Enhancement of bubble transport in porous electrodes and catalysts.

We investigate the formation and transport of gas bubbles across a model porous electrode/catalyst using lattice Boltzmann simulations. This approach enables us to systematically examine the influence of a wide range of morphologies, flow velocities, and reaction rates on the efficiency of gas production. By exploring these parameters, we identify critical parameter combinations that significantly contribute to an enhanced yield of gas output. Our simulations reveal the existence of an optimal pore geometry for which the product output is maximized. Intriguingly, we also observe that lower flow velocities improve gas production by leveraging coalescence-induced bubble detachment from the electrode/catalyst.

Local electroneutrality breakdown for electrolytes within varying-section nanopores.

We determine the local charge dynamics of a [Formula: see text] electrolyte embedded in a varying-section channel. By means of an expansion based on the length scale separation between the axial and transverse direction of the channel, we derive closed formulas for the local excess charge for both, dielectric and conducting walls, in 2D (planar geometry) as well as in 3D (cylindrical geometry). Our results show that, even at equilibrium, the local charge electroneutrality is broken whenever the section of the channel is not homogeneous for both dielectric and conducting walls as well as for 2D and 3D channels. Interestingly, even within our expansion, the local excess charge in the fluid can be comparable to the net charge on the walls. We critically discuss the onset of such local electroneutrality breakdown in particular with respect to the correction that it induces on the effective free energy profile experienced by tracer ions.

Cell-free layer development and spatial organization of healthy and rigid red blood cells in a microfluidic bifurcation.

Bifurcations and branches in the microcirculation dramatically affect blood flow as they determine the spatiotemporal organization of red blood cells (RBCs). Such changes in vessel geometries can further influence the formation of a cell-free layer (CFL) close to the vessel walls. Biophysical cell properties, such as their deformability, which is impaired in various diseases, are often thought to impact blood flow and affect the distribution of flowing RBCs. This study investigates the flow behavior of healthy and artificially hardened RBCs in a bifurcating microfluidic T-junction. We determine the RBC distribution across the channel width at multiple positions before and after the bifurcation. Thus, we reveal distinct focusing profiles in the feeding mother channel for rigid and healthy RBCs that dramatically impact the cell organization in the successive daughter channels. Moreover, we experimentally show how the characteristic asymmetric CFLs in the daughter vessels develop along their flow direction. Complimentary numerical simulations indicate that the buildup of the CFL is faster for healthy than for rigid RBCs. Our results provide fundamental knowledge to understand the partitioning of rigid RBC as a model of cells with pathologically impaired deformability in complex in vitro networks.

Diffusion of gold nanoparticles in porous silica monoliths determined by dynamic light scattering.

HYPOTHESIS: The applicability of the dynamic light scattering method for the determination of particle diffusivity under confinement without applying refractive index matching was not adequately explored so far. The confinement effect on particle diffusion in a porous material which is relevant for particle chromatography has also not yet been fully characterized. EXPERIMENTS: Dynamic light scattering experiments were performed for unimodal dispersions of 11-mercaptoundecanoic acid-capped gold nanoparticles. Diffusion coefficients of gold nanoparticles in porous silica monoliths were determined without limiting refractive index matching fluids. Comparative experiments were also performed with the same nanoparticles and porous silica monolith but applying refractive index matching. FINDINGS: Two distinct diffusivities could be determined inside the porous silica monolith, both smaller than that in free media, showing a slowing-down of the diffusion processes of nanoparticles under confinement. While the larger diffusivity can be related to the slightly slowed-down diffusion of particles in the bulk of the pores and in the necks connecting individual pores, the smaller diffusivity might be related to the diffusion of particles near the pore walls. It shows that the dynamic light scattering method with a heterodyne detection scheme can be used as a reliable and competitive tool for determining particle diffusion under confinement.

Closed Formula for Transport across Constrictions.

In the last decade, the Fick-Jacobs approximation has been exploited to capture transport across constrictions. Here, we review the derivation of the Fick-Jacobs equation with particular emphasis on its linear response regime. We show that, for fore-aft symmetric channels, the flux of noninteracting systems is fully captured by its linear response regime. For this case, we derive a very simple formula that captures the correct trends and can be exploited as a simple tool to design experiments or simulations. Lastly, we show that higher-order corrections in the flux may appear for nonsymmetric channels.

Technological Pathways to Produce Compressed and Highly Pure Hydrogen from Solar Power.

Hydrogen (H2 ) produced from renewables will have a growing impact on the global energy dynamics towards sustainable and carbon-neutral standards. The share of green H2 is still too low to meet the net-zero target, while the demand for high-quality hydrogen continues to rise. These factors amplify the need for economically viable H2 generation technologies. The present article aims at evaluating the existing technologies for high-quality H2 production based on solar energy. Technologies such as water electrolysis, photoelectrochemical and solar thermochemical water splitting, liquid metal reactors and plasma conversion utilize solar power directly or indirectly (as carbon-neutral electrons) and are reviewed from the perspective of their current development level, technical limitations and future potential.

Nucleation as a rate-determining step in catalytic gas generation reactions from liquid phase systems.

The observable reaction rate of heterogeneously catalyzed reactions is known to be limited either by the intrinsic kinetics of the catalytic transformation or by the rate of pore and/or film diffusion. Here, we show that in gas generation reactions from liquid reactants, the nucleation of gas bubbles in the catalyst pore structure represents an additional important rate-limiting step. This is highlighted for the example of catalytic hydrogen release from the liquid organic hydrogen carrier compound perhydro-dibenzyltoluene. A nucleation-inhibited catalytic system produces only dissolved hydrogen with fast saturation of the fluid phase around the active site, while bubble formation enhances mass transfer by more than a factor of 50 in an oscillating reaction regime. Nucleation can be efficiently triggered not only by temperature changes and catalyst surface modification but also by a mechanical stimulus. Our work sheds new light on performance-limiting factors in reactions that are of highest relevance for the future green hydrogen economy.

Rolling microswarms along acoustic virtual walls.

Rolling is a ubiquitous transport mode utilized by living organisms and engineered systems. However, rolling at the microscale has been constrained by the requirement of a physical boundary to break the spatial homogeneity of surrounding mediums, which limits its prospects for navigation to locations with no boundaries. Here, in the absence of real boundaries, we show that microswarms can execute rolling along virtual walls in liquids, impelled by a combination of magnetic and acoustic fields. A rotational magnetic field causes individual particles to self-assemble and rotate, while the pressure nodes of an acoustic standing wave field serve as virtual walls. The acoustic radiation force pushes the microswarms towards a virtual wall and provides the reaction force needed to break their fore-aft motion symmetry and induce rolling along arbitrary trajectories. The concept of reconfigurable virtual walls overcomes the fundamental limitation of a physical boundary being required for universal rolling movements.

Formation of Crystalline Bulk Heterojunctions in Organic Solar Cells: Insights from Phase-Field Simulations.

The performance of organic solar cells strongly depends on the bulk-heterojunction (BHJ) morphology of the photoactive layer. This BHJ forms during the drying of the wet-deposited solution, because of physical processes such as crystallization and/or liquid-liquid phase separation (LLPS). However, the process-structure relationship remains insufficiently understood. In this work, a recently developed, coupled phase-field-fluid mechanics framework is used to simulate the BHJ formation upon drying. For the first time, this allows to investigate the interplay between all the relevant physical processes (evaporation, crystal nucleation and growth, liquid demixing, composition-dependent kinetic properties), within a single coherent theoretical framework. Simulations for the model system P3HT-PCBM are presented. The comparison with previously reported in situ characterization of the drying structure is very convincing: The morphology formation pathways, crystallization kinetics, and final morphology are in line with experimental results. The final BHJ morphology is a subtle mixture of pure crystalline donor and acceptor phases, pure and mixed amorphous domains, which depends on the process parameters and material properties. The expected benefit of such an approach is to identify physical design rules for ink formulation and processing conditions to optimize the cell's performance. It could be applied to recent organic material systems in the future.

Accuracy and performance of the lattice Boltzmann method with 64-bit, 32-bit, and customized 16-bit number formats.

Fluid dynamics simulations with the lattice Boltzmann method (LBM) are very memory intensive. Alongside reduction in memory footprint, significant performance benefits can be achieved by using FP32 (single) precision compared to FP64 (double) precision, especially on GPUs. Here we evaluate the possibility to use even FP16 and posit16 (half) precision for storing fluid populations, while still carrying arithmetic operations in FP32. For this, we first show that the commonly occurring number range in the LBM is a lot smaller than the FP16 number range. Based on this observation, we develop customized 16-bit formats-based on a modified IEEE-754 and on a modified posit standard-that are specifically tailored to the needs of the LBM. We then carry out an in-depth characterization of LBM accuracy for six different test systems with increasing complexity: Poiseuille flow, Taylor-Green vortices, Karman vortex streets, lid-driven cavity, a microcapsule in shear flow (utilizing the immersed-boundary method), and, finally, the impact of a raindrop (based on a volume-of-fluid approach). We find that the difference in accuracy between FP64 and FP32 is negligible in almost all cases, and that for a large number of cases even 16-bit is sufficient. Finally, we provide a detailed performance analysis of all precision levels on a large number of hardware microarchitectures and show that significant speedup is achieved with mixed FP32/16-bit.

Hydrodynamic simulations of sedimenting dilute particle suspensions under repulsive DLVO interactions.

We present guidelines to estimate the effect of electrostatic repulsion in sedimenting dilute particle suspensions. Our results are based on combined Langevin dynamics and lattice Boltzmann simulations for a range of particle radii, Debye lengths and particle concentrations. They show a simple relationship between the slope K of the concentration-dependent sedimentation velocity and the range χ of the electrostatic repulsion normalized by the average particle-particle distance. When χ → 0, the particles are too far away from each other to interact electrostatically and K = 6.55 as predicted by the theory of Batchelor. As χ increases, K likewise increases as if the particle radius increased in proportion to χ up to a maximum around χ = 0.4. Over the range χ = 0.4-1, K relaxes exponentially to a concentration-dependent constant consistent with known results for ordered particle distributions. Meanwhile the radial distribution function transitions from a disordered gas-like to a liquid-like form. Power law fits to the concentration-dependent sedimentation velocity similarly yield a simple master curve for the exponent as a function of χ, with a step-like transition from 1 to 1/3 centered around χ = 0.6.

Phase-Field Simulation of Liquid-Vapor Equilibrium and Evaporation of Fluid Mixtures.

In solution processing of thin films, the material layer is deposited from a solution composed of several solutes and solvents. The final morphology and hence the properties of the film often depend on the time needed for the evaporation of the solvents. This is typically the case for organic photoactive or electronic layers. Therefore, it is important to be able to predict the evaporation kinetics of such mixtures. We propose here a new phase-field model for the simulation of evaporating fluid mixtures and simulate their evaporation kinetics. Similar to the Hertz-Knudsen theory, the local liquid-vapor (LV) equilibrium is assumed to be reached at the film surface and evaporation is driven by diffusion away from this gas layer. In the situation where the evaporation is purely driven by the LV equilibrium, the simulations match the behavior expected theoretically from the free energy: for evaporation of pure solvents, the evaporation rate is constant and proportional to the vapor pressure. For mixtures, the evaporation rate is in general strongly time-dependent because of the changing composition of the film. Nevertheless, for highly nonideal mixtures, such as poorly compatible fluids or polymer solutions, the evaporation rate becomes almost constant in the limit of low Biot numbers. The results of the simulation have been successfully compared to experiments on a polystyrene-toluene mixture. The model allows to take into account deformations of the liquid-vapor interface and, therefore, to simulate film roughness or dewetting.

Two-dimensional Cahn-Hilliard simulations for coarsening kinetics of spinodal decomposition in binary mixtures.

The evolution of the microstructure due to spinodal decomposition in phase separated mixtures has a strong impact on the final material properties. In the late stage of coarsening, the system is characterized by the growth of a single characteristic length scale L ∼ Ctα. To understand the structure-property relationship, the knowledge of the coarsening exponent α and the coarsening rate constant C is mandatory. Since the existing literature is not entirely consistent, we perform phase field simulations based on the Cahn-Hilliard equation. We restrict ourselves to binary mixtures using a symmetric Flory-Huggins free energy and a constant composition-independent mobility term and show that the coarsening for off-critical mixtures is slower than the expected t1/3-growth. Instead, we find α to be dependent on the mixture composition and associate this with the observed morphologies. Finally, we propose a model to describe the complete coarsening kinetics including the rate constant C.

Bio-inspired Acousto-magnetic Microswarm Robots with Upstream Motility.

The ability to propel against flows, i.e., to perform positive rheotaxis, can provide exciting opportunities for applications in targeted therapeutics and non-invasive surgery. To date, no biocompatible technologies exist for navigating microparticles upstream when they are in a background fluid flow. Inspired by many naturally- occurring microswimmers such as bacteria, spermatozoa, and plankton that utilize the non-slip boundary conditions of the wall to exhibit upstream propulsion, here, we report on the design and characterization of self-assembled microswarms that can execute upstream motility in a combination of external acoustic and magnetic fields. Both acoustic and magnetic fields are safe to humans, non-invasive, can penetrate deeply into the human body, and are well-developed in clinical settings. The combination of both fields can overcome the limitations encountered by single actuation methods. The design criteria of the acoustically-induced reaction force of the microswarms, which is needed to perform rolling-type motion, are discussed. We show quantitative agreement between experimental data and our model that captures the rolling behaviour. The upstream capability provides a design strategy for delivering small drug molecules to hard-to-reach sites and represents a fundamental step toward the realization of micro- and nanosystem-navigation against the blood flow.

Regimes of motion of magnetocapillary swimmers.

The dynamics of a triangular magnetocapillary swimmer is studied using the lattice Boltzmann method. We extend on our previous work, which deals with the self-assembly and a specific type of the swimmer motion characterized by the swimmer's maximum velocity centred around the particle's inverse viscous time. Here, we identify additional regimes of motion. First, modifying the ratio of surface tension and magnetic forces allows to study the swimmer propagation in the regime of significantly lower frequencies mainly defined by the strength of the magnetocapillary potential. Second, introducing a constant magnetic contribution in each of the particles in addition to their magnetic moment induced by external fields leads to another regime characterized by strong in-plane swimmer reorientations that resemble experimental observations.

Monolayer Structures of Supramolecular Antagonistic Salt Aggregates.

The speculated presence of monomolecular lamellae of antagonistic salts in oil-water mixtures has left several open questions besides their hypothetical existence, including their microscopic structure and stabilization mechanism. Here, we simulate the spontaneous formation of supramolecular aggregates of the antagonistic salt sodium tetraphenylborate (NaBPh4) in water and 3-methylpyridine (3-MP) at the atomistic level. We show that, indeed, the lamellae are formed by a monomolecular layer of the anion, enveloped by 3-MP and hydrated sodium counterions. To understand which thermodynamic forces drive the aggregation, we compare the full-atomistic model with a simplified one for the salt and show that the strong hydrophobic effect granted by the large excluded volume of the anion, together with electrostatic repulsion, suffice to explain the stability of the monomolecular lamellae.

Transport of neutral and charged nanorods across varying-section channels.

We study the dynamics of neutral and charged rods embedded in varying-section channels. By means of systematic approximations, we derive the dependence of the local diffusion coefficient on both the geometry and charge of the rods. This microscopic insight allows us to provide predictions for the permeability of varying-section channels to rods with diverse lengths, aspect ratios and charge. Our analysis shows that the dynamics of charged rods is sensitive to the geometry of the channel and that their transport can be controlled by tuning both the shape of the confining walls and the charge of the rod. Interestingly, we find that the channel permeability does not depend monotonically on the charge of the rod. This opens the possibility of a novel mechanism to separate charged rods.

Controllable Capillary Assembly of Magnetic Ellipsoidal Janus Particles into Tunable Rings, Chains and Hexagonal Lattices.

Colloidal assembly at fluid interfaces has a great potential for the bottom-up fabrication of novel structured materials. However, challenges remain in realizing controllable and tunable assembly of particles into diverse structures. Herein, the capillary assembly of magnetic ellipsoidal Janus particles at a fluid-fluid interface is reported. Depending on their tilt angle, that is, the angle the particle main axis forms with the fluid interface, these particles deform the interface and generate capillary dipoles or hexapoles. Driven by capillary interactions, multiple particles thus assemble into chain-, hexagonal-lattice-, and ring-like structures, which can be actively controlled by applying an external magnetic field. A field-strength phase diagram is predicted in which various structures are present as stable states. Owing to the diversity, controllability, and tunability of assembled structures, magnetic ellipsoidal Janus particles at fluid interfaces could therefore serve as versatile building blocks for novel materials.

Squeezing multiple soft particles into a constriction: Transition to clogging.

We study numerically how multiple deformable capsules squeeze into a constriction. This situation is largely encountered in microfluidic chips designed to manipulate living cells, which are soft entities. We use fully three-dimensional simulations based on the lattice Boltzmann method to compute the flow of the suspending fluid and on the immersed boundary method to achieve the two-way fluid-structure interaction. The mechanics of the capsule membrane elasticity is computed with the finite-element method. We obtain two main states: continuous passage of the particles and their blockage that leads to clogging the constriction. The transition from one state to another is dictated by the ratio between the size of the capsules and the constriction width and by the capsule membrane deformability. The latter is found to enhance particle passage through narrower constrictions, where rigid particles with similar diameter are blocked and lead to clogging.

Capillary interactions between soft capsules protruding through thin fluid films.

When a suspension dries, the suspending fluid evaporates, leaving behind a dry film composed of the suspended particles. During the final stages of drying, the height of the fluid film on the substrate drops below the particle size, inducing local interface deformations that lead to strong capillary interactions among the particles. Although capillary interactions between rigid particles are well studied, much is still to be understood about the behaviour of soft particles and the role of their softness during the final stages of film drying. Here, we use our recently-introduced numerical method that couples a fluid described using the lattice Boltzmann approach to a finite element description of deformable objects to investigate the drying process of a film with suspended soft particles. Our measured menisci deformations and lateral capillary forces, which agree well with previous theoretical and experimental works in case of rigid particles, show that the deformations become smaller with increasing particle softness, resulting in weaker lateral interaction forces. At large interparticle distances, the force approaches that of rigid particles. Finally, we investigate the time dependent formation of particle clusters at the late stages of the film drying.