Plasmachemische Gasphasenabscheidung und Plasmaätzen bei Atmosphärendruck

Plasma enhanced Chemical Vapour Deposition and plasma etching at atmospheric pressure Plasma processes are applied for a variety of surface modifications. Examples are, e.g. coatings to achieve an improved corrosion and scratch protection, or surface cleaning and texturising. Since these processes, however, usually take place in vacuum, they are unfortunately not applicable for large area industrial use. Plasma enhanced CVD processes at atmospheric pressure enable the deposition of functional coatings on components and semi‐finished parts with in a continuous air‐to‐air process without the use of expensive vacuum systems. By their integration into in‐line production processes the substrate handling and the coating costs are definitely reduced. A thermal plasma source, basing on a linearly extended DC arc discharge at atmospheric pressure, has been tested for the deposition of silicon nitride at substrate temperature of less than 300° in a continuous PECVD process. Furthermore this source has been tested for plasma‐chemical etching and texturising of silicon as well.     

Wirtschaftliche Anwendung von Mikrowellen‐Plasmen vom mittleren bis Atmosphärendruck. Economic utilisation of microwave excited plasma in medium to atmospheric pressure

An overview on the potential of medium to atmospheric pressure processes will be given and discussed in context to production applications. The introduction of the medium to atmospheric pressure plasma source is a huge progress and a valuable, attractive tool. The plasma source bases on the concept of cy lindrical r esonator with annu lar s lots (CYRANNUS®). High process speed and reliability are the most important facts for technical applications. Parameters as gas/flow dynamic can be controlled and lead to further improvements of equipment and process design. The CYRANNUS® plasma is used in down‐stream configuration for several applications such as glass films on polymer substrate to reduce oxygen permeation, protective coatings against corrosion or wear and hydrophilic or hydrophobic surface properties. Also etching or cleaning can be done easily because of arbitrary process gas in the plasma source. The advantage of medium pressure is higher supply of reactive species and improved transportation of reaction products. Various processes with plasma surface interaction are discussed from physical and technical viewpoint as plasma enhanced CVD, plasma polymerisation on metal or polymer substrates. Using the advantages of medium pressure plasma processes consequently leads to new design of equipment and material flow. In‐line/on‐line treatment of 3‐D material becomes most efficient and enables competitive plasma processes for mass productions. For diamond deposition a larger size of the plasma at high pressure processes are essential for a device with best economics.     

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.     

Großflächige Plasmabeschichtungen: Niederdruck oder Atmosphärendruck?

Large area plasma coatings: low pressure or atmospheric pressure? Research in the field of atmospheric pressure plasma is often motivated by the expectation of cost‐saving compared to low pressure plasma processes. A cost analysis based on plasmachemical processes which can also be performed at atmospheric pressure, however, reveals a different picture: high gas flow rates that are required for atmospheric pressure plasmas were found to cause increased costs for large‐area plasma deposition.     

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.     

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.     

Plasma im Beutel

Plasma in a bag — Internal coating of bags using atmospheric pressure plasmas for cell culturing. “Plasma in a bag” stands for a new low‐cost technique for coating the inside of closed plastic bags by means of atmospheric pressure plasma. The technique allows the deposition of homogeneous, long‐term stable functional layers on the inner surfaces of cell culture bags. The area density of functional amino groups was determined by chemical derivatization in combination with ATR‐FTIR spectroscopy. A prototype of an equipment was built for the automated and reproducible deposition of coatings under standard laboratory conditions maintaining the sterility of the bag. High yields of adherent grown human mesenchymal stem cells can be achieved even after long periods of storage of the bag before use. With suitable variation of the film‐forming agent different functionalities can be obtained on the surface. Future goals are the deposition of migration barriers as well as the coating of bottles with hydrophobic surfaces.     

Korrosionsuntersuchungen an mittels PVD mit Zn und Zn/Mn beschichteten Stählen

Corrosion Studies of Steels Coated by means of PVD with Zn and Zn/Mn Alternative methods for hot dip‐ or electrogalvanic deposition of zinc coatings on steel are gas phase depositions (PVD). They posess high flexibility with respect to alloy composition, and are environmentally harmless. However, a PVD‐coated steel must have at least the same corrosion resistance than steels with “classical” surface finishing. Therefore, the corrosion behaviour of Zn‐coatings and Zn/Mn/system‐coatings deposited by electron beam evaporation without and with ion beam assistance (IBAD) on low alloy steel, was determined by means of salt spray test and electrochemical potential/time measurements. At first the influence of chemical and irradiation pre‐treatment and ion bombardment during deposition on the corrosion resistance of the coatings was investigated. Than the effect of the Zn‐layer thickness was determined in comparison with an 8μm thick electrogalvanized reference coating. Finally Zn/Mn‐alloys, Zn/Mn‐multilayers and Zn‐coatings with Mn‐ or Zn/Mn‐surface layers (top layers) were investigated. By means of optimised pre‐treatment and ion bombardment conditions one obtains, considering the layer thickness, PVD‐Zn coatings with corrosion resistance comparable with the reference layer. The best Mn‐containing coatings are Zn‐coatings with Mn‐toplayer. They surpass the corrosion resistance of the reference layer considerably. Additionally it could be shown that in tendency the potential/time measurements agree very well with the results of the salt spray test.     

Funktionale Oberflächen auf Duplex‐Stahl durch Laserfeinbeschichten

Functional surfaces on duplex stainless steel by lasercladding The product‐lubricated axial and radial bearings installed in multistage high‐pressure pumps inevitably encounter severe mixed friction conditions as the pumps start and stop. This leads to extremely high tribological loads on the bearing components, compounded by the effects of a highly corrosive pumped fluid. The present paper describes a laser cladding process which produces near‐net‐shape coatings of new, highly corrosion and wear resistant functional layers which can be deposited directly on high‐alloy stainless steels without requiring additional buffer layers and without affecting the mechanical properties and corrosion resistance of the substrate. The results cover the solidification behaviour of the coatings as well as the microstructure resulting from various heat treatment conditions. In addition, the technological properties of the coatings and the resulting composites are discussed. The coating systems are tested as to their corrosion resistance and tribological characterization in a pump‐specific tribological system.     

Organische UV‐Schutzschichten für die Polycarbonatverglasung

Organic UV‐protective coatings for polycarbonate glazing Polycarbonate as glazing material in outdoor applications requires functional UV protective and scratch resistant coatings. The vacuum coating technology offers a wide range of deposition processes to produce such complex coatings. The Fraunhofer IOF developed an effective UV protection by the deposition of organic UV absorbers. Thermal evaporated organic compounds were investigated as single layers and hybrid layers in a SiO₂ matrix. The UV‐stability of such coatings was increased significantly.     

Plasmagestützte Beschichtung von Bauteilen bei niedrigen Temperaturen

The deposition of wear resistant coatings is possible nowadays at low temperature by the Plasma Assisted CVD process using metall organic precursors. Thus a coating of temperature sensitive materials like aluminium, magnesium and polymer at low temperature is realised. The wear resistant coatings TiCN and ZrCN were deposited on light metals at a temperature below 160°C. The mechanical properties of the layers show the potential of the coatings for parts with wear and friction. The surface hardness, the abrasive wear and the friction value are improved compared to the properties of substrate material and steel. Transparent BCN‐coatings can be used as scratch resistant coatings on polymers like polycarbonate. The layers offers good transmission by high hardness.     

Mikrowellen‐Plasmabrenner bei Atmosphärendruck

Microwave Plasma Torch at Atmospheric Pressure The development of the microwave plasma torch shows that a combination of two resonators is targeting for a reliable ignition under atmospheric pressure and stable continuous operation at high power conditions. An adapted gas management with jacket flow and good mixing can be produced by the coaxial design. The spectroscopic investigation of the torch gives information about the spatial temperature distribution in the plasma. The distribution of the OH‐rotation‐vibration band is observed in the line of sight with a high spectroscopic resolution. In an air plasma a constant core gas temperature of 3600 K is determined. It is independent of the outside parameters, like microwave power or gas flow. Only the plasma volume adapts, in order to keep the energy content constant.     

Abrasiver Verschleiß nitrocarburierter Stähle

Abrasive wear of nitrocarburized steels Diffusion coatings have been used increasingly to improve surface properties of several machine components for tribological applications. In this investigation, the abrasive wear of various diffusion coatings has been studied. These coatings developed by three different nitrocarburizing processes, namely salt-bath, gas and plasma nitrocarburizing, were conducted on five various steel substrates. The substrates were St 52-3, Ck 45, 42 CrMo 4, 30 CrNiMo 8 and X 20 Cr 13. The thickness of the compound layers and their porosity were measured using optical microscopy. The structure of compound layers was characterized using an X-ray diffractometer, and their surface roughness by a stylus profilometer. The surface hardness measurements and the hardness profile were made according to the Vickers principle. The abrasion test was carried out using a pin-on-table machine. The predominant wear mechanisms have been evaluated using scanning electron microscopy. It was found that the employed nitrocarburizing processes have improved the abrasive wear resistance of all tested coating-substrate-combinations. In general, the abrasive wear rate decreases with an increase in the hardness of the compound layer as well as its thickness. The best coating-substrate-combinations to improve abrasion resistance were salt-bath and gas nitrocarburized specimens of the substrate X 20 Cr 13. Plasma nitrocarburized specimens of the substrate St 52-3 and Ck 45 were the worst.     

Maßgeschneiderte Tribologie durch Laseroberflächenbehandlung

Tailored tribology by laser surface treatment There are quite different requirements for tribological properties of surfaces in industry. Both reduction and maximization of friction and/or wear are possible requirements. The friction and wear properties depend on the tribological system consisting of the friction partners, the medium between them and the environment around them. So for each application tailored surfaces with special tribological properties are needed. In the paper examples are presented which deal with the investigation and the implementation of laser based processes to obtain surfaces with very different tribological properties. Wavelengths, output power values, intensity distributions and beam qualities of the available lasers vary in a wide range. Also the available devices for beam formation and beam guidance enable special processes for tailoring properties for particular applications. These processes are for example the single‐layered or multi‐layered laser cladding generating homogeneous or graded claddings, the laser alloying or laser dispersing and the laser stimulated deposition of diamond layers at atmospheric pressure.     

离子辅助制备凹印耐磨层工艺研究

针对凹印版电镀存在的污染和高能耗,采用射频感应偶合(ICP)离子源辅助电子束沉积技术在凹印镍版表面沉积了硬铬薄膜,通过控制离子源参数和加入过渡层来提高薄膜的与基体的结合力和显微硬度.研究了不同工艺条件制备薄膜的组织结构和性能,并与工厂实用的电镀样品做了对比.结果表明,优化工艺条件下的膜层,其硬度较高,表面均匀,与基体结合良好,可以达到甚至超过电镀样品;离子辅助和过渡层起着重要的作用.     

Flächeneinfluss bei der PACVD‐Beschichtung

Impact of the active surface on properties of DLC films in the PACVD coating chamber. In the automotive industry, economic and stable industrial processes to apply hard coatings for tribological applications are required. Hence detailed knowledge about the influence of coating parameters on the film characteristics is essential. the following paper deals with the process of plasma activated chemical vapor deposition with focus on the effect of the parameter “active area in the coating chamber“ on the properties of diamond‐like‐carbons (DLC). the coatings are deposited in an industrial coating chamber using reactive magnetron sputtering with a pulsed bias voltage (40 kHz) and at constant pressure. During the investigation of the influence of active area and current density on the mechanical and tribological properties of the DLC films, the expected correlation between active area and current density could be confirmed. By regulating the current density, consistent film properties could be achieved, independently of the active area in the chamber. Furthermore improved wear characteristics of the film – crucial for the endurance of heavily loaded automotive components – were achieved by adapting the load pattern of the chamber.     

APPLICATION OF HIPING-THICK CERAMIC COATINGS ONTO METALS

The demand for high performance in the combustion equipment used in the automobile and aerospace industries is creating renewed interest in the use of ceramic protective coatings on metal surfaces. Sometimes, thick coating layers are required as thermal barriers or for wear resistance and hardness. Although plasma spraying is one of the promising processes available for depositing thick ceramic coatings onto metal surfaces, the presence of porosity in the coating coupled with lack of corrosion resistance of the coated materials, and the generally low strengths of both the coating layer and the coating-matrix interface may limit the use of the process. HIP treatment of ceramic coatings allows one to obtain dense coatings and also to increase the interfacial bond strength. The present paper reviews the recent advances in the post-HIPing of ceramic coatings as well as the use of HIP for sinter-coating by which a ceramic powder compact is sintered and bonded simultaneously to a metal surface.     

PVD‐Schutzschichten für Werkzeuge des Präzisionsblankpressens

PVD protective coatings for precision molding tools Precision glass molding (PGM) is a replicative hot forming process for the production of complex optical components, such as aspherical lenses for digital and mobile phone cameras or optical elements for laser systems. The efficiency and thus also the profitability of the PGM depend on the unit price per pressed component, which correlates primarily with the service lifetime of the pressing tools. To increase tool lifetime, the tool surfaces are coated with protective coatings based on precious metals or carbon using physical vapour deposition (PVD). The PVD coating technology enables the deposition of thin coatings, which also follow more complex surface geometries and achieve a high surface quality. PVD coatings are also commonly used to protect tools from wear and corrosion. This paper presents two chromium‐based nitride hard coatings produced by an industrial PVD unit and investigated for their applicability for PGM. Two different coating architectures were implemented, on the one hand a single coating chromium aluminium nitride (Cr,Al)N coating and on the other hand a nanolaminar CrN/AlN coating with alternating layers of chromium nitride and aluminium nitride. The latter is a coating consisting of hundreds of nano‐layers, only a few nanometers thick. Both coatings, (Cr,Al)N and CrN/AlN, each have a thickness of s ～ 300 nm in order to follow the tool contour as closely as possible. The properties of the coating systems, which are of particular relevance for PGM, are considered. These include on the one hand the adhesion of glass, the roughness and topography of the surface and the adhesion between the coating and the tool material. In addition, the barrier effect of the coatings against diffusion of oxygen was investigated. In order to reproduce the thermal boundary conditions of the PGM, thermocyclic aging tests are performed and their influence on the different properties is described.     

Entwicklung von Oxid – Keramik zur Anwendung als Wärmedämmschichten

Development of Oxide Ceramics for an Application as TBC The standard thermal barrier coating material yttria stabilised zirconia (YSZ) is limited in long term operation to a maximum temperature of about 1200°C. As a result further increase of the gas inlet temperature and hence the efficiency of gas turbines are hardly to achieve with YSZ coatings. In a screening procedure especially perowskite (ABO₃, A = Sr,Ba, B = Zr) and pyrochlore (A₂B₂O₇, e.g. A = La and other rare earth elements, B = e.g. Zr) materials have been identified as possible candidates for thermal barrier coatings. Basic physical properties (e.g. thermal expansion coefficient, thermal diffusivity and conductivity) of several candidates have been determined using sintered, dense samples. The possibility of optimization of the properties by using specific compositions will be discussed. From promising materials powders which are suitable for plasma‐spraying have been produced by spray‐drying. New TBC systems consisting of new materials (BaZrO₃, La₂Zr₂O₇) deposited by atmospheric plasma spraying and vacuum plasma sprayed MCrAlY bondcoats were tested in a gas burner facility. Especially La₂Zr₂O₇ coatings gave promising results. A further improvements could be achieved by the use of layered or graded coatings with a YSZ coating at the bondcoat interface and on top a layer of the new TBC material. First results of thermal cycling tests with 1250 and 1350°C surface temperature will be presented.