an introductory section outlining the main themes of the chapter and what each section will contain (approx.

250 words) a short commentary on likely future trends (approx. 500 words) a short descriptive section of sources of further information and advice (approx. 300 words). This might provide a brief commentary on key books to consult (cross-referenced to full details given in the references), major trade/professional bodies, research and interest groups, web sites etc. references

Chapter 25. Duplex and hybrid surface treatments of light alloys

Dr. Y. Fu, Heriot Watt University, Edinburgh, UK Abstract 25.1. Introduction

The rapid development in engineering demands the requirement of materials with btter mechanical properties, resistance to frictional wear, resistance to corrosion and erosion etc. These demands can be satisfied by applying various surface engineering techniques which permit modifying the microstructure, phase and chemical composition of the surface layers of the treated parts. In real applications, TiN-, CrNor DLC-coated aluminum alloys using various PVD methods often exhibit limited tribological performance due to the elastic and plastic deformation of the substrate under mechanical loading, which can result in eventual coating failure, since the coatings are usually too thin to support the heavy load and protect the substrate in the contact conditions. Deposition of thick (e.g. >10 m) PVD coatings usually results in high compressive stresses, and thus low adhesion [2]. The problem is even more pronounced if the components are made of light metals, such as aluminum and its alloys due to their poor surface hardness and relatively low yield strength compared to steels and other materials, which usually exhibit poor wear resistance in sliding and rolling contact situations . Consequently, these issues reduce lifetime and limit the applications where a heavy surface load bearing is required. These layers improve essentially the performance properties and service life of the treated parts and widen significantly the application range of the materials, including titanium and its alloys which are now being increasingly used in industry [1]. Many engineering components will operate under severe conditions, such as large loads, high speeds and harsh environments, in order to achieve high productivity, high power efficiency and low energy consumption. There is requirement for properties of such as wear resistance, load bearing capacity, and fatigue performance) are required. These new challenges can be met only through realising the potential of duplex surface engineering [2]. Thin coatings such as PVD TiN can provide a surface with dramatically improved tribological properties in terms of low friction and high resistance to wear, but catastrophical premature failure will occur if the substrate plastically deforms under a high applied load; on the other hand, deep hardened layers produced by such surface modification techniques as energy beam surface alloying can sustain high contact stresses but still exhibit higher friction and wear rates when

compared with most ceramic coatings. It is the combination of such surface engineering technologies that constitutes duplex surface engineering []. Need to correct this part. Titanium and aluminium alloys show relatively high strength to density ratio and good corrosion resistance. Their main disadvantage in many applications is the low hardness and hence low resistance to abrasive wear. The wear resistance of titanium alloys can be enhanced by nitriding, but the compound layer thickness is limited. The requirement of thicker compound layers could be fulfilled by a combination process. The duplex process of nitriding plus moderate temperature chemical vapour deposition (MTCVD) TiCN coating of titanium alloys appears promising. Either pressure nitriding or gas nitriding can be applied to Ti-6Al-4V With pressure nitriding, homogeneous compound layers can produced on complex shaped components; however, the combined process must be carried out discontinuously in two reactors, due to the different process parameters. When using gas nitriding, the combined process can be performed continuously in the CVD equipment. With the combined nitriding + MTCVD coating route, thick compound layers could be produced in relatively short process times. The surface microstructures consist of. a nitrogen diffusion layer, an intermediate layer, a compound layer, and a TiCN coating. The Ti-6Al-4V surface was characterised by high hardness and good layer adhesion [3]. There is ever increasing interest in the applications of titanium and aluminum alloys in such sectors as automotive, medical, power generation and general engineering, in which tribological behaviour is often a major concern. Over the past 10 years significant progress has been made to overcome the inherent tribological problems of titanium alloys by means of surface engineering techniques (Fig. 5) including PVD and plasma nitriding, and also electron beam surface alloying techniques[17, 18, 19, 20]. Thin coatings such as TiN generated by plasma nitriding or by PVD deposition can provide a titanium alloy surface with greatly improved tribological properties in terms of low friction and high resistance to wear. However, premature failure will occur if the substrate deforms plastically under a high load, on the other hand, deep hardened layers produced by electron beam surface alloying can withstand a high contact stress, but do not endure sliding contact. Consequently, these techniques are technologically only suitable for components used under moderate loads or with a low or moderate sliding ratio. These include combining deep hardening with low friction high wear resistant thin coatings, which can provide titanium surfaces with good tribological behaviour to meet different requirements arising from diverse application conditions, especially pure sliding or high contact loads or a combination of both. Therefore, various surface modification technologies have been developed to improve the wear behavior of Ti6Al4V alloys. Among them, hard ceramic coatings such as titanium nitride (TiN) are suggested to be promising materials for this purpose [3 and 4]. Up to now, there are many technologies for producing TiN coatings on Ti6Al4V alloy substrate, the most commonly used methods are conventional nitriding [4], conventional ion implantation [5] and its modified process, e.g. plasma source nitrogen ion implantation [6], Physical vapor deposition [9] and plasma-enhanced chemical vapor deposition [10, 11 and 12] are the most preferable methods used for the synthesis of hard TiN coatings on Ti6Al4V alloy substrates. However, the effective adhesion of the TiN coatings is not good enough because of the lack of load

support provided by the relatively soft substrate beneath the coating. The processes investigated have included plasma nitriding, physical vapour deposition, laser surface alloying and electron beam surface alloying and currently ion implantation and plasma immersion ion implantation [4]. One of the techniques which appears to be most attractive, is producing surface layers under glow discharge conditions. This treatment is widely used for nitriding and oxynitriding of titanium alloys [13], [14] and [15]. The glow discharge conditions promote diffusion and nanocrystalization in the near-surface zone of the layers [16]. It also removes oxides and impurities from the surface, which ensures that the layers are of good quality.

Fig. 12.Towards titanium designer surfaces with desired combinations of properties through a novel duplex surface engineering system (Following T. Bells paper) The processes investigated have included plasma nitriding, physical vapour deposition, laser surface alloying and electron beam surface alloying and currently ion implantation and plasma immersion ion implantation [5].. Some results from plasma nitriding and energy beam surface alloying processing and evaluation achieved to date are included which have culminated in the use of a duplex surface engineering process. This process has allowed a Ti6Al4V alloy (where the compositions is in approximate weight percent) to be tested at 1300 MPa maximum hertzian contact pressure and 50% slip. This represents an improvement of 1200% in contact pressure and 500% in slip ratio survival over untreated Ti6Al4V. This significant increase in wear resistance of the material after duplex treatment is caused by the presence of the Al2O3 on the surface. The presence of the intermetallic phases from the TiAl system is also very important, because they ensure continuous changes in the mechanical properties when passing from the surface (Al 2O3) to the substrate (Ti6Al4V). The step change in the properties may cause a decrease of the wear resistance due to the decreased adhesion of the layer and the higher stresses at the interface between the layer and the substrate. 25.2. Duplex surface treatment and its advantages

Duplex or hybrid surface engineering involves the sequential application of two (or more) established surface technologies to produce a surface composite with combined properties which are unobtainable through any individual surface technology. Duplex surface engineering may invoves two different processes. Some examples of duplex surface engineering technologies are listed in Table 1. Table 1. Typical duplex surface engineering technologies

No 1 2 3 4 5 6 7

Complementary technology PVD coatingof pre-nitrided Plasma nitriding

Supplementary technology

Although the possible combinations of surface technologies are virtually unlimited and the list of duplex surface technologies could be endless, to date only a limited number of duplex treatments have been developed, and few of them have yet found real applications[6, 7]. In most coating systems plastic deformation initiates in the substrate near the coatingsubstrate interface when subject to relatively high intensity loading, and plastic deformation does not initiate in the coating until a large plastic zone has been developed in the substrate. The load bearing capacities of coating substrate systems thus depends upon the substrate properties. Clearly, deep case hardening can significantly enhance the load bearing capacity of a coating-substrate system, for example, nitriding and oxidation, etc. Low friction coatings such as nitrides and oxides used as the top coating layer for duplex systems not only increase wear resistance but also diminish interfacial shear stress and strain, and thus reduce the tendency for debonding of top coatings. In this respect, DLC or diamond coating are more effective since they possess the lowest friction against most engineering surfaces. The reasons for the combination of plasma nitriding and CN X films on Ti-6Al-4V substrate to improve the tribological properties can be listed as follows [Error: Reference source not found,6]: (1)To synthesis carbon nitride films, it is important to provide a structural template to seed the growth of crystalline carbon nitride. An ideal structural template for this purpose is one with at least one low free-energy plane lattice matched to some low free-energy plane of C3N4. TiN is a reasonable substrate to realize this purpose [ 7]. By depositing carbon nitride films on plasma nitrided Ti-6Al-4V (from which TiN can be produced), it is easy to obtain an optimum chemical (both are nitrides) and structure transitions between plasma nitrided layer and carbon nitride film.

(2)Plasma nitriding of Ti-6Al-4V produces a graded hardened case which serves as an excellent supporting layer for the hard CNX film. Plasma nitriding also increases the hardening depth, provides a compressive stress and imparts better stability of carbon nitride film on Ti-6Al-4V substrate. (3)CNX film deposited at low temperature can produce a wear resistant and lowfriction surface without impairing the beneficial effects of plasma nitriding treatment. Smooth and low friction CNX film could effectively reduce both the tangential stress and the interfacial stresses thus providing a good tribological behavior [8]; (4)For CNX film deposited directly on Ti-6Al-4V substrate, the load bearing capacity is relatively poor thus affecting its tribological performance. With the application of CNX film on the pre-nitrided Ti-6Al-4V substrate, the load bearing capacity and adhesion strength increase dramatically, and therefore, the tribological properties can be improved significantly [Error: Reference source not found,9]; (5) For CNX films, if small amount of debris is generated, it might play an important role during wear processes depending on whether it is soft (graphitic) or hard (diamond-like) and how easily it is ejected from the surface [ 10]. From the low coefficient of friction and the presence of the transfer layer on the wear track, it can be concluded that the spalled CNX films act as a solid lubricant during sliding, i.e., as a third lubricating body between the two surfaces. Mechanical-chemical interactions between the sliding interfaces and the environment can lead to micro-graphitisation of the interlayer at the microcontacts as can be deduced from the Raman analysis on the worn surface of wear track shown in Figure 15. Compared with that of as-deposited films shown in Figure 5, the D band (1335 cm -1) and G band (1595 cm -1) of the worn coatings becomes sharp in the spectrum as a result of the graphitisation [ 11,12]. This phenomenon clearly shows that the graphitisation and degradation of CN X films occurs between the contact surfaces and it has a significant lubricating effect on the wear and friction properties of CNX films during sliding. 25.3. Duplex treatment of Ti alloys Many surface engineering techniques have been investigated and applied to titanium alloys, such as laser surface treatments [1], PVD [2], CVD, plasma nitriding [3], plasma spraying [4], plasma immersion ion implantation [5] and plasma oxidising [6], [7] and [8] etc. Among them, carbon based coatings, especially DLC, have distinguished tribological performance due to their high hardness, low coefficient of friction and low wear rate [9]. Hard carbon coatings deposited on hard substrates (ceramics and hardened steels) have displayed excellent tribological performance. However, when deposited on soft substrates such as commercial pure titanium and Ti6Al4V alloy, the softer substrate deformed plastically when the applied load was high [10]. The deformation was considerable and repeated deflection of the coating caused fractures or fatigue cracks that eventually destroyed the film. Stress field analysis on sliding contacts under loading has established that when the coefficient of friction is reduced, significant shear stresses are developed and the location of the maximum shear stress moves gradually into the substrate away from the substrate/coating interface. There is initial evidence suggesting that under these conditions, soft substrate materials, i.e., Ti6Al4V alloy, may not be able to provide

adequate support for the hard carbon films, adversely affecting their tribological performance and durability. Titanium and its alloys have many attractive properties, including high specific strength and modulus, excellent corrosion resistance, and, in some cases, good cryogenic properties [13,14]. They are widely used in aerospace applications and many corrosive environments [15]. Ti6Al4V alloy has also been frequently used for orthopedic devices and other engineering components due to its beneficial properties, such as low density, low modulus of elasticity, excellent corrosion resistance and biocompatibility [1]. However, they are notorious for the poor tribological properties, such as poor abrasive and adhesive wear resistance; being prone to fretting wear and fretting fatigue; a tendency to galling and seizure; etc. [ 16]. Surface engineering methods are widely used to improve the wear resistance of titanium alloys [ 17,18,19,20]. The deposition of adherent diamond, diamond-like carbon (DLC) has been realised as a promising way to solve the above problem [21,22,23,]. Nowadays, carbon nitride films have also been prepared on Ti alloys for improving their tribological property [ 24]. A soft substrate such as Ti6Al4V alloy might not be able to provide adequate support for a hard carbon coating. Novel duplex or hybrid systems combining nickel diffusion (ND) deep case hardening with low friction wear resistant TiN and diamond-like carbon (DLC) coatings have been designed and applied to high strength Timetal 550 titanium alloy [ 25]. The load bearing capacity of these low friction wear resistant coatings can be improved dramatically when deposited on ND-treated Timetal 550 substrate relative to material coated with TiN and DLC alone. Continuous duplex process consisting of low temperature ( 420 C) plasma nitriding followed by in situ deposition of the DLC coating is reported [26]. The duplex treatment significantly increased the composite hardness and reduced the plastic deformation of the substrate. An improvement in the adhesion in the duplex treated sample compared to the non-duplex treated sample. In complex design situations two surface technologies can be combined -duplex surface engineering -to give very substantial improvements in wear and load bearing capacity. This duplex approach is illustrated through the industrially accepted TiN/plasma nitrided combination technology. Recent contact mechanics modelling of this duplex system is reviewed showing that thin ceramic coatings can act as stress barrier coatings on realistic industrial engineered surfaces. A new method of plasma nitriding and plasma-enhanced chemical vapor deposition (plasma-duplex process) was conducted on Ti6Al4V alloy in order to modify its wear performance [ 27]. The results indicate that the plasma nitriding processing temperature plays a dominant role in nitrided layer formation when compared to other nitriding parameters (e.g. treatment time, gas flow ratio of H2/N2 etc.). It is also shown that plasma nitriding and TiN coatings produced by plasma-duplex processing provide a marked improvement in the wear performance of the modified Ti6Al4V alloy surface. However, the friction coefficients of plasma-duplex treated samples increased significantly compared to the substrate. There is also a negative effect on the wear behavior if the TiN coating adhesion is poor. 25.3.1. Plasma nitriding based duplex treatment Amorphous CNX films show attractive mechanical and tribological properties, characterised by high hardness, high elastic recovery, good adhesion to substrate and low friction coefficient [Error: Reference source not found], and it is considered as a

potential material which will compete with DLC films [28, 29]. Amorphous CNX films have already been applied in magnetic recording industry rivalling the amorphous DLC films with their high hardness and elastic property, superior heat conductivity, and low friction coefficient [30]. Amorphous carbon nitride films have also been prepared on Ti alloys for improving the tribological property and biocompatibility of Ti alloys [31,32,33]. However, the soft Ti alloys may not be able to provide adequate support for the hard DLC or CN X films, thereby adversely affecting their load bearing capacity, tribological performance and durability. An approach to solve this problem is to design and develop duplex diffusion/coating treatments [34,35,36]. Duplex surface engineering involves the sequential application of two (or more) established surface technologies to produce a surface composite with combined properties which are unobtainable through any individual surface technology [37]. Current studies on duplex treatments concentrate on combining plasma nitriding with TiN, CrN or DLC coating on steel substrate [ 38,39,40]. The best tribological coating should combine high hardness, low coefficient of friction and high load bearing capacity (not only the high adhesion strength) [Error: Reference source not found,41]. Higher coating hardness and lower coefficient of friction are desirable for the good tribological performances of DLC or CN X films. However, high hardness usually corresponds with brittleness and high stress in the coating, which may deteriorate both the load bearing capacity and the tribological performance [42]. Load bearing capacity evaluated by indentation tests Indentation tests are used to measure the static load bearing capacity of coatingsubstrate system [16,21]. Fig. 4 shows the SEM micrographs of the indentation impressions of CNX films deposited on Ti-6Al-4V and plasma nitrided Ti-6Al-4V. For the CNX films deposited directly on Ti-6Al-4V substrate, there is usually largearea cracking and spallation occurring after indentation (see Fig. 4(a) and (d)) due to the brittle nature of CNX film and their poor load bearing capacity. The poor load bearing capacity of CNX films on Ti-6Al-4V is probably attributed to: (1) the high hardness, brittleness and high internal stresses in thin film; (2) the significant differences in elastic modulus and hardness between CN X film and Ti alloy; (3) the high contact pressure during indentation which causes the severe plastic deformation of the soft substrate, thus inducing the cracking and spallation in thin and hard CNX film. Under a small normal load of 60 kgf, for a 2 m CNX film deposited on plasma nitrided Ti-6Al-4V substrate, there are some small ring cracks within the impression and ejecting radial cracks formed at the circumference of the indentation indicating the brittle nature of the deposited CNX films as shown in Fig. 4(e). During indentation, the circular surface wave-like topographic deformation serves as the driving force for these lateral cracks. Under a high normal load of 150 Kgf, severe radial and ring cracks (but no spallation) can be observed indicating a high load bearing capacity of CNX films deposited on plasma nitrided substrates (see Fig. 4(f)). The above results indicate that with the application of plasma nitrided interlayer between the substrate and coating, the load bearing capacity has been improved significantly. Fig. 5(a) demonstrates a failure mode with only ring cracks and radial cracks around the indentation, which indicate that the coating is brittle but with a high

load bearing capacity [43,44]. Fig. 5(b) shows that during indentation, many cracks which form in the coating reorient along the interface resulting in discrete debonding, but most of the films remain attached to the substrate [ 45]. This situation corresponds to a film with a relatively poor load bearing capacity. When there are high stresses existed in the film due to the sharp difference in elastic modulus or hardness between coating and substrates, the compressed films may buckle at the interface, and these buckles are susceptible to propagation by interface crack growth, followed by largearea spallation as shown in Fig. 5(c). Scratch Tests Scratch testing was used to evaluate the load bearing capacity of coatings under both normal and tangential force, and it is considered to assess the dynamic load bearing capacity of the coating-substrate system [16]. For the scratch tests on CN X films, the load-friction curves of coated samples often show a linear increase at the beginning period, with an abrupt increase at a critical load. The critical loads, i.e., the load bearing capacity of CNX films on untreated and plasma nitrided Ti-6Al-4V substrate are shown in Fig. 6. Compared with that of carbon nitride film deposited directly on Ti-6Al-4V substrate, the load bearing capacity is improved dramatically with the application of plasma nitrided layer between Ti-6Al-4V substrate and CNx film. Fig. 7 (a) to (f) show the typical friction-load curves of scratch tests for Ti-6Al-4V substrate, plasma nitrided layer, CN X film deposited on Ti-6Al-4V substrate and prenitrided layer. Fig. 8 shows the corresponding curves of the coefficient of friction vs. normal load for different specimens. For the stylus scratching on Ti-6Al-4V substrate, the coefficient of friction is extremely high (larger than 1.0, see Fig. 8). Examination on the scratch track shown in Fig. 9 reveals the typical severe abrasive wear (i.e., ploughing) and delamination. With the stylus scratching on the plasma nitrided Ti-6Al-4V substrate, the coefficient of friction is low and stable (around 0.15) as shown in Fig. 8. Examination on the wear track shows that there is no much wear and only slight scratching lines on the wear track indicating a good wear resistance (see Fig. 10). When the load is increased to about 55 N, there is a large variation in coefficient of friction which is probably caused by the collapse of nitrided layer under high normal load. For the scratch test of CNX film deposited on Ti-6Al-4V substrate, during the beginning period, the coefficient of friction is very low (see Fig. 8) indicating a good lubricating effect of CNX films. However, after a short period, the coefficient of friction increases abruptly. SEM observation shown in Fig. 11 reveals that this sudden increase in friction force is attributed to the spallation of CN X film due to the poor adhesion strength and load bearing capacity on CNX film with Ti-6Al-4V substrate. The duplex treated coating shows excellent load bearing capacity and tribological performance. For the 2 m CNX film deposited on pre-nitrided specimen, the longterm coefficient of friction is rather low and stable as shown in Fig. 8. The typical scratch morphology on duplex treated surface indicates a mild wear on CN X film. There is a sudden jump in friction force occurring at a critical load around 60 N as shown in Fig. 8. SEM examination reveals that the film can not endure the combination of the high normal load and frictional force, so it collapses and causes
8

the large-area spallation of the film as shown in Fig. 12. The similar phenomenon can be observed for the 5 m CNX films deposited on plasma nitrided surface, and the only difference is that the long-term coefficient of friction is a little lower and the critical load is slightly smaller. The relatively low coefficient of friction under a higher normal load is probably related to the graphitization of CNX coating under high load and sliding conditions [46], but this needs further investigation. Plasma nitriding of Ti-6Al-4V produces a graded hardened case which can serve as a supporting layer for the hard CNX films improving load bearing capacity, and it also provides a compressive stress which can assist in excellent fatigue resistance and impart better stability of carbon nitride films to the Ti substrate. Hard and low-friction CNX films could effectively reduce the coefficient of friction thus providing a good tribological behaviour. After plasma nitriding, usually the surface becomes rough and the high surface roughness gives rise a highly stressed layer. By depositing CN X films on plasma nitrided specimen, the surface roughness can be decreased, therefore, reinforcing plasma nitrided layer by deposition of CN X films can improve the wear resistance significantly [Error: Reference source not found,47]. Tribological properties Figures 13 (a) to (d) show the comparison of coefficient of friction under different normal loads for four types of specimens. Under a normal load of 1 N and 2 N, it can be observed that both plasma nitrided specimen and duplex treated samples showed a relatively low value of coefficient of friction compared with that of Ti substrate. However, the coefficient of friction of plasma nitrided specimen increased gradually during the further sliding, whereas that of duplex treated specimen remained low and stable. CNX film deposited on Ti-6Al-4V substrate also showed a low value of coefficient of friction. However, due to poor adhesion and the occurrence of spallation, the coefficient of friction varied significantly during sliding. With the normal load increased to 5 N and 10 N, the coefficient of friction of duplex treated specimen remained a low value of about 0.25. However, that of the plasma nitrided specimen jumped to a high level of 0.6 to 0.7 due to the spallation of the compound layer. In brief, the duplex treated system was more effective in maintaining a favourable low and stable coefficient of friction than both individual plasma nitriding and individual CNX films. Figures 14 (a) to (d) show the comparison of wear rates for three types of specimens. Both Plasma nitriding and duplex treated coating could improve the wear resistance significantly under low normal loads of 2 N and 5 N. However, with the normal load increased to 10 N, due to the collapse of the compound layer, wear of plasma nitrided layer became significant. Clearly, the duplex treated system was more effective in terms of improving wear resistance than both individual plasma nitriding and individual CNX film. For untreated Ti-6Al-4V, the long-term coefficient of friction remained a constant at about 0.5-0.6 and was almost independent upon the applied normal load. With an increase in normal load, the wear volume increased significantly. The dominant wear mechanisms for untreated Ti-6Al-4V were abrasive wear, adhesive wear and delamination. Fig. 6 (a) and (b) show the worn surface morphology of wear track indicating the extensive ploughing and delamination on Ti-6Al-4V substrate. There

were usually large quantities of wear debris on wear track which were the oxide particles according to EDX analysis results. Examination on the worn Al2O3 ball using EDX indicated the transfer of substrate materials on the balls. In brief, tribological behaviour of untreated Ti-6Al-4V was characterised by high coefficient of friction and severe wear of materials [48]. Fig. 7(a) shows the coefficient of friction of plasma nitrided samples under different normal loads. It revealed that there was a critical load at which the wear mechanism was probably changed. Under normal loads of 1 N and 2 N, the coefficient of friction remained a low value (about 0.2-0.3) during the long-term sliding. Wear of plasma nitrided sample was difficult to be detected. Fig. 7(b) shows the worn surface morphology of plasma nitrided sample under a normal load of 2 N. There are only some small scratch lines indicating the mild wear of the nitrided layer. However, with the normal load increased to 5 N and 10 N, the dominant wear mechanism changed to spallation and severe abrasive wear. The coefficient of friction of nitrided sample under 5 N increased significantly during the long-term sliding (see Fig. 7(a)). Under a normal load of 10 N, the coefficient of friction also increased abruptly to a high value of 0.6, then varied significantly. On the worn surface, the crushing or spallation of compound layer could be observed as shown in Figure 7 (c). EDX analysis on worn Al2O3 ball indicated the transfer of materials from the plasma nitrided layer. Wear of CNX films on Ti-6Al-4V substrate was only performed under a normal load of 1 N with the consideration of poor load bearing capacity of CN X film. Fig. 8(a) shows the worn surface morphology indicating a large-area spallation of CN X films. Fig. 8(b) shows the coefficient of friction curves of CNX films on Ti-6Al-4V substrate. After a slight increase during the beginning period, the coefficient of friction fluctuated significantly during the further sliding. The sudden fluctuation in coefficient of friction was caused by the rapid spallation of CNX films. It is interesting to note that even though the CN X films were completely worn out during wear, the coefficient of friction still remained a relatively low value. On the worn coating surface, the coating fragments were entrapped within the wear track, comminuted into fine particles, and finally mixed up with the substrate materials to form a mechanically alloyed surface layer (see Fig. 8(a)). Fig. 4 shows the Raman analysis on these mechanically alloyed layer. Compared with that of as-deposited film, the D band (1335 cm-1) and G band (1595 cm-1) became sharp in the spectrum as a result of the graphitization [49,50]. The formation of these graphitized layer can act as a lubricating third layer, and probably this is the reason why after the coating spallation, the coefficient of friction fluctuated significantly but still remained a low value of 0.2 to 0.3 as shown in Figure 8 (b). Wear tests with the normal loads of 2 N, 5 N and 10 N were conducted on CN X films deposited on plasma nitrided layer. Wear of duplex treated specimen was minimal under normal loads of 2 N and 5 N. Only with the normal load increased to 10 N could the wear of CNX films on nitrided layer be detected. Figure 9 (a) shows the surface morphology of the wear track under a normal load of 10 N. There was only some small spallation of the films occurring at the edge of the wear track, probably because of the original rough surface of plasma nitrided layer. The spalled debris were trapped in the wear track and promoted the maintaining of a low coefficient of friction. Figure 9 (b) shows the variation of the coefficient of friction of duplex treated specimen under different normal loads. The frictional response was

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characterised by an initial break-in period which was followed by an intermediate constant stage. This break-in period probably corresponded to the removal of the oxidised top layers and the build-up of a transfer film. Thereafter, the coefficient of friction decreased a little and reached a steady value. The long-term coefficient of friction of duplex treated coating remained roughly about 0.25 under normal loads of 2 N and 5 N. However, under a normal load of 10 N, the long term value of coefficient of friction was less than 0.2. The reason was not clear, and probably under a high normal load, there was more transfer material which further decreased the coefficient of friction. Counterface materials on the tribological characteristics The successful application of duplex coating system for tribological protection requires knowledge of not only the intrinsic properties of the coating composites, but also their dependence on the counterface materials and operating environment [51,52]. Pin-on-disk wear tests with different types of counterfaces, i.e., 52100 steel balls, alumina balls and UHMWPE (ultrahigh molecular weight polyethylene) pins, were performed to evaluate the wear and friction characteristics of the duplex treated coatings. For the wear tests sliding with steel balls, the transferring of materials from steel ball was one of the main wear mechanisms. For the wear tests of duplex treated coating sliding with alumina ball, the generation, compaction and graphitization of coating debris layer (which acted as a lubricating third-body) improved the friction property and wear resistance of the coating. For the wear tests of titanium substrate sliding with UHMWPE pins, severe abrasion was found on both titanium alloy and UHMWPE pin surface. With the application of the duplex treated coating system on titanium substrate, both the coefficient of friction and wear volumes of two counterfaces were reduced significantly. Plasma nitriding was carried out with a total power of 2 kW and a voltage of 1500 V. The deposition temperature was 800oC and the nitriding duration was 9 hours. The surface roughness of plasma nitrided sample was about 0.258 0.12 m. CNX films with a thickness of 2 m were deposited on both untreated and plasma nitrided Ti6Al-4V plates by an unbalanced magnetron sputtering system under a base pressure of 510-5 Torr. A high purity (99.99%) graphite target was used in a pure (99.999%) nitrogen discharge at a gas pressure of 5 Pa and a constant gas flow rate of 40 sccm. The discharge current on the cathode was held at 1 A, the substrate temperature was below 200oC, and the negative substrate bias voltage was -300 V. Fig. 1 (a) to (c) show the coefficient of friction data for untreated Ti-6Al-4V, plasma nitrided Ti-6Al-4V and duplex treated coatings under different normal loads sliding with 52100 steel balls. Fig. 2 shows the wear volumes of above specimens under different normal loads. Table 1 lists the wear volumes of steel balls under different normal loads. For untreated Ti-6Al-4V, the long-term coefficient of friction remains a high value at about 0.5 to 0.6 and is almost independent upon the applied normal load (see Fig. 1(a)). The wear rates of Ti-6Al-4V remain a high value (see Fig. 2). The dominant wear mechanisms for untreated Ti-6Al-4V sliding with steel balls are adhesive and abrasive wear, delamination and transferring of materials from the counterfaces as
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shown in Fig. 3 [53]. EDX analysis can detect the transferred materials from the steel ball. For plasma nitrided Ti-6Al-4V sliding with steel balls, the coefficient of friction is about 0.3 to 0.4 (see Fig. 1(b)). The lower value of coefficient of friction compared with untreated Ti-6Al-4V can be attributed to the surface hardening effect after plasma nitriding [54]. Examination on the worn nitrided layer reveals the large quantities of transfer materials from steel balls as shown in Fig. 4, probably due to the hard and rough nitrided surface. These transferred materials exist within the wear track and act as a third layer, affecting the friction and wear behavior of plasma nitrided layer and maintaining a constant values of coefficient of friction during the long-term sliding. Cross-section of wear scar reveals the transfer materials from the counterface. The wear of the steel balls sliding with plasma nitrided specimen is much higher than that of steel ball sliding with untreated Ti alloy (see Table 1). Fig. 5 shows the worn morphology of the steel balls indicating the abrasive wear. The long-term coefficient of friction for the duplex treated coating sliding with steel balls is about 0.15 to 0.25 (see Fig. 1 (c)). Wear of the duplex treated coating sliding with steel ball is generally minimal, and the wear rate of CN X film deposited on plasma nitrided Ti-6Al-4V is quite low as shown in Fig. 2. Some discrete spallation can be observed on the wear track as shown in Fig. 6. EDX analysis on the wear track of duplex treated coatings reveals the transfer materials from steel balls. Detection on the steel ball using EDX analysis indicates the transfer of carbon nitride coating debris on steel balls, which can be used to explain the low coefficient of friction during sliding wear. The above results indicate the significant improvement in wear resistance and reduction of coefficient of friction with the application of duplex treatment on Ti-6Al-4V substrate. The wear of the steel ball can also be reduced significantly when sliding with the duplex treated coatings (see Fig. 2 (b)). Fig. 7 and 8 show the comparison of coefficient of friction and wear rates for the above three types of specimens sliding with alumina balls under different normal loads. Table 1 lists the wear rates of alumina balls sliding with different specimens. For untreated Ti-6Al-4V, the long-term coefficient of friction remains a high value of about 0.4 to 0.5 as shown in Fig. 7(a). Wear rate is slightly higher for untreated Ti6Al-4V sliding with alumina balls compared with the specimen sliding with steel balls (see Fig. 8). Under dry sliding wear with alumina balls, the dominant wear mechanisms for untreated Ti-6Al-4V were adhesive wear, abrasive wear and delamination as shown in Fig. 9. Compared with the wear rate of the steel balls, the wear volumes of alumina balls are slightly higher (see Table 1). This phenomenon has been well explained by the different tribochemical reactions between these two counterfaces sliding with titanium alloy [55]. For plasma nitrided Ti-6Al-4V sliding with alumina balls, there is a critical load at which the wear mechanism is probably changed. Under a relatively low normal load of 5 N, both the coefficient of friction and wear rate remain low as shown in Fig. 7(b) and 8(a). With the normal load increased to 10 N and 20 N, the coefficient of friction increases abruptly to a high value of 0.4 to 0.5 and the wear rates also show high values (see Fig. 7(b) and 8). The dominant wear mechanism changes from mild wear to spallation (or crushing) of nitrided layer as shown in Fig. 10. The above results

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indicate that plasma nitriding is not effective in improving the friction property and wear resistance under high normal loads. The wear rates of alumina balls is much less than steel balls sliding with plasma nitrided Ti-6Al-4V probably due to its relatively high hardness (see Fig. 7(b)). Fig. 7(c) shows the variation of coefficient of friction for duplex treated specimens under different normal loads sliding with Al2O3 ball. The long-term coefficient of friction for duplex treated coating remains low and stable (less than 0.2). The wear rates of duplex treated specimen (see Fig. 8) are much smaller than those of untreated Ti-6Al-4V and plasma nitrided samples sliding with alumina balls. Fig. 11 shows the surface morphology of wear track under a normal load of 10 N. There is only some small spallation of the films occurring on the wear track due to the fracture and fragmentation of the original coating asperities. Some of the coating fragments are entrapped within the wear track, comminuted into fine particles, and finally mixed up with the substrate materials to form a mechanically alloyed debris layer. Mechanicalchemical interactions between the sliding interfaces can lead to the micrographitization of this debris layer (see Fig. 12). Compared with that of the asdeposited CNX film, the D band (1335 cm-1) and G band (1595 cm-1) of Raman spectrum of worn coating surface becomes sharper as a result of the graphitization [56,57]. The graphitization of CNX films occurring in the contact zone has a selflubricating effect and can be used to explain the good tribological behaviour of duplex treated system. Observation on the worn alumina ball reveals the transferring of lubricating CNX films debris (as shown in Fig. 13). The wear rates of alumina balls sliding with duplex treated specimen are quite low as listed in Table 1. Fig. 14 and 15 show the comparison of coefficient of friction and wear volumes for the above three types of specimens sliding with UHMWPE pins under different normal loads. The wear volumes of UHMWPE pins sliding with different counterfaces are listed in Table 1. When Ti-6Al-4V sliding with UHMWPE, due to the continuous rubbing against UHMWPE, the passive outer layer of the Ti-6Al-4V is broken. Hard titanium oxide particulates are produced that remain between the disc and the pin and start a severe abrasion process, resulting in a quick deterioration of both Ti-6Al-4V specimen and UHMWPE pins. Severe abrasion with deep scratches is present on the surface of UHMWPE when rubbing against the untreated Ti-6Al-4V alloy as shown in Fig. 16. Untreated Ti-6Al-4V also shows severe wear, with deep abrasive grooves plastic deformation and formation of titanium oxide debris (see Fig. 17). For plasma nitrided samples sliding with UHMWPE pins, the coefficient of friction is lower than that of untreated titanium specimens (see Fig. 14 (b)). The wear rates of the UHMWPE are quite high, whereas those of plasma nitrided layer show much less wear (see Table 1 and Fig. 15). SEM observation on the worn surface of UHMWPE pins reveals the severe abrasion. Duplex coating shows a coefficient of friction value between 0.1 to 0.15 against UHMWPE (see Fig. 14 (c)). The wear rates of both UHMWPE and duplex treated coatings are much less than those of UHMWPE pins sliding with untreated and plasma nitrided Ti-6Al-4V as shown in Table 1 and Fig. 15. There is only some mild abrasive wear on UHMWPE pin surface (see Fig. 18) and a uniform pattern of fine

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scratches are visible on duplex treated Ti-6Al-4V (see Fig. 19). There is no much evidence for the formation of extensive transfer film or wear debris on duplex treated coating surface. The good tribological performance of duplex treated coatings sliding with UHMWPE can be mainly attributed to the hardened, smooth and lubricating surface of CNX films on plasma nitrided surface. Further experimental work will be conducted in the friction and wear properties of duplex treated Ti-6Al-4V sliding against UHMWPE pins under the lubricated conditions with the simulated body fluids. Erosion performance of duplex coating[58] Aircraft, rockets and other aeronautical engines are often subjected to severe erosion situation from sands, rains or other solid particles in the space. Erosion by these solid particles or raindrop impingement can cause the rapid degradation of mechanical properties and even catastrophic failure. Examples of the failure components include the blades and discs of aircraft compressors, helicopter rotor blades, and valves, piping etc. [59]. Most of these components are made of titanium alloys, which are notorious for their poor erosion and wear resistance [60]. To design and use protective coatings or surface treatments that withstand solid particle erosion is thought as the best approach to solve this problem. For solidparticle erosion testing, a standard sandblasting apparatus was used to impact the target specimens (with a dimension of 10 mm 10 mm) with erodents at various velocities. The solid particles used in erosion tests were natural angular alumina sands with dimensions of 300-600 m. The impingement angle of the particles on the surface was 90 2o. The erodent was accelerated by compressed air with the impact velocities of the particles 100 m/s and 350 m/s. The nozzle-to-specimen distance was maintained at 50 cm. The erosion performance was measured by weighing specimens to an accuracy of 0.01 mg before and after exposure to the erodent for different test durations, so that the evolution of the mass loss with time could be determined. Fig. 8 (a) and (b) show the eroded mass loss of the duplex treated system under different erosion conditions. The duplex treated coating can improve the erosion resistance of titanium substrate under a low impact velocity. It contains hard layers, being able to resist the particle flux at low velocity. However, under a high velocity, the improvement of erosion resistance is not so significant. Carbon nitride thin films exhibits a unique combination of properties: i.e., extreme hardness, chemical inertness and excellent tribological behavior, however, adhesion problems, high residual stress limit the thickness of the coating. For duplex treated coating, micro-cracks propagating through the interface between CNX film and plasma nitrided layers are observed. This crack deflection mechanism improves the impact resistance until the rupture of the coating happens. This mechanism is only effective under a low impact velocity of erodents, however, under a high impact velocity, the spallation of the CN X layer is more significant thus the erosion resistance is not good. For carbon nitride coating deposited on plasma nitrided layer, when the erodent impacts on the coating surface, the cracks will form in the brittle carbon nitride coating. Then these cracks will grow parallel at the interface between carbon nitride coating and plasma nitrided layer. When cracks have developed thoughout the film, small parts are torn out by impinging particles as shown in Fig. 10 (a). The
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predominant features of the eroded surface were microchipping, some degree of plastic deformation from direct impacts and craters which resulted from the detachment of thin platelets [61] (see Fig. 10 (b) and (c)). Corrosion properties of duplex treatment TiN used as a hard coating is chemically inert, which in turn provides a good corrosion protection. When producing the TiN coatings on the substrate surface, some defects, such as pores or cracks may occur, which leads to a pitting and delamination of the surface [12, 13 and 14]. The corrosion properties of duplex-treated and nitrided Ti6Al4V have been investigated in 0.025, 0.25 and 2.5 M NaCl. The electrochemical results showed a three-fold increase in corrosion rate for every ten-fold increase in chloride concentration. [62].Electrochemical testing of a duplex treated Ti6Al4V alloy is considered [63]. The duplex treatment is carried out in two steps. In the first step, the alloy surface is laser nitrided while in the second step, the nitrided alloy surface is PVD TiN coated. Corrosion rates and electrochemical properties of the treated surfaces are investigated using polarization techniques. It is found that the duplex treated workpiece surface is more resistant to corrosion as compared to TiN coated and untreated surfaces. Among the three metals contained in the alloy, aluminum is found to selectively dissolve in large proportion in solution during oxidation. Yilbas et al. [18] conducted a study on the corrosion properties of TiN coated and nitrided Ti6Al4V alloy. They showed that TiN coating improved the corrosion properties, but nitriding made worse the corrosion resistance of the substrate. A comparative study of the corrosion subjected to nitriding, coating and duplex treatment was carried out by Dingremont et al. [19]. They showed that duplex treatment improved the corrosion resistance of the construction and hot working steels when compared with nitriding or PVD coating. 25.3.2. The duplex DLC coatingoxygen diffusion treated titanium system It is shown that the use of nitrogen or carbon as alloying elements in plasma diffusion treatment of TiAl6V4 is beneficial for the load-supporting properties of the base material. The plasma diffusion treatment produces a compound layer consisting of nitrides or carbides and an inner diffusion zone, essentially characterized by the presence of nitrogen- or carbon-rich -Ti crystals which are embedded in the metal matrix. This results in a hardness gradient from the interior to the surface. To avoid hydrogen embrittlement, plasma nitriding is performed in a pure nitrogen atmosphere. The formation of soot by carburizing could be avoided by optimizing the carbon flow during plasma carburizing. The influence of plasma nitriding and carburizing on the adhesion of the TiC coating depends on the plasma diffusion pretreatment and the conditions of the TiC coating. Plasma-nitrocarburizing pretreatment leads to the best adhesion of the TiC coating; the critical load of failure is 80% higher than in the case of TiC on base material. A critical load of approximately 33 N was found under the optimum parameters. We conclude that the combination of plasma diffusion treatment and TiC coating extends the tribological applicability of TiAl6V4 in many industrial sectors. Fretting fatigue and wear could be increased by a duplex plasma treatment combined with shot peening. [64].

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Advanced adhesion of hard coatings is necessary for the industrial use of Ti alloys under tribological conditions. We found that the use of nitrogen or carbon as alloying elements in plasma diffusion treatment of TiAl6V4 is beneficial for the load-bearing capacity of the latter. The plasma diffusion treatment produces a compound layer, consisting of nitrides or carbides and an inner diffusion layer, characterized essentially by the presence of nitrogen- or carbon-rich -Ti crystals which are embedded in the metal matrix. This results in a hardness gradient from the interior to the surface. The formation of soot by carburizing could be avoided by optimizing the carbon flow during plasma carburizing. The influence of plasma-nitriding, -nitrocarburizing and -carburizing on the adhesion of the TiC coating depends on the compound layer composition, the hardness profile in the diffusion layer, and on the conditions of the TiC coating. Plasma-nitrocarburizing pretreatment leads to the best adhesion of the TiC coating; the critical load is 80% higher than in the case of the base material (Fig. 5). We conclude that the combination of plasma diffusion treatment and TiC coating extends the tribological applicability of TiAl6V4 in many industrial sectors [10]. Fretting fatigue and wear could be increased by a duplex plasma treatment combined with shot peening. TiO/TiN duplex coatings were fabricated on titanium alloys by metal plasma immersion ion implantation and reactive plasma nitriding/oxidation [ 65]. The purpose of TiO is to improve the blood compatibility, and that of TiN is to improve the mechanical properties. The results reveal that the blood compatibility of the TiO/Ti N duplex coatings is better than that of low temperature isotropic pyrolytic carbon (LTIC). The microhardness of TiO/TiN duplex coatings can reach 14 GPa. The wear resistance is also much better than that of Ti6Al4V alloy. The semiconductor nature of non-stoichiometric titanium oxide may be responsible for the observed improvement in the blood compatibility. Titanium nitride is commonly used as a wear and corrosion resistant coating on cutting tools, machine components, and also biomaterials [1], due to its superior mechanical and chemical properties including high hardness, low wear coefficient and chemical stability. The blood compatibility of titanium oxide has also been studied in recent years. Rutile type titanium oxide ceramics and TiO 2 and TiOx prepared by thermal oxidation and ion beam assisted deposition, respectively, generally have blood compatibility better than that of LTIC [2, 3, 4 and 5]. Hence, titanium oxide is a hopeful material for artificial heart valves. Plasma immersion ion implantation (PIII) circumvents the line-of-sight restriction inherent to conventional beam-line ion implantation, eliminates complex focusing elements in the instrument, is capable of processing complex-shaped components such as artificial organs, and is potentially more economical [6 and 7]. It is thus suitable for the processing of artificial heart valves. In this work, TiO/TiN films are synthesised on Ti6Al4V substrates by PIII, utilising titanium metal plasma and reactive plasma nitriding/oxidation. Ti6Al4V alloys have attracted much attention as a biomaterial because they possess excellent mechanical properties, corrosion resistance, and a low modulus of elasticity. As aforementioned, in the duplex Ti N/TiO structure, the presence of TiO improves the blood compatibility and the main effect of TiN is to improve the mechanical properties. Thus, a TiO/TiN

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duplex film on titanium alloy is projected to be an excellent artificial heart valve material. The interaction between blood and the artificial heart material is very complicated, but for simplistic view [9] it can be envisioned as blood coming in contact with the materials surface. The first event is protein adsorption. If the absorbed protein such as fibrinogen is denatured, the coagulation factors or platelet will be activated causing a series of cascade reactions of blood coagulation, and thrombosis eventually results. Hence, in the development of blood-compatible materials, some essential considerations must be taken. First, the materials should effectively inhibit the adsorption of harmful proteins such as fibrinogen or globulin onto the material surface while favouring the absorption of good proteins such as albumin. Secondly, the surface must prevent the absorbed protein from becoming denatured. It has been shown that the denaturing of fibrinogen is related to the charges of fibrinogen transferring to the material. Consequently, the fibrinogen is decomposed into fibrin monomers and fibrinpeptides [10]. As indicated by Gutmann et al. [11], fibrinogen has an electronic structure similar to that of a semiconductor. The valence band and conduction bands are 0.9 eV below and above the Fermi level. Fibrinogen electrons are transferred from their occupied valence band into the free states of the material surface and cause decomposition of the protein. Certain electronic states at the materials surface may inhibit the transfer of the charge carrier. Titanium alloys are characterised by poor tribological properties, and a soft substrate such as Ti6Al4V alloy might not be able to provide adequate support for a hard carbon coating. A boost diffusion oxidation (BDO) process had been used to acquire a deep hardened case in Ti6Al4V. A novel duplex surface treatment combining the BDO treatment with carbon based hard coatings (BDO/Cr-DLC) can significantly improve the tribological properties of the Ti6Al4V titanium alloy and increase its load bearing capacity on the basis of scratch and pin-on-disc testing [66] Recently, a boost diffusion oxidation (BDO) process has been developed [12], which consists essentially of two steps: (I) titanium specimens are thermally oxidised in air and (II) the pre-oxidised specimens are further diffusion treated in vacuum. This process can effectively harden a titanium surface to a depth of about 300 m without evoking inevitable scaling or oxide spallation associated with long time oxidation at high temperatures. The BDO treatment can lead to a significant increase in the effective depth of the surface hardening. However, to improve the tribological performance, it is necessary to introduce some coatings on the hardened titanium alloys. The duplex-treated sample (BDO/Cr-DLC coating) possesses a higher load bearing capacity than the single coating system (Untreated/Cr-DLC coating). The outstanding performance of the duplex system can be attributed to the optimised design. Firstly, carbon based coatings have exceptional tribological properties in terms of low friction and high wear resistance along with extreme hardness; secondly, the graded intermediate layers successfully facilitate a high level of adhesion and bonding strength between the coating and the substrate material; thirdly, the deep-case hardened layer formed from BDO treatment provides strong support to the carbon based coating by suppressing plastic deformation. BDO treatment can result in a deep hard case in the Ti6Al4V alloy which provides strong load support for the Cr-DLC coating.

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 Duplex surface treatments combining BDO treatment with a PVD multilayered composite coating result in a dramatic improvement in the load bearing capacity of Ti6Al4V alloy, as determined by the scratch test and pin on disc sliding wear resistance. Microplasma oxidation (MPO) has recently been studied as a cost-effective plasma electrolytic process to provide thick and hard ceramic coatings with excellent surface load-bearing capacity on aluminum alloys. However, for sliding wear applications, such ceramic coatings often exhibit relatively high friction coefficients against many counterface materials. Although coatings deposited by physical vapour deposition (PVD) techniques such as TiN coatings are well known for providing surfaces with a high hardness, in practice they often exhibit poor performance under mechanical loading, since the coatings are usually too thin to protect the substrate from the contact conditions. In this paper, these challenges were overcome by a duplex process of microplasma oxidation and arc ion plating (AIP), in which an alumina layer Al2O3 was deposited on an Al alloy substrate (using MPO as a pre-treatment process) for load support, and a TiN hard coatings were deposited (using AIP) on top of the Al 2O3 layer for low friction coefficient. The research demonstrates that a hard and uniform TiN coating, with good adhesion and a low coefficient of friction, can successfully be deposited on top of an alumina intermediate layer to provide excellent load support [67]. The investigations indicate that a duplex combination of MPO coating and TiN PVD coating represents a promising technique for surface modification of Al alloys for heavy surface load bearing application. To meet the above design requirement, a novel duplex system combining an oxygen diffusion treatment (OD) with a diamond-like coating (DLC), has been developed[20]. The load bearing capacities of the duplex treated, as well as DLC coated, Ti6Al4V specimens have been evaluated, both statically and dynamically, by employing a friction monitored scratch tester, a ball-on-disc tribometer and an indentation tester. Novel duplex system, combining the oxygen diffusion treatment with DLC coating, possesses excellent load bearing capacity, irrespective of the evaluation method. In short, this novel duplex system has effectively extended the window of the design service conditions for titanium components, in terms of both high sliding ratio and/or higher loads (Fig. 11), and it is thus seen as an important step towards titanium designer surfaces. This outstanding performance can be attributed to the optimised design of the duplex system (Fig. 12). DLC coating is a unique material which has both a high hardness and an extremely low friction coefficient against most engineering materials. In the layered coating system, friction has significant effects on the stress distribution: (a) the maximum Von Mises stress not only increases in value but also moves towards the surface when the friction coefficient increases; and (b) the maximum shear stress at the interface also increases with increasing friction coefficient. Thus it follows that the low friction of DLC could effectively reduce both the interface stress and the stresses near the surface. However, DLC is usually characterised by high levels of residual stress and poor adhesion when coated directly onto most engineering materials. These problems have been successfully addressed by adapting a graded intermediate layer between the DLC and the OD treated sublayer. The compositionally graded intermediate layer, Ti/TiN/TiCN/TiC, eliminates interfacial cracking by homogenising the stress distribution. Experimental results, however, have revealed that the modified DLC coating still showed a relatively low

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load bearing capacity compared with the duplex system. Clearly, a significant improvement in load bearing capacity can be achieved only when the DLC coating is deposited on a deep hardened sublayer (about 300 m) produced by the OD treatment, thus mitigating against plastic deformation. Therefore, it is clear that the duplex treatment is essential to achieve a high load bearing capacity in this titanium based system. Hybrid technology hard coating Electron beam surface hardening [68] Surface treatment technologies with high energy beams {electron beam (EB) or laser beam (LB)} offer a good and modern alternative to the mostly used bulk heat treatment. The energy deposition is precisely focused, so it is possible to exactly limit the heat treatment to highly loaded areas and up to the depth where a transformation (hardening) is necessary. Therefore, the bulk materials are not heated up to critical temperatures. The thermal load of the overall component is minimized and thus distortion can also be avoided. The combination of PVD hard protective coatings {based on Ti(C)N, TiAlN, CrxNy and DLC} with electron beam surface hardening. It is not only the sequence of treatments (beam hardening before or after coating) which has a considerable influence on treatment results, but also the parameters of EB surface treatment (energy density distribution, speed of treatment, vacuum). These modern combined technologies open up new fields of industrial application for tools and components subjected to locally high load. Duplex treatment for diamond coating [69] [70]

One solution is to deposit an interlayer or buffer layer on substrate [ 71,72,73]. The functions of an interlayer to improve adhesion include (1) to enhance diamond nucleation rate; (2) to minimize thermal and interfacial stresses; (3) to provide an intermediate layer for bonding. Nowadays, there are many studies on the deposition of a well adherent diamond coatings on titanium alloy substrate to improve their wear and corrosion resistance [74,75, 76, 77]. The rapid carbon diffusion in titanium alloy reduced significantly the diamond nucleation rate. It is well known that hydrogen is easy to dissolve into Ti substrate and form titanium hydrides, which has a strong influence on the coarsening of microstructure and significant deterioration of mechanical properties [ 78,79,80,81]. Also the poor adhesion to titanium substrate is one of the biggest problem restricting their applications. (1) prevent the rapid diffusion of carbon atoms and increase the diamond nucleation and growth rate; (2) to prevent the hydrogen diffusion into the substrate and prevent the significant coarsening of the substrate microstructure and deterioration of the mechanical properties. Plasma nitriding can effectively prevent the rapid diffusion of hydrogen and carbon into Ti substrate thus preventing the significant deterioration in microstructure and mechanical properties of substrate after diamond deposition. Since plasma nitriding can provide a diffusion-barrier layer for hydrogen and carbon atoms, it can be used as the first step for diamond deposition. On the top of plasma nitrided layer, the plasma

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carbonitriding with (CH4/N2) gas mixture can provide a carbide layer, which serves as the precursor for the nucleation and growth of diamond crystals. The carbide interlayer and/or carbon diffused layer enhances the adhesion of diamond to substrate [82]. Three factors help to explain the relatively good adhesion between the carburized substrate and diamond coatings: (1) The plasma treated surface has some micro-level roughness caused by ion bombardment, which may improve the adhesion of film to substrate by an anchor effect between them. (2) The heteroepitaxial growth of diamond on a carbide layer. (3) The gradient-controlled composition of carbon. The gradual structure changes from plasma nitrided layer, carbonitrided layer to diamond coating (i.e., an interlayer of Ti(N) / Ti 2N / TiN / TiCN / TiC). This compositionally graded interlayer can eliminate the interfacial cracking by homogenizing the stress distribution, facilitate good bonding and improve the load bearing capacity. The preliminary results clearly demonstrate the effectiveness of pre-nitriding/ plasma carbonitriding in improving the nucleation and growth of diamond coating. The prenitriding/ carbonitriding treatment can prevent the rapid diffusion of carbon and hydrogen into the substrate, increase the hardening depth, impart better chemical stability to titanium alloy substrate, and also provides an excellent supporting layer for wear resistance. The whole processing procedures, including plasma nitriding, plasma carbonitriding and diamond deposition can be performed in the same equipment, therefore, the process is convenient. 25.3.4. Fretting wear and fatigue behavior of duplex treatment by shotpeening+IBED CrN Duplex treatment by shot peening and CrN on Ti alloys [83,84] Chromium nitride films have high hardness and good corrosion resistance, and several studies have investigated the deposition of CrN films using reactive ion plating [85,86,87,88], magnetron sputtering [89,90] and IBED [91,92,93,94]. Investigation found that the thermal stability and corrosion resistance of CrN films were better than those of titanium nitride (TiN) films [95]. CrN films are usually in a low compressive stress state, whereas TiN films are generally in a high comparative stress state [ 96] which limits the deposition of thick TiN films [97]. IBED CrN films usually have a good surface finish, however, for the fretting wear, the smoother the surface, the poorer the fretting wear resistance. Another factor which promotes fretting wear is the action of fretting debris on IBED CrN films. The hard and relatively brittle CrN film may have low fracture toughness, thus increasing the rate of wear particle formation. The wear debris become trapped between the contact area and will act as hard abrasive particles to promote fretting wear [98]. However, during fretting fatigue, the smooth surface will reduce the stress concentration and therefore reduce the possibility of the initiation of a fatigue crack. The residual compressive stresses in IBED CrN films enhance the fretting fatigue strength. The high hardness can prevent the formation of surface damage thus also can reduce the occurrence of the surface cracks.

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Shot peening can improve fretting wear and fretting fatigue resistance significantly. The reasons for the significant improvement in fretting wear resistance by using shot peening can be attributed to: (1). hardening of the surface; (2) inducing a compressive residual stresses; (3) roughening of the surface [ 99]. The first two effects are better for the prolongation of the fatigue life, but a rough surface containing potential stress raisers is very dangerous in fatigue conditions [ 100]. This maybe due to the presence of surface folds and subsurface damage in the shot-peened material which then leads to the extensive delamination on surface. In the peened specimen the initiation of the cracks is often accelerated, and this can be attributed to: (1) surface damage, such as folds caused by shot-peening, leading to the initiation of fretting fatigue cracks [101]; (2) the working-hardening of the surface and the resultant reduction in the fracture toughness of surface material. The subsurface damage, which probably takes place at the sites of surface folding in as-peened specimens, provides sites of the initiation of fretting fatigue cracks and the paths for the easy crack growth. This is probably the reason why the fatigue strength of the shot-peened specimens is not better than other treated specimens. For the specimens with IBED CrN film deposited on shot-peened substrate, the fretting wear resistance can be increased and the coefficient of friction can be reduced. A much harder surface can improve the abrasive wear resistance and CrN phase can improve the anti-corrosive and anti-oxidative resistance of as-peened specimen. This kind of duplex treatment combines the benefits of the two surface engineering methods and shows the best performance in fretting wear resistance. Other methods The hybrid methods, in which the Ti6Al4V alloy is first pre-coated with aluminum and then subjected to the glow discharge treatment, produced a multicomponent intermetallic TiAl layer with Al2O3 on the outer surface. The layers have a diffusional character and they contain the Ti3Al + TiAl + TiAl3 + Al2O3 phases. The intermetallic layers obtained increase substantially the surface hardness and improve the wear resistance of the Ti6Al4V titanium alloy in both the dry wear test and the wear test performed in a fluid. Ref/ [102] 25.4. Duplex treatment of Al Alloys For many years, light metals such as titanium add aluminum have also been used to synthesize hard compound coatings such as physically vapor deposited (PVD) AlN, (Ti,Al)N, and chemically vapor deposited (CVD) Al2O3. In ref. [], Aluminum alloys are the most widely used non-ferrous metals in engineering owing to their attractive properties such as high strength-to-weight ratio, good ductility, good corrosion resistance, availability and low cost [103]. However, their applications have often been restricted because conventional Al alloys are soft and notorious for their poor wear resistance [104]. Aluminum alloys do not have allotropic transformation as in iron, cobalt, or titanium alloys, so there is no possibility of a martensitic transformation, and the hardening effects by conventional solid state treatments are very limited. In many cases, surface treatments and coatings are necessary to ensure the optimum performance in service [105].

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The improvement of fretting fatigue resistance of AL-7075 was studied using surface treatments including nitriding and titanium coating by hollow cathode discharge (HCD) and magnetron sputtering techniques [106]. The experimental results indicate that surface nitriding reduces the fretting fatigue resistance of the material. Titanium coating, using HCD technique, may increase the fatigue life up to 85% at low working stresses, while at higher stresses the increase is not considerable. Titanium coating, using magneto sputtering technique, may increase the fatigue life up to 77% at low working stresses, while at higher stresses it gives rise to the reduction in fretting fatigue life. Duplex treatment including nitriding with no temperature control, plus titanium coating by HCD technique, gives rise to the reduction in fatigue life. Duplex treatment including nitriding with substrate's temperature control plus titanium coating by DC magnetron sputtering technique increases the fatigue life up to 185% at low stresses and up to almost 60% at higher stresses. Majzoobi et al. [5] investigated the improvement in fretting fatigue life of Al 7075-T6 by titanium surface coating using magnetron sputtering technique and shot peening. They found that: (i) shot peening can increase the fatigue life up to 400%, (ii) the duplex treatment including titanium coating, using magnetron sputtering technique, plus shot peening may increase the fatigue life of material up to 1000% for low working stresses, while this increase is not significant for higher working stresses. Majzoobi et al. [6] also studied the improvement in fretting fatigue life of AL 7075T6 by titanium surface coating using ion beam enhanced deposition (IBED) technique and shot peening. From their experiments, they found that the duplex treatment including titanium coating, using IBED technique, plus shot peening may increase the fatigue life of material up to 45% for low working stresses, while it can reduce the fatigue life significantly at higher working stresses. Liao [8] studied the surface modification of aluminum by high current Mo ion implantation using a metal vapor vacuum arc (MEVVA). They found that high dose Mo ion implantation can result in a modified layer about 1600-nm thick and thus improve the surface mechanical properties of aluminum matrix significantly. A duplex treatment combining mechanical cold-work with a hard surface layer has been demonstrated to significantly improve the fatigue resistance of Al alloys. compared to the results for a hard coating alone. A further consideration is that of corrosion resistance; Plasma Electrolytic Oxidation (PEO) can be used to reduce the susceptibility to corrosion whereas shot-peening is known in some cases to be detrimental, particularly if a ferrous peening media is used. In this work, the corrosion resistance of three different surface treatments (i.e. single shot-peening and PEO as well as their combination) is investigated on a 2024-T351 aluminium alloy. Corrosion studies were carried out in a 3.5% NaCl solution using open circuit potential and electrochemical impedance spectroscopy techniques. Surface microstructure and phase composition were studied by optical microscopy and XRD analyses, respectively. The effect of the duplex treatment is discussed in comparison with that of the single treatments and as-received (mill finish) surfaces. Shot-peening is seen to reduce the resistance to corrosion whilst PEO substantially improves it; the combination of the two provides a level of resistance comparable to that of PEO alone [107] Aluminium alloys are widely used in the aerospace and automotive industries in structural applications. Exploiting such environments often has the inherent problems

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associated with corrosion, and it is necessary to consider the environmental effects as part of the design process. Frequently, as a result of environmental difficulties, aluminium components are treated with an anodizing or similar process. Plasma Electrolytic Oxidation (PEO) can be used to provide a corrosion resistant surface with substantially increased hardness on aluminium. PEO also has benefits over conventional anodizing as it creates a thicker and harder oxide layer to act as a barrier to corrosion. Recent work has studied the effects of such coatings on the fatigue life of an aluminium alloy and demonstrated that surface treatments such as PEO can have a detrimental effect on the fatigue behaviour of aluminium. However, the loss in fatigue life can be recovered to a certain extent by the application of a suitable surface coldwork process prior to treatment. In a previous study shot-peening was employed as such a cold-working process and was demonstrated to recover fatigue life of PEO treated aluminium by approximately 85% [1]. Shot-peening can, under certain conditions, affect the corrosion behaviour of aluminium, particularly if a ferrous medium is employed in the peening process; it is known that small additions of iron can significantly alter the corrosion behaviour of aluminium [2]. This is generally attributed to the transfer of iron between shot and work-piece during the peening process. In this work the corrosion behaviour of Al alloy 2024-T351 was studied in an as-received condition and after treating with either shot-peening, PEO or a duplex system of shot-peening followed by PEO. Duplex treatments provide a significant benefit in terms of corrosion resistance, more comparable to that of a single PEO treatment. It can be reasoned that since many of the detrimental effects of shot-peening on corrosion are attributable to the presence of Fe transferred from the shot, behaviour closer to that of the singular PEO treatment could be achieved using ceramic media. The improvement of fretting fatigue resistance of AL-7075 is studied using surface treatments including nitriding and titanium coating by hollow cathode discharge (HCD) and magnetron sputtering techniques [108]. The experimental results indicate that surface nitriding reduces the fretting fatigue resistance of the material. Titanium coating, using HCD technique, may increase the fatigue life up to 85% at low working stresses, while at higher stresses the increase is not considerable. Titanium coating, using magneto sputtering technique, may increase the fatigue life up to 77% at low working stresses, while at higher stresses it gives rise to the reduction in fretting fatigue life. Duplex treatment including nitriding with no temperature control, plus titanium coating by HCD technique, gives rise to the reduction in fatigue life. Duplex treatment including nitriding with substrate's temperature control plus titanium coating by DC magnetron sputtering technique increases the fatigue life up to 185% at low stresses and up to almost 60% at higher stresses. Fretting fatigue can decrease the fatigue life from 60% in high cycle region to 30% in the low cycle region. Surface nitriding reduces the fretting fatigue resistance of the material. This reduction is more severe in the case when the temperature rise in the substrate is not controlled. A temperature controlled process can slightly increase the fretting fatigue life at very low stresses. The reduction in the fatigue life for higher stresses is believed to be due to degradation of the material's properties, such as ultimate strength and yield stress. Titanium coating, using HCD technique, may

23

increase the fatigue life up to 85% at low working stresses, while at higher stresses it may not give rise to considerable change in fretting fatigue life. Titanium coating, using magneto sputtering technique, may increase the fatigue life up to 77% at low working stresses, while at higher stresses it brings about the reduction in fretting fatigue life. Duplex treatment including nitriding with no temperature control, plus titanium coating by HCD technique, gives rise to the reduction in fatigue life. Duplex treatment including nitriding with substrate's temperature control plus titanium coating by DC magnetron sputtering technique increases the fatigue life up to 185% at low stresses and up to almost 60% at higher working stresses. The 2024 Al was anodically oxidized first and then coated with REMFMoS 2Au nanocomposite film and Ti/Ag dual layer film by rf-sputtering and multi-arc ionplating, respectively [109]. It is shown that duplex treatment, especially sputtered REMFMoS2Au nanocomposite film, can decrease the friction coefficient and improve the endurance life of 2024 Al in vacuum. The lubrication failure mechanism of the duplex treated 2024 Al is attributed to the generation of the cracks in the anodic oxide coating induced by normal load combined with friction force (shearing force) and the crack propagation mainly caused by friction force. It is proposed that pores of several tens of nanometers in diameter in the anodic oxide coating can postpone the propagation of the cracks. Aluminum and its alloys such as 2024 Al are of high specific strength and good chemical stability and so they are good candidate materials for aerospace applications. Hence they are increasingly used in aerospace as constructional or optical elements [1]. When used as tribological parts, however, they show some serious defects including high friction coefficient, serious wear and a tendency for cold-welding when mated with other metals, especially, steel [2 and 3]. Anodic oxidation is an effective method to enhance the wear resistance of aluminum alloy, e.g. an aluminum oxide coating of a few to several hundred micrometers thick can be formed to increase the hardness of the surface and to improve the wearresistant properties. But the hard surfaces have high friction coefficients when sliding against metals. On the other hand the endurance life cannot meet the increasing demands. Duplex process of microplasma oxidation and arc ion plating (AIP), in which an alumina layer Al2O3 was deposited on an Al alloy substrate (using MPO as a pretreatment process) for load support, and a TiN hard coatings were deposited (using AIP) on top of the Al2O3 layer for low friction coefficient [110]. The research demonstrates that a hard and uniform TiN coating, with good adhesion and a low coefficient of friction, can successfully be deposited on top of an alumina intermediate layer to provide excellent load support. The investigations indicate that a duplex combination of MPO coating and TiN PVD coating represents a promising technique for surface modification of Al alloys for heavy surface load bearing application. Previous coatings applied to aluminum alloys in traditional processes, such as hard anodizing and thermal spraying, have suffered from the low load support from the underlying material and/or insufficient adhesion, which reduces their durability. A novel advancement in this area is coatings prepared by microplasma oxidation (MPO). The MPO technology has recently been studied as a rapid, novel and effective

24

means to provide thick and hard ceramic coating with excellent load bearing and wear resistance properties on light alloy materialsparticularly aluminum alloys [111]. The MPO, also called plasma electrolyte oxidation, or micro-arc oxidation is an unconventional plasmachemicalelectro-chemical treatment. It operates at potentials above the breakdown voltage (typically 400600 V) of an original oxide film growing on the surface of a passivated metal anode dipped in an aqueous solution containing modifying elements (e.g. SiO2) to be incorporated in the resulting coatings. However, a major challenge remaining is how to improve the relatively high friction coefficient (0.670.7) in dry sliding conditions, which as-deposited (and polished) MPO coatings have. A duplex process of arc ion plating and microplasma oxidation was applied for deposition of duplex Al2O3/TiN coatings. A controlled capacitor-based power source has been successfully used in this work to anodically treat Al alloy components, in which an ACC microplasma oxidation mode was used to decrease the porosity of the MPO-treated substrate surface. The relatively high conductivity of the P-containing Al2O3 coatings and the high frequency DC pulse power supply used to bias the target avoided charging-up and associated arcing damage of the substrates during deposition. Depending on the bias voltage, TiN coating structure had a dense and columnar microstructure. The duplex coatings possessed very high hardness and wear resistance, and their mechanical and tribological properties were better than those of single layer coatings alone and the untreated Al alloy substrate. The cubic TiN(2 2 0)/Al2O3 duplex coatings deposited at 10 V bias voltage and 1 Pa gas pressure had the lowest hardness and the worst performance in wear tests. The cubic TiN(1 1 1)/Al2O3 duplex coatings deposited at 80 V bias voltage and 0.5 Pa gas pressure had the highest hardness and the best performance in wear tests. The Al 2O3 intermediate layer is obviously beneficial in providing the load support essential to withstanding sliding wear at high contact loads. This research demonstrates that the duplex process of arc ion plating of TiN and microplasma oxidation shows great promise for protecting light metal alloy substrates in tribological wear applications, which involve high contact stresses. 4. Discussions (1)Plasma nitriding of Ti-6Al-4V produces a graded hardened case which serves as an excellent supporting layer for the hard CNX films. Plasma nitriding also increases the hardening depth, provides a compressive stress and imparts better stability of carbon nitride films to Ti-6Al-4V substrate [Error: Reference source not found]. (2)The CNX films deposited at low temperature can produce a wear resistant and lowfriction surface without impairing the beneficial effects of plasma nitriding treatment. The decrease in coefficient of friction with the application of CN X films on prenitrided specimen is probably one of the explanations for the improvement in wear resistance. Low friction of CNX films could effectively reduce both the interface stresses and the stresses near the surface thus providing a good tribological behaviour. (3) It was reported that in the zone near the PVD TiN-plasma nitrided substrate interface, the highest stresses were only half as large as the values which occurred at the same depth in the untreated case [112]. Even though the stress distribution was not studied in this study, it is probably the same case for CN X films deposited on plasma

25

nitrided layer. This reduction in stress is probably contributed to the improved tribological and bonding strength of engineering components. (4) With the application of CNX films on the pre-nitrided Ti-6Al-4V substrate, the load bearing capacity of coating system increases dramatically, and therefore, the tribological properties can be improved significantly. (5) For CNX films, if small amount of debris is generated, it might play an important role during wear processes depending on whether it is soft (graphitic) or hard (diamond-like) and how easily it is ejected from the surface [113]. From the Raman analysis results shown in Fig. 4, it can be concluded that the spalled CN X films can formed a mechanically alloyed layer on the worn surface and also graphitized under the mechanical-chemical interactions between the sliding interfaces and the environment. This graphitized wear debris layer can acts as a solid lubricant during sliding, and significantly improve the tribological properties of the coating system. Although the integrated duplex processes have the advantages of possibly better process control, simple logistics and better delivery time, they have the economic disadvantage Summary Carbon nitride films were deposited on plasma nitrided Ti-6Al-4V substrate in order to improve the tribological properties of Ti-6Al-4V. Following conclusions can be obtained from the wear test results conducted using different counterface materials: (1) Duplex treated system sliding with different counterfaces was effective in maintaining a favorable low and stable coefficient of friction and improving the wear resistance of Ti-6Al-4V substrate. (2) For the wear tests sliding with steel balls, the transfer of materials from steel ball was one of the main wear mechanisms which affected the wear and friction properties. (3) For the wear tests sliding with alumina balls, the generation, compaction and graphitization of coating debris layer acted as a lubricating third-body and improved the friction property and wear resistance of the coating. (4) For the wear tests of titanium substrate sliding with UHMWPE pins, the severe abrasion process were found on both titanium and UHMWPE pin surface. With the application of the duplex treated coating system on titanium substrate, the coefficient of friction and wear volumes of two counterfaces were reduced significantly. Carbon nitride films were deposited on plasma nitrided Ti-6Al-4V substrate in order to improve the adhesion and tribological properties of Ti-6Al-4V. Following conclusions can be derived from the experimental results: 1. Compared with the CNX film deposited on Ti alloys, the adhesion strength of CN X film deposited on plasma nitrided layer was increased dramatically. 2. Plasma nitriding improved the friction property and wear resistance of Ti-6Al-4V but the formation of a thin and brittle compound layer was not effective in improving the friction property and wear resistance under high normal loads. 3. The duplex treated system was more effective in maintaining a favourable low and stable coefficient of friction and improving wear resistance than both individual plasma nitriding and individual CNX film. The reasons for this significant

26

improvement in tribological behaviours with the application of duplex treatment can be attributed to the combined benefits from both plasma nitriding and CN X films: (1) Duplex treatment provides an optimum chemical composition transition between plasma nitrided layer and carbon nitride films; (2) Plasma nitriding of Ti-6Al-4V produces a graded hardened case which serves as an excellent supporting layer for the hard CNX films; (3) The CNX films deposited at low temperature can produce a wear resistant and low-friction surface without impairing the beneficial effects of preplasma nitriding treatment; (4) Smooth and low friction CNX films could effectively reduce both the interface stresses and the stresses near the surface thus providing a good tribological behaviour; (5) With the application of CNX films on the pre-nitrided Ti-6Al-4V substrate, the adhesion strength increases dramatically, and therefore, the tribological properties can be improved significantly; (6) The graphitisation of the wear debris during dry sliding condition can help to decrease the coefficient of friction and improve the wear resistance. Carbon nitride films were deposited on plasma nitrided Ti-6Al-4V substrate in order to improve the load bearing capacity and tribological behaviour of Ti-6Al-4V. Following conclusions can be derived from the experimental results: (1) Compared with the CNX film deposited on Ti alloys, the load bearing capacity of CNX film deposited on plasma nitrided layer has been improved dramatically which can be obtained form both the indentation and scratch tests. (2) According to the scratch tests, the duplex treated system was effective in maintaining a favourable low and stable coefficient of friction and improving the wear resistance. Carbon nitride films were deposited on plasma nitrided Ti-6Al-4V substrate in order to improve the adhesion and tribological properties of Ti-6Al-4V. Following conclusions can be derived from the experimental results: 1. Compared with the CNX film deposited on Ti alloys, the load bearing capacity of CNX film deposited on plasma nitrided layer was increased dramatically. 2. Plasma nitriding improved the friction property and wear resistance of Ti-6Al-4V but the formation of a thin and brittle compound layer was not effective in improving the friction property and wear resistance under high normal loads. 3. The duplex treated system was more effective in maintaining a favourable low and stable coefficient of friction and improving wear resistance than both individual plasma nitriding and individual CNX film. This improvement in tribological behaviours with the application of duplex treatment can be attributed to the combined benefits from both plasma nitriding and CNX films. (1) Plasma nitriding of Ti-6Al-4V produces a graded hardened case which serves as an excellent supporting and load bearing layer for hard CNX films. (2) The CNX film deposited at low temperature can produce a wear resistant and low-friction surface without impairing the beneficial effects from plasma nitriding treatment, and the smooth CN X films could effectively reduce both the interface stresses and the stresses near the surface thus providing a good tribological behaviour. (3) The graphitisation of the wear debris during dry sliding condition can help to decrease the coefficient of friction and improve the wear resistance. 7.5 References 4. Y. Sun and T. Bell, Combined plasma nitriding and PVD treatments. Transactions

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of the Institute of Metal Finishing 70 1 (1992), pp. 3844. 8. Y. Sun, A. Bloyce and T. Bell, Finite element analysis of plastic deformation of various TiN coating/substrate systems under normal contact with a rigid sphere. Thin Solid Films 271 (1995), pp. 122131. 11. H.-J. Spies, B. Larisch and K. Hoeck, Optimisation of TiN hard coatings on prenitrided low alloy steels. Surface Engineering 11 (1995), pp. 319323. 12. H. Dong, Y. Sun and T. Bell, Enhanced corrosion resistance of duplex coatings. Surface and Coatings Technology 90 (1997), pp. 91101. 16. Bell, T. Sun, Y. Mao, K. and Buchhagen, P., Mathematical modelling of the plasma nitriding process and the resultant load bearing capacity. Advanced Materials and Processes, 1996, No. 4, 40Y40BB. 18. T. Bell, P. H. Morton and A. Bloyce, Towards the design of dynamically loaded titanium engineering components. Materials Science and Engineering A184 (1994), pp. 7386. 26. T. Bell and Y. Sun, Load bearing capacity of plasma nitrided steel under rolling sliding contact. Surface Engineering 6 (1990), pp. 133139. 1. K.G. Budinski , Tribological properties of titanium alloys. Wear 151 (1991), pp. 203217. 9. M.V. Stappen and M. Kerhofs , Introduction in industry of a duplex treatment consisting of plasma nitriding and PVD deposition of TiN. Surf. Coating Technol. 62 (1993), pp. 655661. 10. M. Bin-Sudin, A. Leyland, A.S. James, A. Matthews, J. Housten and B. Garside , Substrate surface finish affects in duplex coating of PAPVD TiN and CrN with electrodes nickelphosphorus interlayers. Surf. Coating Technol. 81 23 (1996), pp. 215224. 11. R. Damasscheck, S. LeRoux and H.W. bergmann , Improved adhesion of TiN deposited on prenitrided steels. Surf. Eng. 13 2 (1997), pp. 128132. 18. B.S. Yilbas, A.Z. Sahin, Z. Ahmad and B.J. Abdul Aleem , Study into corrosion properties of TiN coated and nitrided Ti6Al4V material. Corros. Sci. 37 10 (1995), pp. 16271636. 19. N. Dingremont, E. Bergmann, M. Hans and P. Collignon , Comparison of the corrosion resistance of different steel grades nitrided, coated and duplex treated. Surf. Coating Technol. 7677 (1995), pp. 218224. 23. I. Milosev and B. Navinsek , A corrosion study of TiN (physical vapor deposition) hard coatings deposited on various substrates. Surf. Coatings Technol. 63 (1994), pp. 173180.

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Wierzchon T, Surface engineering of titanium alloys: New prospective applications, Source: THERMEC'2003, PTS 15 Book Series: MATERIALS SCIENCE FORUM Volume: 426-4 Pages: 2563-2568 Published: 2003 2 Tribology International Volume 31, Issues 1-3, January 1998, Pages 127-137 Realising the potential of duplex surface engineering T. Bell, H. Dong and Y. Sun 3 Kessler O, Surm H, Hoffmann F, Mayr P Enhancing surface hardness of titanium alloy Ti-6AI-4V by combined nitriding and CVD coating, SURFACE ENGINEERING Volume: 18 Issue: 4 Pages: 299-304 Published: AUG 2002 4 Towards the design of dynamically loaded titanium engineering components T. Bella, P.H. Mortona and A. BloyceaMaterials Science and Engineering: A Volume 184, Issue 2, 15 August 1994, Pages 73-86
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Towards the design of dynamically loaded titanium engineering components T. Bella, P.H. Mortona and A. BloyceaMaterials Volume 184, Issue 2, 15 August 1994, Pages 73-86
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