The major strategies for designing surfaces that prevent fouling due to proteins, bacteria, and marine organisms are reviewed. Biofouling is of great concern in numerous applications ranging from biosensors to biomedical implants and devices, and from food packaging to industrial and marine equipment. The two major approaches to combat surface fouling are based on either preventing biofoulants from attaching or degrading them. One of the key strategies for imparting adhesion resistance involves the functionalization of surfaces with poly(ethylene glycol) (PEG) or oligo(ethylene glycol). Several alternatives to PEG-based coatings have also been designed over the past decade. While protein-resistant coatings may also resist bacterial attachment and subsequent biofilm formation, in order to overcome the fouling-mediated risk of bacterial infection it is highly desirable to design coatings that are bactericidal. Traditional techniques involve the design of coatings that release biocidal agents, including antibiotics, quaternary ammonium salts (QAS), and silver, into the surrounding aqueous environment. However, the emergence of antibiotic- and silver-resistant pathogenic strains has necessitated the development of alternative strategies. Therefore, other techniques based on the use of polycations, enzymes, nanomaterials, and photoactive agents are being investigated. With regard to marine antifouling coatings, restrictions on the use of biocide-releasing coatings have made the generation of nontoxic antifouling surfaces more important. While considerable progress has been made in the design of antifouling coatings, ongoing research in this area should result in the development of even better antifouling materials in the future.

https://onlinelibrary.wiley.com/doi/pdf/10.1002/adma.201001215

Antifouling coatings: recent developments in the design of surfaces that prevent fouling by proteins, bacteria, and marine organisms.

Hierarchical micropapillae and nanofolds are known to exist on the petals' surfaces of red roses. These micro- and nanostructures provide a sufficient roughness for superhydrophobicity and yet at the same time a high adhesive force with water. A water droplet on the surface of the petal appears spherical in shape, which cannot roll off even when the petal is turned upside down. We define this phenomenon as the “petal effect” as compared with the popular “lotus effect”. Artificial fabrication of biomimic polymer films, with well-defined nanoembossed structures obtained by duplicating the petal's surface, indicates that the superhydrophobic surface and the adhesive petal are in Cassie impregnating wetting state.

Petal Effect: A Superhydrophobic State with High Adhesive Force

A superhydrophobic surface is a surface with a water contact angle close to or higher than 150°. In this feature article, we review the historical and present research on superhydrophobic surfaces, including the characterization of superhydrophobicity, different ways to fabricate rough surfaces, and low-surface-energy modifications on inorganic and organic rough surfaces. It is the combination of surface roughness and low-surface-energy modification that leads to superhydrophobicity. Notably, research on superhydrophobic surfaces has not only fundamental interest but various possible functional applications in micro- and nano-materials and devices.

Superhydrophobic surfaces: from structural control to functional application

Research into extreme water-repellent surfaces began many decades ago, although it was only relatively recently that the term superhydrophobicity appeared in literature Here we review the work on the preparation of superhydrophobic surfaces, with focus on the different techniques used and how they have developed over the years, with particular focus on the last two years We discuss the origins of water-repellent surfaces, examining how size and shape of surface features are used to control surface characteristics, in particular how techniques have progressed to form multi-scaled roughness to mimic the lotus leaf effect There are notable differences in the terminology used to describe the varying properties of water-repellent surfaces, so we suggest some key definitions

Progess in superhydrophobic surface development.

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 (γlv = 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 (γlv = 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.

Robust omniphobic surfaces

The relationship between surface tension and roughness is reviewed. The Cassie-Baxter model is restated in its original form, which better describes the most general cases of surface roughness. Using mechanical and chemical surface modification of nylon 6,6 woven fabric, an artificial superhydrophobic surface was prepared. A plain woven fabric mimicking the Lotus leaf was created by further grafting 1H,1H-perfluorooctylamine or octadecylamine to poly(acrylic acid) chains which had previously been grafted onto a nylon 6,6 woven fabric surface. Water contact angles as high as 168 degrees were achieved. Good agreement between the predictions based on the original Cassie-Baxter model and experiments was obtained. The version of the Cassie-Baxter model in current use could not be applied to this problem since the surface area fractions in this form is valid only when the liquid is in contact with a flat, porous surface. The angle at which a water droplet rolls off the surface has also been used to define a superhydrophobic surface. It is shown that the roll-off angle is highly dependent on droplet size. The roll-off angles of these superhydrophobic surfaces were less than 5 degrees when a 0.5 mL water droplet was applied.

Design of a superhydrophobic surface using woven structures.

New light-activated antimicrobial materials with a potentially wide range of possible uses in civilian settings were synthesized by the grafting of protoporphyrin IX and zinc protoporphyrin IX to nylon fibers. These fibers were shown to be active against Staphylococcus aureus at light exposures of 10,000 lux and greater and against Escherichia coli at 60,000 lux. They were ineffective against both strains in the absence of light. At 40,000 lux, these fibers showed increased antimicrobial activity against S. aureus with increasing exposure time. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2297–2303, 2003

Porphyrin-based, light-activated antimicrobial materials

The relationships among contact angles, surface tensions, and surface roughness are reviewed. The various numerical formulae related to contact angles were used to predict the surface tension and wetting behavior of polymer surfaces. The apparent contact angle of a droplet deposited on a textured surface is presented, and the characteristics required for a superhydrophobic surface are described. This study also presents the effect of the sliding angles of liquid droplets on smooth and rough surfaces. The contact angle hysteresis was found to be very important in understanding the drop motion on a surface. Contact angle hystereses increased on a Wenzel-type surface, while a Cassie-Baxter type surface reduced the hystereses for the same surface roughness and surface tensions.

Lotus effect: Superhydrophobicity

The relationship between the contact angles, surface tension, and surface roughness is reviewed. Numerical formulas related to the superhydrophobic rough surfaces of polymers are predicted with two approaches, the Wenzel and Cassie–Baxter models. With these models as a guide, an artificial superhydrophobic surface is created. Rough nylon surfaces mimicking the lotus leaf are created by the coating of a polyester surface with nylon-6,6 short fibers via the flocking process. Poly(acrylic acid) chains aregrafted onto nylon-6,6 surfaces, and this is followed by the grafting of 1H,1H-perfluorooctylamine onto the poly(acrylic acid) chains. Water contact angles as high as 178° are achieved. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 253–261, 2007.

Preparation of a superhydrophobic rough surface

The relationships between the material parameters, i.e., the fiber fineness, porosity, areal density, layering sequence, and airflow resistivity with the normal- incidence sound absorption coefficient of nonwoven com- posites consisting of three layers have been studied. The monofiber or multifiber needle-punched nonwovens included poly(lactic acid) (PLA), polypropylene (PP), glass fiber, and hemp fibers. Air flow resistivity was statistically modeled and was found to increase with decreasing fiber size and nonwoven porosity. The former models devel- oped for glass fiber mats in the literature were found to be inconsistent with the air flow resistance of the nonwovens reported below. The effects of the layering sequence on air flow resistivity and sound absorption were obtained. It was found that when the layer including reinforcement fibers, i.e., hemp or glass fiber, faced the air flow/sound source, the air flow resistance and the absorption coeffi- cient were higher than the case when the layer including reinforcement fibers was farthest from the air flow/sound source. The difference was more pronounced if there was a greater difference between the resistivity values of the constituent layers of the nonwoven composite. Sound absorption coefficient was statistically modeled in terms of air flow resistivity and frequency. V C 2011 Wiley Periodicals, Inc. J Appl Polym Sci 121: 3056-3069, 2011

Stephen Michielsen

Papers

Design of a superhydrophobic surface using woven structures.

Porphyrin-based, light-activated antimicrobial materials

Lotus effect: Superhydrophobicity

Preparation of a superhydrophobic rough surface

Effects of porosity, fiber size, and layering sequence on sound absorption performance of needle-punched nonwovens