Nanodroplets wetting an elastic half-space.

Wetting of deformable surfaces is a highly debated topic in interface science. A classical approach employing the localized Young's traction γsinθ and curvature-induced traction following from the spherical cap assumption, is commonly used for the evaluation of the deformation - particularly, a wetting ridge - of the surface. This, however, does not provide insight into the nanophysics behind the soft wetting, and the effect the surface forces have on the wetting ridge geometry is still poorly understood. In the present paper, we use the disjoining pressure concept to study statics and dynamics of nanoscale droplets on elastic, infinitely thick surfaces. We show that the wetting ridge tip geometry does depend on the surface forces. We demonstrate that when the droplet comparable with the range of the surface force action spreads, the wetting ridge evolves in a way that its maximal height and solid angle changes with time non-monotonically.

Superspreading and Drying of Trisiloxane-Laden Quantum Dot Nanofluids on Hydrophobic Surfaces.

Nanofluids hold promise for a wide range of areas of industry. However, understanding the wetting behavior and deposition formation in the course of drying and spreading of nanofluids, particularly containing surfactants, is still poor. In this paper, the evaporation dynamics of quantum dot-based nanofluids and evaporation-driven self-assembly in nanocolloidal suspensions on hexamethyldisilazane-, polystyrene-, and polypropylene-coated hydrophobic surfaces have been studied experimentally. Moreover, for the very first time, we make a step toward understanding the wetting dynamics of superspreader surfactant-laden nanofluids. It was revealed that drying of surfactant-free quantum dot nanofluids in contrast to pure liquids undergoes not three but four evaporation modes including last additional pinning mode when the contact angle decreases while the triple contact line is pinned by the nanocrystals. In contrast to previous studies, it was found out that addition of nanoparticles to aqueous surfactant solutions leads to deterioration of the spreading rate and to formation of a double coffee ring. For all surfaces examined, superspreading in the presence and absence of quantum dot nanoparticles takes place. Despite the formation of coffee rings on all substrates, they have different morphologies. In particular, the knot-like structures are incorporated into the ring on hexamethyldisilazane- and polystyrene-coated surfaces.

Electrokinetic investigation of deposition of cationic fabric softener vesicles on anionic porous cotton fabrics.

HYPOTHESIS: Colloidal deposition on porous substrates is a complex process influenced by both, (i) characteristics of colloidal permeation into porous substrates, and (ii) mechanism of colloidal deposition on solid surfaces. Such processes are quintessential to action of products such as hair conditioners and fabric softeners where the substrates to be treated are porous. The performance of these formulations is linked with the distribution of deposited colloids across porous substrates i.e. whether deposition is localized near substrate periphery, or deposition is homogeneously distributed. EXPERIMENTS: In this work, we investigate the deposition of cationic vesicles, commonly used in fabric softeners, on anionic porous cotton yarns via spectrophotometric measurement of adsorption density of vesicles on yarns and electrokinetic measurement of cotton yarn apparent zeta potentials. Under the employed conditions, cotton yarn apparent zeta potentials are sensitive predominantly to external yarn surfaces. Therefore, these measurements can distinguish between deposition on external and internal yarn surfaces. FINDINGS: The phase behavior of lipid bilayers constituting the vesicles is identified as an important governing factor with solid-gel vesicles depositing more near yarn periphery, and liquid-crystalline vesicles depositing more uniformly throughout the yarns. Bulk electrical conductivity also influences the distribution of deposited vesicles. The results are explained with the help of a newly proposed theory.

Effect of Geometry on Electrokinetic Characterization of Solid Surfaces.

An analytical approach is presented to describe pressure-driven streaming current (Istr) and streaming potential (Ustr) generation in geometrically complex samples, for which the classical Helmholtz-Smoluchowski (H-S) equation is known to be inaccurate. The new approach is valid under the same prerequisite conditions that are used for the development of the H-S equation, that is, the electrical double layers (EDLs) are sufficiently thin and surface conductivity and electroviscous effects are negligible. The analytical methodology is developed using linear velocity profiles to describe liquid flow inside of EDLs and using simplifying approximations to describe macroscopic flow. At first, a general expression is obtained to describe the Istr generated in different cross sections of an arbitrarily shaped sample. Thereafter, assuming that the generated Ustr varies only along the pressure-gradient direction, an expression describing the variation of generated Ustr along the sample length is obtained. These expressions describing Istr and Ustr generation constitute the theoretical foundation of this work, which is first applied to a set of three nonuniform cross-sectional capillaries and thereafter to a square array of cylindrical fibers (model porous media) for both parallel and transverse fiber orientation cases. Although analytical solutions cannot be obtained for real porous substrates because of their random structure, the new theory provides useful insights into the effect of important factors such as fiber orientation, sample porosity, and sample dimensions. The solutions obtained for the model porous media are used to device strategies for more accurate zeta potential determination of porous fiber plugs. The new approach could be thus useful in resolving the long-standing problem of sample geometry dependence of zeta potential measurements.

Solid-Liquid Interface Thermal Resistance Affects the Evaporation Rate of Droplets from a Surface: A Study of Perfluorohexane on Chromium Using Molecular Dynamics and Continuum Theory.

We study the role of solid-liquid interface thermal resistance (Kapitza resistance) on the evaporation rate of droplets on a heated surface by using a multiscale combination of molecular dynamics (MD) simulations and analytical continuum theory. We parametrize the nonbonded interaction potential between perfluorohexane (C6F14) and a face-centered-cubic solid surface to reproduce the experimental wetting behavior of C6F14 on black chromium through the solid-liquid work of adhesion (quantity directly related to the wetting angle). The thermal conductances between C6F14 and (100) and (111) solid substrates are evaluated by a nonequilibrium molecular dynamics approach for a liquid pressure lower than 2 MPa. Finally, we examine the influence of the Kapitza resistance on evaporation of droplets in the vicinity of a three-phase contact line with continuum theory, where the thermal resistance of liquid layer is comparable with the Kapitza resistance. We determine the thermodynamic conditions under which the Kapitza resistance plays an important role in correctly predicting the evaporation heat flux.

Intact deposition of cationic vesicles on anionic cellulose fibers: Role of vesicle size, polydispersity, and substrate roughness studied via streaming potential measurements.

HYPOTHESIS: Understanding the mechanism of intact vesicle deposition on solid surfaces is important for effective utilization of vesicles as active ingredient carriers in applications such as drug delivery and fabric softening. In this study, the deposition of large (davg=12µm) and small (davg=0.27µm) cationic vesicles of ditallowethylester dimethylammonium chloride (DEEDMAC) on smooth and rough anionic cellulose fibers is investigated. EXPERIMENTS: The deposition process is studied quantitatively using streaming potential measurements and spectrophotometric determination of DEEDMAC concentrations. Natural and regenerated cellulose fibers, namely cotton and viscose, having rough and smooth surfaces, respectively, are used as adsorbents. Equilibrium deposition data and profiles of substrate streaming potential variation with deposition are used to gain insights into the fate of vesicles upon deposition and the deposition mechanism. FINDINGS: Intact deposition of DEEDMAC vesicles is ascertained based on streaming potential variation with deposition in the form of characteristic saturating profiles which symbolize particle-like deposition. The same is also confirmed by confocal fluorescence microscopy. Substrate roughness is found to considerably influence the deposition mechanism which, in a novel application of electrokinetic methods, is elucidated via streaming potential measurements.

Modulation of Marangoni convection in liquid films.

Non-isothermal liquid films are subject to short- and long-wave modes of Marangoni instability. The short-wave instability leads to the development of convection cells, whereas long-wave instability is one of the primary causes of the film rupture. In this paper different methods for modulation of Marangoni convection and Marangoni-induced interface deformation in non-isotherm liquid films are reviewed. These methods include modification of substrates through topographical features, using substrates with non-uniform thermal properties, non-uniform radiative heating of the liquid-gas interface and non-uniform heating of substrates. All these approaches aim at promotion of temperature gradients along the liquid-gas interface, which leads to emergence of thermocapillary stresses, to the development of vortices and to the interface deformation. Finally, Marangoni convection in a liquid film supported by a substrate with periodic temperature distribution is modeled by solution of steady state creeping flow equations. This approach is justified for low Reynolds numbers and for Marangoni convection in liquids with high Prandtl numbers. The model predicts interaction between Marangoni convection induced by non-uniform wall heating and the Marangoni short-wave instability.

Inverse-Leidenfrost phenomenon on nanofiber mats on hot surfaces.

The Leidenfrost effect is a technically and industrially important phenomenon that severely restricts heat removal from high-heat-flux surfaces. A simple remedy to the Leidenfrost effect is provided by polymer nanofiber mats created and deposited by electrospinning on stainless steel surfaces. The influence of nanofiber mats on hydrodynamics and cooling efficiency of single drop impact onto hot surfaces has been investigated experimentally. The evolution of the drops has been recorded by a high-speed complimentary metal-oxide semiconductor camera, whereas the cooling temperature was measured by a thermocouple. A remarkable phenomenon was discovered: a mat of polymer nanofibers electrospun onto a heater surface can completely suppress the Leidenfrost effect, thereby increasing the rate of heat removal from the surface to the liquid drops significantly. The "inverse-Leidenfrost" effect is described qualitatively and quantitatively, providing clear physical reasons for the observed behavior.

Nonisothermal drop impact and evaporation on polymer nanofiber mats.

The work describes the experimental and theoretical investigation of water drop impact onto electrospun polymer nanofiber mats deposited on heated stainless-steel foils. The measurements encompass water spreading over and inside the mat, as well as the corresponding thermal field. The results show that the presence of polymer nanofiber mats prevents receding motion of drops after their complete spreading and promotes the moisture spreading inside the mat over a large area of the heater, which facilitates a tenfold enhancement of heat removal as the latent heat of drop evaporation.

Dynamics of the cavity and the surface film for impingements of single drops on liquid films of various thicknesses.

This paper presents experimental and numerical investigations of single drop impacts onto liquid films of finite thickness. The dynamics of the drop impingement on liquid surface films, the shape of the cavity, the surface film dynamics and the residual film thickness are investigated and analysed. The shape of the penetrating cavity within the surface film is observed experimentally using a high-speed video system. Additionally, the thickness of the liquid film between the expanding, receding and retracting cavity and the solid wall is monitored in time using an optical sensor based on chromatic confocal imaging. The effects of various influencing parameters, such as the drop impingement velocity, liquid properties (surface tension and viscosity) and the initial liquid film thickness, on the time evolution of the cavity and film dynamics are investigated. Complementary to the experiments direct numerical simulations of the drop impacts and cavity expansion are performed using a volume-of-fluid free-surface capturing model in the framework of the finite volume numerical method. The numerical predictions of the film thickness dynamics agree well with the experiments for most phases of the impingement process. Finally, a scaling analysis of the residual film thickness between the cavity and the solid wall is performed for various impingement parameters.

Drop impact, spreading, splashing, and penetration into electrospun nanofiber mats.

Experiments were conducted to study peculiarities of drop impact onto electrospun polymer nanofiber mats. The nanofiber cross-sectional diameters were of the order of several hundred nanometers, the pore sizes in the mats of about several micrometers, and the mat thicknesses of the order of 200 microm. Polyacrylonitrile (PAN), a polymer which is partially wettable by water, was used to electrospin nanofiber mats. The experiments revealed that drop impact onto nanotextured surfaces of nanofiber mats produce spreading similar to that on the impermeable surfaces. However, at the end of the spreading stage, the contact line is pinned and drop receding is prevented. At higher impact velocities, prompt splashing events with formation of tiny drops were observed. It was shown that the splash parameter K(d) = We(1/2) Re(1/4) (with We and Re being the Weber and Reynolds numbers, respectively) previously used to characterize the experiments with drop impact onto smooth impermeable dry substrates can be also used to describe the onset of splash on substrates coated by nanofiber mats. However its threshold value K(ds) (in particular, corresponding to the minimal impact velocity leading to generation of secondary droplets) for the nanotextured surfaces is higher than that for dry flat substrates. In addition, water penetration and spreading inside wettable nanofiber mats after drop impact was elucidated and quantified. The hydrodynamics of drop impact onto nanofiber mats is important for understanding effective spray cooling through nanofiber mats, recently introduced by the same group of authors.

Static and dynamic contact angles of evaporating liquids on heated surfaces.

We studied both static and dynamic values of the apparent contact angle for gravity-driven flow of a volatile liquid down a heated inclined plane. The apparent contact line is modeled as the transition region between the macroscopic film and ultra-thin adsorbed film dominated by disjoining pressure effects. Four commonly used disjoining pressure models are investigated. The static contact angle is shown to increase with heater temperature, in qualitative agreement with experimental observations. The angle is less sensitive to the details of the disjoining pressure curves than in the isothermal regime. A generalization of the classical Frumkin-Derjaguin theory is proposed to explain this observation. The dynamic contact angle follows the Tanner's law remarkably well over a range of evaporation conditions. However, deviations from the predictions based on the Tanner's law are found when interface shape changes rapidly in response to rapid changes of the heater temperature. The Marangoni stresses are shown to result in increase of the values of apparent contact angles.

Breakup and atomization of a stretching crown.

This study is devoted to experimental and theoretical investigation of splash produced by spray impact onto a smooth, rigid target under microgravity conditions. In particular, the formation of a film by the deposited liquid, the propagation and breakup of uprising sheets created by drop impacts, and the creation of secondary droplets have been observed. Three scenarios of splash have been identified during the experiments: (i) cusp formation and jetting due to the rim transverse instability, (ii) sheet destruction and the consequent rapid axisymmetric capillary breakup of a free rim, and (iii) the rim merging. Experimental data for various geometrical parameters of splash have been collected. Next, in order to predict the typical length scales of the interjet distance, a linear stability analysis of the rim in relation to transverse disturbances has been performed. The influence of the sheet stretching has been investigated and shown to be significant. The experimentally measured average values of the interjet distances agree well with the theoretical predictions. The sheet stretching is responsible for the appearance of the relatively long interjet distances.