non-Newtonian surface rheology.

Design strategies for engineering soluto-inertial suspension interactions.

Soluto-inertial (SI) suspension interactions allow colloidal particles to be driven large distances over sustained periods of time. These interactions involve soluto-inertial "beacons" that establish and maintain solute fluxes over long times by slowly absorbing or emitting solutes in response to changes in the surrounding solution. Suspended particles then migrate in response to solute fluxes via diffusiophoresis (DP). Beacon materials must be chosen to maintain these solute fluxes, with range and duration in mind. Here we present a general strategy to facilitate qualitative design and quantitative prediction of SI interactions for a given beacon-solute pair. Specifically, we look at two classes of SI beacons: those that partition solute and those that associate with solute. We identify the design parameters for these systems to construct a parameter space map, calculate characteristic timescales over which SI fluxes persist, and generate approximate analytical expressions for solute concentration profiles. Further, we use these expressions to predict the DP velocity of colloids interacting with beacons, noting qualitative differences between beacon sources that release solute and beacon sinks that absorb solute. Proof-of-principle experiments of beacon sources and sinks, of partitioning, and associating types highlight the basic findings. More broadly, the conceptual approach outlined here can be adapted to treat SI interactions mediated by other materials such as dissolving solids, gases, evaporating liquids, ion-exchange resins, and others.

Interfacial rheology and direct imaging reveal domain-templated network formation in phospholipid monolayers penetrated by fibrinogen.

Phospholipids are found throughout the natural world, including the lung surfactant (LS) layer that reduces pulmonary surface tension and enables breathing. Fibrinogen, a protein involved in the blood clotting process, is implicated in LS inactivation and the progression of disorders such as acute respiratory distress syndrome. However, the interaction between fibrinogen and LS at the air-water interface is poorly understood. Through a combined microrheological, confocal and epifluorescence microscopy approach we quantify the interfacial shear response and directly image the morphological evolution when a model LS monolayer is penetrated by fibrinogen. When injected into the subphase beneath a monolayer of the phospholipid dipalmitoylphosphatidylcholine (DPPC, the majority component of LS), fibrinogen preferentially penetrates disordered liquid expanded (LE) regions and accumulates on the boundaries between LE DPPC and liquid condensed (LC) DPPC domains. Thus, fibrinogen is line active. Aggregates grow from the LC domain boundaries, ultimately forming a percolating network. This network stiffens the interface compared to pure DPPC and imparts the penetrated monolayer with a viscoelastic character reminiscent of a weak gel. When the DPPC monolayer is initially compressed beyond LE-LC coexistence, stiffening is significantly more modest and the penetrated monolayer retains a viscous-dominated, DPPC-like character.

Long-range, selective, on-demand suspension interactions: Combining and triggering soluto-inertial beacons.

Structures and particles that slowly release solute into solution can attract or repel other particles in suspension via diffusiophoresis, a process we termed "soluto-inertial (SI) interactions." These SI interactions involve "beacons" that establish and sustain nonequilibrium solute fluxes over long durations. Here, we demonstrate the versatility of the SI concept and introduce distinct strategies to manipulate solute gradients and, hence, suspension behavior using beacons with different physicochemical properties. First, we demonstrate on-demand particle migration using beacons that can be actuated with a trigger. We then show the synergy between multiple, distinct beacons that modify solute fluxes in a way that allows directed, yet selective, colloidal migration to specific target sites. Moreover, this multibeacon harmony enhances migration velocities, and delays the equilibration of the SI effect. The different SI techniques highlighted here suggest previously unidentified possibilities for sorting and separating colloidal mixtures, targeting particle delivery, and enhancing rates of suspension flocculation.

Effect of Ethylcellulose on the Rheology and Mechanical Heterogeneity of Asphaltene Films at the Oil-Water Interface.

Asphaltenes are surface-active molecules that exist naturally in crude oil. They adsorb at the water-oil interface and form viscoelastic interfacial films that stabilize emulsion droplets, making water-oil separation extremely challenging. There is, thus, a need for chemical demulsifiers to disrupt the interfacial asphaltene films, and, thereby, facilitate water-oil separation. Here, we examine ethylcellulose (EC) as a model demulsifier and measure its impact on the interfacial properties of asphaltene films using interfacial shear microrheology. When EC is mixed with an oil and asphaltene solution, it retards the interfacial stiffening that occurs between the oil phase in contact with a water phase. Moreover, EC introduces relatively weak regions within the film. When EC is introduced to a pre-existing asphaltene film, the stiffness of the films decreases abruptly and significantly. Direct visualization of interfacial dynamics further reveals that EC acts inhomogeneously, and that relatively soft regions in the initial film are seen to expand. This mechanism likely impacts emulsion destabilization and provides new insight to the process of demulsification.

Evolution and mechanics of mixed phospholipid fibrinogen monolayers.

All mammals depend on lung surfactant (LS) to reduce surface tension at the alveolar interface and facilitate respiration. The inactivation of LS in acute respiratory distress syndrome (ARDS) is generally accompanied by elevated levels of fibrinogen and other blood plasma proteins in the alveolar space. Motivated by the mechanical role fibrinogen may play in LS inactivation, we measure the interfacial rheology of mixed monolayers of fibrinogen and dipalmitoylphosphatidylcholine (DPPC), the main constituent of LS, and compare these to the single species monolayers. We find DPPC to be ineffective at displacing preadsorbed fibrinogen, which gives the resulting mixed monolayer a strongly elastic shear response. By contrast, how effectively a pre-existing DPPC monolayer prevents fibrinogen adsorption depends upon its surface pressure. At low DPPC surface pressures, fibrinogen penetrates DPPC monolayers, imparting a mixed viscoelastic shear response. At higher initial DPPC surface pressures, this response becomes increasingly viscous-dominated, and the monolayer retains a more fluid, DPPC-like character. Fluorescence microscopy reveals that the mixed monolayers exhibit qualitatively different morphologies. Fibrinogen has a strong, albeit preparation-dependent, mechanical effect on phospholipid monolayers, which may contribute to LS inactivation and disorders such as ARDS.

Interfacial Rheology and Heterogeneity of Aging Asphaltene Layers at the Water-Oil Interface.

Surface-active asphaltene molecules are naturally found in crude oil, causing serious problems in the petroleum industry by stabilizing emulsion drops, thus hindering the separation of water and oil. Asphaltenes can adsorb at water-oil interfaces to form viscoelastic interfacial films that retard or prevent coalescence. Here, we measure the evolving interfacial shear rheology of water-oil interfaces as asphaltenes adsorb. Generally, interfaces stiffen with time, and the response crosses over from viscous-dominated to elastic-dominated. However, significant variations in the stiffness evolution are observed in putatively identical experiments. Direct visualization of the interfacial strain field reveals significant heterogeneities within each evolving film, which appear to be an inherent feature of the asphaltene interfaces. Our results reveal the adsorption process and aged interfacial structure to be more complex than that previously described. The complexities likely impact the coalescence of asphaltene-stabilized droplets, and suggest new challenges in destabilizing crude oil emulsions.

Nonlinear chiral rheology of phospholipid monolayers.

Microbutton rheometry reveals that the chiral morphology of dipalmitoylphosphatidylcholine (DPPC) monolayers imparts a chiral nonlinear rheological response. The nonlinear elastic modulus and yield stress of DPPC monolayers are greater when sheared clockwise (C), against the natural winding direction of DPPC domains, than counter-clockwise (CC). Under strong CC shear strains, domains deform plastically; by contrast, domains appear to fracture under strong C shearing. After CC shearing, extended LC domains develop regular patterns of new invaginations as they recoil, which we hypothesize reflect the nucleation and growth of new defect lines across which the tilt direction undergoes a step change in orientation. The regular spacing of these twist-gradient defects is likely set by a competition between the molecular chirality and the correlation length of the DPPC lattice. The macroscopic mechanical consequences of DPPC's underlying molecular chirality are remarkable, given the single-component, non-cross-linked nature of the monolayers they form.

Measuring Interfacial Polymerization Kinetics Using Microfluidic Interferometry.

A range of academic and industrial fields exploit interfacial polymerization in producing fibers, capsules, and films. Although widely used, measurements of reaction kinetics remain challenging and rarely reported, due to film thinness and reaction rapidity. Here, polyamide film formation is studied using microfluidic interferometry, measuring monomer concentration profiles near the interface during the reaction. Our results reveal that the reaction is initially controlled by a reaction-diffusion boundary layer within the organic phase, which allows the first measurements of the rate constant for this system.

Irreversible particle motion in surfactant-laden interfaces due to pressure-dependent surface viscosity.

The surface shear viscosity of an insoluble surfactant monolayer often depends strongly on its surface pressure. Here, we show that a particle moving within a bounded monolayer breaks the kinematic reversibility of low-Reynolds-number flows. The Lorentz reciprocal theorem allows such irreversibilities to be computed without solving the full nonlinear equations, giving the leading-order contribution of surface pressure-dependent surface viscosity. In particular, we show that a disc translating or rotating near an interfacial boundary experiences a force in the direction perpendicular to that boundary. In unbounded monolayers, coupled modes of motion can also lead to non-intuitive trajectories, which we illustrate using an interfacial analogue of the Magnus effect. This perturbative approach can be extended to more complex geometries, and to two-dimensional suspensions more generally.