PVD‐CrN Beschichtungen auf Magnesium AZ91hp und Stahl 100Cr6 – Untersuchung des Substrateinflusses auf die Schichteigenschaften

PVD‐CrN coated magnesium alloy AZ91hp and steel 100Cr6 – Investigation on the influence of the substrate material on coating properties PVD‐chromium‐nitride coated samples of substrates of the magnesium alloy AZ91hp and the roller and ball bearing steel 100Cr6 were investigated regarding structure, mechanical characteristics, adhesion and internal stresses. For the coatings the parameters layer thickness and substrate BIAS voltage were varied. Both substrate materials were coated in one lad. Results of the x‐ray analysis of the internal stresses show significant differences between the coated magnesium and the coated steel substrates. In the case of the variation of the substrate BIAS voltage, for the coated steel a dependency of the internal stresses to coating parameters could be obtained. For the coated magnesium no dependency was recognizable. The coating structure was examined with scanning electron microscopy. Element depth profiles of the coated samples were performed with SIMS.     

Corrosion behaviour of steel with PVD CrxN coatings

The application of PVD coatings for wear protection of tools is well known. Since many years, TiN coated cutting and forming tools are state of the art. In contrast, the application of PVD coatings on machine parts is not standard today. This is caused by the problems of coating deposition on components as well as the fact that wear protection and corrosion protection is demanded for many parts with longer lifetime. TiN produced by means of PVD technique is good for wear protection, but with respect to corrosion there are problems. On the other hand electropolated chromium is a reliable coating to resist corrosion, but wear resistance is limited. PVD Cr_xN coatings promise to combine the advantages of hard coatings and electropolated chromium. The present study focuses on the corrosion properties of magnetron sputtered Cr_xN coatings. Different types of coatings on steel substrates with various amounts of nitrogen were investigated in order to take into account aspects of coating deposition resp. coating material, coating structure and coating morphology. Additionally several graded and multilayer coatings were studied to show influences of coating system design. Electroplated hard chromium was used as reference material for corrosion resistance. To explain the corrosion behaviour, crystallographic phases and structure of coatings were analysed by X‐ray diffraction and morphology by SEM. It could be shown that the corrosion behaviour depends on all these parameters and that 8 μm chromium nitride provides the same corrosion protection as 48 μm electroplated chromium.     

The effect of PVD coatings on the corrosion behaviour of AZ91 magnesium alloy

In this study, multilayered AlN (AlN + AlN + AlN) and AlN + TiN were coated on AZ91 magnesium alloy using physical vapour deposition (PVD) technique of DC magnetron sputtering, and the influence of the coatings on the corrosion behaviour of the AZ91 alloy was examined. A PVD system for coating processes, a potentiostat for electrochemical corrosion tests, X-ray difractometer for compositional analysis of the coatings, and scanning electron microscopy for surface examinations were used. It was determined that PVD coatings deposited on AZ91 magnesium alloy increased the corrosion resistance of the alloy, and AlN + AlN + AlN coating increased the corrosion resistance much more than AlN + TiN coating. However, it was observed that, in the coating layers, small structural defects e.g., pores, pinholes, cracks that could arise from the coating process or substrate and get the ability of protection from corrosion worsened were present.     

An investigation into the tribological performance of Physical Vapour Deposition (PVD) coatings on high thermal conductivity Cu-alloy substrates and the effect of an intermediate electroless Ni-P layer prior to PVD treatment

The use of high thermal conductivity copper alloys in plastic injection moulds provides the benefit of rapid moulding cycles through effective heat transfer. However, copper alloys are relatively soft and wear rapidly so manufacturers are now developing copper alloys with increased hardness and wear resistance. Their wear resistance can be further improved by the deposition of hard coatings such as electroplated chromium, electroless nickel and Physical Vapour Deposition (PVD) coatings. In this paper, the tribological performance of three proprietary high-strength Cu alloys (Ampcoloy® 940, Ampcoloy® 944 and Ampcoloy® 83) coated with PVD CrN and CrAlN coatings has been evaluated. A medium phosphorous content electroless Ni-P (ENi-P) plated layer was also deposited as a pre-treatment to PVD CrN and CrAlN coatings to increase the load support. The effect of this intermediate ENi-P layer was also evaluated. Surface roughness and instrumented hardness measurements were used to characterise all coated systems in both plated (i.e. with the intermediate ENi-P coating) and standard (i.e. unplated) conditions. Scratch tests were also performed to evaluate the effect of the ENi-P on PVD coating adhesion to Cu alloy substrates. The tribological behaviour of PVD-coated Cu alloy systems was evaluated by pin-on-disc wear tests and ball-on-plate impact tests. Results demonstrate that the ENi-P layer improves the load support for PVD coatings on Cu alloys, thereby improving their tribological performance. However, for PVD-coated Cu alloys in the standard condition, the Cu alloy substrate type plays an important role in the tribological performance of PVD coatings. For instance, PVD CrN coatings were more suited to a certain Cu alloy type whilst CrAlN to the other two types.     

物理气相沉积在镁合金表面防护领域的研究现状

镁合金表面耐腐蚀性能、耐磨性能较差,物理气相沉积(PVD)镀膜技术是一种提高镁合金表面性能的有效方法。总结了PVD镀膜防腐蚀层和耐磨层的特性,分析了涂层耐腐蚀耐磨的机理和存在的不足。综述了镁合金表面PVD膜层的研究进展,阐述了物理气相沉积技术对镁合金的表面改性的应用现状,并对该技术在镁合金上的发展进行了概括,指出了目前PVD技术在镁合金表面防护领域的新前景,为今后PVD技术对镁合金表面防护的研究与发展提供了相关参考。     

(Cr1‐x,Alx)N ein Review über ein vielseitig einsetzbares Schichtsystem

(Cr_1‐x,Al_x)N a review about a multi‐purpose coating system Nitride based coatings claimed a big market share for PVD‐coatings. Especially in the field for high temperature die casting and cutting operations chromium based coatings are well used. These coatings are also used in low temperature processes for the coating of machine parts. In the beginning of the nineties first examinations are done on the ternary system Chromium‐Aluminium‐Nitride. This system shows an excellent corrosion behaviour against many different liquids, but gains also a high hardness for a good wear behaviour. By changing the AlN to CrN content and the coating design CrAlN opens up a wide range for different coating applications. A major step for machine parts was the reducing of coating process temperature beneath 200 °C. This was only possible by using pulsed power supplies. CrAlN shows a very good performance on the fast growing market of coated machine parts e.g. on spindle bearings.     

The effect of PVD coatings on the wear behaviour of magnesium alloys

In this study, AlN/TiN was coated on magnesium alloys using physical vapour deposition (PVD) technique of DC magnetron sputtering, and the influence of the coating on the wear behaviour of the alloys was examined. A physical vapour deposition system for coating processes, a reciprocating wear system for wear tests, a universal hardness equipment for hardness measurement, a X-ray diffractometer (XRD) for compositional analysis of the coating, and a scanning electron microscopy (SEM) for surface examinations were used. It was determined that the wear resistance of the magnesium alloys can be increased by PVD coatings. However, small structural defects which could arise from the coating process or substrate were observed in the coating layers.     

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.     

Erosions‐Korrosions‐Untersuchungen an gradierten Multilayer‐Chromkarbidschichten

Erosion corrosion of graded chromium carbide coatings in multi layer structure So far PVD‐ and PECVD‐Layers have proved their value as wear protection mainly on cutting tools for machining. Depending on the composition of the layers not only a reduction in wear but also a reduction in friction is possible, e.g. by integration of hydrogen containing carbon. Furthermore such carbon containing layers use to be electrochemically inert. Thus they don’t corrode in aqueous media. Because they do also have a very dense structure, an application as corrosion protection seems to be promising. For the intended investigations under service‐like erosiv‐corrosiv loading a new testing rig was developed and constructed. The erosiv‐corrosiv loading was achieved by exposure of coated specimen to a flowing medium, that contains abrasive corund‐particles. Thus the erosion‐corrosion‐behaviour of new graded Multilayer‐Chromiumcarbide‐Coatings should be investigated. The aim was to identify the mechanisms of deterioration to promote a further developement of these layers. In addition the potential of PVD/PECVD‐coated low‐alloy steel to be in‐service under such conditions should be evaluated. For comparison an up‐to‐date industrial DLC‐coating and a high‐alloy duplex‐steel were also investigated. As a result of the conducted investigations an application of PVD‐/PECVD‐coated low‐alloy steel under erosive‐corrosive conditions with impingement wear could not yet be recommended. However the graded Multilayer‐Chromiumcarbide‐Coatings have the potential for a good erosion‐corrosion‐protection, if erosion promoting flaws are avoided. Because hard PVD‐ and PECVD‐coatings are relative brittle, a loading with hard particles, which hit the surface under a high angle, is very tough. Hence the question is, if the investigated layers possibly have a better wear behaviour under more abrasive loading in a more tangential flowing medium, which is also typical for in‐service‐conditions. This is intended to be investigated in future tests.     

In vitro corrosion testing of PVD coatings applied to a surgical grade Co–Cr–Mo alloy

Toxic effects and biological reaction of metallic corrosion and wear products are an important concern for metal on metal artificial joints. Corrosion tests were conducted to study the susceptibility to pitting and localized corrosion, with three coatings, CrN, TiN and DLC, applied to a wrought high carbon Co–Cr–Mo alloy substrate material. Corrosion testing involved the measurement of potential time transients during immersion in a physiological solution and cyclic polarization of specimen potentials into the transpassive range followed by reversal of the potential to scan in the cathodic direction to regain the rest potential E_rest. Resistance to pitting and localized corrosion was assessed by determining the transpassive breakdown potential E _bd and if any hysteresis generated during the reverse cyclic scan may have caused crossover with the original anodic scan. Three different surface coating conditions were tested namely: (1) as-coated, (2) polished, and (3) indented to penetrate the coating by diamond pyramid hardness indentor. Results showed that all three coatings produced significant improvements in corrosion resistance compared to performance of the wrought cobalt alloy but that some corrosive attack to both the CrN and TiN coatings occurred and some risk of attack to the cobalt alloy substrate existed due to coating defects or when damage to the coating occurred. TiN coatings were highly effective in preventing corrosion provided they were thick enough to produce complete coverage. Thin TiN coatings displayed some tendency to encourage localized attack of the cobalt alloy at coating defects or where the coating suffered mechanical damage. CrN coatings underwent transpassive breakdown more easily and some degree of pitting at defects within the coating was observed, especially when the CrN coating was polished before the test. No corrosive attack of the cobalt alloy substrate was observed when the CrN coating was mechanically damaged by indentation. DLC coatings produced were much thinner than either of the other two coatings and proved to be rather fragile. They were less effective in preventing apparently high corrosion currents and possibly high rates of corrosion.     

Corrosion behaviour of decorative and wear resistant coatings on steel deposited by reactive magnetron sputtering - Tests and improvements

Depositions of decorative and wear resistant single layer coatings like TiN, Ti(B,N), CrN, NbN, NbON, (Ti,Mg)N and multilayer coatings like Cr/CrN, Nb/NbN, CrN/NbN and NbN/Nb-C:H were performed using reactive magnetron sputtering. The corrosion behaviour of the coated high speed steel substrates was studied in sodium chloride containing media by open-circuit-potential measurements, potentiodynamic corrosion tests and salt spray tests. Up to now, the best improvements with respect to the corrosion resistance in salt spray tests could be obtained for the system (Ti,Mg)N/high speed steel.     

Biodegradable poly(lactide-co-glycolide) coatings on magnesium alloys for orthopedic applications

Polymeric film coatings were applied by dip coating on two magnesium alloy systems, AZ31 and Mg4Y, in an attempt to slow the degradation of these alloys under in vitro conditions. Poly(lactic-co-glycolic acid) polymer in solution was explored at various concentrations, yielding coatings of varying thicknesses on the alloy substrates. Electrochemical corrosion studies indicate that the coatings initially provide some corrosion protection. Degradation studies showed reduced degradation over 3 days, but beyond this time point however, do not maintain a reduction in corrosion rate. Scanning electron microscopy indicates inhomogeneous coating durability, with gas pocket formation in the polymer coating, resulting in eventual detachment from the alloy surface. In vitro studies of cell viability utilizing mouse osteoblast cells showed improved biocompatibility of polymer coated substrates over the bare AZ31 and Mg4Y substrates. Results demonstrate that while challenges remain for long term degradation control, the developed polymeric coatings nevertheless provide short term corrosion protection and improved biocompatibility of magnesium alloys for possible use in orthopedic applications.     

Effect of mono and composite coating on dynamic fracture toughness of metals at different temperatures

It is well known that during the operating condition of any metallic structural system the dynamic crack growth speed is in the order of 1–2 km/s. Industrial finishes like coating which form the integral part of manufacturing is adopted to improve fracture toughness of metals. These coated samples coated with thin films are mechanically tested by Charpy V-notch impact tester for estimating dynamic fracture toughness. Coatings improve the wear and corrosion resistance of materials; they tend to reduce the strength of materials, because of the increased residual stresses due to the coating process. Defects cannot be precluded from these coated and treated components; strength of those components in the presence of these defects can be analyzed by fracture mechanics approach. An attempt has been made to analyze the effectiveness of coating methods like electroplating, PVD (Physical Vapour Deposition), coating thickness and the service temperature on the fracture behaviour of metals. Experiments have been carried out on EN8 steel and aluminium for different temperatures and the later samples were corroded for 2400 h and tested for corrosion resistance. The specimen preparation and experimentations were carried out according to the ASTM standard E-23. Finite element analysis was done by FRANC 2D (Fracture Analysis Code) for estimating the stress intensity factor at different crack lengths along with influence of temperature and corrosion. PVD coated samples of Al–N (aluminium nitride) and nano-crystalline layer of Ti–Al–N (titanium aluminium nitride) showed improved dynamic fracture toughness properties. The same set of samples showed decrease in stress intensity factors and excellent corrosion resistance compared to conventional Ni (nickel) and Cr (chromium) coated samples. Mechanical behaviour of selected metals under heat affected zone is of also discussed in this paper, the study aims at both coated and uncoated cases. Performances of metals in cryogenic condition are also paid attention in this paper.     

Einfluss der HiPIMS‐Parameter beim PVD‐Verfahren

Effect of PVD process parameters on structural properties of CrN layers Commonly, imperfections on substrate surfaces influence layer nucleation unfavorably. They cause growth defects in the coating structures prepared by physical vapor deposition. In consequence this leads to local loss of adhesion, higher friction, voids and thus favoring pitting corrosion. CrN‐coatings are known for their high hardness and good wear resistance. Further they have a better resistance to corrosion than Ti‐based nitrides. Among other parameters, the structure and the mechanical properties of those coatings can be influenced by varying bias voltage and gas flow during film growth. Due to variation of those parameters during reactive magnetron sputtering CrN‐coatings were deposited with preferred crystallized lattice orientation (111) and (200). The main objective of investigation is the potential to cover imperfections.     

Beanspruchungsverhalten von PVD-CrN Beschichtungen auf Leichtmetallwerkstoffen

Behaviour of light metals with PVD-CrN coatings using different test methods The application of thin hard coatings on machining tools, e.g. drilling tools is state of the art. The increase of lifetime of coated Tools compared to uncoated tools is well known. [1]. In this context ?separation of functions”? is an often used phrase, by meaning the separation of functions of the volume and the surface of materials. Going one step forward, from the point of view of tribology or corrosion this means, you have ?only”? to protect the surface by using a ?good”? coating without looking at the material underneath. In the past the influence of substrate materials or the optimization of the system (substrate-coating) was not the main aim of PVD development. Looking at substrate and coating as a system is especially necessary, if the differences of the properties of substrate and coating are large (e.g. hard coating – light metals). This paper shows different aspect of the tribological and electrochemical characterization of PVD coated light metals (CrN coating).     

Electrochemical behaviour of chromium nitride coatings with various preferred orientations deposited on steel by unbalanced magnetron sputtering

Abstract

Chromium nitride coatings Cr₂N(111) and preferred orientations of CrN(111) and CrN(200) were successfully deposited on AISI 304 stainless steel by an unbalanced magnetron sputtering method. The electrochemical corrosion properties of the deposited films were studied in a 0·5M H₂SO₄ + 1M NaCl aqueous solution at ambient temperature by electrochemical measurements, including the corrosion potential E _corr, linear polarisation, potentiodynamic polarisation and electrochemical impedance spectroscopy. The structural characterisation and surface morphology were investigated using X-ray diffraction, scanning electron microscopy and atomic force microscopy. The experimental results indicated that the CrN(200) coating possesses the best corrosion resistance property, followed by the CrN(111) coating, while the Cr₂N coating has the least resistance among the three types of CrN(111), CrN(200) and Cr₂N(111) coatings. The porosity, corresponding to the ratio of the polarisation resistance of the uncoated and the coated substrates, was higher in the Cr₂N(111) coating than in the other CrN coatings. The CrN(200) coating had a dense microstructure almost without porosity. The void defects of CrN(111) and Cr₂N(111) coatings are responsible for the decrease in corrosion protection.     

Corrosion protection of carbon fibre reinforced aluminium composite by diamondlike carbon coatings

Abstract

Carbon fibre reinforced aluminium exhibits poor resistance against electrochemical corrosion in 3·5 wt-%NaCl solution. Diamondlike carbon (DLC) coatings provide properties which make them interesting materials for external corrosion protection on metal matrix composites (MMCs). The electrochemical corrosion behaviour of uncoated and DLC coated carbon fibre reinforced aluminium was tested in 3·5 wt-%NaCl solution. It has been found that the pitting potential is shifted significantly in the anodic direction and the corrosion current density is much lower due to the presence of the sealing DLC coating. Additionally, scratch tests and SEM studies were carried out in order to characterise the adhesion of the DLC films on the heterogeneous MMCs. Reliable corrosion protection is connected with sufficient coating durability under loading. In order to ensure sufficient loading capacity of the DLC coating under tribological conditions, wear tests were undertaken which revealed a considerable improvement in wear resistance due to deposition of the DLC coatings.     

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.     

Galvanisches Verzinken von Magnesiumlegierungen

Zinc‐Plating of Magnesium Alloys Magnesium alloys are highly susceptible to corrosion that limits their application when exposure to corrosive service conditions is needed. One of the ways to prevent corrosion is to coat the magnesium‐based substrate to avoid a contact with an aggressive environment. Results concerning corrosion behaviour of wrought AZ31 magnesium alloy with electrolytic zinc coatings deposited from different electrolyte solutions are described. Evaluation of corrosion processes in chlorides containing solutions was performed by electrochemical measurements. It was found that thick and dense electrolytic zinc coatings formed on AZ31 significantly improve the corrosion behaviour of magnesium alloy after one hour immersion of zinc coated magnesium alloys in corrosive media. Further increase of immersion time leads to relatively fast decrease of corrosion properties. Electrolytic zinc coatings obtained in consecutive alkaline / acidic process demonstrate an improvement of corrosion resistance of coated AZ31. The time to coating degradation strongly increases.