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Surface fouling occurs when undesired matter adheres and accumulates on a surface, resulting in a decrease or loss of functionality. Polymer and wax fouling can cause costly blockages to crude oil pipelines, clog jet fuel injectors, foul chemical reaction vessels, and significantly decrease the efficiency of heat exchangers. Fouling occurs in many forms but can be segmented based on adherent size, modulus, and chemical functionality. Depending on the foulant, surface design strategies can vary greatly. Few strategies exist to prevent the buildup of wax and polymers on surfaces. In this report, we investigate the potential of highly disordered, siloxane liquid-like layers as a strategy for reducing wax and polymer deposition. In our tests, it was found that the liquid-like layers developed here were able to reduce postadsorption roughness for polymer and wax by as much as 35- and 47-fold, respectively, when compared to the control. SFG was utilized to investigate the molecular-level interfacial properties for each of the modified surfaces to help understand the antifouling mechanism. The data showed that the likely higher grafting density and a large degree of random conformational freedom at the liquid-surface interface make the developed siloxane-covered surfaces energetically unfavorable for polymer and wax accretion.

Surfaces contaminated with bacteria and viruses contribute to the transmission of infectious diseases and pose a significant threat to global public health. Modern day disinfection either relies on fast-acting (3-log reduction within a few minutes), yet impermanent, liquid-, vapor-, or radiation-based disinfection techniques, or long-lasting, but slower-acting, passive antimicrobial surfaces based on heavy metal surfaces, or metallic nanoparticles. There is currently no surface that provides instant and persistent antimicrobial efficacy against a broad spectrum of bacteria and viruses. In this work, we describe a class of extremely durable antimicrobial surfaces incorporating different plant secondary metabolites that are capable of rapid disinfection (4-log reduction) of current and emerging pathogens within minutes, while maintaining persistent efficacy over several months and under significant environmental duress. We also show that these surfaces can be readily applied onto a variety of desired substrates or devices via simple application techniques such as spray, flow, or brush coating.

Separation operations are critical across a wide variety of manufacturing industries and account for about one-quarter of all in-plant energy consumption in the United States. Conventional liquid-liquid separation operations require either thermal or chemical treatment, both of which have a large environmental impact and carbon footprint. Consequently, there is a great need to develop sustainable, clean methodologies for separation of miscible liquid mixtures. The greatest opportunities to achieve this lie in replacing high-energy separation operations (e.g., distillation) with low-energy alternatives such as liquid-liquid extraction. One of the primary design challenges in liquid-liquid extraction is to maximize the interfacial area between two immiscible (e.g., polar and nonpolar) liquids for efficient mass transfer. However, this often involves energy-intensive methods including ultrasonication, pumping the feed and the extractant through packed columns with high tortuosity, or using a supercritical fluid as an extractant. Emulsifying the feed and the extractant, especially with a surfactant, offers a large interfacial area, but subsequent separation of emulsions can be energy-intensive and expensive. Thus, emulsions are typically avoided in conventional extraction operations. Herein, we discuss a novel, easily scalable, platform separation methodology termed CLEANS (continuous liquid-liquid extraction and in-situ membrane separation). CLEANS integrates emulsion-enhanced extraction with continuous, gravity-driven, membrane-based separation of emulsions into a single unit operation. Our results demonstrate that the addition of a surfactant and emulsification significantly enhance extraction (by >250% in certain cases), even for systems where the best extractants for miscible liquid mixtures are known. Utilizing the CLEANS methodology, we demonstrate continuous separation of a wide range of miscible liquid mixtures, including soluble organic molecules from oils, alcohols from esters, and even azeotropes.

Abstract In the present study, the drag-reducing effect of sprayed superhydrophobic surfaces (SHSs) is determined for two external turbulent boundary layer (TBL) flows. We infer the modification of skin friction created beneath TBLs using near-wall laser Doppler velocity measurements for a series of tailored SHSs. Measurements of the near-wall Reynolds stresses were used to infer reduction in skin friction between 8%and 36%in the channel flow. The best candidate SHS was then selected for application on a towed submersible body with a SUBOFF profile. The SHS was applied to roughly 60% of the model surface over the parallel midbody of the model. The measurements of the towed resistance showed an average decrease in the overall resistance from 2% to 12% depending on the speed and depth of the towed model, which suggests a SHS friction drag reduction of 4–24% with the application of the SHS on the model. The towed model results are consistent with the expected drag reduction inferred from the measurements of a near-zero pressure gradient TBL channel flow. Introduction Nature has provided a plethora of materials to be studied and mimicked for everyday applications (Jung & Bhushan 2010). One material pertinent for use in the marine environment is the lotus leaf, which is known for its self-cleansing properties and resistance to wetting (Neinhuis & Barthlott 1997). More specifically, lotus-inspired superhydrophobic surfaces (SHSs) have been biomimetically developed for skin friction reduction in various flow applications (Bhushan et al. 2009; Samaha et al. 2012). Being exhaustively studied in small-scale laminar flows (see Rothstein [2010] for a review of SHS drag reduction and slip on SHSs), advances in the design and fabrication of SHSs have permitted application of these materials in more naval-relevant flows. Previously, it has been shown that in laminar flow, SHSs can reduce drag (Watanabe et al. 1999; Ou et al. 2004; Ou & Rothstein 2005; Zhao et al. 2007; Daniello et al. 2009; Woolford et al. 2009), and in low–Reynolds number turbulent flows, SHS drag reduction has been observed using small-scale, structured surfaces and large air–water interfaces (Henoch et al. 2006; Daniello et al. 2009; Park et al. 2014). However, these surfaces, in higher turbulence flows, can be unstable or become wetted. If the SHS possesses roughness features with small scales compared with the viscous length scale of the flow, researchers have demonstrated SHS friction drag reduction for wall-bounded, high–Reynolds number turbulent flows (Zhao et al. 2007; Aljallis et al. 2013; Bidkar et al. 2014; Golovin et al. 2016; Ling et al. 2016b; Gose et al. 2018a).

Multicellular spheroids are superior to other culture geometries in reproducing critical physiological conditions of tumors, such as the diffusion of oxygen, nutrients, waste, and drugs, leading to a more precise model of in vivo drug sensitivity and resistance. Previously reported spheroid culture platforms are often difficult to use, expensive, single-use, or mechanically unstable. Here, we report a facile, mechanically stable, high-throughput spheroid culture platform based on hierarchically textured omniphobic surfaces. The developed omniphobic surfaces display very high contact angles with a range of different liquids, including the cell-laden culture media, thereby minimizing the cell surface contact area. Additionally, these surfaces maintain these high contact angles for extended periods of time to ensure cell aggregation. Using this novel platform, we demonstrate the generation and maintenance of robust multicellular spheroids, as well as heterogeneous, multicell-type spheroids. The platform is extremely robust, resistant to mechanical shock, allows for on-plate imaging, and is also the first-ever spheroid generation platform that can be reused repeatedly. Finally, the platform is suitable for on-plate drug screening and enables the first-ever, on-plate immunofluorescence staining and imaging of spheroids.

Surfaces that are resistant to both liquid fouling and solid fouling are critical for many industrial and biomedical applications. However, surfaces developed to address these challenges thus far have been generally susceptible to mechanical damage. Herein, we report the design and fabrication of robust solid- and liquid-repellent elastomeric coatings that incorporate partially crosslinked lubricating chains within a durable polymer matrix. In particular, we fabricated partially crosslinked omniphobic polyurethane (omni-PU) coatings that can repel a broad range of liquid and solid foulants. The fabricated coatings are an order of magnitude more resistant to cyclic abrasion than current state-of-the-art slippery surfaces. Further through the integration of classic wetting and tribology models, we introduce a new material design parameter (

A wide range of liquid and solid contaminants can adhere to everyday functional surfaces and dramatically alter their performance. Numerous surface modification strategies have been developed that can reduce the fouling of some solids or repel certain liquids but are generally limited to specific contaminants or class of foulants. This is due to the typically distinct mechanisms that are employed to repel liquids vs solids. Here, we demonstrate a rapid and facile surface modification technique that yields a thin film of linear chain siloxane molecules covalently tethered to a surface. We investigate and characterize the liquid-like morphology of these surfaces in detail as the key contributing factor to their anti-fouling performance. This surface treatment is extremely durable and readily repels a broad range of liquids with varying surface tensions and polarities, including water, oils, organic solvents, and even fluorinated solvents. Additionally, the flexible, liquid-like nature of these surfaces enables interfacial slippage, which dramatically reduces adhesion to various types of solids, including ice, wax, calcined gypsum, and cyanoacrylate adhesives, and also minimizes the nucleation of inorganic scale. The developed surfaces are durable and simple to fabricate, and they minimize fouling by both liquids and solids simultaneously.

Coliforms are one of the most common families of bacteria responsible for water contamination. Certain coliform strains can be extremely toxic, and even fatal if consumed. Current technologies for coliform detection are expensive, require multiple complicated steps, and can take up to 24 hours to produce accurate results. Recently, open-channel, paper-based microfluidic devices have become popular for rapid, inexpensive, and accurate bioassays. In this work, we have created an integrated microfluidic coliform lysis and detection device by fabricating customizable omniphilic regions via direct printing of omniphilic channels on an omniphobic, fluorinated paper. This paper-based device is the first of its kind to demonstrate successful cell lysing on-chip, as it can allow for the flow and control of both high and low surface tension liquids, including different cell lysing agents. The fabricated microfluidic device was able to successfully detect E. coli, via the presence of the coliform-specific enzyme, β-galactosidase, at a concentration as low as ~10(4) CFU/mL. Further, E. coli at an initial concentration of 1 CFU mL(−1) could be detected after only 6 hours of incubation. We believe that these devices can be readily utilized for real world E. coli contamination detection in multiple applications, including food and water safety.

The benefits of being repellent The accumulation of foreign substances on a surface, whether it is dirt on a window or ice on an airplane wing, can lead to hazardous conditions. Many surfaces have been engineered to resist the accumulation of one type of fluid or matter in a particular state, but engineering broader resistivity has remained a challenge. For example, surfaces that repel water droplets may still be susceptible to fog accumulation. Dhyani et al. review the wetting performance and fouling resistance of different liquid-repellent coatings, focusing on superhydrophobic, superomniphobic, lubricant-infused, and liquid-like surfaces. Two key aspects are the performance of the surface to different foulants and the relevance of considering different length scales. Science , aba5010, this issue p. eaba5010

There has been a recent drive to develop non-fluorinated superhydrophobic coatings due to the toxicity, cost, and environmental impact of perfluorinated components. One of the main challenges in developing superhydrophobic coatings in general and non-fluorinated superhydrophobic coatings in particular is optimization of mechanical durability, as the rough asperities required for maintaining superhydrophobicity tend to be easily removed by abrasion. Although rough and self-similar hydrophobic surfaces composed of loosely adhered particles or highly porous structures tend to produce excellent superhydrophobicity, they have low inherent mechanical durability and their longevity under real conditions is compromised. To address this issue, this work investigates the addition of a polymeric matrix material (the binder) to hydrophobic nanoparticles (the filler) to produce spray-coated superhydrophobic surfaces with improved inherent mechanical durability. Hansen solubility parameters were used to tune the interactions between the binder, filler, and solvent used to deliver the coating. It was found that lowering the binder/filler miscibility and using a poor solvent mixture generates more surface roughness, thereby lowering the minimum filler load required to achieve superhydrophobicity. This leads to an overall more inherently durable system that remains hydrophobic for thousands of light abrasion cycles.

A significant amount of the fuel consumed by marine vehicles is expended to overcome skin-friction drag resulting from turbulent boundary layer flows. Hence, a substantial reduction in this frictional drag would notably reduce cost and environmental impact. Superhydrophobic surfaces (SHSs), which entrap a layer of air underwater, have shown promise in reducing drag in small-scale applications and/or in laminar flow conditions. Recently, the efficacy of these surfaces in reducing drag resulting from turbulent flows has been shown. In this work we examine four different, mechanically durable, large-scale SHSs. When evaluated in fully developed turbulent flow, in the height-based Reynolds number range of 10 000 to 30 000, significant drag reduction was observed on some of the surfaces, dependent on their exact morphology. We then discuss how neither the roughness of the SHSs, nor the conventional contact angle goniometry method of evaluating the non-wettability of SHSs at ambient pressure, can predict their drag reduction under turbulent flow conditions. Instead, we propose a new characterization parameter, based on the contact angle hysteresis at higher pressure, which aids in the rational design of randomly rough, friction-reducing SHSs. Overall, we find that both the contact angle hysteresis at higher pressure, and the non-dimensionalized surface roughness, must be minimized to achieve meaningful turbulent drag reduction. Further, we show that even SHSs that are considered hydrodynamically smooth can cause significant drag increase if these two parameters are not sufficiently minimized.

Precise control over micro- and nano-particle composition, size and shape is critical for developing the next generation of successful drug carriers. Fabrication methods also need to be able to create charged and multiphasic particles with ease in order to improve the overall efficiency of drug delivery systems. Multiple phases in a single particle allow for the delivery of multiple payloads without negative payload interactions. The addition of charged polyelectrolyte (PEL) multilayers can improve particle stability, targeting efficacy, drug-release kinetics, and increase the types of payloads that can be delivered. Many of the traditional methods for PEL functionalization of multiphasic particles are time and energy intensive which significantly limits their scalability, and therefore therapeutic potential. In this work, we combine the bulk layer-by-layer PEL application methodology with our previously developed technique of fabricating multiphasic particles on substrates with patterned wettability to synthesize biocompatible, monodisperse, Janus polymer-PEL particles.

Herein we report the development of a cytometric analysis platform for measuring the contents of individual cells in absolute (picogram) scales; this study represents the first report of Raman-based quantitation of the absolute mass - or the total amount - of multiple endogenous biomolecules within single-cells. To enable ultraquantitative calibration, we engineered single-cell-sized micro-calibration standards of known composition by inkjet-printer deposition of biomolecular components in microarrays across the surface of silicon chips. We demonstrate clinical feasibility by characterizing the compositional phenotype of human skin fibroblast and porcine alveolar macrophage cell populations in the respective contexts of Niemann-Pick disease and drug-induced phospholipidosis: two types of lipid storage disorders. We envision this microanalytical platform as the foundation for many future biomedical applications, ranging from diagnostic assays to pathological analysis to advanced pharmaco/toxicokinetic research studies.

Easy ice removal The accumulation of ice on a surface can lead to hazardous conditions, such as on the surface of an airplane wing or the side of a tall building. Ice adhesion, even to a surface treated to minimize the bonded force, will usually depend on the amount of surface coverage. Golovin et al. compared strength-limited deicing with toughness-limited deicing. Whereas normal deicing materials focus on minimizing the adhesion strength, the authors show that if a material is designed with low-adhesion toughness, deicing is no longer a function of the coverage area. Science , this issue p. 371

The utility of omniphobic surfaces stems from their ability to repel a multitude of liquids, possessing a broad range of surface tensions and polarities, by causing them to bead up and either roll or slide off. These surfaces may be self-cleaning, corrosion-resistant, heat-transfer enhancing, stain-resistant or resistant to mineral- or biofouling. The majority of reported omniphobic surfaces use texture, lubricants, and/or grafted monolayers to engender these repellent properties. Unfortunately, these approaches often produce surfaces with deficiencies in long-term stability, durability, scalability, or applicability to a wide range of substrates. To overcome these limitations, we have fabricated an all-solid, substrate-independent, smooth, omniphobic coating composed of a fluorinated polyurethane and fluorodecyl polyhedral oligomeric silsesquioxane. Liquids of varying surface tension, including water, hexadecane, ethanol, and silicone oil, exhibit low-contact-angle hysteresis (15°) on these surfaces, allowing liquid droplets to slide off, leaving no residue. Moreover, we demonstrate that these robust surfaces retained their repellent properties more effectively than textured or lubricated omniphobic surfaces after being subjected to mechanical abrasion.

The separation of oil-water mixtures is a widely utilized unit operation, used for handling a wide variety of mixtures from industry including: petroleum drilling and refining, fracking, waste-water treatment, mining, metal fabrication and machining, textile and leather processing, and rendering. Membrane-based methods have become increasingly attractive for the separation of oil-water mixtures because they are relatively energy-efficient, can be readily used to separate a variety of industrial feed streams, and provide consistent permeate quality. In this perspective, we discuss the design strategies for membranes with selective wettability i.e., membranes that are either selectively wet by, or prevent wetting by, the oil or water phase. The design strategies include the parameterization of two important physical characteristics: the surface porosity and the breakthrough pressure. We also discuss how they are related for membranes with a periodic geometry. On the basis of this understanding, we explore principles that allow for the systematic design of membranes with selective wettability. A review of the current literature on the separation of oil-water mixtures using membranes with differing wettabilities is also presented. Finally, we conclude by discussing the current challenges and outlook for the future of the field.

Precise control over the geometry and chemistry of multiphasic particles is of significant importance for a wide range of applications. In this work, we have developed one of the simplest methodologies for fabricating monodisperse, multiphasic micro- and nanoparticles possessing almost any composition, projected shape, modulus, and dimensions as small as 25 nm. The synthesis methodology involves the fabrication of a nonwettable surface patterned with monodisperse, wettable domains of different sizes and shapes. When such patterned templates are dip-coated with polymer solutions or particle dispersions, the liquids, and consequently the polymer or the particles, preferentially self-assemble within the wettable domains. Utilizing this phenomenon, we fabricate multiphasic assemblies with precisely controlled geometry and composition through multiple, layered depositions of polymers and/or particles within the patterned domains. Upon releasing these multiphasic assemblies from the template using a sacrificial layer, we obtain multiphasic particles. The templates can then be readily reused (over 20 times in our experiments) for fabricating a new batch of particles, enabling a rapid, inexpensive, and easily reproducible method for large-scale manufacturing of multiphasic particles.

Here, we show how to predictably impart extremely low ice adhesion to a range of different plastic materials., Ice accretion remains a costly, hazardous concern worldwide. Icephobic coatings reduce the adhesion between ice and a surface. However, only a handful of the icephobic systems reported to date reduce the ice adhesion sufficiently for the facile and passive removal of ice, such as under its own weight or by mild winds. Most of these icephobic surfaces have relied on sacrificial lubricants, which may be depleted over time, drastically raising the ice adhesion. In contrast, surfaces that use interfacial slippage to lower their adhesion to ice can remain icephobic indefinitely. However, the mechanism of interfacial slippage, as it relates to ice adhesion, is largely unexplored. We investigate how interfacial slippage reduces the ice adhesion of polymeric materials. We propose a new, universally applicable framework that may be used to predict the reduction in the adhesion of ice to surfaces exhibiting interfacial slippage. This framework allows one to rationally engender icephobicity in essentially any polymeric system, including common thermoplastics. Hence, we present several new, extremely icephobic systems fabricated from a wide range of materials, including everyday engineering plastics and sustainable, natural oils.

Open-channel microfluidic devices have shown great potential in achieving a high degree of fluid control, at relatively low-cost, while enabling the opportunity for rapid fabrication. However, thus far, work in open channel microfluidics has largely focused on controlling the flow of water or other aqueous solutions. In this work we present new open channel microfluidic devices based on surfaces with patterned wettabilty that are capable of controlling the flow of virtually all high and low surface tension liquids. The fabricated open channel devices are capable of constraining a variety of low surface tension oils at high enough flow rates to enable, for the first time, water-in-oil microfluidic emulsification in an open channel device. By changing the flow rates for both the aqueous (dispersed) and organic (continuous) phases, we show that it is possible to vary the size of the emulsified droplets produced in the open channel device. Finally, we utilized the fabricated devices to synthesize relatively monodisperse, hydrogel microparticles that could incorporate a drug molecule. We also investigated the drug release characteristics of the fabricated particles.

The past decade saw a drastic increase in the understanding and applications of superhydrophobic surfaces (SHSs). Water beads up and effortlessly rolls off a SHS due to its combination of low surface energy and texture. Whether being used for drag reduction, stain repellency, self-cleaning, fog harvesting, or heat transfer applications (to name a few), the durability of a SHS is critically important. Although a handful of purportedly durable SHSs have been reported, there are still no criteria available for systematically designing a durable SHS. In the first part of this work, we discuss two new design parameters that can be used to develop mechanically durable SHSs via the spray coating of different binders and fillers. These parameters aid in the rational selection of material components and allow one to predict the capillary resistance to wetting of any SHS from a simple topographical analysis. We show that not all combinations of sprayable components generate SHSs, and mechanically durable components do not necessarily generate mechanically durable SHSs. Moreover, even the most durable SHSs can eventually become damaged. In the second part, utilizing our new parameters, we design and fabricate physically and chemically self-healing SHSs. The most promising surface is fabricated from a fluorinated polyurethane elastomer (FPU) and the extremely hydrophobic small molecule 1H,1H,2H,2H-heptadecafluorodecyl polyhedral oligomeric silsesquioxane (F-POSS). A sprayed FPU/F-POSS surface can recover its superhydrophobicity even after being abraded, scratched, burned, plasma-cleaned, flattened, sonicated, and chemically attacked.

We investigate the influence of statistical measures of surface roughness on the turbulent drag reduction (DR) performance of four scalable, randomly rough superhydrophobic (SH) textures. Each surface was fabricated using readily scalable surface texturing processes to generate a random, self-affine height profile on the base substrate. The frictional drag on all four SH surfaces was measured when fully submerged in shear-driven turbulent flow inside a bespoke Taylor-Couette apparatus at Reynolds numbers in the range 1 × 104 ≲ Re ≲ 1 × 105. An “effective” slip length quantifying the overall drag-reducing ability for each surface was extracted from the resulting Prandtl-von Karman friction plots. Reductions in the frictional drag of up to 26% were observed, with one of the hierarchically textured surfaces exceeding a wall shear stress of 26 Pa (corresponding to a Reynolds number Re ≈ 7 × 104) before the onset of flow-induced plastron collapse. The surface morphology of each texture was characterized using noncontact optical profilometry, and the influence of various statistical measures of roughness on the effective slip length was explored. The lateral autocorrelation length was identified as the key textural parameter determining the drag-reducing ability for randomly rough SH textures, playing the role analogous to the spatial periodicity of regularly patterned SH surfaces. A large autocorrelation length, a small surface roughness, and the presence of hierarchical roughness features were observed to be the three important design requirements for scalable SH textures for optimal DR in turbulent flows.

See-through surfaces: High transparency is required to use superomniphobic surfaces, which can be self-cleaning, stain-proof, anti-bio-fouling, drag-reducing, or anti-fogging, for smartphone screens, eye glasses, windshields, or flat panel displays. A spray-based method has now been developed that can fabricate transparent, flexible, and highly superomniphobic surfaces. HD=hexadecane.

A novel synthetic route for the preparation of amphiphilic Janus particles based on electrohydrodynamic cojetting has been developed. In this approach, selective encapsulation of hydrophobic fluorodecyl-polyhedral oligomeric silsesquioxane (F-POSS) in one compartment and a poly(vinyl alcohol) in the second compartment results in colloidal particles with surfactant-like properties including the self-organization at oil-water and air-water interfaces. Successful localization of the respective polymers in different compartments of the same particle is confirmed by a combination of fluorescence microscopy, vibrational spectroscopy, and ζ-potential measurements. We believe that this straightforward synthetic approach may lead to a diverse class of surface-active colloids that will have significant relevance ranging from basic scientific studies to immediate applications in areas, such as pharmaceutical sciences or cosmetics.

Surfaces that display contact angles greater than 150° along with a low contact angle hysteresis for low surface tension liquids such as oils and alcohols are known as superoleophobic surfaces. Such surfaces are of interest for a diverse array of applications including self-cleaning, nonfouling, stain-free clothing and spill-resistant protective wear, drag reduction, microrobots for aqueous and chemical environments and icephobicity. Recently, significant advances have been made in understanding the criteria required to design superoleophobic surfaces. In this article, the authors discuss the roles of surface energy and roughness, the critical role of re-entrant texture and the role of hierarchical structure in fabricating superoleophobic surfaces. On the basis of this understanding, the authors also discuss two design parameters that allow for the systematic design of superoleophobic surfaces. The authors also summarize the recent studies on superoleophobic surfaces and emphasize the need for careful and diligent characterization. Finally, the authors conclude with the major challenges and opportunities for research on superoleophobic surfaces.

Surfaces that display liquid contact angles greater than 150° along with low contact angle hysteresis for liquids with both high and low surface tension values are known as superomniphobic surfaces. Such surfaces are of interest for a diverse array of applications, including self-cleaning surfaces, nonfouling surfaces, stain-free clothing, spill-resistant protective wear, drag reduction, and fingerprint-resistant surfaces. Recently, significant advances have been made in understanding the criteria required to design superomniphobic surfaces. In this article, we discuss the roles of surface energy, roughness, re-entrant texture, and hierarchical structure in fabricating superomniphobic surfaces. We also provide a review of different superomniphobic surfaces reported recently in the literature and emphasize the need for mechanical, chemical, and radiation durability of superomniphobic surfaces for practical applications. Finally, we conclude with a discussion of the unresolved challenges in developing durable superomniphobic surfaces that define the scope for further improvements in the field.

Superomniphobic surfaces display contact angles of θ*150° and low contact angle hysteresis with virtually all high and low surface tension liquids. The introduction of hierarchical scales of texture can increase the contact angles and decrease the contact angle hysteresis of superomniphobic surfaces by reducing the solid-liquid contact area. Thus far, it has not been possible to fabricate superomniphobic surfaces with three or more hierarchical scales of texture where the size, spacing, and angular orientation of features within each scale of texture can be independently varied and controlled. Here, we report a method for tunable control of geometry in hyperbranched ZnO nanowire (NW) structures, which in turn enables the rational design and fabrication of superomniphobic surfaces. Branched NWs with tunable density and orientation were grown via a sequential hydrothermal process, in which atomic layer deposition was used for NW seeding, disruption of epitaxy, and selective blocking of NW nucleation. This approach allows for the rational design and optimization of three-level hierarchical structures, in which the geometric parameters of each level of hierarchy can be individually controlled. We demonstrate the coupled relationships between geometry and contact angles for a variety of liquids, which is supported by mathematical models. The highest performing superomniphobic surface was designed with three levels of hierarchy and achieved the following advancing/receding contact angles with water 172°/170°, hexadecane 166°/156°, octane 162°/145°, and heptane 160°/130°.

In this review, we discuss how superhydrophobic surfaces (SHSs) can provide friction drag reduction in turbulent flow. Whereas biomimetic SHSs are known to reduce drag in laminar flow, turbulence adds many new challenges. We first provide an overview on designing SHSs, and how these surfaces can cause slip in the laminar regime. We then discuss recent studies evaluating drag on SHSs in turbulent flow, both computationally and experimentally. The effects of streamwise and spanwise slip for canonical, structured surfaces are well characterized by direct numerical simulations, and several experimental studies have validated these results. However, the complex and hierarchical textures of scalable SHSs that can be applied over large areas generate additional complications. Many studies on such surfaces have measured no drag reduction, or even a drag increase in turbulent flow. We discuss how surface wettability, roughness effects and some newly found scaling laws can help explain these varied results. Overall, we discuss how, to effectively reduce drag in turbulent flow, an SHS should have: preferentially streamwise-aligned features to enhance favourable slip, a capillary resistance of the order of megapascals, and a roughness no larger than 0.5, when non-dimensionalized by the viscous length scale. This article is part of the themed issue ‘Bioinspired hierarchically structured surfaces for green science’.

Digital holographic microscopy is used for characterizing the profiles of mean velocity, viscous and Reynolds shear stresses, as well as turbulence level in the inner part of turbulent boundary layers over several super-hydrophobic surfaces (SHSs) with varying roughness/texture characteristics. The friction Reynolds numbers vary from 693 to 4496, and the normalized root mean square values of roughness $(k_{rms}^{+})$ vary from 0.43 to 3.28. The wall shear stress is estimated from the sum of the viscous and Reynolds shear stress at the top of roughness elements and the slip velocity is obtained from the mean profile at the same elevation. For flow over SHSs with $k_{rms}^{+}, drag reduction and an upward shift of the mean velocity profile occur, along with a mild increase in turbulence in the inner part of the boundary layer. As the roughness increases above $k_{rms}^{+}\sim 1$, the flow over the SHSs transitions from drag reduction, where the viscous stress dominates, to drag increase where the Reynolds shear stress becomes the primary contributor. For the present maximum value of $k_{rms}^{+}=3.28$, the inner region exhibits the characteristics of a rough wall boundary layer, including elevated wall friction and turbulence as well as a downward shift in the mean velocity profile. Increasing the pressure in the test facility to a level that compresses the air layer on the SHSs and exposes the protruding roughness elements reduces the extent of drag reduction. Aligning the roughness elements in the streamwise direction increases the drag reduction. For SHSs where the roughness effect is not dominant ($k_{rms}^{+}), the present measurements confirm previous theoretical predictions of the relationships between drag reduction and slip velocity, allowing for both spanwise and streamwise slip contributions.

hasexplainedhowre-entrantsurface texture, in conjunction with surface chemistry androughness, can be used to design superomniphobic surfaces.In this work, we report a simple, fast, and practical method-ology to develop patterned superomniphobic–superomni-philic surfaces that exhibit stark contrast in wettability witha wide range of polar and nonpolar liquids. Using thesesurfaces, we demonstrate the site-selective self-assembly ofheptane upon dipping and spraying on textured surfaces, site-selective condensation and boiling with low-surface-tensionliquids, and site-selective self-assembly of both polymers andmicroparticles.When a liquid comes in contact with a textured surface, itadopts either the fully wetted Wenzel

Hierarchically structured, superoleophobic surfaces are demonstrated that display one of the lowest contact angle hysteresis values ever reported - even with extremely low-surface-tension liquids such as n-heptane. Consequently, these surfaces allow, for the first time, even ≈2 μL n-heptane droplets to bounce and roll-off at tilt angles. ≤ 2°.

The liquid repellency and surface topography characteristics of coatings comprising a sprayed-on mixture of fluoroalkyl-functional precipitated silica and a fluoropolymer binder were examined using contact and sliding angle analysis, electron microscopy, and image analysis for determination of fractal dimensionality. The coatings proved to be an especially useful class of liquid repellent materials due to their combination of simple and scalable deposition process, low surface energy, and the roughness characteristics of the aggregates. These characteristics interact in a unique way to prevent the buildup of binder in interstitial regions, preserving re-entrant curvature across multiple length scales, thereby enabling a wide range of liquid repellency, including superoleophobicity. In addition, rather than accumulating in the interstices, the binder becomes widely distributed across the surface of the aggregates, enabling a mechanism in which a simple shortage or excess of binder controls the extent of coating roughness at very small length scales, thereby controlling the extent of liquid repellence.

The Cassie-Baxter model is widely used to predict the apparent contact angles obtained on composite (solid-liquid-air) superhydrophobic interfaces. However, the validity of this model has been repeatedly challenged by various research groups because of its inherent inability to predict contact angle hysteresis. In our recent work, we have developed robust omniphobic surfaces which repel a wide range of liquids. An interesting corollary of constructing such surfaces is that it becomes possible to directly image the solid-liquid-air triple-phase contact line on a composite interface, using an electron microscope with non-volatile organic liquids or curable polymers. Here, we fabricate a range of model superoleophobic surfaces with controlled surface topography in order to correlate the details of the local texture with the experimentally observed apparent contact angles. Based on these experiments, in conjunction with numerical simulations, we modify the classical Cassie-Baxter relation to include a local differential texture parameter which enables us to quantitatively predict the apparent advancing and receding contact angles, as well as contact angle hysteresis. This quantitative prediction also allows us to provide an a priori estimation of roll-off angles for a given textured substrate. Using this understanding we design model substrates that display extremely small or extremely large roll-off angles, as well as surfaces that demonstrate direction-dependent wettability, through a systematic control of surface topography and connectivity.

Superhydrophobic surfaces display water contact angles greater than 150° in conjunction with low contact angle hysteresis. Microscopic pockets of air trapped beneath the water droplets placed on these surfaces lead to a composite solid-liquid-air interface in thermodynamic equilibrium. Previous experimental and theoretical studies suggest that it may not be possible to form similar fully-equilibrated, composite interfaces with drops of liquids, such as alkanes or alcohols, that possess significantly lower surface tension than water (γ lv = 72.1 mN/m). In this work we develop surfaces possessing re-entrant texture that can support strongly metastable composite solid-liquid-air interfaces, even with very low surface tension liquids such as pentane (γ lv = 15.7 mN/m). Furthermore, we propose four design parameters that predict the measured contact angles for a liquid droplet on a textured surface, as well as the robustness of the composite interface, based on the properties of the solid surface and the contacting liquid. These design parameters allow us to produce two different families of re-entrant surfaces— randomly-deposited electrospun fiber mats and precisely fabricated microhoodoo surfaces—that can each support a robust composite interface with essentially any liquid. These omniphobic surfaces display contact angles greater than 150° and low contact angle hysteresis with both polar and nonpolar liquids possessing a wide range of surface tensions.

Recent experiments have revealed that the wax on the lotus leaf surface, by itself, is weakly hydrophilic, even though the lotus leaf is known to be superhydrophobic. Conventional understanding suggests that a surface of such waxy composition should not be able to support superhydrophobicity and high contact angles between a liquid and the surface. Here, we show that the unexpected superhydrophobicity is related to the presence of “reentrant texture” (that is, a multivalued surface topography) on the surface of the lotus leaf. We exploit this understanding to enable the development of superoleophobic surfaces (i.e., surfaces that repel extremely low-surface-tension liquids, such as various alkanes), where essentially no naturally oleophobic materials exist. We also develop general design parameters that enable the evaluation of the robustness of the composite interface on a particular surface. Based on these design parameters, we also rank various superhydrophobic and superoleophobic substrates discussed in the literature, with particular emphasis on surfaces developed from inherently hydrophilic or oleophilic materials.

Every day millions of gallons of oil–water mixtures are produced in industries ranging from oil extraction, fracking and mining, to wastewater treatment. Separating these mixtures involves multiple unit operations, which can be expensive and sometimes insufficient, especially as environmental restrictions become increasingly strict on contaminants in discharged water. Other occurrences, such as large oil spills, also require new technologies that enable effective yet economic clean-up. Energy efficient, selective wettability-based membrane technology has the potential to meet these needs. In this chapter, we discuss the fundamentals of wettability and how they can be applied to systematically design membranes with selective wettability that can readily separate free oil and water, as well as emulsions. We also look at membrane surface morphology, surface energy, and the relationships that govern the selective breakthrough of an oil or water phase. Finally, we discuss the recent work in developing oil–water separation membranes based on the idea of selective wettability, the merits and shortcomings of each approach, and the potential areas of future interest in the field.

It is demonstrated that nanocomposites exhibiting reduced viscosity and multifunctional performance enhancements may be fabricated using simple processing procedures. These behaviors are elucidated by analysis of the effects of dispersed organic (fullerene) nanoparticles and inorganic (magnetite) nanoparticles on the behavior of polystyrene, demonstrating that simple spherical nanoparticles can induce a range of unexpected behavior due to nanoscale effects. In general, multifunctional performance improvements including enhanced mechanical, electrical, magnetic and thermal degradation properties as well as reduced viscosity are promoted when simple design guidelines are followed. These guidelines are tabulated.

Cadmium selenide nanoparticles are found to diffuse approximately 200 times faster in a polymeric liquid than predicted by the Stokes-Einstein relation. This remarkable behavior is hypothesized to be due to the nanoparticles being smaller than the entanglement mesh to create a frictional drag that does not follow continuum expectations, in line with a theoretical calculation presented before. This is one of the first demonstrations of X-ray photo correlation spectroscopy applied to polymeric liquids, which we use to explain the simultaneous 60% viscosity reduction of the mixture through a proposed constraint release mechanism.

Novel polystyrene nanoparticles were synthesized by the controlled intra- molecular crosslinking of linear polymer chains to produce well-defined single-mole- cule nanoparticles of varying molecular mass, corresponding directly to the original linear precursor chain. These nanoparticles are ideal to study the relaxation dynam- ics/processes of high molecular mass polymer melts, as the high degree of intramolec- ular crosslinking potentially inhibits entanglements. Both the nanoparticles and their linear analogs were characterized by measuring their intrinsic viscosity, hydrody- namic radius (Rh), and radius of gyration (Rg). The ratio Rg/Rh was computed to char- acterize the molecular architecture of the nanoparticles in solution, revealing a shift toward the constant density sphere limit with increasing crosslink density and molec- ular mass. Further, confirming particulate behavior, Kratky plots obtained from neu- tron scattering data show a shift toward particle-like nature. The rheological behav- ior of the particles was found to be strongly dependent on both the extent of intramo- lecular crosslinking and molecular mass, with a minimal viscosity change at low crosslinking levels and a gel-like behavior evident for a large degree of crosslinking. These and other results suggest the presence of a secondary mode of polymer relaxa- tion/movement besides reptation, which in this case, is influenced by the total num- ber of crosslinked loops present in the nanoparticle. V C 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1930-1947, 2006

Traditionally the dispersion of particles in polymeric materials has proven difficult and frequently results in phase separation and agglomeration. We show that thermodynamically stable dispersion of nanoparticles into a polymeric liquid is enhanced for systems where the radius of gyration of the linear polymer is greater than the radius of the nanoparticle. Dispersed nanoparticles swell the linear polymer chains, resulting in a polymer radius of gyration that grows with the nanoparticle volume fraction. It is proposed that this entropically unfavorable process is offset by an enthalpy gain due to an increase in molecular contacts at dispersed nanoparticle surfaces as compared with the surfaces of phase-separated nanoparticles. Even when the dispersed state is thermodynamically stable, it may be inaccessible unless the correct processing strategy is adopted, which is particularly important for the case of fullerene dispersion into linear polymers.

The effect of nanoscopic, shape persistent polystyrene (PS) nanoparticles on the rheological properties of linear PS is studied and a dramatic viscosity reduction is observed. This is an ideal blend which simplifies enthalpic interactions between the components and can be used to delineate the effect of particle size on the properties of the blends. Homogeneous blends are assured through small-angle neutron scattering (SANS) experiments which establish the absence of phase segregation (depletion flocculation) in the nanoparticle-polymer blend. We previously found that nanoparticles reduce the viscosity of high molecular mass linear PS when the interparticle gap is smaller than the linear polymer size. In the present study, we find that such confinement of entangled polymers is necessary for the viscosity reduction since lower concentrations provide a viscosity increase. Furthermore, the behavior is found to be dependent on the presence or absence of entanglements and confinement is seemingly not important for unentangled polymers. It is proposed that constraint release caused by the addition of nanoparticles is responsible for some of the observed changes in viscosity although it is suspected this is a very complicated phenomenon and introduction of free volume by the nanoparticles is certain to play a key role.

This Young Investigator Proposal has so far lead to 10 publications in high impact journals, as well as, widespread domestic and international popular press coverage. Results from this work have also been presented in 15 different invited talks. The project involved five undergraduate students, two graduate students and a postdoctoral research associate. A few of the publications resulting from this work have been summarized below. A list of all 10 manuscripts published based on this work is provided in the end. Three more publications based on this work are either submitted or in preparation.

We fabricate high-efficiency, ultrathin (∼12 μm), flexible, upgraded metallurgical-grade polycrystalline silicon solar cells with multiple plasmonic layers precisely positioned on top of the cell to dramatically increase light absorption. This scalable approach increases the optical absorptivity of our solar cells over a broad range of wavelengths, and they achieve efficiencies η ≈ 11%. Detailed studies on the electrical and optical properties of the developed solar cells elucidate the light absorption contribution of each individual plasmonic layer. Finite-difference time-domain simulations were also performed to yield further insights into the obtained results. We anticipate that the findings from this work will provide useful design considerations for fabricating a range of different solar cell systems.

There is a critical need for new energy-efficient solutions to separate oil-water mixtures, especially those stabilized by surfactants. Traditional membrane-based separation technologies are energy-intensive and limited, either by fouling or by the inability of a single membrane to separate all types of oil-water mixtures. Here we report membranes with hygro-responsive surfaces, which are both superhydrophilic and superoleophobic, in air and under water. Our membranes can separate, for the first time, a range of different oil-water mixtures in a single-unit operation, with >99.9% separation efficiency, by using the difference in capillary forces acting on the two phases. Our separation methodology is solely gravity-driven and consequently is expected to be highly energy-efficient. We anticipate that our separation methodology will have numerous applications, including the clean-up of oil spills, wastewater treatment, fuel purification and the separation of commercially relevant emulsions.

In this work, the first-ever membrane-based single unit operation that enables gravity driven, on-demand separation of various oil-water mixtures is developed. Using this methodology, the on-demand separation of free oil and water, oil-in-water emulsions, and water-in-oil emulsions is demonstrated, with ≥99.9% separation efficiency. A scaled-up apparatus to separate larger quantities (several liters) of oil-water emulsions is also developed.