Shreerang S. Chhatre

Scale dependence of omniphobic mesh surfaces

We provide a simple design chart framework to predict the apparent contact angle on a textured surface in terms of the equilibrium contact angle on a chemically identical smooth surface and details of the surface topography. For low surface tension liquids such as methanol (gamma(lv) = 22.7 mN/m) and octane (gamma(lv) = 21.6 mN/m), a solid-liquid-air composite interface on a textured surface is inherently metastable. Thus, on application of a sufficient pressure difference (e.g., an externally applied pressure or a sufficiently large Laplace pressure at small droplet size) the metastable composite interface transitions to a fully wetted interface. A dimensionless robustness factor is used to quantify the breakthrough pressure difference necessary to disrupt a metastable composite interface and to predict a priori the existence of a robust composite interface. The impact of the length scale (radius of the cylindrical features R varying from 18 to 114 microm) and the feature spacing ratio (D(*) = (R + D)/R varying from 2.2 to 5.1, where 2D is the spacing between the cylindrical features) on the robustness is illustrated by performing contact angle measurements on a set of dip-coated wire-mesh surfaces, which provide systematically quantifiable cylindrical texture. The design chart for a given feature size R shows how the two independent design parameters--surface chemistry as revealed in the equilibrium contact angle and texture spacing embodied in the dimensionless spacing ratio (D(*))--can be used to develop surfaces with desirably large values of the apparent contact angle and robustness of the metastable composite interface. Most revealing is the scaling of the robustness with the dimensionless parameter l(cap)/R (where l(cap = (gamma(lv)/rho g)(1/2) is the capillary length), which indicates clearly why, in the consideration of self-similar surfaces, smaller is better for producing omniphobic surfaces that resist wetting by liquids with low surface tension.

Optimal Design of Permeable Fiber Network Structures for Fog Harvesting

Fog represents a large untapped source of potable water, especially in arid climates. Numerous plants and animals use textural and chemical features on their surfaces to harvest this precious resource. In this work, we investigate the influence of the surface wettability characteristics, length scale, and weave density on the fog-harvesting capability of woven meshes. We develop a combined hydrodynamic and surface wettability model to predict the overall fog-collection efficiency of the meshes and cast the findings in the form of a design chart. Two limiting surface wettability constraints govern the re-entrainment of collected droplets and clogging of mesh openings. Appropriate tuning of the wetting characteristics of the surfaces, reducing the wire radii, and optimizing the wire spacing all lead to more efficient fog collection. We use a family of coated meshes with a directed stream of fog droplets to simulate a natural foggy environment and demonstrate a five-fold enhancement in the fog-collecting efficiency of a conventional polyolefin mesh. The design rules developed in this work can be applied to select a mesh surface with optimal topography and wetting characteristics to harvest enhanced water fluxes over a wide range of natural convected fog environments.

Thermal annealing treatment to achieve switchable and reversible oleophobicity on fabrics

Surfaces that are strongly nonwetting to oil and other low surface tension liquids can be realized by trapping microscopic pockets of air within the asperities of a re-entrant texture and generating a solid-liquid-vapor composite interface. For low surface tension liquids such as hexadecane (gamma(lv) = 27.5 mN/m), this composite interface is metastable as a result of the low value of the equilibrium contact angle. Consequently, pressure perturbations can result in an irreversible transition of the metastable composite interface to the fully wetted interface. In this work, we use a simple dip-coating and thermal annealing procedure to tune the liquid wettability of commercially available polyester fabrics. A mixture of 10% 1H,1H,2H,2H-heptadecafluorodecyl polyhedral oligomeric silsesquioxane (fluorodecyl POSS) and 90% polyethyl methacrylate (PEMA) is used to uniformly coat the fabric surface topography. Contact angle measurements show that a robust metastable composite interface with high apparent contact angles can be supported for hexadecane (gamma(lv) = 27.5 mN/m) and dodecane (gamma(lv) = 25.3 mN/m). To tune the solid surface energy of the coated surface, we also developed a reversible treatment using thermal annealing of the surface in contact with either dry air or water. The tunability of the solid surface energy along with the inherent re-entrant texture of the polyester fabric result in reversibly switchable oleophobicity between a highly nonwetting state and a fully wetted state for low surface tension liquids such as hexadecane and dodecane. This tunability can be explained within a design parameter framework, which provides a quantitative criterion for the transition between the two states, as well as accurate predictions of the measured values of the apparent contact angle (theta*) for the dip-coated polyester fabrics.

Fluoroalkylated Silicon-Containing Surfaces−Estimation of Solid-Surface Energy

The design of robust omniphobic surfaces, which are not wetted by low-surface-tension liquids such as octane (γlv=21.6 mN/m) and methanol (γlv=22.7 mN/m), requires an appropriately chosen surface micro/nanotexture in addition to a low solid-surface energy (γsv). 1H,1H,2H,2H-Heptadecafluorodecyl polyhedral oligomeric silsesquioxane (fluorodecyl POSS) offers one of the lowest solid-surface energy values ever reported (γsv≈10 mN/m) and has become the molecule of choice for coating textured surfaces. In this work, we synthesize and evaluate a series of related molecules that either retain the POSS cage and differ in fluoroalkyl chain length or that retain the fluorodecyl chains surrounding a linear or cyclic molecular structure. The solid-surface energy (γsv) of these molecules was estimated using contact angle measurements on flat spin-coated silicon wafer surfaces. Zisman analysis was performed using a homologous series of n-alkanes (15.5≤γlv≤27.5 mN/m), whereas Girifalco-Good analysis was performed using a set of polar and nonpolar liquids with a wider range of liquid surface tension (15.5≤γlv≤72.1 mN/m). The hydrogen-bond-donating, hydrogen-bond-accepting, polar, and nonpolar (dispersion) contributions to the solid-surface energy of each compound were determined by probing the surfaces using a set of three liquid droplets of either acetone, chloroform, and dodecane or diiodomethane, dimethyl sulfoxide, and water.

Examination of wettability and surface energy in fluorodecyl POSS/polymer blends†

Fluorodecyl Polyhedral Oligomeric SilSesquioxane (POSS) is a low surface energy material (γsv ≈ 10 mN m−1) that has been used as a coating to prepare a variety of liquid repellent surfaces. There are several drawbacks to employing pure fluorodecyl POSS as a coating, including high cost, poor adherence to the underlying substrate, and a lack of optical transparency. One potential strategy for overcoming these shortcomings while retaining liquid repellency is to prepare composite coatings by judiciously blending polymers with fluorodecyl POSS. Here varying amounts of fluorodecyl POSS are blended with commercially available poly(methyl methacrylate) (PMMA), poly(ethyl methacrylate) (PEMA), poly(butyl methacrylate) (PBMA), and the commercial fluoroelastomer Tecnoflon BR9151. A film of each blend is spin cast onto a silicon wafer and its surface wettability is probed by measuring advancing and receding contact angles of six liquids: water, ethylene glycol, dimethyl sulfoxide, diiodomethane, rapeseed oil, and hexadecane. Surface energy analysis techniques developed by Girifalco, Good, and colleagues are used to extract the hydrogen bond donating (acidic), hydrogen bond accepting (basic), and nonpolar (dispersion) components of the solid surface energy from both advancing and receding contact angle measurements. It is emphasized that a proper assessment of the wetting behavior of a liquid on a surface requires consideration of the complementary acid–base interactions between the solid and the liquid, not just a determination of the polar contribution to the solid surface energy. Maximum liquid repellency is attained in composite PMMA or PEMA films with fluorodecyl POSS loadings of at least 20 wt %. Furthermore, cross-cut adhesion tests reveal that the optically transparent methacrylate-containing fluorodecyl POSS coatings adhere quite strongly to the underlying substrate, unlike the Tecnoflon-containing blends and the pure fluorodecyl POSS. These results will potentially facilitate the incorporation of fluorodecyl POSS into commercial coatings.

Quantification of feather structure, wettability and resistance to liquid penetration.

Birds in the cormorant (Phalacrocoracidae) family dive tens of metres into water to prey on fish while entraining a thin layer of air (a plastron film) within the microstructures of their feathers. In addition, many species within the family spread their wings for long periods of time upon emerging from water. To investigate whether wetting and wing-spreading are related to feather structure, microscopy and photographic studies have previously been used to extract structural parameters for barbs and barbules. In this work, we describe a systematic methodology to characterize the quasi-hierarchical topography of bird feathers that is based on contact angle measurements using a set of polar and non-polar probing liquids. Contact angle measurements on dip-coated feathers of six aquatic bird species (including three from the Phalacrocoracidae family) are used to extract two distinguishing structural parameters, a dimensionless spacing ratio of the barbule (D*) and a characteristic length scale corresponding to the spacing of defect sites. The dimensionless spacing parameter can be used in conjunction with a model for the surface topography to enable us to predict a priori the apparent contact angles of water droplets on feathers as well as the water breakthrough pressure required for the disruption of the plastron on the feather barbules. The predicted values of breakthrough depths in water (1–4 m) are towards the lower end of typical diving depths for the aquatic bird species examined here, and therefore a representative feather is expected to be fully wetted in a typical deep dive. However, thermodynamic surface energy analysis based on a simple one-dimensional cylindrical model of the feathers using parameters extracted from the goniometric analysis reveals that for water droplets on feathers of all six species under consideration, the non-wetting ‘Cassie–Baxter’ composite state represents the global energy minimum of the system. By contrast, for other wetting liquids, such as alkanes and common oils, the global energy minimum corresponds to a fully wetted or Wenzel state. For diving birds, individual feathers therefore spontaneously dewet once the bird emerges out of water, and the ‘wing-spreading’ posture might assist in overcoming kinetic barriers associated with pinning of liquid droplets that retard the rate of drying of the wet plumage of diving birds.