Molecular Simulation Study on the Wettability of a Surface Texturized with Hierarchical Pillars.

By using molecular dynamics simulation, we investigate the wettability of a surface texturized with a periodic array of hierarchical pillars. By varying the height and spacing of the minor pillars on top of major pillars, we investigate the wetting transition from the Cassie-Baxter (CB) to Wenzel (WZ) states. We uncover the molecular structures and free energies of the transition and meta-stable states existing between the CB and WZ states. The relatively tall and dense minor pillars greatly enhance the hydrophobicity of a pillared surface, in that, the CB-to-WZ transition requires an increased activation energy and the contact angle of a water droplet on such a surface is significantly larger.

Rates of cavity filling by liquids.

Understanding the fundamental wetting behavior of liquids on surfaces with pores or cavities provides insights into the wetting phenomena associated with rough or patterned surfaces, such as skin and fabrics, as well as the development of everyday products such as ointments and paints, and industrial applications such as enhanced oil recovery and pitting during chemical mechanical polishing. We have studied, both experimentally and theoretically, the dynamics of the transitions from the unfilled/partially filled (Cassie-Baxter) wetting state to the fully filled (Wenzel) wetting state on intrinsically hydrophilic surfaces (intrinsic water contact angle <90°, where the Wenzel state is always the thermodynamically favorable state, while a temporary metastable Cassie-Baxter state can also exist) to determine the variables that control the rates of such transitions. We prepared silicon wafers with cylindrical cavities of different geometries and immersed them in bulk water. With bright-field and confocal fluorescence microscopy, we observed the details of, and the rates associated with, water penetration into the cavities from the bulk. We find that unconnected, reentrant cavities (i.e., cavities that open up below the surface) have the slowest cavity-filling rates, while connected or non-reentrant cavities undergo very rapid transitions. Using these unconnected, reentrant cavities, we identified the variables that affect cavity-filling rates: (i) the intrinsic contact angle, (ii) the concentration of dissolved air in the bulk water phase (i.e., aeration), (iii) the liquid volatility that determines the rate of capillary condensation inside the cavities, and (iv) the presence of surfactants.

Flood tolerance of Glyceria fluitans: the importance of cuticle hydrophobicity, permeability and leaf gas films for underwater gas exchange.

Background and Aims: Floating sweet-grass ( Glyceria fluitans ) can form aerial as well as floating leaves, and these both possess superhydrophobic cuticles, so that gas films are retained when submerged. However, only the adaxial side of the floating leaves is superhydrophobic, so the abaxial side is directly in contact with the water. The aim of this study was to assess the effect of these different gas films on underwater net photosynthesis ( P N ) and dark respiration ( R D ). Methods: Evolution of O 2 was used to measure underwater P N in relation to dissolved CO 2 on leaf segments with or without gas films, and O 2 microelectrodes were used to assess cuticle resistance of floating leaves to O 2 uptake in the dark. Key Results: The adaxial side of aerial leaves was more hydrophobic than the abaxial side and also initially retained a thicker gas film when submerged. Underwater P N vs. dissolved CO 2 of aerial leaf segments with gas films had a K m of 172 mmol CO 2 m -3 and a P max of 7·1 µmol O 2 m -2 s -1 , and the leaf gas films reduced the apparent resistance to CO 2 uptake 12-fold. Underwater P N of floating leaves measured at 700 mmol CO 2 m -3 was 1·5-fold higher than P N of aerial leaves. The floating leaves had significantly lower cuticle resistance to dark O 2 uptake on the wettable abaxial side compared with the superhydrophobic adaxial side. Conclusions: Glyceria fluitans showed high rates of underwater P N and these were obtained at environmentally relevant CO 2 concentrations. It appears that the floating leaves possess both aquatic and terrestrial properties and thus have 'the best of both worlds' so that floating leaves are particularly adapted to situations where the plant is partially submerged and occasionally experiences complete submergence.

A theoretical approach to the relationship between wettability and surface microstructures of epidermal cells and structured cuticles of flower petals.

BACKGROUND AND AIMS: The epidermal surface of a flower petal is composed of convex cells covered with a structured cuticle, and the roughness of the surface is related to the wettability of the petal. If the surface remains wet for an excessive amount of time the attractiveness of the petal to floral visitors may be impaired, and adhesion of pathogens may be promoted. However, it remains unclear how the epidermal cells and structured cuticle contribute to surface wettability of a petal. METHODS: By considering the additive effects of the epidermal cells and structured cuticle on petal wettability, a thermodynamic model was developed to predict the wetting mode and contact angle of a water droplet at a minimum free energy. Quantitative relationships between petal wettability and the geometries of the epidermal cells and the structured cuticle were then estimated. Measurements of contact angles and anatomical traits of petals were made on seven herbaceous species commonly found in alpine habitats in eastern Nepal, and the measured wettability values were compared with those predicted by the model using the measured geometries of the epidermal cells and structured cuticles. KEY RESULTS: The model indicated that surface wettability depends on the height and interval between cuticular steps, and on a height-to-width ratio for epidermal cells if a thick hydrophobic cuticle layer covers the surface. For a petal epidermis consisting of lenticular cells, a repellent surface results when the cuticular step height is greater than 0·85 µm and the height-to-width ratio of the epidermal cells is greater than 0·3. For an epidermis consisting of papillate cells, a height-to-width ratio of greater than 1·1 produces a repellent surface. In contrast, if the surface is covered with a thin cuticle layer, the petal is highly wettable (hydrophilic) irrespective of the roughness of the surface. These predictions were supported by the measurements of petal wettability made on flowers of alpine species. CONCLUSIONS: The results indicate that surface roughness caused by epidermal cells and a structured cuticle produces a wide range of petal wettability, and that this can be successfully modelled using a thermodynamic approach.

Estimation of the Structure of Hydrophobic Surfaces Using the Cassie-Baxter Equation.

The effect of extreme water repellency, called the lotus effect, is caused by the formation of a Cassie-Baxter state in which only a small portion of the wetting liquid droplet is in contact with the surface. The rest of the bottom of the droplet is in contact with air pockets. Instrumental methods are often used to determine the textural features that cause this effect-scanning electron and atomic force microscopies, profilometry, etc. However, this result provides only an accurate texture model, not the actual information about the part of the surface that is wetted by the liquid. Here, we show a practical method for estimating the surface fraction of texture that has contact with liquid in a Cassie-Baxter wetting state. The method is performed using a set of ethanol-water mixtures to determine the contact angle of the textured and chemically equivalent flat surfaces of AlSI 304 steel, 7500 aluminum, and siloxane elastomer. We showed that the system of Cassie-Baxter equations can be solved graphically by the wetting diagrams introduced in this paper, returning a value for the texture surface fraction in contact with a liquid. We anticipate that the demonstrated method will be useful for a direct evaluation of the ability of textures to repel liquids, particularly superhydrophobic and superoleophobic materials, slippery liquid-infused porous surfaces, etc.

Unconventional Dually-Mobile Superrepellent Surfaces.

The ability of water droplets to move freely on superrepellent surfaces is a crucial feature that enables effective liquid repellency. Common superrepellent surfaces allow free motion of droplets in the Cassie state, with the liquid resting on the surface textures. However, liquid impalement into the textures generally leads to a wetting transition to the Wenzel state and droplet immobilization on the surface, thereby destroying the liquid repellency. This study reports the creation of a novel type of superrepellent surface through rational structural control combined with liquid-like surface chemistry, which allows for the free movement of water droplets and effective repellency in both the Cassie and Wenzel states. Theoretical guidelines for designing such surfaces are provided, and experimental results are consistent with theoretical analysis. Furthermore, this work demonstrates the enhanced ice resistance of the dually-mobile superrepellent surfaces, along with their distinctive self-cleaning capability to eliminate internal contaminants. This study expands the understanding of superrepellency and offers new possibilities for the development of repellent surfaces with exceptional anti-wetting properties.

Elucidating the lotus and rose-petal effects on hierarchical surfaces: Study of the effect of topographical scales on the contact angle hysteresis.

In nature, superhydrophobicity is almost systematically associated with a multiscale topography. Nevertheless, multiscale-textured natural surfaces can either produce water-repellent properties such as on the sacred lotus leaf or high liquid-to-solid adhesion such as on the rose petal. To conceive bio-inspired surfaces with self-cleaning properties, the proper contributions of each topographical scale to the wetting behavior need to be investigated. Conditions for the equilibrium of menisci produced at a given topographical scale are derived, yielding a recursion relation between each topographical scale. We introduce the equilibrium anchorage depth to quantify the penetration of water at equilibrium. To study the contact angle hysteresis (CAH), we thoroughly describe the mechanisms driving the advancing and receding motions of the triple line. Both phenomena depend on what we define as precursor advancing and receding motions. Eventually, the equilibrium, advancing and receding anchorage depths are related to the CAH. Topographical heterogeneities at a topographical subscale i are always associated with a reduced equilibrium anchorage depth and an enhanced robustness at all topographical scales of higher orders of magnitude. Eventually, it is demonstrated that advancing and receding anchorage depths are bounded by the equilibrium anchorage depth, elucidating how rose-petal-like surfaces systematically produce a high CAH.

Wetting of soap bubbles on topographic surfaces.

HYPOTHESIS: There is a relationship between the static contact angle of droplets and soap bubbles on flat homogeneous surfaces, therefore, it should be possible to derive a relationship between the static contact angle of a soap bubble on a periodic topographic surface and a droplet on a flat homogeneous surface. EXPERIMENTS: A free energy model of the static contact angle of soap bubbles on a topographic surface in the Cassie-Baxter state was derived. Polydimethylsiloxane surfaces of varying area fraction (0.125, 0.250, 0.500, 0.750, and 1.00) and periodic topographies (lined and pillared) were fabricated using 3D printed moulds for pattern transfer. A bubble goniometer was developed to accommodate bubbles of 40,000 ± 5,000 mm3 and 50,000 ± 5,000 mm3 volumes. Then, the static contact angle of bubbles of both volumes were measured on the varying topographic surfaces. FINDINGS: The derived predictions imply that the relationship between the static contact angle for bubbles on a flat homogeneous surface and on a composite surface, has the same form as the Cassie-Baxter equation for a droplet. The experimental results for the measured static contact angle for both bubble volumes on the varying surfaces had good agreement with the predicted trends.

Does the aquatic invertebrate nipple array prevent bubble adhesion? An experiment using nanopillar sheets.

The nipple array is a submicrometre-scale structure found on the cuticle surfaces of various invertebrate taxa. Corneal nipples are an antiglare surface in nocturnal insects, but the functional significance of the nipple array has not been experimentally investigated for aquatic organisms. Using nanopillar sheets as a mimetic model of the nipple array, we demonstrated that significantly fewer bubbles adhered to the nanopillar surface versus a flat surface when the sheets were hydrophilic. Many more bubbles adhered to the hydrophobic surface than the hydrophilic surfaces. Bubbles on the body surface may cause buoyancy problems, movement interference and water flow occlusion. Here, bubble repellence is proposed as a function of the hydrophilic nipple array in aquatic invertebrates and its properties are considered based on bubble adhesion energy.

Friction force-based measurements for simultaneous determination of the wetting properties and stability of superhydrophobic surfaces.

HYPOTHESIS: Contact angle and sliding angle measurements are widely used to characterize superhydrophobic surfaces because of the simplicity and accessibility of the technique. We hypothesize that dynamic friction measurements, with increasing pre-loads, between a water drop and a superhydrophobic surface is more accurate because this technique is less influenced by local surface inhomogeneities and temporal surface changes. EXPERIMENTS: A water drop, held by a ring probe which is connected to a dual-axis force sensor, is sheared against a superhydrophobic surface while maintaining a constant preload. From this force-based technique, static and kinetic friction forces measurements are used to characterize the wetting properties of the superhydrophobic surfaces. Furthermore, by applying increased pre-loads to the water drop while shearing, the critical load at which the drop transitions from the Cassie-Baxter to Wenzel state is also measured. FINDINGS: The force-based technique predicts sliding angles with reduced standard deviations (between 56 and 64%) compared to conventional optical-based measurements. Kinetic friction force measurements show a higher accuracy (between 35 and 80%) compared to static friction force measurements in characterizing the wetting properties of superhydrophobic surfaces. The critical loads for the Cassie-Baxter to Wenzel state transition allows for stability characterization between seemingly similar superhydrophobic surfaces.