Superomniphobic surfaces, which repel droplets of polar and apolar liquids, are used for reducing frictional drag, packaging electronics and foods, and separation processes, among other applications. These surfaces exploit perfluorocarbons that are expensive, vulnurable to physical damage, and have a long persistence in the environment. Thus, new approaches for achieving superomniphobicity from common materials are desirable. In this context, microtextures comprising “mushroom-shaped” doubly reentrant pillars (DRPs) have been shown to repel drops of polar and apolar liquids in air irrespective of the surface make-up. However, it was recently demonstrated that DRPs get instantaneously infiltrated by the same liquids on submersion because while they can robustly prevent liquid imbibition from the top, they are vulnerable to lateral imbibition. Here, we remedy this weakness through bio-inspiration derived from cuticles of Dicyrtomina ornata, soil-dwelling bugs, that contain cuboidal secondary granules with mushroom-shaped caps on each face. Towards a proof-of-concept demonstration, we created a perimeter of biomimicking pillars around arrays of DRPs using a two-photon polymerization technique; another variation of this design with a short wall passing below the side caps was investigated. The resulting gas-entrapping microtextured surfaces (GEMS) robustly entrap air on submersion in wetting liquids, while also exhibiting superomniphobicity in air. To our knowledge, this is the first-ever microtexture that confers upon intrinsically wetting materials the ability to simultaneously exhibit superomniphobicity in air and robust entrapment of air on submersion. These findings should advance the rational design of coating-free surfaces that exhibit ultra-repellence (or superomniphobicity) towards liquids.
The generation of structural color from wrinkled polydimethylsiloxane (PDMS) surfaces, fabricated by plasma exposure, subjected to uni‐ and multi‐axial, and sequential strain fields is examined. The approach is based on the well‐known, mechanically‐induced, buckling instability of a supported bilayer, whereby the top glassy “skin” is formed by plasma oxidation. Surface periodicities 200 nm ≲ d ≲ 3 μm, encompassing the visible spectrum, are investigated in terms of the observed color, intensity spectrum, and color mixing from different diffraction orders, exhibiting good agreement with model predictions. By contrast with complex fabrication methods, color tunability and mechanochromic response are readily achieved by adjusting plasma and strain parameters, and by dynamically varying strain (ε ≲ 50%). Prescribed strain directionality, employing uniaxial, isotropic, gradient strain, and wave‐sum wrinkling superposition, as well as skin thickness (and thus d) and amplitude gradients, using facile and scalable fabrication approaches, yield striking spatial color variation, homogeneity, and directionality.
Surfaces that entrap air underwater serve numerous practical applications, such as mitigating cavitation erosion and reducing frictional drag. These surfaces typically rely on perfluorinated coatings. However, the non‐biodegradability and fragility of the coatings limit practical applications. Thus, coating‐free, sustainable, and robust approaches are desirable. Recently, a microtexture comprising doubly reentrant cavities (DRCs) has been demonstrated to entrap air on immersion in wetting liquids. While this is a promising approach, insights into the effects of surface chemistry, hydrostatic pressure, and cavity dimensions on wetting transitions in DRCs remain unavailable. In response, Cassie‐to‐Wenzel transitions into circular DRCs submerged in water are investigated and compared with those in cylindrical “simple” cavities (SCs). It is found that at low hydrostatic pressures (≈50 Pa), DRCs with hydrophilic (θo ≈ 40°) and hydrophobic (θo ≈ 112°) make‐ups fill within 105 and 107 s, respectively, while SCs with hydrophilic make‐up fill within <10−2 s. Under elevated hydrostatic pressure (P ≤ 90 kPa), counterintuitively, DRCs with hydrophobic make‐up fill dramatically faster than the commensurate SCs. This comprehensive report should provide a rational framework for harnessing microtexturing and surface chemistry toward coating‐free liquid repellency.
Desalination through direct contact membrane distillation (DCMD) exploits water-repellent membranes to robustly separate counterflowing streams of hot and salty seawater from cold and pure water, thus allowing only pure water vapor to pass through. To achieve this feat, commercial DCMD membranes are derived from or coated with water-repellent perfluorocarbons such as polytetrafluoroethylene (PTFE) and polyvinylidene difluoride (PVDF). However, the use of perfluorocarbons is limiting due to their high cost, non-biodegradability, and vulnerability to harsh operational conditions. Unveiled here is a new class of membranes referred to as gas-entrapping membranes (GEMs) that can robustly entrap air upon immersion in water. GEMs achieve this function by their microstructure rather than their chemical make-up. This work demonstrates a proof-of-concept for GEMs using intrinsically wetting SiO2/Si/SiO2 wafers as the model system; the contact angle of water on SiO2 is θo ≈ 40°. Silica-GEMs had 300 μm-long cylindrical pores whose diameters at the (2 μm-long) inlet and outlet regions were significantly smaller; this geometrically discontinuous structure, with 90° turns at the inlets and outlets, is known as the "reentrant microtexture". The microfabrication protocol for silica-GEMs entails designing, photolithography, chrome sputtering, and isotropic and anisotropic etching. Despite the water loving nature of silica, water does not intrude silica-GEMs on submersion. In fact, they robustly entrap air underwater and keep it intact even after six weeks (>106 seconds). On the other hand, silica membranes with simple cylindrical pores spontaneously imbibe water (< 1 s). These findings highlight the potential of the GEMs architecture for separation processes. While the choice of SiO2/Si/SiO2 wafers for GEMs is limited to demonstrating the proof-of-concept, it is expected that the protocols and concepts presented here will advance the rational design of scalable GEMs using inexpensive common materials for desalination and beyond.
Wrinkling of polydimethylsiloxane (PDMS) has unlocked a plethora of technological applications, from tunable surface wetting to photonic response. Surface undulations with prescribed wavelength and amplitude are excited by in‐plane mechanical compression of bilayers comprising a thin, stiff outer skin on a soft elastomer or gel. Plasma oxidation has become ubiquitous for creating such thin (≈10 nm) glassy interfacial layers. Spontaneous wrinkling can occur even in the absence of external mechanical strain fields, which has been rationalized in terms of a thermally‐induced strain that accompanies the expansion‐contraction cycle of such laminate films. It is shown that exposure to water vapor is, instead, responsible for surface wrinkling, due to the swelling the oxidized skin layer. This interpretation of surface wrinkling provides a rationale for the apparent experimental variability of the wrinkling process. This hypothesis is verified experimentally by observing and modelling the spatiotemporal evolution of the reversible wrinkling process under a range of controlled environmental conditions. From a practical standpoint, it is found that this effect provides for a facile approach for humidity sensing through structural color changes arising from the diffractive wrinkled skin.