Generic theory of colloidal transport

We discuss the motion of colloidal particles relative to a two component fluid consisting of solvent and solute. Particle motion can result from (i) net body forces on the particle due to external fields such as gravity; (ii) slip velocities on the particle surface due to surface dissipative phenomena. The perturbations of the hydrodynamic flow field exhibits characteristic differences in cases (i) and (ii) which reflect different patterns of momentum flux corresponding to the existence of net forces, force dipoles or force quadrupoles. In the absence of external fields, gradients of concentration or pressure do not generate net forces on a colloidal particle. Such gradients can nevertheless induce relative motion between particle and fluid. We present a generic description of surface dissipative phenomena based on the linear response of surface fluxes driven by conjugate surface forces. In this framework we discuss different transport scenarios including self-propulsion via surface slip that is induced by active processes on the particle surface. We clarify the nature of force balances in such situations.Comment: 22 pages, 1 figur

Hydration and Ordering of Lamellar Block Copolymer Films under Controlled Water Vapor

Amphiphilic block copolymers within a range of volume fraction spontaneously form vesicles in aqueous solution, where a water core is enclosed by a polymer bilayer. Thin-film rehydration is a method used to produce vesicles routinely; a thin film is immersed in water, the film swells, and vesicles are formed which bleb off from the film surface. We have studied the early stages of hydration for PEO–PBO block copolymer thin films under controlled water vapor conditions to understand this formation mechanism and so enable more efficient ways to encapsulate molecules using this method. Neutron and X-ray measurements show that the initial film exhibits weakly ordered structure with isotropic parallel and vertical orientation; the films initially swell and maintain the same orientation. At a critical point the layer swells rapidly and makes highly ordered lamellae structure at the same time. The lamellae are almost exclusively oriented parallel to the substrate and swell with increasing water absorption

Phoretic Motion of Spheroidal Particles Due To Self-Generated Solute Gradients

We study theoretically the phoretic motion of a spheroidal particle, which generates solute gradients in the surrounding unbounded solvent via chemical reactions active on its surface in a cap-like region centered at one of the poles of the particle. We derive, within the constraints of the mapping to classical diffusio-phoresis, an analytical expression for the phoretic velocity of such an object. This allows us to analyze in detail the dependence of the velocity on the aspect ratio of the polar and the equatorial diameters of the particle and on the fraction of the particle surface contributing to the chemical reaction. The particular cases of a sphere and of an approximation for a needle-like particle, which are the most common shapes employed in experimental realizations of such self-propelled objects, are obtained from the general solution in the limits that the aspect ratio approaches one or becomes very large, respectively.Comment: 18 pages, 5 figures, to appear in European Physical Journal

In-situ full-wafer metrology via coupled white light and monochromatic stroboscopic illumination

This work presents a novel optical setup to provide scalable in-situ metrology during spin coating. Stroboscopic white light imaging provides high resolution color videos of the process, at a temporal resolution matching the spin speed, where thin film interference colors are observed. Monochromatic specular reflection intensity data from the center of rotation provides a thickness profile at this point. By developing a color to thickness relationship in-situ with the combination of these techniques and leveraging the large-area data provided by color imaging, the thickness at any point on the wafer is reconstructed via a mapping procedure with minimal a-priori information. Experiments are carried out on full 3″ diameter wafers spun with pure xylene or pure butyl acetate, and the thickness profile at all points on the wafer can be determined. Differences in the topology of these solvents whilst drying are linked back to the solvent properties. The color to thickness mapping procedure is shown to have less than 5 % error in determined thickness values between 2μm and 100nm. The possible length scale resolved by the imaging is fully discussed as a function of radius, spin speed, strobe pulse duration and hardware used. The studies in this work achieved a minimum lateral resolution of 315μm when observing a full wafer, which is sufficiently detailed to properly reconstruct thickness variations caused by common spin-coating defects such as comets. The large area and scalable nature of this metrology technique lends itself to applications in semiconductor manufacturing where substrates of 300 mm are standard

Perovskite crystallization dynamics during spin-casting : an In situ wide-angle x-ray scattering study

In situ wide-angle X-ray scattering (WAXS) has been measured during the spin coating process used to make the precursor films required for the formation of thin films of perovskite. A customized hollow axis spin coater was developed to permit the scattered X-rays to be collected in transmission geometry during the deposition process. Spin coating is the technique most commonly used in laboratories to make thin perovskite films. The dynamics of spin-casting MAPbI3–xClx and FAPbI3–xClx films have been investigated and compared to investigate the differences between the dynamics of MAPbI3–xClx and FAPbI3–xClx film formation. In particular, we focus on the crystallization dynamics of the precursor film formation. When casting MAPbI3–xClx, we observed relatively fast 1D crystallization of the intermediate product MA2PbI3Cl. There was an absence of the desired perovskite phase formed directly; it only appeared after an annealing step that converted the MA2PbI3Cl to MAPbI3. In contrast, slower crystallization via a 3D precursor was observed for FAPbI3–xClx film formation compared to MAPbI3–xClx. Another important finding was that some FAPbI3–xClx perovskite was generated directly during spin-casting before annealing. These findings indicate that there are significant differences between the crystallization pathways for these two perovskite materials. These are likely to explain the differences in the lifetimes of the resulting perovskite solar cell devices produced using FA and MA cations

Periodic and Quasiperiodic Motion of an Elongated Microswimmer in Poiseuille Flow

We study the dynamics of a prolate spheroidal microswimmer in Poiseuille flow for different flow geometries. When moving between two parallel plates or in a cylindrical microchannel, the swimmer performs either periodic swinging or periodic tumbling motion. Although the trajectories of spherical and elongated swimmers are qualitatively similar, the swinging and tumbling frequency strongly depends on the aspect ratio of the swimmer. In channels with reduced symmetry the swimmers perform quasiperiodic motion which we demonstrate explicitely for swimming in a channel with elliptical cross section

Extensional flow affecting shear viscosity: experimental evidence and comparison to models

The effect of extensional flow on apparent shear viscosity has never previously been directly measured nor is it often considered. Here, for the first time, through using a novel flow configuration (two-phase shear response under extensional flow), we have directly measured the effect extensional flow has on the apparent shear viscosity of a viscoelastic polymer solution in a controlled and kinematically mixed manner. We show, via a control transient shear experiment, that the apparent shear viscosity of the solution under mixed deformation depends not only on the shear rate but also on the extension rate and their relative direction: shear thinning being enhanced by parallel and reduced by perpendicular extensional flow, respectively. A 62% reduction in apparent viscosity with parallel extension was seen in this work. We then test the ability of the commonly used Giesekus and Carreau–Yasuda (incorporating generalized shear rate) models to predict the effect of extension rate on apparent shear viscosity against our data. The Giesekus model was found to predict the correct qualitative behavior under both parallel and perpendicular extensional flow, and depending on the fitting parameters, also provided a loosely quantitative agreement. Conversely, the generalized shear rate description does not capture the qualitative behavior, with the most significant errors occurring for perpendicular extension (i.e., expansion) flows. This work emphasizes the rarely noted shortcomings of the latter approach when used for experimental analysis and engineering design when extensional flows are additionally present

Surrogate-assisted optimization of roll-to-roll slot die coating

Roll-to-roll slot die coating is a key wet processing technique, where achieving a specific thickness with minimal variability is crucial. However, the numerous input parameters make optimization complex. Despite its advanced applications, computer-aided optimization remains underutilized, leaving potential performance improvements untapped. Due to the lack of accurate first-principle models, machine learning offers a promising approach. This study employs Radial Basis Function Neural Networks as surrogate models trained on experimental data to optimize roll-to-roll slot die coating. These models predict coating thickness and uniformity with mean absolute errors below 11.5 %. Key process parameters are identified, with shim thickness and substrate velocity having the greatest impact on coating uniformity, while coating gap played a lesser role. An evolutionary optimization approach identified new operating parameters, leading to improved coating properties. Experimentally, these optimized conditions achieved the five lowest recorded uniformity values and increased the hyper-volume fraction from 0.68 to 0.84. Some prediction inconsistencies were observed, likely due to the high sensitivity of lab-scale equipment, which is expected to improve at an industrial scale. This work paves the way for wider adoption of machine learning and accurate metrology in slot die coating

Active Brownian Particles. From Individual to Collective Stochastic Dynamics

We review theoretical models of individual motility as well as collective dynamics and pattern formation of active particles. We focus on simple models of active dynamics with a particular emphasis on nonlinear and stochastic dynamics of such self-propelled entities in the framework of statistical mechanics. Examples of such active units in complex physico-chemical and biological systems are chemically powered nano-rods, localized patterns in reaction-diffusion system, motile cells or macroscopic animals. Based on the description of individual motion of point-like active particles by stochastic differential equations, we discuss different velocity-dependent friction functions, the impact of various types of fluctuations and calculate characteristic observables such as stationary velocity distributions or diffusion coefficients. Finally, we consider not only the free and confined individual active dynamics but also different types of interaction between active particles. The resulting collective dynamical behavior of large assemblies and aggregates of active units is discussed and an overview over some recent results on spatiotemporal pattern formation in such systems is given.Comment: 161 pages, Review, Eur Phys J Special-Topics, accepte

pH‐responsive catalytic janus motors with autonomous navigation and cargo‐release functions

The fabrication of multifunctional polymeric Janus colloids that display catalytically driven propulsion, change their size in response to local variations in pH, and vary cargo release rate is demonstrated. Systematic investigation of the colloidal trajectories reveals that in acidic environments the propulsion velocity reduces dramatically due to colloid swelling. This leads to a chemotaxis‐like accumulation for ensembles of these responsive particles in low‐pH regions. In synergy with this chemically defined accumulation, the colloids also show an enhancement in the release rate of an encapsulated cargo molecule. Together, these effects result in a strategy to harness catalytic propulsion for combined autonomous transport and cargo release directed by a chemical stimulus, displaying a greater than 30 times local cargo‐accumulation enhancement. Lactic acid can be used as the stimulus for this behavior, an acid produced by some tumors, suggesting possible eventual utility as a drug‐delivery method. Applications for microfluidic transport are also discussed