Diffusiophoresis-enhanced particle deposition for additive manufacturing.

The ability to govern particle assembly in an evaporative-driven additive manufacturing (AM) can realize multi-scale features fundamental to creating printed electronics. However, existing techniques remain challenging and often require templates or contaminating solutes. We explore the control of particle deposition in 3D-printed colloids by diffusiophoresis, a previously unexplored mechanism in multi-scale AM. Diffusiophoresis can introduce spontaneous phoretic particle motion by establishing local solute concentration gradients. We show that diffusiophoresis can play a dominant role in complex evaporative-driven particle assembly, enabling a fundamentally new and versatile control of particle deposition in a multi-scale AM process.

CO2-Driven diffusiophoresis for maintaining a bacteria-free surface.

Dissolution and dissociation of CO2 in an aqueous phase induce diffusiophoretic motion of suspended particles with a nonzero surface charge. We report CO2-driven diffusiophoresis of colloidal particles and bacterial cells in a circular Hele-Shaw geometry. Combining experiments and model calculations, we identify the characteristic length and time scales of CO2-driven diffusiophoresis in relation to system dimensions and CO2 diffusivity. The motion of colloidal particles driven by a CO2 gradient is characterized by measuring the average velocities of particles as a function of distance from the CO2 sources. In the same geometrical configurations, we demonstrate that the directional migration of wild-type V. cholerae and a mutant lacking flagella, as well as S. aureus and P. aeruginosa, near a dissolving CO2 source is diffusiophoresis, not chemotaxis. Such a directional response of the cells to CO2 (or an ion) concentration gradient shows that diffusiophoresis of bacteria is achieved independent of cell shape, motility and the Gram stain (cell surface structure). Long-time experiments suggest potential applications for bacterial diffusiophoresis to cleaning systems or anti-biofouling surfaces, by reducing the population of the cells near CO2 sources.

Colloid Separation by CO2-Induced Diffusiophoresis.

We present a microfluidic crossflow separation of colloids enabled by the dissolution of CO2 gas in aqueous suspensions. The dissolved CO2 dissociates into H+ and HCO3- ions, which are efficient candidates for electrolytic diffusiophoresis, because of the fast diffusion of protons. By exposing CO2 gas to one side of a microfluidic flow channel, a crossflow gradient can be created, enabling the crossflow diffusiophoresis of suspended particles. We develop a simple two-dimensional model to describe the coupled transport dynamics that is due to the competition of advection and diffusiophoresis. Furthermore, we show that oil nanoemulsions can be effectively separated by utilizing highly charged particles as a carrier vehicle, which is otherwise difficult to achieve. These results demonstrate a portable, versatile method for separating particles in broad applications including oil extraction, drug delivery, and bioseparation.

Particle entrainment in dead-end pores by diffusiophoresis.

The transport of particulate matter to and from dead-end pores is difficult to achieve due to confinement effects. Diffusiophoresis is a phenomenon that results in the controlled motion of colloids along solute concentration gradients. Thus, by establishing an electrolyte concentration gradient within dead-end pores, it is possible to induce the flow of particles into and out of the pores via diffusiophoresis, as has been demonstrated recently. In this paper, we explain the pore-scale mechanism by which individual colloids are entrained in dead-end pores by diffusiophoresis. We flow particles past a series of dead-end pores in the presence of a solute concentration gradient. Our results reveal that particles execute pore-to-pore hops before ultimately being captured. We categorize an event as particle capture when the particle's trajectory terminates within the dead-end pore. Experiments and numerical simulations demonstrate that particle capture only occurs when flowing particles are positioned sufficiently close to the pore entry. Outside this capture region, the particles have insufficient diffusiophoretic velocities to induce capture and their dynamics are largely dominated by their free-stream advective velocities. We observe that the particles move closer to the device wall as they hop, thereby reducing the effect of flow advection and increasing that of diffusiophoresis. These results enhance our understanding of suspension dynamics in a driven system and have implications for the development, design, and optimization of diffusiophoretic platforms for drug delivery, cosmetics, and material recovery.

Characterization of surface-solute interactions by diffusioosmosis.

The accurate measurement of wall zeta potentials and solute-surface interaction length scales for electrolyte and non-electrolyte solutes, respectively, is critical to the design of many biomedical and microfluidic applications. We present a novel microfluidic approach using diffusioosmosis for measuring either the zeta potentials or the characteristic interaction length scales for surfaces exposed to, respectively, electrolyte or non-electrolyte solutes. When flows containing different solute concentrations merge in a junction, local solute concentration gradients can drive diffusioosmotic flow due to electrokinetic, steric, and other interactions between the solute molecules and solid surfaces. We demonstrate a microfluidic system consisting of a long, narrow pore connecting two large side channels in which solute concentration gradients drive diffusioosmosis within the pore, resulting in predictable fluid velocity/pressure and solute profiles. Furthermore, we present analytical results and a methodology to determine the zeta potential or interaction length scale for the pore surfaces based on the solute concentrations in the main side channels, the flow rate in the pore, and the pressure drop across the pore. We apply this method to the experimental data of Lee et al. to predict the zeta potentials of their system, and we use 3D numerical simulations to validate the theory and show that end effects caused by the junctions are negligible for a wide range of parameters. Because the dynamics in the proposed system are driven by diffusioosmosis, this technique does not suffer from certain disadvantages associated with the use of sensitive electronics in traditional zeta potential measurement approaches such as streaming potential, streaming current, or electroosmosis. To the best of our knowledge this is the first flow-based approach to characterize surface/solute interactions with non-electrolyte solutes.

Invisible Anchors Trap Particles in Branching Junctions.

We combine numerical simulations and an analytic approach to show that the capture of finite, inertial particles during flow in branching junctions is due to invisible, anchor-shaped three-dimensional flow structures. These Reynolds-number-dependent anchors define trapping regions that confine particles to the junction. For a wide range of Stokes numbers, these structures occupy a large part of the flow domain. For flow in a V-shaped junction, at a critical Stokes number, we observe a topological transition due to the merger of two anchors into one. From a stability analysis, we identify the parameter region of particle sizes and densities where capture due to anchors occurs.

Diffusiophoresis in one-dimensional solute gradients.

The diffusiophoretic motion of suspended colloidal particles under one-dimensional solute gradients is solved using numerical and analytical techniques. Similarity solutions are developed for the injection and withdrawal dynamics of particles into semi-infinite pores. Furthermore, a method of characteristics formulation of the diffusion-free particle transport model is presented and integrated to realize particle trajectories. Analytical solutions are presented for the limit of small particle diffusiophoretic mobility Γp relative to the solute diffusivity Ds for particle motions in both semi-infinite and finite domains. Results confirm the build up of local maxima and minima in the propagating particle front dynamics. The method of characteristics is shown to successfully predict particle motions and the position of the particle front, although it fails to accurately predict suspended particle concentrations in the vicinity of sharp gradients, such as at the particle front peak seen in some injection cases, where particle diffusion inevitably plays an important role. Results inform the design of applications in which the use of applied solute gradients can greatly enhance particle injection into and withdrawal from pores.

Low-Cost Zeta Potentiometry Using Solute Gradients.

The zeta potential is an electric potential in the Debye screening layer of an electrolyte, which represents a key physicochemical surface property in various fields ranging from electrochemistry to pharmaceuticals. Thus, characterizing the zeta potential is essential for many applications, but available measurement techniques are limited. Electrophoretic light scattering is typically used to measure the zeta potential of particles in suspension, whereas zeta potential measurements of a solid wall in solution rely on either streaming potential or electroosmotic mobility measurement techniques, both of which are expensive and sophisticated. Here, a simple, robust method to simultaneously measure the zeta potential of particles in suspension and solid walls is presented. The method uses solute gradients to induce particle and fluid motions via diffusiophoresis and diffusioosmosis, respectively, which are both sensitive to the zeta potential of the particle and the wall. By visualizing the particle dynamics, both zeta potentials can be determined independently. Finally, a compact microscope is used to demonstrate low-cost zeta potentiometry that allows measurement of both particle and wall zeta potentials, which suggests a cost-effective tool for pharmaceuticals as well as for educational purposes.

Vortex-Breakdown-Induced Particle Capture in Branching Junctions.

We show experimentally that a flow-induced, Reynolds number-dependent particle-capture mechanism in branching junctions can be enhanced or eliminated by varying the junction angle. In addition, numerical simulations are used to show that the features responsible for this capture have the signatures of classical vortex breakdown, including an approach flow aligned with the vortex axis and a pocket of subcriticality. We show how these recirculation regions originate and evolve and suggest a physical mechanism for their formation. Furthermore, comparing experiments and numerical simulations, the presence of vortex breakdown is found to be an excellent predictor of particle capture. These results inform the design of systems in which suspended particle accumulation can be eliminated or maximized.

Size-dependent control of colloid transport via solute gradients in dead-end channels.

Transport of colloids in dead-end channels is involved in widespread applications including drug delivery and underground oil and gas recovery. In such geometries, Brownian motion may be considered as the sole mechanism that enables transport of colloidal particles into or out of the channels, but it is, unfortunately, an extremely inefficient transport mechanism for microscale particles. Here, we explore the possibility of diffusiophoresis as a means to control the colloid transport in dead-end channels by introducing a solute gradient. We demonstrate that the transport of colloidal particles into the dead-end channels can be either enhanced or completely prevented via diffusiophoresis. In addition, we show that size-dependent diffusiophoretic transport of particles can be achieved by considering a finite Debye layer thickness effect, which is commonly ignored. A combination of diffusiophoresis and Brownian motion leads to a strong size-dependent focusing effect such that the larger particles tend to concentrate more and reside deeper in the channel. Our findings have implications for all manners of controlled release processes, especially for site-specific delivery systems where localized targeting of particles with minimal dispersion to the nontarget area is essential.

Flow-Driven Rapid Vesicle Fusion via Vortex Trapping.

Fusion between suspended lipid vesicles is difficult to achieve without membrane proteins or ions because the vesicles have extremely low equilibrium membrane tension and high poration energy. Nonetheless, vesicle fusion in the absence of mediators can also be achieved by mechanical forcing that is strong enough to induce membrane poration. Here, we employ a strong fluid shear stress to achieve vesicle fusion. By utilizing a unique vortex formation phenomenon in branched channels as a platform for capturing, stressing, and fusing the lipid vesicles, we directly visualize using high-speed imaging the vesicle fusion events, induced solely by shear, on the time scale of submilliseconds. We show that a large vesicle with a size of up to ∼10 µm can be achieved by the fusion of nanoscale vesicles. This technique has the potential to be utilized as a fast and simple way to produce giant unilamellar vesicles and to serve as a platform for visualizing vesicle interactions and fusions in the presence of shear.