Einfluss der PVD‐Prozessparameter auf die Schichtnukleation und Struktur von CrN‐Schichten

Störstellen in Bauteiloberflächen wirken sich negativ auf die Schichtnukleation bei PVD‐Schichtsystemen aus. Sie können im anschließenden Schichtwachstum zu Defekten in der Schichtstruktur führen. Die Konsequenz ist eine Minderung der lokalen Haftfestigkeit, höhere Reibwerte und Fehlstellen in der Schicht. Diese begünstigen in korrosiven Medien die Entstehung von Korrosion. CrN‐Schichten sind für ihre hohe Härte und ihre guten Verschleißeigenschaften bekannt. Zudem weisen sie eine bessere Korrosionsbeständigkeit als Titan basierte Nitride auf. Die strukturellen und mechanischen Eigenschaften dieser Schichtsysteme können unter anderem durch die Veränderung der Biasspannung und des Stickstoffgehalts während des Schichtwachstums beeinflusst werden. Durch gezielte Variation dieser Beschichtungsparameter wurden CrN‐Schichten mit den bevorzugten Kristallgitterstrukturen (111) und (200) abgeschieden, mit dem Ziel deren Abdeckungsfähigkeit von Störstellen zu untersuchen. Für die gezielte Untersuchung und Vergleichbarkeit der Ergebnisse wurden Vickerseindrücke HV 0,5 als bewusst gestaltete Störstellen auf der Grundwerkstoffoberfläche aufgebracht. Als Grundwerkstoff diente niedriglegierter Stahl (100Cr6). Die Kristallgitterorientierungen der abgeschiedenen Schichten wurden zunächst anhand von röntgenographischen Messungen (XRD) identifiziert. Anhand weiterer rasterelektronenmikroskopischer Aufnahmen (REM) wurden die bewusst erzeugten Störstellen in Form von Vickerseindrücken und Ritzspuren sichtbar gemacht, mit dem Ziel die Schichtqualität und die Mikrostruktur um Fehlstellen zu beschreiben. Imperfections on substrate surfaces can cause growth defects in hard coatings prepared by magnetron sputtering, leading to local loss of adhesion, higher friction, voids and corrosion at coating defects. CrN‐coatings are known for their high hardness and good wear resistance. In addition CrN‐coatings are better corrosion resistant than Ti based nitrides. 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 CrN‐coatings were deposited with preferred crystallized lattice orientations (111) and (200). The main objective of investigation is the potential to cover imperfections. Vickers indentations (HV 0.5) were applied as designed imperfections. As base material low alloyed steel was used (100Cr6). At first crystallized lattice orientations were identified by X‐ray diffraction (XRD). Further scanning electron microscope analysis (SEM) was applied to identify and study crystallized lattice orientations near those imperfections.     

CrN和CrNiN涂层在模拟质子交换膜燃料电池环境中的电化学性能及疏水性能EI北大核心CSCD

用闭合场非平衡磁控溅射离子镀在304不锈钢表面沉积CrN和CrNiN涂层。采用X射线衍射和场发射扫描电镜表征涂层的结构和形貌。采用电化学测试、界面接触电阻测试以及疏水性测试等方法,研究两种不同涂层在模拟质子交换膜燃料电池(Proton Exchange Membrane Fuel Cell,PEMFC)环境下的电化学腐蚀性能、界面接触电阻以及疏水性能。结果表明:CrN涂层主要包含CrN和Cr2N相,CrNiN涂层中CrN和Cr2N相较少,Ni在CrNiN涂层中以单质形式存在;动态极化测试表明涂层的耐蚀性能较好,其中CrNiN涂层的耐蚀性能较CrN涂层差,恒电位极化测试表明CrN和CrNiN涂层的电流密度相当;CrN和CrNiN涂层都显著降低了304不锈钢的界面接触电阻,其中CrN涂层的接触电阻最小;CrNiN涂层疏水性能优于CrN涂层,更有利于质子交换膜燃料电池中的水管理。     

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.     

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.     

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.     

Untersuchung des Sputter‐Ätzens auf die Eigenschaften von PVD‐CrN Hartstoffschichten auf Magnesium AZ91hp

Investigating the Influence of the Sputter Etching Process on the Properties of PVD‐CrN Coatings on Magnesium Die Cast Alloy AZ91hp A common method prior to the PVD deposition is the sputter etching process of the substrate itself to clean the surface from adhesion products and to improve the coating adhesion. This report deals with the sputter etching of magnesium die cast alloy AZ91hp to investigate the influences on the coating‐substrate interface, the surface properties and the mechanical properties of PVD‐CrN hard coatings. The coating‐substrate interface of the Cr‐AZ91 coating systems was investigated with XPS and SIMS. Surface studies were carried out by high resolution electron microscopy and AFM. The characterization of the mechanical properties of the CrN‐AZ91 compound systems includes thickness, coating hardness and hardness depth profiles, coating adhesion, structure and residual stresses. Some properties show a strong dependency of the etching time, especially the mechanical properties and the coating roughness. Increasing etching times lead to an improvement of the coating quality.     

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.     

Microstructures and corrosion behaviors of Zr modified CrN coatings deposited by DC magnetron sputtering

Zirconium modified chromium nitride coatings with various Zr contents have been prepared by a DC reactive magnetron sputtering technique. The detailed investigations in terms of composition, phase structure, morphology and corrosion properties have been performed by GDOES, XRD, SEM and electrochemical measurements, respectively. The as-deposited coatings with Zr contents ranging from 0 to 3.2 at. % form nanocrystalline solid solutions, where Zr substitute Cr in the CrN lattice. With increasing Zr contents, the lattice parameters increase but the grain sizes show little effects. All the coatings exhibit dense compact columnar structures in SEM cross-sectional observations. Electrochemical measurements in 3.5% NaCl solutions revealed that the additions of Zr into CrN coatings improved their chemical inertness. The coated samples with much low corrosion current densities in nA/cm² range show their excellent protective characteristics to the stainless steel substrates. The corrosion mechanism, however, was due to the slight pitting corrosions, which were mainly localized in the growth defects.     

Investigation of wear resistance and microstructure of a newly developed chromium and vanadium containing iron‐based hardfacing alloy

Plasma transferred arc (PTA) welded Ni and Co‐based alloys have gained high acceptance in many industrial applications for the wear protection of components. Recently, the cost of nickel and cobalt is rising drastically. This paper presents the development of a cost‐effective high chromium and vanadium containing iron‐based hardfacing alloy with high hardness and wear resistance. The welding processing of the alloy is carried out by PTA welding of atomized powders. Investigations on powder production as well as on weldability are presented. The coatings are metallographically studied by optical microscopy, SEM, EDX and micro‐hardness measurements. The wear resistance properties of the coatings are examined using pin on disk, dry sand rubber wheel and Miller testing, the corrosion properties are determined by immersion corrosion tests. The newly developed iron‐based alloy has nearly the same wear resistance as Ni‐based alloys with fused tungsten carbides at a higher level of corrosion resistance and much lower cost.     

Verarbeitung von feinen Spritzwerkstoffen zur Verbesserung von Korrosions‐ und Verschleißschutzeigenschaften von thermisch gespritzten Schichten

About the application of fine spray materials for improvements in terms of corrosion and wear protection of thermal spray coatings Within a research project the spray materials Cr₂O₃, Cr₃C₂ NiCr and WCCoCr were considered. Process parameters were determined, optimized and validated allowing the application of very fine spray material fractions (< 25 μm) with plasma and high velocity oxy‐fuel spray systems. In addition to improved coating properties like low porosity and improved corrosion resistance the application of near net shape coatings was enabled. The subsequent reduced effort for after‐treatment of the coatings can contribute to further rationalization of thermal spray processes.     

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.     

Surface density of growth defects in different PVD hard coatings prepared by sputtering

Growth defects are present in all PVD hard coatings. They have detrimental influence on their tribological properties (higher sticking of workpiece material, higher friction coefficient, worse corrosion resistance, higher gas permeation). In order to improve the tribological properties of PVD hard coatings it is important to minimize the concentration of growth defects. Conventional TiAlN single layer as well as AlTiN/TiN and TiAlN/CrN nanolayer coatings were deposited on cemented carbide, powder metallurgical high speed steel (ASP30) and cold work tool steel (D2) by magnetron sputtering in the CC800/7 and CC800/9 sinOx ML (CemeCon) deposition systems, respectively. The surface morphology of the coated substrates was examined by scanning electron microscope (FE-SEM) in combination with focused ion beam (FIB), and 3D stylus profilometer. By means of 3D-profilometry we performed several measurements and detailed analysis on a series of samples from the several hundred production batches. The influence of growth defects on GDOES (glow-discharge optical emission spectrometry) depth resolution and pitting corrosion was also studied.     

(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.     

Nitridische und oxinitridische HPPMS‐Beschichtungen für den Einsatz in der Kunststoffverarbeitung (Teil 1)

Nitride and oxy‐nitride HPPMS coatings for the application in the plastics processing (Part 1) In plastics processing adhesive and abrasive wear are some of the main damage mechanisms. For the wear protection and in order to increase the tool life time as well as to improve the quality of the plastic products, binary or ternary chrome‐based coatings like CrN and (Cr,Al)N deposited by physical vapor deposition (PVD) are used. As the chemical composition of the coating has a significant impact on the surface oxide layer formed after deposition and therefore on the wetting behavior of the plastic melt on the tool surface, the aim on this work was to synthesize different coatings from the system Cr‐Al‐O‐N. Therefore, a nitride coating (Cr,Al)N and two quaternary oxy‐nitride coatings (Cr,Al)ON were deposited by using a dcMS/HPPMS (direct current magnetron sputtering/high power pulse magnetron sputtering) hybrid process by varying the oxygen flux. This articles emphasis is on explaining the influence of varying the oxygen flux during the coating process on the coating properties as well as the composite properties towards the plastic mould steel. On this basis a follow up article in the next issue will concentrated on the more application oriented system properties of the three coating systems towards a polycarbonate melt.     

Corrosion protection of CrN/TiN multi-coating for bipolar plate of polymer electrolyte membrane fuel cell

The electrochemical corrosion cells will be generated from the possible pinholes of the promising CrN and TiN coatings in a PEMFC environment. To prevent the elution of possible pinholes, CrN/TiN multi-coatings on SS have been considered. This study examined the electrochemical behavior of three CrN/TiN coatings on 316L stainless steel deposited at different CrN/TiN thickness ratios by rf-magnetron sputtering as potential bipolar plate materials. Potentiodynamic tests of CrN/TiN-coated 316L stainless steel carried out in a 1 M H₂SO₄ + 2 ppm HF solution at 70 °C revealed a significantly lower corrosion current density than that of uncoated 316L SS, as well as a decrease in the corrosion current density with decreasing inner-layer CrN thickness. Electrochemical impedance spectroscopy also showed that the CrN/TiN-coated 316L SS sample had higher charge transfer resistance than the uncoated 316L SS sample, which increased with decreasing inner-layer CrN thickness. This was attributed to the crystalline-refined CrN/TiN(200).     

Microstructure and corrosion characteristics of CrN/NiP sputtering thin films

The CrN top layer and NiP interlayer were sequentially deposited to form a CrN/NiP composite coating through sputtering technique. The CrN/NiP coating systems deposited at 350 °C, 450 °C, and 550 °C, showed amorphous/nanocrystalline, nanocrystallize with precipitations, and fully crystallized microstructure respectively for the NiP interlayers. With the introduction of NiP interlayer, the coating assemblies exhibited superior corrosion characteristics than single CrN coatings. The amorphous NiP interlayer deposited at 350 °C revealed a lower corrosion current as compared to those with crystallized NiP layers owing to their structural defects in the alloy layer. With the combination of CrN and NiP layers the corrosion attach was retarded and a better corrosion resistance was found for the CrN/NiP composite coating.     

冷作模具钢等离子渗镀CrVN复合涂层摩擦磨损性能研究

采用等离子渗镀技术在DC 53冷作模具钢表面制备CrN和CrVN复合涂层,利用X射线衍射仪(XRD)、X射线光电子能谱(XPS)、扫描电镜(SEM)、显微硬度计和摩擦磨损试验机,对比研究了两种涂层的组织结构、力学性能以及摩擦磨损性能。结果表明:所制备的CrN和CrVN涂层均为面心立方(fcc)结构,并呈现(111)择优取向,其中CrVN涂层形成了以fcc-CrN相为基础的CrVN固溶体结构。CrN涂层中掺入V抑制了柱状晶生长,涂层结构更加致密,硬度和结合力明显提高,摩擦系数及磨损率降低。CrVN涂层表面粗糙度较低,并在摩擦过程中生成具有自润滑性的VO2,涂层抗粘铝性能得到改善。     

Exploring the Nickel–Graphene Nanocomposite Coatings for Superior Corrosion Resistance: Manipulating the Effect of Deposition Current Density on its Morphology,Mechanical Properties,and Erosion‐Corrosion Performance

The use of graphene‐based composite as anti‐corrosion and protective coatings for metallic materials is still a provocative topic worthy of debate. Nickel–graphene nanocomposite coatings have been successfully fabricated onto the mild steel by electrochemical co‐deposition technique. This research demonstrates the properties of nickel–graphene composite coatings influenced by different electrodeposition current densities. The effect of deposition current density on the; surface morphologies, composition, microstructures, grain sizes, mechanical, and electrochemical properties of the composite coatings are executed. The coarseness of deposited coatings increases with the increasing of deposition current density. The carbon content in the composite coatings increases first and then decreases by further increasing of current density. The improved mechanical properties and superior anti‐corrosion performance of composite coatings are obtained at the peak value of current density of 9 A dm^?2. The incorporation of graphene sheets into nickel metal matrix lead to enhance the micro hardness, surface roughness, and adhesion strength of produced composite coatings. Furthermore, the presence of graphene in composite coating exhibits the reduced grain sizes and the enhanced erosion–corrosion resistance properties.

     

Analysis on microstructure and characteristics of TiAlN/CrN nano-multilayer films deposited by cathodic arc deposition

In this study, TiAlN/CrN multilayer thin films were deposited on SUS 403 stainless steel by cathodic arc deposition. The effects of substrate orientation (substrate surface parallel/perpendicular to target surface) and rotation speed were investigated in detail. Microstructure of the coatings was analyzed by X-ray diffraction, X-ray photoelectron spectroscopy and scanning electron microscopy. Meanwhile, tribological and corrosion tests were performed. The experimental results showed that the as-deposited films exhibit a nano-scale multilayer structure consisting of TiAlN and CrN phases. The TiAlN/CrN multilayer films prepared by a parallel orientation and a rotation speed of 4 rpm not only possesses the best coating hardness and hardness/elastic modulus ratio, but also reveals superior abrasion resistance and corrosion resistance.