Durable ultra‐hydrophobic surfaces for self‐cleaning applications

Self‐cleaning surfaces have received a great deal of attention, both in research studies and commercial applications. Both transparent and non‐transparent self‐cleaning surfaces are highly desirable as they offer many advantages, and their potential applications are endless. The self‐cleaning mechanism can be seen in nature. The Lotus flower, a symbol of purity in Asian cultures, grows in muddy waters, but it stays clean and untouched by dirt, organisms, and pollutants. The Lotus leaf self‐cleaning surface is hydrophobic and rough, showing a multi‐layer morphology of nanoscaled roughness. While hydrophobicity produces a high contact angle, the surface morphology reduces the adhesion of water drops to the surface, which slides easily across the leaf surface carrying the dirt particles with them. Different ultra‐hydrophobic, non‐transparent, and transparent coatings, for potential self‐cleaning applications, were produced on polycarbonate (PC) substrates, using hydrophobic chemistry and different configurations of roughening micro‐ and nano‐particles. However, in most cases, these coatings present low adhesion and durability. The stability and durability of the ultra‐hydrophobic surfaces is of key importance for potential, commercially viable, self‐cleaning applications thus durability and stability enhancement of such coatings was attempted by different methods, evaluated, and eventually improved using a solvent‐bonding technique. Copyright © 2008 John Wiley & Sons, Ltd.     

Counterion‐Dictated Self‐Cleaning Behavior of Polycation Coating upon Water Action: Macroscopic Dissection of Hydration of Anions

The counterions of polydiallyldimethylammonium (PDADMA) coatings were altered by incubation in aqueous solutions of different electrolytes. Oil de‐wetting on the resulting polycationic surfaces upon water action exhibited a straightforward connection with the Jones–Dole viscosity B‐coefficient (Bη) sign of surface counteranions. Upon water action, surface counteranions with negative Bη render PDADMA coatings oil‐adhering, but those with positive Bη furnish PDADMA coatings with excellent self‐cleaning. The oil‐adhering PDADMA surfaces can become self‐cleaning upon water action in response to the Bη of surface counteranions sign‐switching with increasing water temperature. Courtesy of surface counter‐anions with Bη>0, self‐cleaning PDADMA coatings enable not only conversion of conventional meshes into self‐cleaning membranes for oil/water separation, but also regioselective maneuver of oil flow on polycationic surfaces according to the Bη sign of surface counteranions patterned atop.     

Lotus bioinspired superhydrophobic,self‐cleaning surfaces from hierarchically assembled templates

The super hydrophobic, self‐cleaning properties of natural species derive from the fine hierarchical topography evolved on their surfaces. Hierarchical architectures which are function‐mimetic of the lotus leaf are here described and created from multi‐scale hierarchical assembled templates. The first level of hierarchy was a micromachined dome structure template and the second level of hierarchy was added by layering a thin nanoporous membrane such as porous anodized alumina or an ion track etch membrane. The assembled templates were nanoimprinted by a single step process on thermoplastic films. The wetting angle of the surfaces reached a value of 160° and the self‐cleaning behavior was observed. The superhydrophobic behavior remained over 1 year after fabrication, which demonstrates the stability of these polymeric self‐cleaning topographies. © 2014 Wiley Periodicals, Inc. J. Polym. Sci. Part B. Polym. Phys. 2014 , 52, 603–609     

Recent developments in polymeric superoleophobic surfaces

The construction and application of superoleophobic surfaces have aroused worldwide interest during the past few years. These surfaces are of great significance not only for fundamental research but also for various practical applications in self‐cleaning, oil‐repellent coatings, and antibioadhesion. The unique properties of polymers have made them one of the most important materials for constructing superoleophobic materials. This article reviews recent developments in the design, fabrication, and application of polymeric superoleophobic surfaces. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Self‐Cleaning and Next Generation Anti‐Fog Surfaces and Coatings

Due to their high surface energy, hydrophilic surfaces are susceptible to contaminations which are difficult to remove and often ruin the surface. Traditional anti‐fog coatings are especially limited by contaminants, as the prevention of fogging is enhanced as hydrophilicity increases. Thus, advanced solutions to fogging are required which incorporate some degree of self‐cleaning ability without significant losses in anti‐fog character. Potential next generation anti‐fog surfaces are characterized with particular emphasis on extended lifetime stimuli‐responsive surfaces. Surfactant‐based surfaces exhibited simultaneous hydrophilicity, necessary for anti‐fogging, and oleophobicity, necessary for contamination resistance. The combination of these features rendered the surface as self‐cleaning.

     

Literature review on superhydrophobic self‐cleaning surfaces produced by electrospinning

Self‐cleaning surface is potentially a very useful addition for many commercial products due to economic, aesthetic, and environmental reasons. Super‐hydrophobic self‐cleaning, also called Lotus effect, utilizes right combination of surface chemistry and roughness to force water droplets to form high contact angle on a surface, easily roll off a surface and pick up dirt particles on its way. Electrospinning is a promising technique for creation of superhydrophobic self‐cleaning surfaces owing to a wide set of parameters that allow effectively controlling roughness of resulted webs. This article gives a brief introduction to the theory of super‐hydrophobic self‐cleaning and basic principles of the electrospinning process and reviews the scientific literature where electrospinning was used to create superhydrophobic surfaces. The article reviewed are categorized into several groups and their results are compared in terms of superhydrophobic properties. Several issues with current state of the art and highlights of important areas for future research are discussed in the conclusion. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Durable bonding of silica nanoparticles to polymers by photoradiation for control of surface properties

Improvement of superhydrophobic surfaces durability is a critical key for potential commercial applications such as self‐cleaning and ice repellency. In this study, functionalization of silica nanoparticles by photoreactive benzophenone groups was made in order to covalently bond nanoparticles to polymer substrates to obtain durable coatings. Upon ultraviolet irradiation reactive excited triplet benzophenone species are formed enabling them to react with the polymer matrix through hydrogen abstraction. Two matrices were studied: radiation‐curable urethane acrylate and epoxy. The bonding of the particles to the surfaces was evaluated using atomic force microscope nanomanipulation and cross‐section analysis. The results have shown a greater stability of the photoreactive silica nanoparticles. Copyright © 2014 John Wiley & Sons, Ltd.     

Hierarchical structure microspheres of PCL block copolymers via electrospraying as coatings for fabric with mechanical durability and self‐cleaning ability

The various morphology and structure microspheres were fabricated via one‐step single‐solvent electrospraying of hydrophilic and hydrophobic block modified copolymer of polycaprolactone (PCL). A honeycomb‐like hierarchical structure microspheres of PCL‐b‐PTFOA(4h) and abundant nanometer pores of PCL‐b‐PEG400 microspheres were obtained due to the solvent evaporation, thermally and polymer diffusion‐induced phase separation effect. Furthermore, a superhydrophobic coatings and robust superhydrophobic‐coated cotton woven fabric surfaces were prepared by using PCL‐b‐PTFOA(4h) microspheres with hierarchical structure and low surface energy. The contact angle (CA) and sliding angle (SA) of PCL‐b‐PTFOA(4h) microspheres‐coated cotton woven fabric surfaces reached 164.4 ± 5.5° and 6.8 ± 0.5°, respectively, which allows for self‐cleaning. The self‐cleaning test demonstrated that the coated superhydrophobic surface could shed aqueous dyes and dust without any trace. The superhydrophobic‐coated fabric shows good soaping fastness against mechanical abrasion without significant reduction of CA. This electrospraying coating of block copolymers can provide a simple, facile, and promising technique for producing multifunctional textiles.     

Super‐Hydrophobic PDMS Surface with Ultra‐Low Adhesive Force

Summary: Rough polydimethylsiloxane (PDMS) surface containing micro‐, submicro‐ and nano‐composite structures was fabricated using a facile one‐step laser etching method. Such surface shows a super‐hydrophobic character with contact angle higher than 160° and sliding angle lower than 5°, i.e. self‐cleaning effect like lotus leaf. The wettabilities of the rough PDMS surfaces can be tunable by simply controlling the size of etched microstructures. The adhesive force between etched PDMS surface and water droplet is evaluated, and the structure effect is deduced by comparing it with those own a single nano‐ or micro‐scale structures. This super‐hydrophobic PDMS surface can be widely applied to many areas such as liquid transportation without loss, and micro‐pump (creating pushing‐force) needless micro‐fluidic devices.

Etched PDMS surface containing micro‐, submicro‐, and nano‐composite structures shows a self‐cleaning effect with water CA as high as 162° and SA lower than 5°.     

Preparation of composited Nano‐TiO2 and its application on antimicrobial and self‐cleaning coatings

Composite nano‐TiO₂ with doping Fe³⁺ and Ag was prepared, and further modified by 3‐methacryloxypropyltrimethoxysilane. They were characterized by Zetasizer Nano ZS Particle and Zeta Potential Analyzer, X‐ray diffraction, UV–Vis spectrophotometer, FT–IR spectra, and transmission electron microscopy. The modified composite nano‐TiO₂ was applied to prepare multifunctional fluorocarbon coatings (FCC). Antibacterial activity of multifunctional FCC containing modified composite nano‐TiO₂ was investigated. Its photocatalytic antibacterial activity reached 92%. The influence of doping ingredients, amount of composite nano‐TiO₂, different light houses, or surface modification was discussed. The surface of FCC cannot be easily smirched by oiliness, dust or water because of hydrophobic fluorosilicone emulsion. It would be an available modern interior building coating for its remarkable photocatalytic antibacterial property as well as self‐cleaning function. Copyright © 2009 John Wiley & Sons, Ltd.     

Preparation and Characterisation of Super‐Hydrophobic Surfaces

The interest in highly water‐repellent surfaces has grown in recent years due to the desire for self‐cleaning surfaces. A super‐hydrophobic surface is one that achieves a water contact angle of 150° or greater. This article explores the different approaches used to construct super‐hydrophobic surfaces and identifies the key properties of each surface that contribute to its hydrophobicity. The models used to describe surface interaction with water are considered, with attention directed to the methods of contact angle analysis. A summary describing the different routes to hydrophobicity is also given.     

Designing superhydrophobic surface based on fluoropolymer–silica nanocomposite via RAFT‐mediated polymerization‐induced self‐assembly

Superhydrophobic surfaces (SHS) find versatile applications as coatings due to their very high water‐repellency, self‐cleaning, and anti‐icing properties. This investigation describes the preparation of a SHS from surfactant‐free hybrid fluoropolymer latex. In this case, reversible addition‐fragmentation chain transfer (RAFT) polymerization was adopted to prepare a copolymer of 4‐vinyl pyridine (4VP) and vinyl triethoxysilane (VTES), where the pyridine units were quaternized to make the copolymer soluble in water. The copolymer was further used as a macro‐RAFT agent to polymerize 2,2,2‐trifluoroethyl methacrylate (TFEMA) in a surfactant‐free emulsion via polymerization‐induced self‐assembly (PISA). The macro‐RAFT agent contained a small amount of VTES as co‐monomer which was utilized to graft silica nanoparticles (SNPs) onto the P(TFEMA) spheres. The film prepared using the nanocomposite latex exhibited a nano‐structured surface as observed by SEM and AFM analyses. Surface modification of the film with fluorinated trichlorosilane produced an SHS with a water contact angle (WCA) of 151.5°. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 266–275     

A Simple Nanocellulose Coating for Self‐Cleaning upon Water Action: Molecular Design of Stable Surface Hydrophilicity

Coating solid surfaces with cellulose nanofibril (CNF) monolayers via physical deposition was found to keep the surfaces free of a variety of oils, ranging from viscous engine oil to polar n ‐butanol, upon water action. The self‐cleaning function was well correlated with the unique molecular structure of the CNF, in which abundant surface carboxyl and hydroxy groups are uniformly, densely, and symmetrically arranged to form a polar corona on a crystalline nanocellulose strand. This isotropic core–corona configuration offers new and easily adoptable guidance to design self‐cleaning surfaces at the molecular level. Thanks to its excellent self‐cleaning behavior, the CNF coating converted conventional meshes into highly effective membranes for oil–water separation with no prior surface treatment required.     

Fabricating Super‐Hydrophobic Lotus‐Leaf‐Like Surfaces through Soft‐Lithographic Imprinting

Summary: A soft‐lithographic imprinting approach to fabricate super‐hydrophobic surfaces has been developed in this work. In this process, fresh lotus leaves were used as masters and PDMS stamps were prepared by replica molding against the lotus‐leaf surfaces. By using the stamps and an epoxy‐based azo polymer solution as “ink”, the mimicked lotus‐leaf surfaces made of the polymer were fabricated by pressing the featured faces of the stamps against “inked” substrates and drying under a proper condition after peeling off the stamps. The lotus‐leaf‐like surfaces show super‐hydrophobic characteristics with the water contact angle higher than 150° and contact angle hysteresis less than 3°.

SEM images of lotus‐leaf‐like papillary structures on the imprinted surface.     

One‐Step Assembly of Phytic Acid Metal Complexes for Superhydrophilic Coatings

While of immense scientific interest, superhydrophilic surfaces are usually difficult to prepare, and preparation methods are typically substrate specific. Herein, a one‐step coating method is described that can endow superhydrophilicity to a variety of substrates, both inorganic and organic, using the coordination complexes of natural phytic acid and Fe^III ions. Coating deposition occurs in minutes, and coatings are ultrathin, colorless, and transparent. Superhydrophilicity is attributed, in part, to the high density of phosphonic acid groups. The ease, rapidness, and mildness of the assembly process, which is also cost‐effective and environmental‐friendly, points towards potential applications, such as self‐cleaning, oil/water separation, antifogging.     

Self‐assembly of metal–organic framework thin films containing metalloporphyrin and their photocatalytic activity under visible light

With [5,10,15,20‐tetra(4‐carboxyphenyl)porphyrin]Mn(III) and sterically controlled 2,2¢‐dimethyl‐4,4¢‐pyridine as the main raw materials, metal–organic framework thin films containing metalloporphyrin (MnPor‐MOF) with catalytically active sites were built up on functionalized quartz glass surfaces using a layer‐by‐layer self‐assembly method. Retaining active catalytic sites and having a porous reticular structure, the MnPor‐MOF films possessed remarkable photocatalytic activity for oxidative degradation of methylene blue in the presence of hydrogen peroxide under visible‐light irradiation. Most meaningfully, the MnPor‐MOF films were highly stable and simply and conveniently reusable, and are thus a potentially new organic material for photocatalytic wastewater treatment. Copyright © 2015 John Wiley & Sons, Ltd.     

Wrinkled Graphene Monoliths as Superabsorbing Building Blocks for Superhydrophobic and Superhydrophilic Surfaces

Superhydrophobic and superhydrophilic surfaces are of great interest because of a large range of applications, for example, as antifogging and self‐cleaning coatings, as antibiofouling paints for boats, in metal refining, and for water–oil separation. An aqueous ink based on three‐dimensional graphene monoliths (Gr) can be used for constructing both superhydrophobic and superhydrophilic surfaces on arbitrary substrates with different surficial structures from the meso‐ to the macroscale. The surface wettability of a Gr‐coated surface mainly depends on which additional layers (air for a superhydrophobic surface and water for a superhydrophilic surface) are adsorbed on the surface of the graphene sheets. Switching a Gr‐coated surface between being superhydrophobic and superhydrophilic can thus be easily achieved by drying and prewetting with ethanol. The Gr‐based superhydrophobic membranes or films should have great potential as efficient separators for fast and gravity‐driven oil–water separation.     

Lotus-Effect® – surfaces

Surfaces are often characterized with phrases like “easy to clean”, “dirt repellent”, “dirt resistant”, “self cleaning” or “ Lotus -Effect^®”. Every one of those phrases is used to describe a behavior of surfaces - similar to each other but still different. This article is providing the definition of the Lotus -Effect^®, techniques to manufacture self cleaning surfaces and methods to characterize them as well. How to generate a self cleaning surface depends on the substrate and the use later on. It can be as easy as a spray on but on the other hand as complicated as a three step process. Self cleaning surfaces are defined by four parameters - contact angle, roll-off angle, hystereses and C.I.E-Lab Δ-L value.     

Self‐assembled silane monolayers: an efficient step‐by‐step recipe for high‐quality,low energy surfaces

Organosilane self‐assembled monolayers (SAMs) are commonly used for modifying a wide range of substrates. Depending on the end group, highly hydrophobic or hydrophilic surfaces can be achieved. Silanization bases on the adsorption, self‐assembly and covalent binding of silane molecules onto surfaces and results in a densely packed, SAM. Following wet chemical routines, the quality of the monolayer is often variable and, therefore, unsatisfactory. The process of self‐assembly is not only affected by the chemicals involved and their purity but is also extremely sensitive to ambient parameters such as humidity or temperature and to contaminants. Here, a reliable and efficient wet‐chemical recipe is presented for the preparation of ultra‐smooth, highly ordered alkyl‐terminated silane SAMs on Si wafers. The resulting surfaces are characterized by means of atomic force microscopy, X‐ray reflectometry and contact angle measurements. Copyright © 2015 John Wiley & Sons, Ltd.     

On the respective effect of the surface energy and micro-geometry in the cleaning ability of bare and coated steels

It is aimed in this paper to assess the respective effect of surface energy and topography in the cleaning kinetics of soiled surfaces. Different flat and engraved stainless steels are characterized using contact angle measurements, topographic analysis and cleaning kinetics in presence of surfactants. Two coatings are also distinguished: silicon oxide (hydrophilic) and polysiloxane (hydrophobic).Except for the engraved surfaces, the determining parameter for the cleaning ability is the polar component of the surface energy: the larger this component, the better the cleaning performance. We proposed a simple model following which favorable interactions take between polar sites and the heads of surfactant. However, for engraved surfaces, the cleaning kinetics is strongly modified by some impregnation phenomena.