Superhydrophobic Coatings on Cellulose‐Based Materials: Fabrication,Properties, and Applications

Wettability of a solid surface by a liquid plays an important role in several phenomena and applications, for example in adhesion, printing, and self‐cleaning. In particular, wetting of rough surfaces has attracted great scientific interest in recent decades. Superhydrophobic surfaces, which possess extraordinary water repelling properties due to their low surface energy and specific nanometer‐ and micrometer‐scale roughness, are of particular interest due to the great variety of potential applications ranging from self‐cleaning surfaces to microfluidic devices. In recent years, the potential of superhydrophobic cellulose‐based materials in the function of smart devices and functional clothing has been recognized, and in the past few years cellulose‐based materials have established themselves among the most frequently used substrates for superhydrophobic coatings. In this Review, over 40 different approaches to fabricate superhydrophobic coatings on cellulose‐based materials are discussed in detail. In addition to the anti‐wetting properties of the coatings, particular attention is paid to coating durability and other incorporated functionalities such as gas permeability, transparency, UV‐shielding, photoactivity, and self‐healing properties. Potential applications for the superhydrophobic cellulose‐based materials range from water‐ and stain‐repellent, self‐cleaning and breathable clothing to cheap and disposable lab‐on‐a‐chip devices made from renewable sources with reduced material consumption.     

Beschichtung und Reinigung von Oberflächen mit Atmosphärendruck‐Plasmen. Coating and cleaning of surfaces with atmospheric pressure plasmas

Since long time dielectric barrier discharges have been in use for technical applications such as ozone synthesis and surface activation treatment of polymers for subsequent printing, pasting, or laquering. A new field of applications for these discharges is opened by their use for plasma‐based coating and cleaning processes at atmospheric pressure. By introducing gaseous monomers (like hydrocarbons, fluorocarbons, silicon‐organic compounds) into the discharge zone, coatings can be deposited on electrically conductive or insulating substrates. Barrier discharges in oxygen containing gases can also be used for the degreasing of surfaces. Owing to the possibility, to sustain barrier discharges in very small volumes, new perspectives are opened for the geometrically structured modification of chemical and physical properties of surfaces as well as for the modification or coating of internal surfaces in microfluidic devices.     

Solid‐Supported Biomolecules on Modified Silica Surfaces—A Tool for Fast Physicochemical Characterization and High‐Throughput Screening

Biofunctionalization for a wide variety of applications can be achieved by coating silica surfaces with biomolecules such as lipids or proteins. However, specific surface optimization of the inorganic SiO₂ is necessary to achieve biocompatible surfaces. Surface shielded porous silica beads can be non‐covalently coated with a single lipid bilayer. The lipids retain their fluidity in this handy solid‐supported system, perfectly mimicking the soft‐surface properties of cellular membranes. A supramolecular architecture can also be used for functional immobilization of membrane proteins: An artificial cytosolic compartment can be created with the aid of polymers; coating by lipid membranes and integration of membrane proteins results in a solid‐supported biofunctional cellular surface. Another surface modification enables a direct immobilization of human serum albumin (HSA) molecules onto silica surfaces. The HSA on this otherwise passivated surface provides a convenient material for the investigation of unspecific protein binding of pharmaceuticals on a high‐throughput scale.     

Ultra‐precision Surface Finishing by Ion Beam Techniques

Ion beam etching based ultra precision surface finishing is a versatile technology with a high degree of predictability due to the high stability of state of the art ion sources and the acquired knowledge of the physics of beam surface interaction. The independent control of the ion energy and the ion current density over wide ranges and the possible additional use of chemical reactive species in combination with physical sputter removal allow solving tasks in a wide variety of applications. The paper summarizes the present status of more than 20 years of development of ion beam finishing technology in IOM. It gives an overview on the equipment and the components developed for production purposes and on the ion beam technologies developed to achieve nanometer and sub‐nanometer depth accuracies over the entire spectrum of spatial surface wavelength from the full aperture size down to the microroughness level of only micrometer lateral feature size. Results of the finishing of high‐end optical surfaces shown demonstrate the outstanding performances of the techniques with topography and roughness control on the atomic scale.     

N2‐Plasma‐Assisted One‐Step Alignment and Patterning of Graphene Oxide on a SiO2/Si Substrate Via the Langmuir–Blodgett Technique

Precise control of the placement and patterning of graphene on various substrates has tremendous impact in many fields, such as nanoscale electronics, multifunctional optoelectronic devices, and molecular sensing. A one‐step facile technique involving N₂‐plasma promotes surface modification and enhances the surface wettability of the substrate. The technique is employed to create partially hydrophilic surfaces on SiO₂/Si substrate with the aid of various templates, enabling the selective deposition, alignment, and formation of patterns comprising monolayer graphene oxide (GO) sheets; it successfully uses the Langmuir–Blodgett (LB) deposition technique over a large area without the need of any sophisticated equipment. Various characterization techniques are carried out in order to understand the possible mechanism behind the pinning of the GO on the partially treated areas. It is a relatively easy and swift process that can reliably accomplish specific surface modification with high bonding strength between GO and the substrate. This technique allows the creation of patterns with controllable dimensions. For example, the thickness of the GO sheets can be controlled; this is particularly important in creating arrays and devices at wafer‐scale. Being simple yet effective and inexpensive, this technique holds tremendous potential that can be exploited for numerous applications in the field of bio‐nanoelectronics.     

Kalte Normaldruck‐Jetplasmen zur lokalen Oberflächenbehandlung

Cold non‐thermal plasma jets for local surface treatment under normal pressure Plasmas at normal pressure are of considerable interest for surface technology because the industrial application requires no vacuum devices. Among other approaches, cold non‐thermal plasma jets represent an emerging technique to generate plasmas at normal pressure with attractive advantages. They allow ambient process temperatures and require only moderate operating voltages (1.5‐2.5 kV). They offer the advantage that the treated surfaces are not placed between the electrodes thus favoring local treatment of non flat, structured 3D surfaces. Moreover, the dimension of the sources is scalable and their integration into automated processes is simple. A capacitively coupled version (27.12 MHz) of a cold plasma jet suitable for surface treatment at atmospheric pressure is presented along with its plasma physical and technical properties and a series of successful applications, including plasma activation of surfaces for increasing printability, adhesion control, surface cleaning, microfluidics, decontamination, its use in plasmamedicine and for deposition of thin SiO₂ films as protective coatings. The device allows the operation with rare gases (e.g. Ar) and reactive gases as N₂, air or admixtures of silicon‐containing compounds.     

Multiscale Plasma‐Catalytic On‐Surface Assembly

Controlled modification of surfaces is one of the key pursuits of the nanoscience and nanotechnology fields, allowing for the fabrication of bespoke materials with targeted functionalities. However, many surface modifications currently require painstakingly precise and/or energy intensive processing to implement, and are thus limited in scope and scale. Here, a concept which can enhance the capacity for control of surfaces is introduced: plasma‐assisted nucleation and self‐assembly at atomic to nanoscales, scalable at atmospheric pressures.     

Anti‐Eis‐Oberflächenbeschichtungen

Anti‐icing coating — optimization by means of plasma technology Ice on surfaces can significantly limit the function of devices and has to be removed by processes with high energy consumption. E. g., the formation of ice on rotor blades of wind turbines is not desired, on the wings of aircrafts it is even dangerous. With the aid of plasma technology, the Fraunhofer IGB has developed an anti‐icing coating for polymeric surfaces. Water‐repellent micro‐ and nanostructured coatings are applied to polymer foils made of impact‐resistant and shockproof polyurethane. Optimization of various process parameters has made it possible to produce ultra‐thin coatings, which reduces the ice's adhesion by over 90 percent. The new nanostructured foils open a wide range of applications.     

Plasmapolymerschichten als Basis für maßgeschneiderte funktionale Oberflächen

Plasmapolymer coatings for tailor‐made functional surfaces The tailoring of surface properties via polymer coatings is currently a strongly pursued topic in various fields ranging from microsystem technology to bioanalytics. A precise tuning of surface properties, however, is only possible if chemically well‐defined processes are used that usually require reactive surface moieties to which molecules can be coupled. In this contribution we summarize studies that aimed at the modification of inert surfaces. For this purpose reactive groups at the surfaces are generated by plasma polymerisation of allyl amine which results in layers that contain amino groups. Initiator molecules for free radical polymerization processes are then coupled to these amino groups resulting in surfaces from which polymers can then be grown via surface‐initiated polymerization. Using these processes, polymer monolayers with very different properties can be generated by simply using different monomers.     

Controlled Micro/Nanodome Formation in Proton‐Irradiated Bulk Transition‐Metal Dichalcogenides

At the few‐atom‐thick limit, transition‐metal dichalcogenides (TMDs) exhibit strongly interconnected structural and optoelectronic properties. The possibility to tailor the latter by controlling the former is expected to have a great impact on applied and fundamental research. As shown here, proton irradiation deeply affects the surface morphology of bulk TMD crystals. Protons penetrate the top layer, resulting in the production and progressive accumulation of molecular hydrogen in the first interlayer region. This leads to the blistering of one‐monolayer thick domes, which stud the crystal surface and locally turn the dark bulk material into an efficient light emitter. The domes are stable (>2‐year lifetime) and robust, and host strong, complex strain fields. Lithographic techniques provide a means to engineer the formation process so that the domes can be produced with well‐ordered positions and sizes tunable from the nanometer to the micrometer scale, with important prospects for so far unattainable applications.     

Easy‐to‐clean Schichten – spezielle Anwendungen

Easy to clean surfaces – special applications Easy to clean surfaces can be made by wet‐chemical coating with subsequent heat‐treatment. Organically modified metal oxide films form the base reinforced by nano composite structures. The hydro‐ and oleophobic effect is obtained by perfluorinated organic molecule chains in the nano composite sol‐gel coatings. Application specific materials can be synthesized by the proper choice of suitable starting compounds and process parameters. The resulting coatings consist of a three‐dimensional cross‐linked inorganic part (such as a silica network) combined with an organic part. The organic material acts either as a surface modifier (example: alkyl, phenyl) or as crosslinker (example: acrylic, epoxy). The properties of such coating systems can be adjusted to obtain a wide range of glass‐ceramic or polymer‐like properties. The incorporation of nanoparticles into these materials significantly enhances the abrasion and the scratch resistance. Such coatings mainly on metal parts are used in diagnostics, analytical chemistry and medical technology.     

Ortselektive laserchemische Oberflächenfunktionalisierung von Polymeren im Mikrometerbereich. Selective laser‐chemical micro surface modification of polymers

Polymeric substrate materials like polystyrene (PS), polycarbonate (PC) or cyclic olefins (COC) are getting more attention besides silica, glass and ceramic for the preparation of reaction vessels, optical slides, microfluidic components or microtiterplates in applications like medical diagnostics and pharmaceutical drug screening. Actually, the market of transparent polymeric chips is demanding the availability of modified surfaces with well defined arrays of wettable areas or special chemical functionalities. The modified areas are starting point to graft bioactive molecules, for instance proteins or DNA‐oligomers. Another application is pretreatment of adhesive bonded joints. Presently surface modifications are performed chemically and physically by plasma surface interaction. IWS has developed a new technique for dry chemical structuring of polymeric surfaces based on the principle of excimer laser irradiation in reactive gas atmosphere. This technique is characterized by a high resolution and a negligible amount of chemicals. The procedure consists of only a few processing steps, in contrast to conventional lithographic structuring methods. Also wetting problems do not play a role as they do in printing techniques. The technology provides the possibility of tailoring the chemical and topographical surface properties from ultrahydrophobic to hydrophilic or to functionalize areas of choice in the μm range with a chemical group of defined density. Using an excimer‐laser to induce reactions, mask imaging can be applied for microstructuring the surface with new properties, e. g. for microarrays. In addition, the laser allows defined amount of energy into the elementary reaction, according to the wavelength applied, which opens the possibility of replacing atoms in the polymer molecules by other atoms or molecules taken from an agent in the environment, in a selective way. The precondition is that both the polymer and the agent absorb the same wavelength. For instance 193 nm radiation (ArF excimer laser) is absorbed by polyolefines and by ammonia allowing an exchange of H atoms for amino groups by which the surface is changed to starting point to graft bioactive molecules. Chemical microstructures for instance amino group arrays have been realized on a variety of polymeric materials like cyclic olefin foil. This array of monofunctionality is the starting point for the preparation of parallel microreactors. These samples of topographical and chemical microstructures are the first step for biochemical preparations in medical diagnostic kits, DNA‐, protein‐ or cell biochips. The upscaling of the laser modification process in a multi‐chamber reactor offers the semicontinuous functionalization of polymers in pilot scale or in batch processing. On this basis the surface modification step can be adapted into a mass production line of “Lab‐on‐a‐chip” systems.     

Reinigung von Vakuumbauteilen für UHV‐ und UCV‐Anwendungen

Cleaning of vacuum components for UHV and UCV applications Ultra‐clean vacuum components and assemblies are fundamental to some cutting edge high‐tech sectors like semiconductor industry, particle accelerators, and surface analytics. Exceptionally critical for these applications are particles that stick at the vacuum facing surfaces as well as desorption of water and hydrocarbons from the surfaces into the system, because this may interfere with the sensitive ultra‐high vacuum (UHV) and ultra‐clean vacuum (UCV) processes. In this contribution, some established cleaning methods and surface treatments are discussed with respect to their effect on reducing particle contamination and outgassing of water and organic compounds from stainless steel surfaces. It is clarified that the resulting cleanliness severely depends on the detailed steps during the surface treatment and subsequent cleaning. As a consequence, the discussed methods should be chosen and adapted with great care according to the specific demands of the final application area.     

3D‐Printed Biomimetic Super‐Hydrophobic Structure for Microdroplet Manipulation and Oil/Water Separation

Biomimetic functional surfaces are attracting increasing attention for various technological applications, especially the superhydrophobic surfaces inspired by plant leaves. However, the replication of the complex hierarchical microstructures is limited by the traditional fabrication techniques. In this paper, superhydrophobic micro‐scale artificial hairs with eggbeater heads inspired by Salvinia molesta leaf was fabricated by the Immersed surface accumulation three dimensional (3D) printing process. Multi‐walled carbon nanotubes were added to the photocurable resins to enhance the surface roughness and mechanical strength of the microstructures. The 3D printed eggbeater surface reveals interesting properties in terms of superhydrophobilicity and petal effect. The results show that a hydrophilic material can macroscopically behave as hydrophobic if a surface has proper microstructured features. The controllable adhesive force (from 23 μN to 55 μN) can be easily tuned with different number of eggbeater arms for potential applications such as micro hand for droplet manipulation. Furthermore, a new energy‐efficient oil/water separation solution based on our biomimetic structures was demonstrated. The results show that the 3D‐printed eggbeater structure could have numerous applications, including water droplet manipulation, 3D cell culture, micro reactor, oil spill clean‐up, and oil/water separation.     

Anodization: a promising nano-modification technique of titanium implants for orthopedic applications

Anodization is a well-established surface modification technique that produces protective oxide layers on valve metals such as titanium. Many studies have used anodization to produce micro-porous titanium oxide films on implant surfaces for orthopedic applications. An additional hydrothermal treatment has also been used in conjunction with anodization to deposit hydroxyapatite on titanium surfaces; this is in contrast to using traditional plasma spray deposition techniques. Recently, the ability to create nanometer surface structures (e.g., nano-tubular) via anodization of titanium implants in fluorine solutions have intrigued investigators to fabricate nano-scale surface features that mimic the natural bone environment. This paper will present an overview of anodization techniques used to produce micro-porous titanium oxide structures and nano-tubular oxide structures, subsequent properties of these anodized titanium surfaces, and ultimately their in vitro as well as in vivo biological responses pertinent for orthopedic applications. Lastly, this review will emphasize why anodized titanium structures that have nanometer surface features enhance bone forming cell functions.     

Charakterisierung plasma‐ modifizierter Polymere mittels SSXPS und XPS‐Imaging

For many years now, engineering polymers with tailor‐made surface properties are of widespread interest. One of the most commonly used technique to functionalize or coat polymers is the plasma technique. One of the most important reasons is the possibility to tailor the surface properties without alteration of the versatile bulk properties. Many engineering polymers applied in medical equipment, life‐science, and biotechnological purposes demand monofunctionalized and structured surfaces. Those can be obtained with appropriate process parameters. The characterization of such tailored surfaces as well as of surfaces with structured functionality can be performed by several analytical tech niques. Besides AFM and FTIR the photoelectron spectroscopy (XPS, ESCA) is used.     

Modifizierung unpolarer Polymeroberflächen

Modification of non‐polar polymer surfaces In numerous technological relevant processes the adhesion in compound systems is of central importance. It concerns for example surface coatings and the manufacturing of composites. Particular problems result at the compounding of polyolefins, silicones and fluoropolymers due to their very low surface energy. The modification of such polymer surfaces with the aim of functionalisation and with it of increasing the surface energy results in an improvement of adhesion properties of the materials. A well‐established procedure, particularly in the automotive industry, is the flame treatment of the surfaces. However, a defined chemical modification of the surface depends on many parameters and thus is very difficult to standardize. A defined change of the surface can be better achieved through a targeted plasma treatment, in which in our case the surface is stabilized by a subsequent wet chemical process step.     

Plasmaprozesse für funktionelle Polymeroberflächen

Plasma Processes for Functional Polymer Surfaces Plasma‐based processes were originally developed for microelectronics, but have exceeded this limits since then. Today the plasma technology is a key technology with numerous applications. A great technological potential can be seen particularly in the field of surface modification because in a plasma any organic bond can be broken and thus reactions can be initiated which cannot be carried out wet‐chemically. Besides, the small depth effect leaves the bulk properties of the material unchanged. This article points out the fundamental characteristics of non‐thermal low pressure plasmas and shows some procedure examples, which were developed at the Fraunhofer‐Institut für Angewandte Polymerforschung (IAP). Finally analysis methods (XPS, labeling techniques) are presented, which are essential for an effective development of plasma processes.     

Großflächige Quellen f�r die industrielle Plasmatechnik

Plasma‐technological processes in modern thin film technologies for the refinement of surfaces are of constantly growing interest. Plasma‐technical procedures for the surface modification and film deposition mainly are contributed to the low pressure regime and use ion and/or plasma techniques. In particular plasma‐technological process concepts in the industrial field require adapted and scalable large area plasma sources. A new source concept, based on a coaxial structure, unites these specifications and permits plasma arrangements of nearly any required size.     

Mikrowellen‐PECVD für kontinuierliche Großflächenbeschichtung bei Atmosphärendruck

Microwave PECVD for continuous wide area coating at atmospheric pressure Plasma processes are applied for a variety of surface modifications. Examples are coatings to achieve an improved corrosion and scratch protection, or surface cleaning. Normally, these processes are vacuum based and therefore suitable to only a limited extend for large area industrial applications. By use of atmospheric pressure plasma technology integration in continuously working manufacturing lines is advantageously combined with lower costs and higher throughput. Microwave plasma sources present powerful modules for plasma enhanced chemical vapour deposition at atmospheric pressure. At Fraunhofer IWS processes and equipment as well as application specific materials are developed. The coatings are suitable for scratch resistant surfaces, barrier and corrosion protective layers or anti‐reflex layers on solar cells. The film properties achieved are comparable with those produced by low pressure processes.