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。     

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.     

Design of wear and corrosion resistant PVD‐coatings for magnesium alloys

Although magnesium alloys became popular in the first half of the 20^th century, the bad corrosion properties prevented their breakthrough in industrial mass production. Since the technology for the production of high purity alloys was introduced in the 1970s, magnesium alloys became more and more in the focus of industrial attention. Today magnesium alloys are state of the art in structural parts in automotive industry. Despite its outstanding properties like good castability, low density and nearly unlimited availability the negative aspects like weak corrosion and wear behaviour still limit the application of magnesium in industry [1]. So, the only economic solution is the deposition of a coating or a suitable surface treatment which provides both, wear and corrosion resistance. Today, plasma electrolytic anodisations are state of the art [2–5]. They provide acceptable corrosion resistance and protect the magnesium from mechanical damage due to their high hardness. On the other hand, their high porosity limits their use in combination with electrochemically noble materials, leading to galvanic corrosion [6]. In addition, the high surface roughness of the plasma electrolytic anodisations restricts their use in tribological applications, particularly under dry sliding conditions [7]. On the other hand, due to the high life time recommendations the application of magnesium in the automotive industries motion component field is a long term process. Nevertheless, there is a quite high industrial interest to apply magnesium in the motion component field in consumer applications like do‐it‐yourself or gardenig. Some examples are motor components of lawnmovers, motor saws or drills. Especially for these fields of application there are quite high demands on the corrosion properties due to undefined storage and the conditions during usage. In order to achieve smooth surfaces with high quality, the PVD technology moves into the centre of interest. Since the 1980s PVD coatings are well established and widely used for different industrial applications, mainly for steel and tool coatings. The authors were the first who carried out serious studies on the development of PVD coatings for magnesium alloys since 1999 [6, 7]. The extensive research activities lead to the recent development of a coating system, which provides both, good wear properties as well as good corrosion behaviour.     

不同表面处理工艺下H13钢的高温耐磨性能

首先对调质处理状态的H13钢进行了渗氮、物理气相沉积(PVD)镀膜、渗氮+PVD镀膜三种不同的表面处理,然后在UMT-3型摩擦磨损试验机上,对处理后的试样进行600℃的高温摩擦磨损试验,研究了不同工艺下H13钢的高温耐磨性能。结果表明:试样的磨损形式主要是粘着磨损+磨粒磨损,经表面处理后试样的表面硬度大幅度提高,摩擦系数大幅度降低;其中渗氮+PVD镀膜表面处理试样的高温耐磨性能最好。     

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.     

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.     

High energy xenon ion beam assisted deposition of TiN film and its industrial application

TiN films have been synthesized by ion beam assisted deposition employing xenon ions with an energy of 40 keV. The formed TiN films were investigated systematically in respect of surface morphology, composition, structure and mechanical properties. Then, they were applied to surface protection of scoring dies. Atomic force microscopy and interferometric observation showed that the TiN film is relatively smooth. Rutherford backscattering spectroscopy analysis indicated that few xenon atoms are retained in the film. It was found by transmission electron microscopy and X-ray diffraction experiments that the formed TiN is a nanocrystal (< 10 nm) film and exhibits slightly (200) preferred orientation. An ultra low load microhardness indentor system was used to examine the plastic property of the film and a hardness of 2300 kgf mm^–2 was calculated from the measured data. Scratch tests showed that the adhesion of TiN film deposited by ion beam assisted deposition at ambient temperature is superior to that of high temperature physical vapour deposited (PVD) TiN film. Both a pin-on-dick tribotest and SRV wear test revealed that the wear resistance of the specimen can be greatly improved by TiN coating. A five times increase of service life of different scoring dies could be obtained by protection of TiN coating.     

物理气相沉积在耐腐蚀涂层中的应用

PVD(物理气相沉积)作为一种新型绿色的镀膜技术,由于涂层具备硬度高、耐磨性好、摩擦系数低、化学性能稳定、耐热耐氧化的特点,使其在机械、电子和光学行业得到广泛应用。近些年来随着PVD技术应用领域的不断扩展,对涂层的性能提出了更高要求,在保障力学性能的同时,如何提高涂层耐蚀性成为研究热点。概述了PVD技术应用于材料防腐的相关研究,综述了PVD涂层的成分、结构与耐蚀行为的关系,同时分别阐述了在PVD技术中提高涂层耐蚀性能的方法与机理。     

Non-equilibrium synthesis of new materials

Over the last few decades it has become apparent that metallic materials produced by conventional casting processes have reached their limit. Some improvements have been obtained by rapidly cooling bulk alloys but major increases have required the development of rapid solidification processes. However, more radical approaches, such as mechanical alloying (MA) and physical vapour deposition (PVD), are also being explored and these are the subject of this paper. This paper describes the physical basis behind the development of MA and PVD in the Structural Materials Centre and presents the results of some materials development programmes on aluminium, magnesium and titanium based materials.     

基于PVD-TiN和TiSiN涂层的Al2O3/TiCN陶瓷刀具及其切削性能研究

采用物理气相沉积(Physical vapor deposition, PVD)工艺在Al₂O₃/TiCN陶瓷刀具表面分别沉积了TiN和TiSiN涂层。通过扫描电子显微镜(SEM)观察涂层微观结构, 采用显微硬度计和划痕仪分别表征涂层硬度和测量涂层与基体的结合强度。通过对涂层刀具进行连续干切削灰铸铁实验, 研究TiN和TiSiN涂层对刀具磨损特征的影响并探讨其磨损机理, 同时研究了涂层对工件加工表面质量的影响。结果表明: PVD涂层可显著提高Al₂O₃/TiCN陶瓷的刀具硬度。TiN涂层和TiSiN涂层可分别提高刀具表面硬度25%和65%, 从而增加刀具耐磨性。两种涂层刀具在连续切削灰铸铁实验中主要的失效机理均是挤压变形下的磨粒磨损, 其中TiN涂层刀具还伴随有粘结磨损; 刀具上的PVD-TiN和TiSiN涂层可以有效保护Al₂O₃/TiCN陶瓷刀具基体, 防止崩刃, 进而改善工件表面加工质量。     

Tungsten/tungsten nitride performance at elevated temperature

Abstract

Multilayer physical vapour deposition (PVD) coating of W/W₂N (tungsten/tungsten nitride) on Orvar Supreme steel was tested under the different conditions to investigate their friction and wear behaviour with their mechanical properties. Coatings were sputtered by reactive magnetron sputtering in a N₂/Ar atmosphere. Pin on disc test was performed on Orvar Supreme steel at room temperature to elevated temperature (800°C). Steel ball (100Cr6) and alumina ball are used to evaluate the frictional and wear properties. Scanning electron microscopy (SEM) and energy dispersive X-ray analyses were performed to obtain the microstructure and chemical composition of the material. Mechanical properties of coating were evaluated using nanoindentation and scratch test.     

气相沉积膜层在镁合金表面改性中的应用

综述了气相沉积膜层的特性、制备技术的发展及其在镁合金表面改性中的应用,重点介绍了利用PVD和CVD技术在镁合金表面沉积保护性膜层的研究现状,并指出气相沉积膜层是传统电化学镀层的良好替代物,在镁合金表面改性中具有广阔的应用前景.     

基于TiC_(0.5)N_(0.5)/Si_3N_4复相陶瓷基体的PVD及CVD涂层刀具性能

首先,以15vol%或25vol%的TiC0.5N0.5粉体为导电第二相,利用热压烧结法制备了TiC0.5N0.5/Si3N4复相陶瓷;然后,分别通过物理气相沉积(PVD)和化学气相沉积(CVD)技术在TiC0.5N0.5/Si3N4陶瓷刀具表面沉积了CrAlN和TiN/Al2O3/TiN涂层;最后,通过对TiC0.5N0.5/Si3N4刀具进行连续切削灰铸铁实验,研究了TiC0.5N0.5含量和涂层类型对刀具磨损特征的影响,并探讨了刀具的磨损机制。结果表明:TiC0.5N0.5含量的增加有利于提高TiC0.5N0.5/Si3N4复相陶瓷刀具基体的硬度和电导率,但对耐磨性和切削寿命的影响较小;采用PVD技术沉积CrAlN涂层时,随着TiC0.5N0.5含量的增加,涂层的厚度、结合强度和硬度都得到提高,涂层刀具的磨损性能显著提高,切削寿命也明显延长;而采用CVD技术沉积TiN/Al2O3/TiN涂层时,TiC0.5N0.5含量的变化对涂层的厚度、结合强度和硬度基本没有影响,TiN/Al2O3/TiN涂层刀具整体切削性能变化不大。CrAlN涂层和TiN/Al2O3/TiN涂层都可明显改善TiC0.5N0.5/Si3N4复相陶瓷刀具的耐磨性和切削寿命;相对于TiN/Al2O3/TiN涂层,CrAlN涂层具有更高的涂层硬度和粘着强度,但TiN/Al2O3/TiN涂层具有较大的涂层厚度,TiN/Al2O3/TiN涂层刀具表现出更加优异的耐磨性和切削寿命。TiC0.5N0.5/Si3N4复相陶瓷刀具的磨损机制以机械摩擦导致的磨粒磨损为主,伴随有少量的粘结磨损。     

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.     

Sputtering simulation of multilayer coatings in industrial PVD system with three-fold rotation

Multilayer coatings in physical vapour deposition (PVD) systems are usually prepared by rotation of substrates along different targets. In industrial PVD systems two- or three-fold rotations are typically applied. When substrates rotate around the targets, deposition rate of material varies. Rotation therefore influences the thickness and sequence of layers in the multilayer coating. Structure of the multilayer coating depends on the parameters of rotation, initial position and orientation of the substrates. A computer simulation of deposition process with four unbalanced magnetron sources was made for two- and three-fold rotation. Time dependence of growth rate and thickness was calculated. Calculations for three-fold rotation show that additional modulation is super-imposed on the basic period. Results of simulation are in accordance with experimental data from scanning electron microscope (SEM) and Auger electron spectroscopy (AES).     

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.     

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.     

Development of physical vapour deposited Mg–Zr alloys Part 1 – Characterisation of as deposited alloys

Abstract

Alloys of Mg–Zr produced via physical vapour deposition (PVD) were studied in the as deposited condition using bulk characterisation and surface analysis techniques. The solid solubility of Zr in Mg was extended up to ～3·07 at.-%. The Mg–Zr deposits showed a preferred growth orientation, and microstructural studies revealed typical PVD features such as domed colonies of grains, porosity, compositional inhomogeneity, and a high dislocation density. Zirconium oxide was found to coexist with magnesium oxide/hydroxide in the surface film.