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Technical Sessions Proceedings of CIST2008 & ITS-IFToMM2008 Beijing, China

Hard Wear-Resistant Coatings: A Review


T. Hoornaert1,2, Z. K. Hua1, J. H . Zhang1* School of Mechatronics Engineering and Automation, Shanghai University, Yanchang Road, Shanghai 200072, P.R. China 2 University of Technology of Troyes, 12 rue Marie Curie, 10000 Troyes, France E-mail address: jhzhang@staff.shu.edu.cn
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ABSTRACT Hard coatings have been used for many decades to provide wear resistance. In this paper, the industrial requirements and benefits of such hard coatings are introduced. Common hard coatings (nitrides, carbides, multi-components, etc.) and some of the new generation coatings (multiple layers, multi-layers, gradient and nano-scaled) are reviewed and compared. Furthermore, typical industrial applications and performances as well as common coating processes characteristics are summarized. Finally, recent development directions and new possibilities for coating manufacturers to produce films with better performances are briefly discussed. Keywords: hard coating, wear resistant film 1 INTRODUCTION Coatings have been widely used for many decades in tribological applications to protect various tools and parts from wear. The development of wear-resistant coatings started in the 1960s along with both chemical vapour deposition (CVD) and physical vapour deposition (PVD) techniques, which are nowadays a key figure in many industrial fields providing dramatic improvements in terms of productivity, part lifetimes and therefore cost reductions [1-3]. However, selections of the best coating and its deposition process is not often straight forward, as the number of proper hard coating materials, their combinations, as well as the different deposition techniques are constantly increasing. Materials such as nitrides, carbides, carbon-based, oxides and borides [4], are widely used in hard coating technology for their outstanding mechanical and tribological properties. Besides the high hardness and wear resistance, excellent chemical stability and oxidation resistance in severe environments are also regarded as the recurrent features. In this review, the different coating materials and their combinations, from common coatings to new generation hard thin films, are introduced. Then, the benefits of the hard coatings in the industry are demonstrated, providing some typical coating application examples and related performances. Finally, the new trends and future developments in coating technology are also discussed. 2 COATING MATERIALS 2.1. COMMON COATINGS Whereas some hard coatings have an intrinsic hardness directly related to the raw materials properties (diamond, cubic boron nitride, etc.), extrinsically hard coatings get their superior hardness from a combination of different materials, layers, phases and structures (multi-components, multiple layers, multilayered, solid lubricants and nano-composite films). The materials applied in hard coating technology consist mainly of nitrides, carbides, carbon-based, oxides and borides. 2.1.1 .NITRIDES Recently, the common hard coatings in the industry are mostly based on nitrides, including Titanium nitride (TiN),

chromium nitride (CrN), zirconium nitride (ZrN), silicon nitride (SiN) and cubic boron nitride (c-BN). Titanium nitride, known as one of the most common hard coatings in use today, combines hardness, toughness, inertness, and usually shows good adhesion strength on the substrates. It is therefore called a general purpose coating and it has been widely used, especially on tools [5]. Besides TiN, both zirconium nitride and chromium nitride [6] coatings exhibit high hardness and ability to withstand elevated temperatures (up to 600C and 700C respectively) and generally lead to slightly different properties than TiN. Cubic boron nitride (c-BN) is the second hardest single phase material after diamond. Although polycrystalline c-BN is well established as one of the hardest cutting material, such coatings just begin to find their use in the industry because of adhesion and stability issues [7], and mainly their high cost. As to silicon nitride (SiN), it is widely applied as single protective layer for its good thermal shock resistance and low coefficient of thermal expansion. Furthermore, it is found that SiN can also be deposited on top of other hard layers, (e.g. metal nitrides) in order to improve thermal stability, or as an inter layer to improve diamond growth on cemented carbide tools [8]. Carbon nitride coatings (CNx) have raised an important interest to the coating community as it is theoretically expected to be harder than diamond under a specific crystalline structure ( -C3N4) [9]. 2.1.2. CARBIDES Silicon carbide (SiC) is widely used in tool coating technology due to its high hardness. It is also commonly applied in conjunction with other elements (e.g. thermal sprayed Si-C-N coatings [10]) or with a dry-film lubricant coating to enhance its mechanical properties and tribological performance. Tungsten carbide (WC), one of the traditional coating materials, can be deposited through various processes. Combined with cobalt, tungsten carbide has particularly shown very good properties when deposited with high velocity oxyfuel (HVOF) [11], and it is believed to be one of the most promising alternatives to hard chromium. Vanadium carbide (VC), which has good thermal shock resistance and high thermal conductivity, is suitable for coating applications under high temperature conditions, such as forging and forming operations. It exhibits good performances and properties on carbon-containing substrates especially when applied as a thermal diffusion coating, which enables to get high thickness, good adhesion and hardness [12]. Boron carbide (BC) coatings offer smooth and non-porous surfaces with natural lubricity, which will drastically reduce friction and heat during machining. However, it should be mentioned that brittleness and poor adhesion on substrates may be the disadvantages of such a material. Titanium carbide can be used in both single layer coatings and

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Hard Wear-Resistant Coatings: A Review

as a component in multi-layered PVD or CVD configurations. It has been applied as one of the most successful hard coating material, and it is typically used on cutting tools as well as high-load forming tools. Finally, chromium carbide (CrC) coatings can effectively replace electroplated hard chromium and TiN coatings utilized as protective layers against abrasive wear and corrosion. They are nowadays widely applied to many substrates for a large variety of applications, such as metal forming and plastic injection molding [13]. 2.1.3. CARBON-BASED Diamond, the hardest known material, provides an impressive combination of properties. However, it also has limitations as the reaction with strong carbide forming metals and dissolves in Fe, Co, Mn, Ni, Cr and the platinum-group metals. Polycrystalline diamond (micro-, nano- or ultra-nano crystalline [14]) leading to properties similar to varying degrees to single crystal diamond can be deposited on tools and various parts. Although diamond layers cannot be directly applied to ferrous substrates, it has been demonstrated that diamond can be deposited on steels and cemented carbides by using inter layers (silicon, silicon nitride, chromium nitride, etc.) which enable their growth with good adhesion [15]. Diamond-like carbon (DLC) coatings show outstanding tribological properties. One of the recurrent problems of DLC films is the low adhesion resulting from high internal stresses. Therefore, in order to improve adherence onto metal substrates, DLC layers can be applied on top of interface layers such as Si, Ti, Zr, W, Nb, Cr or WC. In comparison to traditional diamond, DLC film fabrication requires less processing times, hence lower costs. In addition, while CVD diamond film fabrication requires very high temperatures and pressures, DLC can be deposited from ambient temperature gas phase species, even rending polymer coating possible. According to these advantages, the use of DLC films has become economically feasible for industrial mass production [16]. 2.1.4. OXIDES Alumina (Al2O3) is one of the most widely used wear-resistant ceramics. The coating structure can be amorphous or exhibit several crystalline phases, which generally show higher hardness [17]. The structure obtained strongly depends upon the process parameters, and thus, the film properties can vary considerably. Chromium oxide thin films (Cr2O3) can be applied as single layers and nucleation inter layers (e.g. allowing alumina growth on some substrates) and in combination with other layers (CrN for instance), so as to improve adhesion and tribological properties.

Additionally, zirconium oxide (ZrO2) films have considerably attracted attention for wear-resistant coating uses, as it also provides an interesting combination of thermal, chemical and mechanical properties. Finally, some of the other oxides that are often utilized in hard coating technology consist mainly of zinc oxide [18], silicon- and titanium sub oxides (SiOx, TiOx respectively), although they are mainly used for electronic and optical applications [19] , [20]. 2.1.5. BORIDES Among the different ceramic coating materials, less research and development have been carried out on borides for industrial applications. They show however a unique combination of properties. Because of their high hardness and good adhesion on the underlying substrate, crystalline coatings based on the diborides of transition metals (e.g. Ti, Cr, Mo, V) offer a good alternative for wear-protective films. Especially when dry machining non-ferrous materials such as aluminum and its alloys, diboride coatings offer chemical inertness and hardness. Moreover, alloying borides with nitrogen enables to obtain finely grained multiphase hard coatings which show outstanding wear resistance and anti-corrosion behavior [21, 22]. 2.1.6. MULTICOMPONENT COATINGS One of the very first successful applications of the binary hard coating materials were titanium nitride and titanium carbide, of which properties and performances have been extensively studied. Applying such titanium-based binary hard coatings on parts and tools shows a significant improvement in terms of wear and abrasion resistance. From these initial binary materials, it had been shown that alloying metal and/or metalloid components leads to a considerable coating performance enhancement, particularly when adding aluminum (e.g. (Ti,Al)N) and carbonitrides of various compositions (e.g. Ti(C,N)). In most cases, the base metal for multi-component hard coatings is titanium or chromium, and a large variety of alloying elements has been studied, comprising of W, V, Nb, Mo, Al, Si, Cr, Zr and B elements with many different chemical compositions [23]. Furthermore, quaternary or higher components are chosen and used in coating technology resulting in different properties. For instance, (Ti,Al,Y)N and (Ti,Al,Cr)N have shown considerable improvements particularly in terms of high temperature oxidation resistance [24, 25], while in some recent studies, it was observed that coatings like (Ti,Si)(C,N), (Ti,Si,B)N, (Ti,Al,B)N, and (Ti,Al)(C,N) have shown an ideal combination of high hardness, low friction and good adhesion strength which makes them good candidates for tribological and machining applications [26].

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Technical Sessions Proceedings of CIST2008 & ITS-IFToMM2008 Beijing, China

Fig.1. Alloying elements of ternary Ti- and Cr-based nitride hard coatings [23] The ideal combination of coating properties required for most tribological applications has become possible through the use of multi-components. From this basis, advanced coatings, such as multiple-films, multi-layers, as well as gradient are realized and well developed. 2.2. NEW GENERATION COATINGS 2.2.1. MULTIPLE-FILM COATINGS Multiple-layer coatings consist of two or more stacked films that achieve complimentary properties, and which are generally constituted by the basic materials listed in part 2.1. The use of such coatings leads to a considerable enhancement in terms of adhesion or tribological performances. Common two-layer systems consisting of a nitride coating with a metallic interlayer, such as Ti/TiN, result in an improvement in adhesion onto the underlying substrate. Other two layer sequences such as TiN/Al2O3 or TiN/Ti(C,N) resulted in an increase in performance, and lubricating/hard layer pairs have been applied exhibiting good tribological properties, especially under dry or low lubrication machining (e.g. TiC/(WC/C) ; DLC/MoS2 [27]). Fig.2 shows the simple schematic structure of a three-layer coated carbide tool. 2.2.2. MULTI-LAYERS Multi-layer coatings consist of a periodically repeated arrangement of lamellae that are composed of 2 or more materials, with thicknesses up to a few tens of a micrometer. The numerous interfaces between layers result in an increase in hardness and strength, with structure differing from those which can be found with individual thicker layers. Again, materials most frequently investigated are Ti compounds where a TiN layer is often applied first for its strong adhesion to various substrates. As examples, among the different multilayer coating structures which are particularly used in cutting tool technology are CN/TiCN/TiN; TiN/TiCN/TiC; TiAlN/CrNx; CrN/CrC/(Mo,W)S2; TiN/TiCN/TiC/Al2O3/TiN ([23], [28- 30]). 2.2.3. GRADED COATINGS The development of multi-component coatings led to the appearance of graded coatings. Consequently, desirable characteristics of each of the constituent phases can be achieved, such as a combination of a hard and a soft phase, or an association of a highly and a lower thermally conductive phase [31]. Layers presenting a continuous variation of concentration of the different components can be obtained by a drastic control of the deposition process. Hence, a reduction of the possible mismatch in chemical or mechanical properties between two different components is possible. Furthermore, such coatings can considerably improve adhesion of particular coatings on substrates such as DLC, mentioned above.

Fig.2 Schematic structure of a three-layer sandwich coating applied on a carbide cutting insert

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Hard Wear-Resistant Coatings: A Review

2.2.4. NANO-SCALED COATINGS The development of hard and wear resistant coatings on the nano-scale has been an exciting field of research in the recent years. Nano-scaled films consist mainly of nano-crystallized films, nano-composites and super-lattices. Nano-crystallized coatings involve single layers which have a grain size in the nanometer range, whereas nano-composites consist either of nano-crystalline phases embedded in amorphous ones, or a stacking sequence of different layers, each of a thickness of a few nanometers, such as super- and ultra-hard nano-composite coatings [32,33]. Super-lattices are multilayer coatings with the thickness of lamellae in the nanometer range which usually involve the combination of two different compounds with a close match of lattice parameters.

3 INDUSTRIAL APPLICATIONS AND PERFORMANCES 3.1 CUTTING TOOL INDUSTRY High-tech productivity requires high quality cutting tools that are able to withstand high cutting speeds and feed rates and resist extreme heat, high pressure, and vibration, together with abrasion. In order to meet such requirements, protective hard coatings are applied to a great majority of cutting tools, such as inserts, blades, saws, broaches, reamers, drills, end mills, and so on. The use of hard coatings in the cutting tool industry enables making cost savings and enhancing tools performances by using tools which have a longer life and are dramatically more productive. In Fig.3, the most important properties required for cutting tool coatings are summarized.

Fig.3 Desirable properties of coating material in cutting tool technology The different cutting tools can be classified into five groups, namely high speed steels, cemented tungsten carbides, ceramics, cermets and super-hard materials. On the other hand, there is quite a large variety of hard coatings applied on cutting tools, including carbides (TiC, WC, ZrC, etc.), nitrides (TiN, CrN, ZrN, etc.), carbonitrides (TiCN, ZrCN) and oxides (Al2O3, ZrO2). Furthermore, other coatings comprising of multilayer (TiC/TiN, TiC/Al2O3, etc.) and multiphase (MoS2/TiN, Al2O3+ZrO2, etc) systems have also been successfully utilized for cutting tools in the last twenty years. Finally, high performance films (diamond, c-BN, hard DLC, WS2, etc.) are used in applications in which, despite their high costs, their use is justified. 3.2. AUTOMOTIVE INDUSTRY The employment of surface treatments and high performance tribological coatings in the automotive industry implies many advantages in terms of performance, reliability, fuel consumption and exhaust gas emissions reduction. By using traditional or advance coating materials such as DLC-, MoS2-, carbide- based coatings, opportunities are available for improving car systems and components, such as coatings for gears, piston rings, cylinder bores, bearings, valve seats/springs. Several approaches are attempted to improve engine efficiency
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as well as drastically reduce emissions. One of them is the reduction of energy losses through friction and wear, which amount to approximately 15% of the total energy losses in a vehicle. In particular, the system cylinder liner/piston ring-piston is responsible for most of the friction related losses. Therefore, a typical use of coating technology in the automotive industry is piston ring films. Piston rings can be made of a wide variety of materials, including cast irons, bronze, steels, etc. Traditionally, they have mostly been coated using chromium electroplating, but in the recent years, research and developments have been made to employ other coating materials, due to environmental issues related to the latter process. Nowadays, a wide variety of surface treatments and coating materials are available for piston ring coatings, depending on the type of engine and manufacturing costs. Thermal spraying, nitriding and PVD have become common techniques used to apply such films. It is noteworthy that PVD is the most expensive technique for piston rings coatings among these processes. 4 CONCLUSION The hard coatings have an impressive record of innovation and will have more effect on industrial efficiency and economic growth. In this paper, the coating materials and their

Technical Sessions Proceedings of CIST2008 & ITS-IFToMM2008 Beijing, China

Surface and Coatings Technology, 120-121, pp. 622-628. [14] Mubarok, F., Carrapichano, J.M., Almeida, F.A., Fernandes, A.J.S., Silva, R.F., 2008, Enhanced sealing performance with CVD nanocrystalline diamond films in self-mated mechanical seals , Diamond and Related Materials, In Press. [15] Reinoso, M., lvarez, F., Huck, H., 2007, Hard carbon coatings deposited on steel, Applied Surface Science, ACKNOWLEDGEMENTS The corresponding author, Dr. J.H. Zhang, would like to 254, pp. 181-184. acknowledge the financial support provided by the Science and [16] Erdemir, A., Donnet, C., 2006, Tribology of diamond-like Technology Committee of Shanghai under the grant number of carbon films: recent progress and future prospects, 04 QMX1442 and partially support by Shanghai Leading Journal of physics. D, Applied physics, 39, no18, pp. Academic Discipline Project, Project Number: Y0102. Mr. T. 311-327. Hoornaert and Mr. Z.K. 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