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.     

Verschleiß- und Korrosionsschutz durch Chrom und Chromnitrid (PVD-Abscheidung auf Al und Mg)

Wear and corrosion protection using Cr and CrN (PVD coating on Al and Mg) Investigations of the wear behaviour of uncoated Magnesium and Aluminium alloys (AZ 91hp, AlSi 7Mg) are showing very high wear rates of these materials. To improve the wear behaviour both materials were coated with 9 μm CrN using PVD (Physical Vapour Deposition) technology. The tribological behaviour of the coated light metals was tested afterwards by using a plate on cylinder tribometer. Looking at the results, wear is reduced enormously. The great number of defects in the coating of the magnesium alloy is showing almost no influence to the wear behaviour. The corrosion behaviour of chromium and chromium nitride coatings was tested on the magnesium alloy. Because of the defects in the coating, caused by defects like pores in the magnesium, only a short term protection of the alloy can be achieved. The corrosion behaviour of multilayer coatings is better than the behaviour of single layer 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.     

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.     

Failure of tools for metallic powder compaction

Surfacing with single- or multilayer hard coatings represents a modern trend in the prolongation of tool lifetime. The tools for metal powder compaction were vacuum heat treated, pulsed plasma ion nitrided and coated with TiN or CrN by PVD. Industrial tests of tools, during normal production, showed that, after the same hard coating process, the lifetime of some tools was prolonged by at least twice, but some tools failed very quickly. Research showed that the main reason for early tool wear or failure was improper diameter of the tools after coating.     

氮化物硬质涂层中Cr、Ti和Al元素对摩擦磨损特性的影响

利用四靶闭合场非平衡磁控溅射(CFUBMS)技术在石英玻璃和抛光不锈钢片两种基底上制备含有Cr、Ti和Al元素组合的各种氮化物涂层.采用摩擦磨损仪测试涂层摩擦系数,应用金相显微镜对各个涂层磨痕形态进行分析,结果表明TiN、CrN、TiAlN、CrAlN以及CrTiAlN涂层的摩擦系数依次减小,耐磨特性依次提高;结合涂层的X射线光电子能谱分析,可以得到含有Al元素涂层中形成了AlN的结构,提高涂层的硬度,增加耐磨特性;在涂层中含有Cr元素形成了氧化物Cr2O3可以提高涂层自排屑能力,减小摩擦系数,增加耐磨特性,含Ti元素形成的氧化物TiO2则不利于涂层的摩擦磨损特性;由于CrTiAlN本身具有比三元氮化物更高的涂层硬度,且含有Al和Cr元素,因此该涂层具有最好的摩擦磨损性能.     

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.     

(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.     

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).     

CrN/AlN superlattice coatings synthesized by pulsed closed field unbalanced magnetron sputtering with different CrN layer thicknesses

CrN/AlN superlattice coatings with different CrN layer thicknesses were prepared using a pulsed closed field unbalanced magnetron sputtering system. A decrease in the bilayer period from 12.4 to 3.0 nm and simultaneously an increase in the Al/(Cr + Al) ratio from 19.1 to 68.7 at.% were obtained in the CrN/AlN coatings when the Cr target power was decreased from 1200 to 200 W. The bilayer period and the structure of the coatings were characterized by means of low angle and high angle X-ray diffraction and transmission electron microscopy. The mechanical and tribological properties of the coatings were studied using the nanoindentation and ball-on-disc wear tests. It was found that CrN/AlN superlattice coatings synthesized in the current study exhibited a single phase face-centered cubic structure with well defined interfaces between CrN and AlN nanolayers. Decreases in the residual stress and the lattice parameter were identified with a decrease in the CrN layer thickness. The hardness of the coatings increased with a decrease in the bilayer period and the CrN layer thickness, and reached the highest value of 42 GPa at a bilayer period of 4.1 nm (CrN layer thickness of 1.5 nm, AlN layer thickness of 2.5 nm) and an Al/(Cr + Al) ratio of 59.3 at.% in the coatings. A low coefficient of friction of 0.35 and correspondingly low wear rate of 7 × 10^− 7 mm³N^− 1m^− 1 were also identified in this optimized CrN/AlN coating when sliding against a WC-6%Co ball.     

Comparison of microstructure and phase transformation for nanolayered CrN/AlN and TiN/AlN coatings at elevated temperatures in air environment

CrN/AlN and TiN/AlN multilayer coatings with modulation period of 4 nm and thickness ratio equal to 1.0 were manufactured by RF magnetron sputtering. Both films were annealed at temperatures of 800 °C in air for 1 h and then for an additional 9 h. Both coatings in as-deposited and after heat treatment were evaluated with a transmission electron microscope (TEM) equipped with EDS. After heat treatment at 800 °C for 1 h, a thick oxide layer around 260 nm was formed on the surface of the TiN/AlN coating. The oxide layer which formed on the coating was composed of three different regimes, including Al-enriched oxide with excess oxygen on the top surface, a crystalline Al-depleted TiO₂ layer 30-80 nm thick above the nitride coating and in between, mixed nano-crystalline Al₂O₃ and TiO₂ films. In comparison, only one oxide layer smaller than 50 nm in thickness was found in the annealed CrN/AlN coating. This amorphous or nanocrystalline oxide layer identified by EDS was a metal-deficient oxide, in which Al₂O₃ and Cr₂O₃ were mixed together forming a solid solution. As a result, the CrN/AlN coating exhibited superior stability compared to the TiN/AlN coating at elevated temperatures.     

Effect of layer thickness on thermal properties of multilayer thin films produced by PVD

Cr/CrN/CrAlN, CrN/CrAlN and Cr/CrN thin layers were deposited by PVD (Physical Vapor Deposition). The multilayers were obtained from the combined deposition of different layers Cr, CrN and CrAlN thick films on on AISI4140 steel and silicon substrates at 200 °C, and evaluated with respect to fundamental properties such as structure and thermal properties. Cr, CrN and CrAlN single layers were also prepared for comparison purposes. The structural and morphological properties of PVD layers were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM) coupled with EDS + WDS microanalyses, stresses were determined by the Newton’s rings methods using the Stoney’s equation and surface hardening and hardness profiles were evaluated by micro hardness measurements. The XRD data and HRTEM showed that both the Cr/CrN, CrN/CrAlN and Cr/CrN/CrAlN multilayer coatings exhibited B1NaCl structure with a prominent reflection along (200) plane, and CrAlN sub-layer microstructures composed of nanocrystallites uniformly embedded in an amorphous matrix. The innovation of this work was to use the thickness of three different coating types to determine the thermal properties. Furthermore, an empirical equation was developed for the thermal properties variations with temperature of AISI4140 steel coated with different multilayer coatings. The thermal conductivity of CrAlN single layered was lower than the multilayer and the bulk material AISI4140. Moreover, the influences of structure and composition of the multilayer coatings on the thermal properties are discussed.The thermal conductivity of nanoscale thin film is remarkably lower than that of bulk materials because of its various size effects.     

耐特种气体腐蚀涡旋干泵的研制

采用化学镀、氟涂料和真空离子镀(PVD)技术对涡旋干泵实施防护涂层,对转子和定子采用化学镀镍磷和氟涂料封闭技术制备防护涂层;对曲柄轴和曲柄销采用PVD技术制备Cr/CrN多层复合防护镀层。通过腐蚀试验表明,防护涂层可以长时间抵抗高腐蚀性气体的腐蚀,能够有效地提高涡旋干泵的使用寿命。     

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.     

Depth-resolved residual stress analysis of thin coatings by a new FIB-DIC method

A new methodology for the measurement of depth sensitive residual stress profiles of thin coatings with sub-micrometer resolution is presented. The two step method consists of incremental focused ion beam (FIB) ring-core milling, combined with high-resolution in situ SEM-FEG imaging of the relaxing surface and a full field strain analysis by digital image correlation (DIC). The through-thickness profile of the residual stress can be obtained by comparison of the experimentally measured surface strain with finite element modeling using Schajer's integral method. In this work, a chromium nitride (CrN) CAE-PVD 3.0 μm coating on steel substrate, and a gold MS-PVD 1.5 μm on silicon were selected for the experimental implementation. Incremental FIB milling was conducted using an optimized milling strategy that produces minimum re-deposition over the sample surface. Results showed an average residual stress of σ = −5.15 GPa in the CrN coating and σ = +194 MPa in the Au coating. These values are in reasonable agreement with estimates obtained by other conventional techniques. The depth profiles revealed an increasing residual stress from surface to the coating/surface interface for both coatings. This observation is likely related to stress relaxation during grain growth, which was observed in microstructural cross sections, as predicted by existing models for structure-stress evolution in PVD coatings. A correlation between the observed stress gradients and the in-service mechanical behavior of the coatings is proposed. Finally, critical aspects of the technique and the influence of microstructure and elastic anisotropy on stress analysis are analyzed and discussed.     

Effect of heat treatment on mechanical properties and microstructure of CrN/AlN multilayer coatings

Polycrystalline CrN/AlN multilayer coatings were deposited by RF magnetron sputtering on silicon (001) substrates. The bilayer periods of CrN/AlN were controlled from 4 nm to 20 nm by the use of shutters, which were adjusted by a programmable logic control (PLC). To evaluate the thermal stability, the films were annealed at 500 °C, 600 °C, 700 °C, 800 °C, and 850 °C, for 1 h in both vacuum and air environments. The phase transformation during thermal evolution was studied by X-ray diffraction (XRD). The microstructure of CrN/AlN multilayer coatings as-deposited and after annealing was observed by transmission electron microscopy (TEM). The hardness of as-deposited CrN/AlN coating with a period of 4 nm was 28.2 GPa, which was 60% higher than that predicted by the rule of mixtures. The hardness of CrN/AlN multilayer coatings annealed at 850 °C in vacuum remained similar to the as-deposited state, and the nano-layered structure still persisted. The thermal stability of CrN/AlN coatings was better than that of CrN coating. The hardness degradation ratio of CrN/AlN coating with modulation period of 4 nm was only 8.1% at 700 °C, which was superior to that of a simple CrN coating.     

Ionen- und plasmagestützte Verfahren der Oberflächentechnik für die Randschichtbehandlung von Leichtmetallwerkstoffen

Surface engineering of light weight materials with ion- and plasma-assisted methods Increasing applications of light weight materials are expected in the future. Pursuing this trend surface engineering of these materials – especially ion- and plasma-assisted methods – swill be of increasing interest to enhance their wear and corrosion resistance. In a research co-operation some promising methods were examined on different aluminium and titanium alloys to assess their potential to increase the surface properties. Among these were magnetron sputtering of chromium nitride, ion beam assisted deposition of Cr/CrN and Al/A₂O₃ layers, ion implantation and ion beam assisted nitriding. Compared to the steel substrates the assessment of the mechanical properties such as the critical load of the scratch test of the coated light weight materials is different. Furthermore, it could be shown that both spherical section and glow discharge optical spectroscopy are useful methods to characterize the near-surface zone influenced by ion implantation.     

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.     

Deposition of nano-scaled CrTiAlN multilayer coatings with different negative bias voltage on Mg alloy by unbalanced magnetron sputtering

In a magnetron sputtering system, the negative substrate bias voltage has been used as a basic process parameter to modify the deposition structure and properties of coatings. In this paper we report the effect of bias voltage ranging from −40 V to −90 V on nano-scaled CrN/TiN/CrN/AlN (CrTiAlN) multilayer coatings synthesized on a Mg alloy by a closed-field unbalanced magnetron sputtering ion plating system in a gas mixture of Ar + N₂. The technological temperature and atomic concentration in the multilayer coatings were controlled by adjusting the current density of different metal magnetron targets and the plasma optical emission monitor. The composition, crystallographic structure, deposition model and friction coefficient of multilayer coatings were characterized by X-ray photoelectron spectrometry (XPS), X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and ball-on-disc testing. The experimental results show that the deposition model and friction coefficient of nano-scaled CrTiAlN multilayer coatings were significantly affected by the negative bias voltage (V_b). The nitride species in multilayer coatings mainly involve CrN, AlN and TiN, and XRD analysis shows that the crystallographic structure was face-centered cubic. Under different bias voltage conditions, the multilayer coating composition shows a fluctuation, and the Al and Cr concentrations respond in the opposite sense to the bias voltage, attaining their greatest values at V_b = −70 V. The surface and cross-sectional morphology shows deposition model change from a columnar model into non-columnar model with the increase in negative bias voltage. The friction coefficient of the nano-scaled multilayer coatings at V_b = −55 V stabilize after 10 000 cycles.     

Protective coatings on orthorhombic Ti2AlNb alloys

Abstract

The oxidation behaviour of an orthorhombic Ti–22Al–25Nb alloy, bare and with protective coatings, was investigated at 750°C in air under quasi-isothermal and thermal cycling conditions. As found by post-oxidation analysis, the uncoated substrate material was severely degraded by formation of spalling oxide scales and ingress of oxygen and nitrogen causing nitride precipitation, internal oxidation and interstitial embrittlement. Metallic Ti–51Al–12Cr coatings as well as nitride coatings based on Ti–Al–Cr–Y–N, either monolithically grown or with superlattice structure, provided an effective diffusion barrier against oxygen. The excellent oxidation resistance of the TiAlCr coatings was associated with the ternary Ti(Al,Cr)₂ Laves phase promoting the formation of a protective alumina scale. The different intermetallic phases formed in the interdiffusion zone caused neither cracking nor spallation of the protective coating. Both, monolithically grown TiAlCrYN and superlattice TiAlYN/CrN coatings, exhibited slow, but nearly linear oxidation kinetics at 750°C in air. In the subsurface region of the substrate a niobium rich phase and the α₂-phase formed. At the coating/substrate interface pores and a thin, fine-grained TiN layer were found.