Pressure Changes Across a Membrane Formed by Coacervation of Oppositely Charged Polymer-Surfactant Systems.

We investigate the mass transfer and membrane growth processes during capsule formation by the interaction of the biopolymer xanthan gum with CnTAB surfactants. When a drop of xanthan gum polymer solution is added to the surfactant solution, a membrane is formed by coacervation. It encapsulates the polymer drop in the surfactant solution. The underlying mechanisms and dynamic processes during capsule formation are not yet understood in detail. Therefore, we characterized the polymer-surfactant complex formation during coacervation by measuring the surface tension and surface elasticity at the solution-air interface for different surfactant chain lengths and concentrations. The adsorption behavior of the mixed polymer-surfactant system at the solution-air interface supports the understanding of observed trends during the capsule formation. We further measured the change in capsule pressure over time and simultaneously imaged the membrane growth via confocal microscopy. The cross-linking and shrinkage during the membrane formation by coacervation leads to an increasing tensile stress in the elastic membrane, resulting in a rapid pressure rise. Afterward, the pressure gradually decreases and the capsule shrinks as water diffuses out. This is not only due to the initial capsule overpressure but also due to osmosis caused by the higher ionic strength of the surfactant solution outside the capsule compared to the polymer solution inside the capsule. The influence of polymer concentration and surfactant type and concentration on the pressure changes and the membrane structure are studied in this work, providing detailed insights into the dynamic membrane formation process by coacervation. This knowledge can be used to produce capsules with tailored membrane properties and to develop a suitable encapsulation protocol in technological applications. The obtained insights into the mass transfer of water across the capsule membrane are important for future usage in separation techniques and the food industry and allow us to better predict the capsule time stability.

Unraveling dispersion and buoyancy dynamics around radial A + B → C reaction fronts: microgravity experiments and numerical simulations.

Radial Reaction-Diffusion-Advection (RDA) fronts for A + B → C reactions find wide applications in many natural and technological processes. In liquid solutions, their dynamics can be perturbed by buoyancy-driven convection due to concentration gradients across the front. In this context, we conducted microgravity experiments aboard a sounding rocket, in order to disentangle dispersion and buoyancy effects in such fronts. We studied experimentally the dynamics due to the radial injection of A in B at a constant flow rate, in absence of gravity. We compared the obtained results with numerical simulations using either radial one- (1D) or two-dimensional (2D) models. We showed that gravitational acceleration significantly distorts the RDA dynamics on ground, even if the vertical dimension of the reactor and density gradients are small. We further quantified the importance of such buoyant phenomena. Finally, we showed that 1D numerical models with radial symmetry fail to predict the dynamics of RDA fronts in thicker geometries, while 2D radial models are necessary to accurately describe RDA dynamics where Taylor-Aris dispersion is significant.

Functionalization of Ti64 via Direct Laser Interference Patterning and Its Influence on Wettability and Oxygen Bubble Nucleation.

The nucleation of bubbles on solid surfaces is an important phenomenon in nature and technological processes like electrolysis. During proton-exchange membrane electrolysis, the nucleation and separation of the electrically nonconductive oxygen in the anodic cycle plays a crucial role to minimize the overpotential it causes in the system. This increases the efficiency of the process, making renewable energy sources and the "power-to-gas" strategy more viable. A promising approach is to optimize gas separation by surface functionalization in order to apply a more advantageous interface to industrial materials. In this work, the connection between the wettability and bubble nucleation of oxygen is investigated. For tailoring the wettability of Ti64 substrates, the direct laser interference patterning method is applied. A laser source with a wavelength of 1064 nm and a pulse duration of 12 ps is used to generate periodic pillar-like structures with different depths up to ∼5 µm. The resulting surface properties are characterized by water contact angle measurement, scanning electron microscopy, confocal microscopy, and X-ray photon spectroscopy. It was possible to generate structures with a water contact angle ranging from 20° up to nearly superhydrophobic conditions. The different wettabilities are validated based on X-ray photon spectroscopy and the different elemental composition of the samples. The results indicate that the surface character of the substrate adapts depending on the surrounding media and needs more time to reach a steady state for deeper structures. A custom setup is used to expose the functionalized surfaces to oxygen-oversaturated solutions. It is shown that a higher hydrophobicity of the structured surface yields a stronger interaction with the dissolved gas. This significantly enhances the oxygen nucleation up to nearly 350% by generating approximately 20 times more nucleation spots, but also smaller bubble sizes and a reduced detachment rate.

Interfacial Behavior of Particle-Laden Bubbles under Asymmetric Shear Flow.

The behavior of moving bubbles has mostly been studied in an axisymmetric flow field. To extend the knowledge to practical conditions, we investigate the interfacial and hydrodynamic properties of bubbles under asymmetric shear forces. Experiments are performed with a buoyant bubble at the tip of a capillary placed in a defined shear flow in the presence of surfactants, nanoparticles, and glass beads. The response of the interface to the surrounding asymmetric flow is measured under successive reduction of the surface area. Profile analysis tensiometry is utilized to investigate the dynamic surface tension and the surface rheology of the surfactant- and nanoparticle-laden interfaces. Microscopic particle image and tracking velocimetry are used to study the bulk flow and the interfacial mobility of the buoyant bubble. According to our results, the rotational component of the shear flow provokes an interfacial flow, which redistributes the adsorbed surfactants and particles at the interface. In the presence of NPSCs, a contiguous network of particles forms at the interface through densification of surface structures. We show that this interconnected nanoparticle network eventually stops the interfacial flow and decreases the mobility of the glass beads at the interface. The immobilization of the interface is characterized by a dimensionless number, defined as the ratio of the interfacial elasticity to bulk shear forces. This number provides an estimate of the interfacial forces required to impose interfacial immobility at a defined flow field. Our findings can serve as a basis to formulate boundary conditions for refined modeling and to predict the hydrodynamics of bubbles and droplets.

Interfacial flow of a surfactant-laden interface under asymmetric shear flow.

HYPOTHESIS: The shear stress of the axisymmetric flow field triggers a nonuniform distribution of the surfactants at the surface of a rising bubble, known as stagnant cap. The formation of the stagnant cap gives rise to Marangoni stresses that reduce the mobility of the interface, which in return reduces the rising velocity. However, the conditions in technological processes usually deviate from the linear rise of a single bubble in a quiescent unbounded liquid. Asymmetric shear can act on the bubble surface e.g. due to the vorticity in the surrounding flow, bubble-bubble interactions, or influence of the reactor wall. A different surfactant distribution at the interface is expected under asymmetric shear, which can change the hydrodynamic behavior of the interface drastically. EXPERIMENTS: Here we conduct model experiments with a bubble or a drop at the tip of a capillary placed in a defined flow field. Thereby we investigate the influence of asymmetric shear forces on the interface in the presence of surfactants. Microscopic particle tracking velocimetry is employed to measure the velocity of the surfactant-laden interface for different degrees of asymmetry in the surrounding liquid flow. FINDINGS: We show a direct experimental observation of the circulating flow at the interface under asymmetric shear, which prevents the formation of the typical stagnant cap. Additionally, we reveal that the interface remains mobile regardless of the surfactant concentration. Our results confirm that increasing the degree of asymmetry increases the shear forces and thus the interfacial velocity.

Magnetically Induced Aggregation of Iron Oxide Nanoparticles for Carrier Flotation Strategies.

On the nanoscale, iron oxides can be used for multiple applications ranging from medical treatment to biotechnology. We aimed to utilize the specific properties of these nanoparticles for new process concepts in flotation. Magnetic nanoparticles were synthesized by alkaline coprecipitation, leading to a primary particle size of 9 nm, and coated with oleate. The nanomaterial was characterized for its superparamagnetism and its colloidal stability at different ionic strengths, with and without an external magnetic field. The nanomaterial was used for model experiments on magnetic carrier flotation of microplastic particles, based on magnetically induced heteroagglomeration. We were able to demonstrate the magnetically induced aggregation of the nanoparticles which allows for new flotation strategies. Since the nanomaterial has zero remanent magnetization, the agglomeration is reversible which facilitates the process control. Magnetic carrier flotation based on iron oxide nanoparticles can pave the way to promising new recycling processes for microplastic wastes.

The influence of negatively charged silica nanoparticles on the surface properties of anionic surfactants: electrostatic repulsion or the effect of ionic strength?

The presence of negatively charged nanoparticles affects the surface activity of anionic surfactants in an aqueous phase. Recent studies suggest that electrostatic repulsive forces play an important role in increasing the surface activity of surfactants. However, the addition of nanoparticles also increases the ionic strength of the system, which has a significant impact on the surfactant's properties, e.g. its critical micelle concentration (CMC). To investigate how and to what extent electrostatic forces and ionic strength influence the behavior of ionic surfactants, the surface tension and elasticity of different solutions were measured using drop profile tensiometry as a function of the surfactant (SDBS), nanoparticle (silica) and salt (KNO3) concentration. It is observed that the surface activity of the surfactants is mainly influenced by the change in the system's ionic strength due to the presence of nanoparticles. Several characteristic parameters including the equivalent concentration of the surfactant, the CMC and the apparent partial molar area of the adsorbed surfactant are theoretically calculated and further employed to validate experimental observations. Both the nanoparticles and electrolyte decrease the CMC, while the equivalent concentration of the surfactant remains nearly constant. This paper presents a criterion to estimate the possible influence of such forces for nanoparticles of different sizes and mass fractions.

Formation of Structured Membranes by Coacervation of Xanthan Gum with CnTAB Surfactants.

We present a novel approach for studying membrane formation by the interaction of polymers and surfactants with opposite charge using a Hele-Shaw experimental setup. A solution of the anionic biopolymer xanthan gum is placed in direct contact with a CnTAB surfactant solution (n = 10, 12, 14, and 16). Thereby, a polymer-surfactant membrane spontaneously forms between the two solutions due to the precipitation of polymer-surfactant complexes, which grows afterwards in the direction of the polymer solution. The dynamics of the growth of the membrane thickness and the mass transfer of polymer are evaluated for different surfactant types and concentrations. The experiments and supporting numerical calculations indicate that polymer mass transfer is driven by diffusion of the charged macromolecules along the concentration gradient, which is coupled to the electric field induced by the faster diffusion of the more mobile counterions. The properties and structure of the formed membrane significantly depend on the surfactant hydrophobicity and concentration. In addition, in a wide range of experiments, the formation of a porous structure in the membrane is observed whose characteristics can be tuned by the process parameters. A mechanism is proposed for the pore formation explaining it as an instability of the growing membrane surface in interaction with the supply of polymer across the depleted zone in the vicinity of the membrane front.

Influence of microscopic precipitate structures on macroscopic pattern formation in reactive flows in a confined geometry.

Thanks to the coupling between chemical precipitation reactions and hydrodynamics, new dynamic phenomena may be obtained and new types of materials can be synthesized. Here we experimentally investigate how the characteristic microscopic crystal properties affect the macroscopic pattern obtained. To shed light on such interactions, different reactant solutions are radially injected into a calcium chloride solution at different volumetric flow rates in a confined geometry. Depending on the reactants used and the flow conditions, deformed precipitate membranes have been observed due to reaction-driven viscous fingering. In such cases we show that upon injection a large number of small particles is produced in situ by the reaction at the miscible interface between the two reactant solutions. Therefore, a colloidal gel composed of those tiny particles is pushed forward by the injected aqueous solution giving rise to a viscosity gradient-driven hydrodynamic instability.

Adaptive Micromixer Based on the Solutocapillary Marangoni Effect in a Continuous-Flow Microreactor.

Continuous-flow microreactors are an important development in chemical engineering technology, since pharmaceutical production needs flexibility in reconfiguring the synthesis system rather than large volumes of product yield. Microreactors of this type have a special vessel, in which the convective vortices are organized to mix the reagents to increase the product output. We propose a new type of micromixer based on the intensive relaxation oscillations induced by a fundamental effect discovered recently. The mechanism of these oscillations was found to be a coupling of the solutal Marangoni effect, buoyancy and diffusion. The phenomenon can be observed in the vicinity of an air⁻liquid (or liquid⁻liquid) interface with inhomogeneous concentration of a surface-active solute. Important features of the oscillations are demonstrated experimentally and numerically. The periodicity of the oscillations is a result of the repeated regeneration of the Marangoni driving force. This feature is used in our design of a micromixer with a single air bubble inside the reaction zone. We show that the micromixer does not consume external energy and adapts to the medium state due to feedback. It switches on automatically each time when a concentration inhomogeneity in the reaction zone occurs, and stops mixing when the solution becomes sufficiently uniform.

Information transmission by Marangoni-driven relaxation oscillations at droplets.

Marangoni-driven relaxation oscillations can be observed in many systems where concentration gradients of surface-active substances exist. In the present paper, we describe the experimentally observed coupling between relaxation oscillations at neighboring droplets in a concentration gradient. By a numerical parameter study, we evaluate the oscillation characteristics depending on relevant material parameters and the pairwise droplet distance. Based on these findings, we demonstrate that hydrodynamic interaction in multidroplet configurations can lead to a synchronization of the oscillations over the whole ensemble. This effect has the potential to be used as a novel approach for information transmission in microfluidic applications.

Pattern formation and mass transfer under stationary solutal Marangoni instability.

According to the seminal theory by Sternling and Scriven, solutal Marangoni convection during mass transfer of surface-active solutes may occur as either oscillatory or stationary instability. With strong support of Manuel G. Velarde, a combined initiative of experimental works, in particular to mention those of Linde, Wierschem and coworkers, and theory has enabled a classification of dominant wave types of the oscillatory mode and their interactions. In this way a rather comprehensive understanding of the nonlinear evolution of the oscillatory instability could be achieved. A comparably advanced state-of-the-art with respect to the stationary counterpart seemed to be out of reach a short time ago. Recent developments on both the numerical and experimental side, in combination with assessing an extensive number of older experiments, now allow one to draw a more unified picture. By reviewing these works, we show that three main building blocks exist during the nonlinear evolution: roll cells, relaxation oscillations and relaxation oscillations waves. What is frequently called interfacial turbulence results from the interaction between these partly coexisting basic patterns which may additionally occur in different hierarchy levels. The second focus of this review lies on the practical importance of such convection patterns concerning their influence on mass transfer characteristics. Particular attention is paid here to the interaction between Marangoni and buoyancy effects which frequently complicates the pattern formation even more. To shed more light on these dependencies, new simulations regarding the limiting case of stabilizing density stratification and vanishing buoyancy are incorporated.