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Wetting phenomena are widespread in both natural and technological contexts. Despite the well-established nature of this scientific field and our extensive knowledge of its underlying principles, wetting remains a dynamic and vibrant area of study. It continues to pose fundamental questions while offering innovative avenues for controlling these phenomena to develop novel applications. By tailoring the wetting properties of surfaces, researchers and engineers can design materials with specific functionalities, such as self-cleaning surfaces, anti-fog coatings, and enhanced slipperiness. Recent years have witnessed significant advancements in wetting research, owing to the exquisite control achieved in surface topography and chemistry and to the development of novel experimental techniques. Additionally, simulations and theory have played a crucial role in these advancements. They provid the fundamental knowledge and quantitative tools to control wettability and design surfaces with enhanced properties. Given these recent breakthroughs, this special collection Chemical Physics of Controlled Wettability and Super Surfaces becomes particularly timely and significant. It serves as a platform to showcase some of the latest developments in the field of wetting. It highlights the exciting progress and potential applications in controlling wetting properties that are enabled by the synergy between theory, simulations, and experiments., Comment: EDITORIAL: Special Topic: Chemical Physics of Controlled Wettability and Super Surfaces

Heat exchangers are made of metals because of their high heat conductivity and mechanical stability. Metal surfaces are inherently hydrophilic, leading to inefficient filmwise condensation. It is still a challenge to coat these metal surfaces with a durable, robust and thin hydrophobic layer, which is required for efficient dropwise condensation. Here, we report the non-structured and ultrathin (~6 nm) polydimethylsiloxane (PDMS) brushes on copper that sustain high-performing dropwise condensation in high supersaturation. Due to the flexible hydrophobic siloxane polymer chains, the coating has low resistance to drop sliding and excellent chemical stability. The PDMS brushes can sustain dropwise condensation for up to ~8 h during exposure to 111 {\deg}C saturated steam flowing at 3 m/s, with a 5-7 times higher heat transfer coefficient compared to filmwise condensation. The surface is self-cleaning and can reduce bacterial attachment by 99%. This low-cost, facile, fluorine-free, and scalable method is suitable for a great variety of condensation heat transfer applications., Comment: Submitted to ACS Materials and Interfaces

Modification of surfaces to enable dropwise condensation is a promising approach for achieving high condensation rates. In this work, we present an experimental study on condensation of water on copper surfaces coated with an ultrathin, 5 nm - 10 nm thick polydimethylsiloxane (PDMS) layer. This hydrophobic coating possesses a very low thermal resistance, which in combination with copper substrate enables achieving high condensation rates in heat transfer applications. The PDMS-coated copper substrates have been fabricated with a newly developed method, which involves turning, sanding, polishing, oxidation, and polymer coating steps. The measured static contact angle was 110{\deg}, and a the contact angle hysteresis was 2{\deg}. The achieved very low hysteresis is advantageous for promoting dropwise condensation. The surface showed no ageing effects during 100 repetitions of advancing and receding contact angle (ARCA) measurements. Condensation heat transfer on uncoated and PDMS-coated copper surfaces surfaces has been studied experimentally in a saturated water vapor atmosphere at 60{\deg}C. An enhancement factor for heat flux and heat transfer coefficient of up to 1.6 was found on PDMS-coated copper surfaces compared to uncoated surfaces, which decreased to 1.1 on second and third day of condensation operation. Images of the condensation surface were recorded while conducting condensation experiments and post processed to evaluate drop departure diameter and frequency of drop sweeping events. It has been shown that the behavior of the heat transfer coefficient correlates with the frequency of the sweeping events.

Charge separation at moving three-phase contact lines is observed in nature as well as technological processes. Despite the growing number of experimental investigations in recent years, the physical mechanism behind the charging remains obscure. Here we identify the origin of charge separation as the dewetting of the bound surface charge within the electric double layer by the receding contact line. This charge depends strongly on the local electric double layer structure close to the contact line, which is affected by the gas-liquid interface and the internal flow of the liquid. We summarize the charge separation mechanism in an analytical model that captures parametric dependencies in agreement with our experiments and numerical simulations. Charge separation increases with increasing contact angle and decreases with increasing dewetting velocity. Our findings reveal the universal mechanism of charge separation at receding contact lines, relevant to many dynamic wetting scenarios, and provide a theoretical foundation for both fundamental questions, like contact angle hysteresis, and practical applications.

Slide electrification - the spontaneous charge separation by sliding water drops - can lead to an electrostatic potential of 1 kV and change drop motion substantially. To find out, how slide electrification influences the contact angles of moving drops, we analyzed the dynamic contact angles of aqueous drops sliding down tilted plates with insulated surfaces, grounded surfaces, and while grounding the drop. The observed decrease in dynamic contact angles at different salt concentrations is attributed to two effects: An electrocapillary reduction of contact angles caused by drop charging and a change in the free surface energy of the solid due to surface charging.

Slide electrification is a spontaneous charge separation between a surface and a sliding drop. Here, we describe this effect in terms of a voltage generated at the three-phase contact line. This voltage moves charges between capacitors, one formed by the drop and one on the surface. By introducing an adaptation of the voltage upon water contact, we can model drop charge experiments on many surfaces, including more exotic ones with drop-rate dependent charge polarity. Thus, the adaptive two capacitor model enables new insights into the molecular details of the charge separation mechanism., Comment: The experimental results are accurate, but the physical model proposed in the paper does not fully capture the underlying physics behind the data. We are actively working to develop an improved model that better describes the experimental observations

The charge state of dielectric surfaces in aqueous environments is of fundamental and technological importance. Here, we study the influence of dissolved molecular CO$_2$ on the charging of three, chemically different surfaces (SiO$_2$, Polystyrene, Perfluorooctadecyltrichlorosilane). We determine their charge state from electrokinetic experiments. We compare an ideal, CO$_2$-free reference system to a system equilibrated against ambient CO$_2$ conditions. In the reference system, the salt-dependence is weakened for SiO$_2$ and inverted for the organic surfaces. We show that screening and pH-driven charge regulation alone cannot explain the observed effects. As additional cause, we tentatively suggest dielectric regulation of surface charges due to a diffusively adsorbed thin layer of molecular CO$_2$. The formation of such a dynamic layer even at the hydrophilic and partially ionized silica surfaces is supported by a minimal theoretical model and results from molecular simulations., Comment: Extended and thoroughly revised version with newly generated data from MD simulation, improved interpretation, Main text and supplementary materials, 29 Pages, 17 figures, published in JACS

Soft substrates such as polydimethylsiloxane (PDMS) enhance droplet nucleation during the condensation of water vapour, because their deformability inherently reduces the energetic threshold for heterogeneous nucleation relative to rigid substrates. However, this enhanced droplet nucleation is counteracted later in the condensation cycle, when the viscoelastic dissipation inhibits condensate droplet shedding from the substrate. Here, we show that bulk lubricant infusion in the soft substrate is a potential pathway for overcoming this limitation. We demonstrate that even 5% bulk lubricant infusion in PDMS reduces viscoelastic dissipation in the substrate by more than 30 times and more than doubles the droplet nucleation density. We correlate the droplet nucleation and growth rate with the material properties controlled by design, i.e. the fraction and composition of uncrosslinked chains, shear modulus, and viscoelastic dissipation. Through in-situ, microscale condensation on the substrates, we show that the increase in nucleation density and reduction in pre-coalescence droplet growth rate is insensitive to the percentage of lubricant in PDMS. Our results indicate the presence of a lubricant layer on the substrate surface that cloaks the growing condensate droplets. We visualize the cloaking effect and show that lubricant infusion in PDMS significantly increases the rate of cloaking compared to PDMS without any lubricant infusion. Finally, we show that the overall enhanced condensation due to bulk lubricant infusion in PDMS leads to more than 40% increase in dewing on the substrate.

The dynamics of wetting and dewetting is largely determined by the velocity field near the contact lines. For water drops it has been observed that adding surfactant decreases the dynamic receding contact angle even at a concentration much lower than the critical micelle concentration (CMC). To better understand why surfactants have such a drastic effect on drop dynamics, we constructed a dedicated a setup on an inverted microscope, in which an aqueous drop is held stationary while the transparent substrate is moved horizontally. Using astigmatism particle tracking velocimetry, we track the 3D displacement of the tracer particles in the flow. We study how surfactants alter the flow dynamics near the receding contact line of a moving drop for capillary numbers in the order of $10^{-6}$. Even for surfactant concentrations $c$ far below the critical micelle concentration ($c \ll$ CMC) Marangoni stresses change the flow drastically. We discuss our results first in a 2D model that considers advective and diffusive surfactant transport and deduce estimates of the magnitude and scaling of the Marangoni stress from this. Modeling and experiment agree that a tiny gradient in surface tension of a few $\mu N \, m^{-1}$ is enough to alter the flow profile significantly. The variation of the Marangoni stress with the distance from the contact line suggests that the 2D advection-diffusion model has to be extended to a full 3D model. The effect is ubiquitous, since surfactant is present in many technical and natural dewetting processes either deliberately or as contamination., Comment: 12 pages, 7 figure plus supporting information

Responsive poly-N-isopropylacrylamide-based microgels are commonly used as model colloids with soft repulsive interactions. It has been shown that the microgel-microgel interaction in solution can be easily adjusted by varying the environmental parameters, e.g., temperature, pH, or salt concentration. Furthermore, microgels readily adsorb to liquid-gas and liquid-liquid interfaces forming responsive foams and emulsions that can be broken on-demand. In this work, we explore the interactions between microgel monolayers at the air-water interface and a hard colloid in the water. Force-distance curves between the monolayer and a silica particle were measured with the Monolayer Particle Interaction Apparatus. The measurements were conducted at different temperatures and lateral compression, i.e., different surface pressures. The force-distance approach curves display long-range repulsive forces below the volume phase transition temperature of the microgels. Temperature and lateral compression reduce the stiffness of the monolayer. The adhesion increases with temperature and decreases with a lateral compression of the monolayer. When compressed laterally, the interactions between the microgels are hardly affected by temperature, as the directly adsorbed microgel fractions are nearly insensitive to temperature. In contrast, our findings show that the temperature-dependent swelling of the microgel fractions in the aqueous phase strongly influences the interaction with the probe. The microgel monolayer changes from a soft to a hard repulsive interface.

We present a new flexible high speed laser scanning confocal microscope and its extension by an astigmatism particle tracking device (APTV). Many standard confocal microscopes use either a single laser beam to scan the sample at relatively low overall frame rate, or many laser beam to simultaneously scan the sample and achieve a high overall frame rate. Single-laser-beam confocal microscope often use a point detector to acquire the image. To achieve high overall frame rates, we use, next to the standard 2D probe scanning unit, a second 2D scan unit projecting the image directly on a 2D CCD-sensor (re-scan configuration). Using only a single laser beam eliminates cross-talk and leads to an imaging quality that is independent of the frame rate with a lateral resolution of 0.235\unit{\mu m}. The design described here is suitable for high frame rate, i.e., for frame rates well above video rate (full frame) up to a line rate of 32kHz. The dwell time of the laser focus on any spot in the sample (122ns) is significantly shorter than in standard confocal microscopes (in the order of milli or microseconds). This short dwell time reduces phototoxicity and bleaching of fluorescent molecules. The new design opens further flexibility and facilitates coupling to other optical methods. The setup can easily be extended by an APTV device to measure three dimensional dynamics while being able to show high resolution confocal structures. Thus one can use the high resolution confocal information synchronized with an APTV dataset., Comment: 10 pages, 8 figures

We analyse the dewetting of printing plates for gravure printing with well-defined gravure cells. The printing plates were mounted on a rotating horizontal cylinder that is half immersed in an aqueous solution of the anionic surfactant sodium 1-decanesulfonate. The gravure plates and the presence of surfactants serve as one example of a real-world dewetting situation. When rotating the cylinder, a liquid meniscus was partially drawn out of the liquid forming a dynamic contact angle at the contact line. The dynamic contact angle is decreased on a structured surface as compared to a smooth one. This is due to contact line pinning at the borders of the gravure cells. Additionally, surfactants tend to decrease the dynamic receding contact angle. We consider the interplay between these two effects. We compare the height differences of the meniscus on the structured and unstructured area as function of dewetting speeds. The height difference increases with increasing dewetting speed. With increasing size of the gravure cells this height difference and the induced changes in the dynamic contact angle increased. By adding surfactant, the height difference and the changes in the contact angle for the same surface decreased. We further note that although the liquid dewets the printing plates some liquid is always left in the gravure cell. At high enough surfactant concentrations or high enough dewetting speed, the dynamic contact angles in the structured surface approach those in flat surfaces. We conclude that surfactant reduces the influence of surface structure on dynamic dewetting.

Evaporation of multi-component drops is crucial to various technologies and has numerous potential applications because of its ubiquity in nature. Superamphiphobic surfaces, which are both superhydrophobic and superoleophobic, can give a low wettability not only for water drops but also for oil drops. In this paper, we experimentally, numerically and theoretically investigate the evaporation process of millimetric sessile ouzo drops (a transparent mixture of water, ethanol, and trans-anethole) with low wettability on a superamphiphobic surface. The evaporation-triggered ouzo effect, i.e. the spontaneous emulsification of oil microdroplets below a specific ethanol concentration, preferentially occurs at the apex of the drop due to the evaporation flux distribution and volatility difference between water and ethanol. This observation is also reproduced by numerical simulations. The volume decrease of the ouzo drop is characterized by two distinct slopes. The initial steep slope is dominantly caused by the evaporation of ethanol, followed by the slower evaporation of water. At later stages, thanks to Marangoni forces the oil wraps around the drop and an oil shell forms. We propose an approximate diffusion model for the drying characteristics, which predicts the evaporation of the drops in agreement with experiment and numerical simulation results. This work provides an advanced understanding of the evaporation process of ouzo (multi-component) drops., Comment: 41 pages, 8 figures

Classical density functional theory is applied to investigate the validity of a phenomenological force-balance description of the stability of the Cassie state of liquids on substrates with nanoscale corrugation. A bulk free-energy functional of third order in local density is combined with a square-gradient term, describing the liquid-vapor interface. The bulk free energy is parameterized to reproduce the liquid density and the compressibility of water. The square-gradient term is adjusted to model the width of the water-vapor interface. The substrate is modeled by an external potential, based upon Lennard-Jones interactions. The three-dimensional calculation focuses on substrates patterned with nanostripes and square-shaped nanopillars. Using both the force-balance relation and density-functional theory, we locate the Cassie-to-Wenzel transition as a function of the corrugation parameters. We demonstrate that the force-balance relation gives a qualitatively reasonable description of the transition even on the nanoscale. The force balance utilizes an effective contact angle between the fluid and the vertical wall of the corrugation to parameterize the impalement pressure. This effective angle is found to have values smaller than the Young contact angle. This observation corresponds to an impalement pressure that is smaller than the value predicted by macroscopic theory. Therefore, this effective angle embodies effects specific to nanoscopically corrugated surfaces, including the finite range of the liquid-solid potential (which has both repulsive and attractive parts), line tension, and the finite interface thickness. Consistently with this picture, both patterns (stripes and pillars) yield the same effective contact angles for large periods of corrugation., Comment: 13 pages 9 figures