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.     

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.     

Interrupted cutting tests of cemented carbide tools coated by physical vapor deposition and chemical vapor deposition techniques

Refractory compound coatings prolong the life of cemented carbide inserts. The structure of these coatings is vastly different when the same coating is produced by chemical vapor deposition (CVD) and physical vapor deposition (PVD) methods. TiC and HfN coatings were applied to cemented carbide tools by both CVD and PVD processes. The coated inserts were tested under interrupted cutting conditions using slotted bar tests. The CVD-coated inserts failed after a few (less than 100) cycles whereas the PVD-coated inserts lasted well past 2000 cycles without failure as did the uncoated inserts. PVD coatings have a much greater fracture toughness than CVD coatings due to their very fine-grained microstructure with a distribution of fine cavities which act as crack stoppers. In contrast, CVD coatings have a fully dense microstructure with a large grain size which does not have much fracture toughness. Another reason for the difference in behavior is the much lower deposition temperature (about 500°C) used in the PVD process as compared with the much higher deposition temperature (about 1000°C) used in the CVD process. Chemical attack of the cemented carbide substrate occurs at high deposition temperatures, thus weakening the area near the coating-substrate interface.     

物理气相沉积技术制备的硬质涂层耐腐蚀的研究进展

根据物理气相沉积技术制备的硬质涂层的腐蚀机制，指出提高硬质涂层的抗腐蚀性能的关键在于提高涂层的致密性和涂层/基材界面的性能，对提高硬质涂层耐蚀性的各种措施分别予以评述，提出了今后的研究方向。     

Potentiale moderner PVD‐Beschichtungen

Potentials of Innovative PVD Coatings Hard PVD‐Coatings for wear protection of tools are commonly used in many production purposes for about 20 years. Based on the experiences made with PVD‐processes for deposition of hard coatings “tribological coatings” with optimized friction properties have been developed. These friction optimized coatings can take over some of the lubricants functions in unlubricated processes. Today in many operations the use of additional lubricants can be avoided or at least minimized using innovative tool coatings. As a consequence expensive cleaning processes of the parts can be omitted and environmental pollution is reduced.     

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.     

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.     

Preparation and characterization of nanostructured ZrO2 coatings on dense and porous substrates

Nanostructured ZrO₂ coatings are prepared on both dense and porous substrates by wet-chemical deposition of non-agglomerated 5 nm precursor particle dispersions, followed by thermal processing. The precursor particle dispersions are made by modified emulsion precipitation and a purification treatment to remove reaction products and additives. The coatings are formed by depositing the precursor nanoparticle dispersion directly onto the substrate, followed by drying and heating at 600 °C. Scanning electron microscopy and cross-sectional transmission electron microscopy observations of the heat-treated coatings indicate that the ZrO₂ coating on dense Si wafer substrate has a homogeneous, dense particle packing structure with shallow meniscus-shaped depressions in the surface, and microcracks below the meniscus surface. On the other hand, coatings formed on a meso-porous γ-alumina membrane substrate are free of defects, but with a lower packing density. The mechanism of the substrate effect on the particle packing behavior and defect formation during coating deposition is discussed. It is expected that by using a thin porous substrate with reduced capillary force, a defect-free, homogenously dense-packed coating structure can be achieved.     

Microstructural design of hard coatings

Microstructural design has attracted increasing interest in modern development of hard coatings for wear-resistant applications. In plasma-assisted vapor deposited thin films, the material’s microstructure can be designed during growth or post-deposition annealing treatments. In this review, we demonstrate the correlation between microstructure and mechanical as well as tribological properties of hard ceramic coatings. This is done for single-phase coatings and composition or phase modulated layers. In the latter case, the microstructure can be designed by choice of the deposition technique chosen, understanding the growth processes taking place on a film surface, either by sequential deposition of layers or by taking advantage of newly discovered self-organization processes including segregation effects of the elements. Consequently, the effects of individual microstructural features like grain size, defect density (and hence residual stress), phase arrangements in a one-, two- or three-dimensional manner on the mechanical properties are treated. Here, especially TiN–TiB₂ is used as a model system to describe the development of two- and three-dimensional coating nanostructures. Due to their particular structures, such coatings can exhibit superhardness (H  40 GPa). The microstructural changes of hard ceramic coatings during a post-deposition annealing treatment are discussed in detail. Although the significance of heat treatments to optimize properties (by a well-designed microstructure) for specific applications is recognized in bulk material science, only a few elements have been applied for hard ceramic coatings so far. Due to limited atomic assembly kinetics during the deposition process (e.g., by using a low substrate temperature), defects (point-, line-, and area-defects), supersaturated, and metastable phases can easily be obtained. For example, growth of (Ti,Al)N and Ti(B,N) films can result in the formation of a supersaturated TiN based phase. Such films undergo age hardening processes during post-deposition annealing due to the decomposition of the supersaturated phases into their stable constituents. The review clearly shows that nanostructure dependent hardness increase (compared to hardness of the bulk counterparts) sustains higher annealing temperatures than hardness increase due to an increased density of point- and/or line-defects. Tribological properties of hard thin films can be engineered by adding phases with lubricious properties at operation temperature (either room or elevated temperatures) and prevailing environment. Especially in high speed and dry cutting applications, low-friction and lubricating mechanisms of the thin film itself are required in addition to excellent mechanical properties.     

Deposition of PVD Coatings on different geometries and local characterization for reliable properties

Although the characteristics of PVD coatings in research and development papers are very promising, in the field of tribology the industrial application of these coating types is restricted to special market segments up to now: the deposition of hard coatings is state of the art on tools, whereas PVD coated machine components are quite rare. This is caused by the coatings profile of properties, the various surroundings and the demands for application reliability. The last aspect is the main topic of this contribution. Reliability is especially important for machine components, because tools may fail after relative short life time compared to machine parts. Besides this tools and the corresponding production equipment are designed for fast tool replacement in contrast to other machines, which should work without standstill and with a minimum of maintenance. Characteristics of coated systems must be guaranteed in practice theory and laboratory experiments have to show what is possible. On the one hand reproduction of the deposition process must be guaranteed to enter application fields with high demands for reliability, on the other hand characterization of coated systems must be standardized with admissible deviations for communication between coaters and users. These aspects are important for decisions concerning the use of coating substrate systems in tribology besides the topics of technical function. The present investigation shows main reasons for deviations in results of PVD coatings.     

IMPROVEMENT OF CUTTING TOOLS BY TiN PVD HARD COATING

A review of recent results obtained in the field of cutting tools improved with a TiN physical vapor deposition (PVD) ion-plated hard coating is presented. Optimization of the tool material, tool surface morphology and interface problems between the TiN coating and the tool surface are discussed in view of their importance in optimum performance tests and the resulting workplace surface quality. The high effectiveness of the TiN PVD coating is demonstrated by selected data from our own data bank and from other sources on six groups of cutting tools, made of high-speed steels (HSS), powder metallurgical high-speed steels (PM-HSS) and of WC based hard metals. We also describe recently introduced, novel hard coatings (TiCN and TiAIN) for cutting tools, and new applications of cutting tools, improved by PVD hard coatings.     

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.     

Fatigue resistance of PECVD coated steel alloy

The thin hard coating deposition techniques CVD and PVD have been used for a long time in industry. Such coatings prove very effective in improving the tribological and corrosive resistant properties of the substrate. It was shown that the compressive residual stresses are introduced on the surface layer from the PVD deposition process that helps to increase the fatigue limit of coated structural components. The aim of this work is to evaluate the effect of a SiO_x coating, deposited by means of PECVD technique, on the fatigue resistance of a quenched and tempered alloy steel (39NiCrMo3). Rotating bending fatigue tests were carried out to assess its fatigue limit and characterize any possible variation between the coated and the uncoated material. Fracture surface observations were made using SEM on fracture surfaces, and scratch tests were performed on samples to assess the coating-substrate interface delamination.     

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).     

SEM study of defects in PVD hard coatings

Hard coating defects are produced by foreign particle contamination on substrate surface before and during coating, or due to arcing. In this work, CrN, TiAlN and CrN/TiAlN multilayer hard coatings were prepared by thermoionic arc ion plating deposition system BAI 730 (Balzers) and by sputter deposition in CC800 (CemeCon). We investigated the concentration of defects, its size and structure after tool steel substrate surface pretreatment (polishing, ion etching) as well as after deposition by means of atomic force microscopy (AFM) and scanning electron microscopy (SEM).     

Performance evaluation of reactive direct current unbalanced magnetron sputter deposited nanostructured TiN coated high-speed steel drill bits

The stainless steels, in general, are considered to be difficult-to-machine materials. In order to machine these materials the surface of the tool is generally coated with physical vapour deposition (PVD) hard coatings such as titanium nitride (TiN), titanium aluminum nitride (TiAlN), etc. The adhesion is of vital importance for the performance of tools coated with PVD coatings. Proper surface treatments (in situ and ex situ) are required to achieve highly adherent PVD coatings on tools. We have deposited nanostructured TiN coatings on high-speed steel (HSS) drill bits and mild steel substrates using an indigenously built semi-industrial four-cathode reactive direct current (d.c.) unbalanced magnetron sputtering system. Various treatments have been given to the substrates for improved adhesion of the TiN coatings. The process parameters have been optimized to achieve highly adherent thick good quality TiN coatings. These coatings have been characterized using X-ray diffraction, nanoindentation and atomic force microscopy techniques. The performance of the coated HSS drill bits is evaluated by drilling a 13 mm thick 304 stainless steel plate under wet conditions. The results show significant improvement in the performance of the TiN coated HSS drill bits.     

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.     

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.     

Nitridische und oxinitridische HPPMS‐Beschichtungen für den Einsatz in der Kunststoffverarbeitung (Teil 2)

Nitride and oxy‐nitride HPPMS coatings for the application in the plastics processing (Part 2) In the previous issue three oxy‐nitridic hard coatings on CrAl‐basis were investigated. These coatings were deposited by physical vapour deposition (PVD) as protective coatings against adhesive and abrasive wear in polymer extrusion. The coatings were developed using a variation of the oxygen content to investigate the influence of the chemical composition on the coating properties as well as composite properties between the coating and the coated tool. Following up on these findings this article will focus on the application oriented system properties of the three investigated coating systems towards the polycarbonate melt.     

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.