24

Tribology of Diamond, Diamond-Like Carbon, and Related Films*
24.1 24.2 Introduction Diamond Films
Microcrystalline Diamond Films • Nanocrystalline Diamond Films • Tribology of Diamond Coatings • Tribological Applications

24.3

Diamond-like Carbon (DLC) Films
Background on DLC Films • Tribology of DLC Films • Applications of DLC Films

Ali Erdemir
Argonne National Laboratory

Christophe Donnet
École Centrale de Lyon

24.4 24.5

Other Related Films
Cubic Boron Nitride (CBN) • Carbon Nitride Films

Summary and Future Direction

24.1 Introduction
Diamond, diamond-like carbon (DLC), and other related materials (i.e., carbon nitride and cubic boron nitride [CBN]) are some of the hardest materials known and offer several other outstanding properties, such as high mechanical strength, chemical inertness, and very attractive friction and wear properties, that make them good prospects for a wide range of tribological applications, including rolling and sliding bearings, machining, mechanical seals, biomedical implants, microelectromechanical systems (MEMS), etc. The dry sliding friction and wear coefficients of these materials are among the lowest recorded to date (Brookes and Brookes, 1991; Feng and Field, 1991; Field, 1992; Miyoshi, 1995; Erdemir, 2001a,b). In fact, if they were inexpensive and readily available, they would undoubtedly be the materials of choice for a wide range of applications. Besides their exceptional mechanical and tribological properties, most of these superhard materials offer broad optical transparency, high refractive index, wide bandgap, low or negative electron affinity, transparency to light from deep UV through visible to far infrared, excellent thermal conductivity, and extremely low thermal expansion. Briefly, these exceptional qualities make diamond, DLC, and other related materials ideal for numerous industrial applications in addition to tribology.
* The submitted manuscript has been created by the University of Chicago as Operator of Argonne National Laboratory (“Argonne”) under Contract No. W-31-109-ENG-38 with the U.S. Department of Energy. The U.S. Government retains for itself, and others acting on its behalf, a paid-up, nonexclusive, irrevocable worldwide license in said article to reproduce, prepare derivative works, distribute copies to the public, and perform publicly and display publicly, by or on behalf of the Government. Work supported by U.S. Department of Energy, Office of Energy Research, under Contract W-31-109-Eng-38.

© 2001 by CRC Press LLC

The purpose of this chapter is to provide an overview of the tribology of diamond and related coatings that have attracted overwhelming interest in recent years. Emphasis is placed on the current state-of-theart of our understanding of the friction and wear mechanisms of these films as well as on their uses for demanding tribological applications. Referring to the structural and fundamental tribological knowledge gained during the past decade, this chapter emphasizes the importance of surface physical and chemical effects on friction and wear of these materials and describes new deposition procedures that can lead to the production of novel films that afford ultralow friction and very long wear life to sliding tribological interfaces. Tribological issues associated with metal cutting and contact sliding are also addressed. By referring to recent tribological studies, one observes that the surface roughness of these materials plays a major role in their friction and wear performance. Smooth diamond films obtained by polishing and by controlling grain size hold promise for future tribological applications, including mechanical seals and MEMS. The chapter is divided into three main subject areas. The first area is devoted to the synthesis, tribology, and applications of diamond films. The second deals with DLC films and their tribology; and the third is devoted to the tribology and applications of other related films such as CBN and carbon nitride.

24.2 Diamond Films
Natural diamonds are expensive and difficult to machine into useful wear parts for large-scale industrial applications. Except for a few cases (e.g., diamond-studded rotary drill bits, dressers, diamond-tipped glass cutters, and fine powders as superabrasives in grinding wheels), natural diamond is rarely used for tribological purposes. However, synthetic polycrystalline diamonds (PCDs) have been available for more than 30 years and they are widely used in many industrial applications. PCDs are produced in large quantities by a high-pressure/high-temperature (HPHT) method in which diamond is crystallized from a graphitic or carbonaceous precursor at pressures of 50 to 100 kbar and temperatures of 1600 to 2000°C. The end product is a fine diamond powder that is used mostly as a superabrasive in grinding and polishing media. The phase diagram in Figure 24.1 indicates the stability ranges of diamond, graphite, and other

FIGURE 24.1 indicated.

Carbon diagram in which the stability ranges of diamond, graphite, and other forms of carbon are

© 2001 by CRC Press LLC

forms of C. It is possible to sinter these diamond powders with metallic or ceramic binders (e.g., Co, Ni, TiC, etc.) at high pressures and temperatures and then use them as tool bits or sharp blades in metalcutting or machining operations.

24.2.1 Microcrystalline Diamond Films
The prospects for inexpensive and large-scale production of diamond increased tremendously in the 1970s, when researchers discovered that diamond can be grown as a thin film at low deposition pressures (102 to 103 Pa) from a hydrocarbon/hydrogen mixture by chemical vapor deposition (CVD). Early attempts to produce diamond by CVD date to when HPHT synthesis of diamond was being explored. The tube oven experiments of Eversole (1962) and Angus (1994) and low-pressure synthesis of diamond from hydrocarbon gas mixtures by Deryagin and Fedoseev (1975) and Fedoseev (1994) can be regarded as the earliest attempts to produce synthetic diamond by CVD. In fact, Eversole of Union Carbide was able to produce diamond phases by a thermal pyrolysis method in 1962 (Eversole, 1962). Progress slowed thereafter until Angus of Case Western University found a more efficient method in which graphite is etched simultaneously with atomic H in the deposition system (Angus, 1994). His work motivated Deryagin and co-workers to focus on the uses of H/hydrocarbon mixtures for low-pressure diamond growth (Deryagin and Fedoseev, 1975). Since these studies, there has been an explosion in research on diamond and related materials, with the expectation that low-pressure methods will allow faster, less expensive, and easier production of synthetic diamonds. During the past 2 decades, great strides have been made in both the production and industrial applications of diamond films. At present, several techniques can be used to produce high-quality diamond films with micro- and nanocrystalline structures at fairly high deposition rates over reasonably large surface areas (Banholzer, 1992; Gruen et al., 1994; Hatta and Hiraki, 1998; Komplin and Hauge, 1998). The most widely used methods are plasma-enhanced CVD, hot-filament CVD, microwave CVD, DC-arc jet, combustion flame, and laser-assisted CVD (Haubner and Lup, 1992; Anthony, 1992; Butler and Windischmann, 1998). These methods have greatly reduced the unit production cost of diamond and increased the prospects for large-scale industrial applications in tribological and other fields. In fact, several commercial companies now offer diamond-coated products at reasonable cost. The high-quality diamond coatings produced by CVD methods exhibit most of the desired mechanical and tribological properties of natural diamonds (Field, 1992; Miyoshi, 1995; Lux et al., 1997). Low-pressure synthesis of diamond coatings involves the use of hydrogen (H) and methane (CH4) gas mixtures. Typical deposition pressures in these syntheses are 102 to 103 Pa, and the gas mixture primarily consists of H and very little CH4. In the case of microwave CVD, 0.5 to 5% CH4 is mixed with H gas and introduced into the deposition reactor. Small amounts of O and N can also be blended. In the case of microwave CVD, a 2.45-GHz power source is used to initiate and maintain a gas discharge plasma in which the substrate material is immersed. At very high plasma temperatures, electrons intensely interact with the H-rich gas mixture, and the ionic species that are created during this interaction lead to the formation of diamond nuclei on the surface of a suitable substrate (i.e., Si, SiC, W, Mo). Plasma conditions in deposition reactors are tailored to control the film microstructure and chemistry, as well as growth rates and orientation. Typical substrate temperatures for high-quality diamond deposition can range from 700 to 1000°C. Deposition of diamond at temperatures below 700°C has also been demonstrated but growth rates are reduced significantly and the amount of non-diamond precursors in these coatings is increased (Hatta and Hiraki, 1998). Hydrogen is extremely important for the synthesis of high-quality diamond coatings in most CVD processes. It plays a critical role in the stabilization of the sp3 bond character of the growing diamond surfaces. It also controls the size of the initial nuclei, dissolution of C and generation of condensable C radicals in the gas phase, abstraction of H from hydrocarbons attached to the surfaces, and production of vacant surface sites where sp3-bonded C precursors can be inserted. It etches most of the double or sp2-bonded C from the surface, and thus hinders the formation of graphitic and/or amorphous C (Banholzer, 1992). Hydrogen also continuously etches out the smaller diamond grains and suppresses

© 2001 by CRC Press LLC

new methods have been developed for the deposition of finegrained or nanocrystalline diamond (NCD) films with a very smooth surface finish. The soot is heated to 200°C under vacuum for 2 h to remove residual gases and hydrocarbons.2 Nanocrystalline Diamond Films The very rough nature of the above-described microcrystalline diamond films renders them useless for most tribological applications. a higher than normal C:H ratio is used in a microwave plasma.3 shows the surface morphology of a rough microcrystalline diamond film before and after laser polishing. and thermomechanical polishing with hot Fe or Ni plates (Zaitsev et al. As these nuclei grow larger. Grains with more favorable growth orientation grow most quickly and overshadow the grains with less favorable growth orientation.. Hogmark et al. the most widely used methods. The measured Raman © 2001 by CRC Press LLC . To ensure that C60 is transported into the chamber. or a DC bias is applied to the substrates (Hollman et al. Cappelli et al. 1998... substrate temperature. Thereafter. Ramesham and Rose.4 is attached. it may be necessary to remove large amounts of material before a smooth surface is obtained. As demonstrated by numerous investigators. Bhushan et al. Grains with less favorable growth orientation will be buried between the large grains. and final growth stages of a diamond film on an Si substrate. Erdemir et al. Depending on the polishing method.. Deposition of NCD coatings has also been achieved by microwave CVD in the near absence of H. 1994. 1994. 1998.2 shows initial.continuous renucleation. Pimenov et al. In these methods. Gupta et al...c). Only those grains that attain a certain critical ratio of bulk-to-surface atoms survive. the polishing processes are tedious. The methane fraction in the source gas. 1993. Consequently. 25 nm. an Si wafer is placed in front of the transport tube while maintaining a 14-sccm Ar flow. 1994.4.. 1998. Argon gas is passed through the transpirator to carry the C60 vapor into the plasma. 1996. Recently. Figure 24. The source gas consists of mostly Ar. mechanical lapping with fine diamond powders. rms). Erdemir et al. 1996). 1998. 1998). allow polishing of large areas.. With the reactor pressure at 100 torr and the transpirator at 600°C.. the growth process and growth rates are dominated by nearby neighbors and growth orientation. such rough coatings cause high friction and very high wear losses on mating surfaces. 1996b...2. and substrate pretreatment were also shown to exert a strong effect on the crystallinity and grain size of these films (Gilbert et al. intermediate. During the initial stage of film growth. time-consuming.. The tube furnace and transport tube are heated to between 550 and 600°C to sublime C60 into the gas phase. and. 1997a. a 1. Although growth rates are somewhat reduced and the amount of non-diamond phase is somewhat increased... 1996).7-mg brown film was deposited on the wafer in 1 h. Fullerene-rich soots that contain ≈10% C60 are placed in the transpirator.. independent nuclei form. 1994. Hogmark et al. The generally rough surface finish of these coatings precludes their immediate use for most tribological applications. 1993. The film displayed only strong C60 infrared absorption features. 1997a. 24. when used in sliding-wear applications. ion-beam or plasma etching.e. in the case of complex geometries. Bhusari et al. Erz et al.. Mechanical lapping and polishing with hot Fe plates. High-quality microcrystalline diamond coatings are rough and often nonuniform in thickness or slightly bowed because of internal stresses and differences in deposition rate from the edges to the center of the samples. The rough diamond coatings can be polished by laser beams. Figure 24. the polished diamond coatings can provide friction coefficients comparable to that of natural diamond (Erdemir et al. Gruen. Pimenov et al. However. 1998. 1995. To introduce C60 into the reactor. The CVD reactor used in this process is essentially a modified version of a conventional microwave CVD reactor. with either C60 or CH4 as the C precursor (Gruen et al. Bhushan et al. As discussed in detail later. Gupta et al. 1996). Depending on the desired film thickness or the degree of original roughness. a quartz transpirator. they close the gaps between them and merge to form a continuous film. details of which are schematically depicted in Figure 24.. Zuiker et al. these diamond coatings consist primarily of large grains with highly faceted surface finishes that exhibit a surface roughness value of ≈10% of the film thickness. 1998.. also shown in Figure 24. eventually. the surface finish of the resultant coatings is very smooth (i. highly impractical. nucleation starts at preferred sites.. one can achieve mirror finish surfaces with an rms surface roughness of 10 nm or less..

Film growth is monitored in situ by laser reflectance interferometry to determine growth rate and to stop growth at the desired film thickness. The substrate temperature can vary between 700 and 950°C. sintered SiC.2 (a) Initial. with CH4 instead of C60 as the C source. (b) intermediate. WC. and (c) final growth stages of a microcrystalline diamond film produced in a microwave CVD reactor. etc. Initially. Based on these measurements.FIGURE 24. The NCD coatings can also be grown under similar low-Hcontent conditions. a bias of –150 V is applied to enhance diamond nucleation density. Si3N4. The NCD coatings can be grown on various substrates. and © 2001 by CRC Press LLC . the transpirator is considered an effective source of C60 for diamond growth. spectrum was also attributable to C60. including single-crystal Si wafers. W.

. Feng and Field. 2% H2. 1951.3 Surface morphology of a rough diamond film (a) before and (b) after laser polishing. A typical gas composition for NCD diamond film can be 97% Ar. Miyoshi et al.33 × 104 Pa and a microwave power of 800 W. Figure 24. Hayward and Field. 1981. However. and 1% C60 or CH4 at a total pressure of 1. 1992. Bowden and Young. 1966. The growth mechanism of NCD differs radically from that of a microcrystalline diamond film. Specifically. Bowden and Hanwell. Gardos 1994. Enomoto and Tabor. Tabor. diamond provides some of the lowest friction coefficients to sliding tribological interfaces when tested in open air. Chandrasekar and Bhushan. 1979. 1994).4. Kohzaki and Noda. 1950. 1964.FIGURE 24. Most previous studies have confirmed the finding that the friction coefficient © 2001 by CRC Press LLC . 1993.2. The resultant coatings are phase-pure NCD. The C dimer growth mechanism is unique in that it is capable of producing a continuous diamond coating that can be as thin as 30 to 60 nm. 1998). with an average grain size of ≈15 nm. 1992. 24. extraction of a C dimer (C2) from C60 and CH4 molecules and its subsequent insertion into the diamond surface has been proposed for the growth of these coatings (Gruen.5 shows atomic force microscopy (AFM) and scanning electron microscopy (SEM) images of the surface of an NCD film produced by the method depicted in Figure 24. the total gas flow rate is ≈100 sccm. 1987. recent fundamental studies have confirmed that there are several factors that can adversely affect the friction and wear performance of bulk diamond and thin diamond films (Bowden and Tabor.3 Tribology of Diamond Coatings In addition to being the hardest material known to mankind. This combination of extreme hardness (and hence wear resistance) and ultralow friction in one material is very rare in the field of tribology and it renders diamond ideal for a wide range of tribological applications.

In particular. Specifically. and Fenske. and Chandrasekar and Bhushan (1992) has confirmed that the presence or absence of surface contaminants in the test chamber © 2001 by CRC Press LLC . C. and hence lead to reduced adhesion and/or friction.) of bulk diamond sliding against itself in open air is 0.C. Erdemir. 1992). it is now possible to visualize and better understand the extent of chemical. physical. This hypothesis for the low-friction mechanism of diamond has existed for a long time... Thin Solid Films. or solid third-body and/or transfer film on the sliding surface.R.1 Early Studies Early tribological studies have led to the conclusion that the low-friction property of diamond is largely due to the highly inert or very passive nature of its sliding contact surfaces (Bowden and Young.05. A. (1993).4 Schematic illustration of a modified microwave CVD reactor used for deposition of nanocrystalline diamond films. liquid.g.02 to 0. 270. Bindal. Gardos and Ravi (1994).. J. Dugger et al... the friction coefficient of diamond increases by more than 1 order of magnitude (Hayward and Field. and the presence or formation of gaseous. Krauss. D. G. R. surface roughness. 1993.3. Li. can attach to and effectively passivate the dangling σ-bonds of diamond surfaces. with the advent of new experimental tools (e.. Gaseous adsorbates in the surrounding atmosphere. C. X. 1992. Chandrasekar and Bhushan. However.M. In addition to the early studies that were performed at micro-to-meso scales. 154-159. 1966). and mechanical events that occur at atomic or molecular levels and hence gain a better understanding of the mechanisms that govern the friction and wear behavior of diamonds. it has been proposed that the low friction of diamond was associated with the lack of adhesive forces between sliding diamond surfaces. Dugger et al. (1992). Miyoshi et al.2.. More recent work by Gardos (1999). Pan. Gruen. recent fundamental tribological studies at atomic-to-nano scales have greatly increased our understanding of the influence of each of the above-mentioned factors on friction and wear of diamond. or water molecules. 1951. Some of the other factors that influence the friction and wear behavior of diamond are contact pressure.g. crystallographic orientation. Csencsits. Bowden and Hanwell.. 1987. (From Zuiker. AFM) and computer simulation methods (e. (1995). Miyoshi et al.. A.. molecular dynamic simulation)... when tested in ultrahigh vacuum (UHV) or at high temperatures. With permission. Physical and tribological properties of diamond films grown in argon-carbon plasmas.FIGURE 24. 24. such as H. O.

Molian et al. 1982. mainly because surface contaminants are desorbed or mechanically removed from the sliding surfaces and hence are not available to passify the dangling σ-bonds of the sliding diamond surfaces.3. 1993)... Gaseous species in the surrounding air such as water molecules. for example.2 Friction and Wear Mechanisms Carbon atoms in bulk diamond crystals are held together by strong covalent bonds in a tetrahedral bond configuration.. 1996. However. 1997. the extent of adhesion and hence friction between sliding diamond surfaces is drastically reduced. Knowing the critical role that dangling bonds play on friction.FIGURE 24.6) (Holmberg.. 24. sliding diamond surfaces always exhibit high friction and wear. makes a huge difference in the friction and wear performance of bulk diamond and/or thin diamond films.5 (a) AFM and (b) SEM images of the surface morphology of nanocrystalline diamond film produced by microwave CVD in Ar-C60 plasma. When dangling bonds are tied up and passivated. O. 1998.. and H. C atoms on diamond surfaces can only establish three covalent bonds with their near neighbors. Recent fundamental studies have shown very clearly that. can chemisorb and effectively passivate these dangling surface bonds (Figure 24. F atoms.. while the fourth bond is left open and dangling out of the surface. 1994.2.e.. Derry et al. Pate et al. researchers have developed more effective means to passivate them with. The extent of interaction between passive diamond surfaces that are sliding against each other drops to the level of very weak van der Waals attractions. When tested in ultraclean and ultradry test environments (i. UHV) or at high ambient temperatures. Wei et al. Smentkowski et al. the friction coefficient increases © 2001 by CRC Press LLC . 1983. and have thus achieved extremely low friction and wear coefficients for bulk diamond and diamond films (Miyake et al. 1995). when adsorbed gases are removed from the sliding surfaces of diamond by thermal desorption at high temperatures.

Dugger et al. K. 1992). number of sliding passes for a CVD-coated SiC pin sliding against a CVD diamond-coated Si wafer in air and UHV environments. The repassivation of dangling bonds by atomic or molecular adsorbates during cooling or exposure to gaseous species causes reduced adhesion and hence low friction.6 UHV µ 0. American Chemical Society. as shown in Figure 24. finally. Tribology of diamond and diamond coatings — A review. and Pope. Figure 24.7 Friction coefficient vs. G.E. 52% RH 500 Cycles FIGURE 24. in Surface Science Investigations in Tribology. presumably because of the repassivation of the dangling surface bonds. the friction coefficient drops precipitously.M. Conversely. With permission.Dangling bond orbital Free electron Shear plane -C-C-C-C-C-C-C-C-C-CI I I I I I I I I I H H H H H H H H H H H H H H H H H H H H I I I I I I I I I I -C-C-C-C-C-C-C-C-C-C- C C C C C C C C C FIGURE 24. 1994.8 0. Tribologia. L. 72-102.4 0.-W. As summarized in a recent review article by Gardos (1999).6 Schematic illustration of dangling surface bonds of diamond and weak shear plane between hydrogenterminated diamond surfaces.B. © 2001 by CRC Press LLC .. 55% RH 1. or O). Experimental Approaches.. 12. reconstructed diamond surfaces provide relatively reduced friction and. 33-62. However..C. 1992). Specifically. H.. (1992). presumably. E. if the surface of diamond is exposed to gaseous contaminants or open air again.7 (Dugger et al. Homolo.0 0. ACS Symposium Series 485.. Most of the vacuum tribological studies on diamond were performed by Gardos and co-workers. by atomic or molecular adsorbates such as H2O. (From Dugger. (From Holmberg. (1998).e..) rapidly. Using an SEM tribometry test device.. the dangling surface bonds are reactivated and are available to form strong adhesive bonds with the surface atoms of the counterface materials (Gardos.). Chung. the incipient linking of the sliding diamond surfaces by totally unsaturated dangling bonds (created by thermal desorption) causes the highest friction.8 illustrates the frictional behavior of diamond films in the passive. With permission. D. D. Counterface material and ambient atmosphere: role in the tribological performance of diamond films. Peebles. and Street. their studies show that the lowest friction is achieved under conditions where complete passivation of dangling bonds of diamond surfaces is feasible (i.2 0 100 200 300 400 air.. (Eds. their studies provide circumstantial evidence for the effect of surface dangling bonds on friction (in the absence of shear-induced phase transformation and/or graphitization). A.) air. Y. Washington. they have explored the effects of surface chemistry-induced changes on friction and wear of self-mated sliding diamond surfaces as a function of ambient temperature.

Johnson et al. open air. and Erdemir et al. 1990. surface adsorbates begin to desorb and leave some of the dangling surface bonds exposed and available for strong adhesive interactions. 1997b). However.FIGURE 24.. bulk diamond and thin diamond films tend to gradually oxidize and transform to graphite in open air (Erdemir et al.. (From Gardos. (1999). in inert test environments or under high vacuum. With permission. It has been shown that surface roughness profoundly influences the friction and wear performance of thin diamond films. As demonstrated by Casey and Wilks (1973). In addition to the effects of surface chemistry and/or environment. Bhushan et al.. but relatively high friction in dry. which largely control the adhesion component of friction. Erdemir et al. As mentioned above. as the temperature increases. 1994. or vacuum environments (Gardos et al. Tribological fundamentals of polycrystalline diamond films. high levels of structural defects. 1990). Technol. they tend to oxidize at relatively lower temperatures (Tankala.. 1996d. room temperature.) active. and the surfaces of diamond films begin to act like graphite.. they give low friction in moist air. (1993). For example. 1997. higher surface roughness leads to higher levels of vibration and. Coat. low velocity). Apparently. Miyoshi et al. The oxidation behavior of diamond films is also similar to that of natural diamond but. 1999). As the extent of adhesive interactions increases. Erdemir et al. a few studies have indicated that micrographitization of sliding diamond surfaces can occur at high temperatures or at high sliding velocities. (1992). the effects of crystal orientation and surface roughness on friction and wear of diamond have also been studied rather extensively in previous years.N. When tribotested at elevated temperatures. high friction. Recent systematic studies by Hayward (1991). Surf.. diamond may experience some wear by shear or ambient-induced phase transformation. Gardos and Ravi.. inert. bulk diamond and thin diamond film hardly wear under normal sliding conditions (i. (1996b) further confirm the results of above-mentioned studies © 2001 by CRC Press LLC .e. and Samuels and Wilks (1988). Briefly. and film thickness. However. Natural diamond is chemically very stable and does not appreciably oxidize until the temperature reaches 600°C. growth orientation. 113. hence. grain size.7 until some of them reconstruct and reduce the extent of adhesion and hence friction. and Hayward et al. the extent of interaction between sliding-surface asperities of diamond may contribute to the amount of total energy being dissipated in the form(s) of phonons and/or vibrations. Kohzaki et al. under certain test conditions. the friction coefficient increases sharply and reaches values ≈0. diamond films are not suitable for use at high temperatures in open air. 183-200. Because of its extreme hardness. Among all of the surface adsorbates. H provided the lowest friction (Gardos and Gabelish. 1992). (1993).. depending on deposition conditions. that is. In general. diamond films are more stable and do not undergo oxidation or graphitization. 1997c. because they contain some non-diamond phases. and reconstructed regimes of sliding. the surface rms roughness of synthetic diamond films can vary from 10 to >1000 nm. and grain boundaries. M.8 Variation of friction coefficient of CVD diamond films sliding against themselves in vacuum at temperatures to 850°C.

.. 1992..M. Appl. Yee et al. Wolter et al. and Konov. eventually. 1991. Malshe. Tribological properties of polished diamond films.. and Gruen. Y. (1997c). researchers have developed special procedures to control growth orientation and. Blau et al..).. (1997a).. Subramanian.. sliding contact largely occurs between the transferred and original material of the non-diamond counterfaces.9).03 (for ultra-smooth nanocrystalline or polished diamond films) to >0. diamond-against-diamond or diamond films give lower friction than diamond-against-nondiamond counterfaces (Hayward et al. the steady-state friction and wear are largely controlled by the extent of surface roughness of the sliding diamond side and by the tendency of the counterface material to form a transfer layer (Hayward et al. Fine debris particles can easily fill in the valleys between sharp asperities of diamond films and. 1997a. C. 1997b).. the surface roughness of diamond films. 1992. or ceramic counterfaces. Tribol. Erdemir. 1995.. 4178-4185... 1993).. V. 1996).. Erdemir. Conversely. 537-541. Krauss.. Fenske. Halter. Usually. 74. A. Vol.9 Relationship between rms surface roughness of CVD diamond films and their friction coefficients. and Ruan. 667-673. and Barna. Erdemir et al. A.M..M. (1993). B.. Films with large grains and highly faceted surface finish usually cause high friction and wear (Hayward...I. when polished or NCD coatings are used in sliding-contact experiments.R. Coat. Technol. R.FIGURE 24. J.. P.. the friction coefficients are initially low but go up significantly as sliding continues (Miyoshi et al. A. Kluwer Academic. 1999. 21.. Csencsits. London. Reported friction values typically range from 0. Gruen. hence. Gangopadhyay et al. but decreases substantially as sliding continues in open air.5 (for very rough microcrystalline films). Miyoshi et al. V. Krauss. B. Erdemir et al.. 1993.. Miyoshi et al.. (Eds. Surf. 94/96. D... 1997. The trend appears to be the opposite during tests in UHV environments where. in Protective Coatings and Thin Films: Synthesis. The type of counterface material used during friction tests also makes a substantial difference in the measured friction coefficients of bulk diamond and/or diamond films. regardless of the counterface materials. Pimenov. Erdemir. When bulk diamond or diamond films are slid against relatively softer metals. (1997b). NATO ASI-High Technology Series. Characterization and Applications..K. Fenske... and Wilbur.. With permission. Friction and wear mechanisms of smooth diamond films during sliding in air and dry nitrogen. M.. Rougher diamond surfaces usually cause greater plowing and abrasive wear on the softer metallic or ceramic counterfaces and also facilitate the transfer of worn debris particles to its sliding surface. Halter.V. Fenske. Zuiker.R. S. Durability and tribological performance of smooth diamond films produced by Ar-C60 microwave plasmas and by laser polishing. alloys. Erdemir et al. Previous research has demonstrated that growth orientation of microcrystalline diamond films can significantly affect friction and wear. Gupta.) in that the diamond films with high surface roughness always lead to high friction and wear. 1993) (Figure 24. Wolden et al. 〈100〉 type growth orientation is very desirable and can be achieved by controlling deposition conditions and by pretreatment of the substrate surfaces (Yee et al. 1990. very low friction coefficients are attained (Erdemir et al.. Pauleau. From a tribological standpoint. In all cases. M. 1997.. 169-184. friction tends to be higher initially. Trans. 40. G..R. J. (Data from Bhushan. 1996b).. In recent years. A. D. G. A. High-temperature durability and tribological performance of diamond and diamondlike carbon films. Diamond films with coarse © 2001 by CRC Press LLC . G. A. 1993). B. Phys.

1997). Phase transformation can readily occur even in natural diamond (see Gogotsi et al.1. 1996b). Gardos and Ravi.R. 735-741. whereas the friction coefficient of the film with 〈111〉 growth orientation and micropyramidal asperities remained high and unsteady but continued to decrease steadily during successive sliding passes..FIGURE 24. despite relatively higher measured surface roughness. diamond can transform to a graphitic form (Lee et al. With permission. and Wilbur. P.. G. 1994. Real contact occurs first between these asperities.. (From Erdemir. Erdemir et al. It is also known that when excited thermally or by ion bombardment.. graphite is the most stable form of C. Fenske.. The friction coefficients of the film with 〈100〉 growth orientation stabilized at ≈0. Tribological properties of hard carbon films on zirconia ceramics. Thermodynamically.. Figure 24.) grains and 〈111〉 type growth orientation tend to be very rough and can cause severe abrasive wear (Erdemir et al. These films were grown in an H2/CH4 plasma. © 2001 by CRC Press LLC . If a favorable 〈100〉 growth orientation is present. 39. The high friction coefficients of rough diamond coatings with 〈111〉 orientation can be attributed to the abrasive cutting and ploughing effects of sharp surface asperities on the softer counterface pins. diamond coatings with a smooth surface finish provide very low friction to sliding counterfaces. The graphitic debris particles can gradually accumulate at the sliding contact interface and then begin to dominate the long-term sliding friction and wear performance of these coatings. A. The extent of such changes can be dominated by environmental species or by ambient temperature (Jahanmir et al. such coatings can also afford low friction coefficients to sliding surfaces. C. (1996a). whereas diamond is metastable. Apart from physical roughness and chemical passivation effects. phase transformation or structural changes can also play a major role in the friction and wear performance of diamond coatings..10 Friction coefficients of Si3N4 balls sliding against diamond films with 〈111〉 and 〈100〉 type growth orientations. In general. Bindal. 1989. 1998) when extreme contact pressures and/or high frictional heating are present at local asperity levels. the friction coefficients of both coatings decreased.. Tribol.1993). After an initial run-in period. previous studies confirmed that regardless of the grain size.. and their tips can either fracture or undergo phase transformation because of the extreme pressures and high frictional heating. Trans.10 shows the frictional performance of two films with 〈111〉 and 〈100〉 growth orientation.

Some of the major reasons for the slow progress in large-scale utilization of diamond coatings are high fabrication cost. great strides have been made in the deposition. which represent the largest segment of industrial machining.3 Tribology of Diamond at Nanoscale Recent fundamental studies on nanometer and molecular scales with new experimental tools (e. and excellent environmental compatibility. molecular dynamics simulation) have allowed friction studies on very fine scales (Mate. 1994). others have been fully established and are offered on a commercial scale. 1992a. ambient temperature..to mesoscale studies. Our fundamental understanding of the structure.. and quartz crystal microbalance) and computational methods (e. 1993. Recent laboratory and field tests confirm that these coated tools provide much improved performance during metal-cutting operations by allowing high-speed machining at increased feed rates. and customize new diamond coatings that can meet the increasingly stringent needs of advanced tribological applications. Harrison and Brenner. 1995). properties. in which standard tribology test machines were used. VIIa. 1994.2. VIa. and slow growth rates. For example. Ravi. electron diffraction. Also. Germann et al. etc. 1993. Diamond can chemically react with and/or dissolve in these materials at the high temperatures generated during machining. molecular dynamics simulation has provided significant insight into the extent of physical.. 1995.g. or solid debris particles that are present or generated at the sliding diamond interfaces play critical roles in the friction and wear of diamond. excellent resistance to abrasion.) are offered commercially by several industrial manufacturers. (1989) revealed that most of the debris particles derived from sliding diamond surfaces exhibited a graphitic microstructure. 24. low friction. erosion. high surface roughness of finished products.3. and gaseous. Superhigh-speed computers with high memory and processing capability have allowed simulation and real-time visualization of atomic-scale phenomena that occur at sliding diamond surfaces. Thus far.4 Tribological Applications Over the years. tab tools. and corrosion. liquid. high deposition temperatures. Va.g. 1994. 1993. Raman spectroscopy.Previous research by Erdemir et al. push pins. limitations on the type and size of substrate materials.b. Lux and Haubner. and VIIIa of the Periodic Table. Harrison and Brenner. and mechanical interactions that occur at sliding diamond interfaces on the atomic scale. friction increases rapidly.. characterization. Bhushan. surface force apparatus. oxidation when used at elevated temperatures. 1993. high thermal conductivity. diamond coatings cannot be produced on the surfaces of tools that are made of materials such as high-speed steels. 24. high chemical inertness.. chemical. Despite a large discrepancy in time and length scales. In particular.. and thus it wears out rather quickly. Murakawa. Miyake et al. While some uses are still in the exploratory stage and require further development. results from fundamental nanoscale experimental studies are consistent with those from earlier micro. Some of the advantages that diamond provides in these applications include extreme hardness and wear resistance.g. cutting tools (e. 1998. 1997). © 2001 by CRC Press LLC . EELS.. These studies have greatly increased our fundamental knowledge base of the tribology of diamond. and industrial utilization of diamond films (Seal. because the dangling surface bonds are free and highly activated to form strong bonds across the sliding contact interface (Harrison et al. design.2. The current market share of diamond-coated cutting tools is relatively small. which are widely used in the tooling industry. inserts. For the most part. it was shown that when adsorbed gases are removed from sliding diamond surfaces. and transmission electron microscopy have concurrently confirmed the presence of highly disordered graphitic debris particles at sliding contact interfaces (Erdemir et al. somewhat poor adhesion. Harrison et al. good fatigue strength. The nanoscale studies have revealed that surface adsorbates. friction force microscopy. and the widespread utilization of diamond coatings in other tribological fields has not yet been fully realized. (1997b) and Jahanmir et al. insufficient reliability and reproducibility. 1997b). microdrills. Diamond-coated tool inserts cannot be used to machine pure Fe and Fe-base materials and the alloys of groups IVa. end mills. 1992a.. and performance of these coatings has increased tremendously in recent years and this understanding has been used to optimize.

and various wear parts that are used against erosion and abrasion (e. Other potential applications for diamond coatings include sliding bearings. Finally. Si. MEMS. Subsequently..2.diamond films can only be deposited on certain refractory metals (e. edge chipping or deterioration due to easy cleavage of highly oriented needle-like diamond grains of CVD diamond films can occasionally occur and limit the lifetime of the coated tools.g. © 2001 by CRC Press LLC . and it can be prepared in any style or geometry to provide better efficiency and overcome limitations on depth of cuts — always a problem with brazed tool bits. diamond-coated tools are primarily used in the machining of nonferrous metals. the shape and area of a coated carbide insert can be prepared in such a way that it will allow better chip handling and breaking capability than the very small brazeable diamond tips.. jet nozzles). 24. 1998) have also been demonstrated.. 0. WC.e. W and Mo) and a few ceramics (e. their large-scale utilization has not yet been realized because of high fabrication costs and insufficient reliability in actual operation. As a last step. Hollman et al.. Among others. whereas the brazed diamond tips come in a strict geometric form and cover only the sections of the sharp tips of tool inserts. and composite materials that are inherently very difficult to cut or machine. fine diamond powders are first sintered into the shape of a tool tip and then brazed directly onto the cutting edges of the tool inserts.11 Cutting-edge morphology of a CVD diamond-coated tool insert. As mentioned above.11 shows the morphology of the cutting edge of a diamondcoated tool insert. Although prototypes of other tribological parts (e. Second. the entire functional surface of a tool insert can be coated with diamond. Specifically.5 to 1 mm thick) diamond film on an Si wafer from which small bits are laser-cut into a desired cutting-edge shape. the Si substrate is etched out and the cut diamond tips are recovered.4. SiC. Figure 24. wire-drawing dies. mechanical seals. and Si3N4) that can endure the high deposition temperatures of the CVD process. The second form is based on the CVD of a relatively thick (i. The third form is the direct deposition of diamond onto cutting tools by various CVD methods. First. There are some fundamental differences between brazed and coated diamond tool bits.g. However. In particular.g. the freestanding diamond tips are bonded or brazed onto the cutting edges of the tool inserts or end mills.. diamond FIGURE 24. One is based on the use of synthetic diamond powders produced by HPHT methods. alloys.1 Industrial Machining Diamond has been used for machining purposes in three distinct forms.g. CVD diamond coatings perform equally well or even better than PCD diamonds in cutting and turning operations. diamondcoated tools can be tailor-made to meet the specific machining needs of an application.. WC-based tools have been coated successfully with diamond and made available for commercial machining.

diamond is brittle and will readily fracture.g. 1998). HCl. Inspektor et al. Higher Co contents can adversely affect the adhesion of diamond coatings to carbide inserts. Several methods are used by industry to remove surface Co from cemented carbide tool inserts. very high compressive stresses can build up at the interface region. WC-Co). diamond coatings are primarily produced on WC-Co-based cemented carbide tool inserts. 1996). Karner et al. Co serves as a binder and controls the toughness of these materials. fiberreinforced plastics. researchers have heat treated WC-Co substrates at very high temperatures for an extended period of time in a protective © 2001 by CRC Press LLC . 1993. engine blocks and heads. 1997. the selection and pretreatment of the substrate materials are extremely important for achieving strong adhesion between the diamond coating and the substrate material. green ceramic. mainly because of their light weight. premature adhesive failures can occur at or near the cutting edges. 1998). and these stresses can significantly affect the film/substrate adhesion (Olson and Dawes. The major applications for Al-Si alloys include pistons. during deposition at high temperatures. Pb. Some of the chemicals that have proved to be effective in etching Co are HNO3. such as film thickness. Other factors. hence. In particular. 1994. epoxy resins. Other engineering materials suitable for machining by diamond-coated tools include alloys of Mg. The increased use of lightweight materials in the automotive industry is likely to continue and. as well as various composites (e. Cappelli et al. Shen.has been the material of choice for machining of high-Si-content Al alloys for automotive applications. plastics. bulk graphite. the coatings will not stick to the tools (Menningen et al. and various mining and rock-drilling operations (Kubel. It also slows the nucleation process and reduces nucleation density. Co can play a catalytic role in the formation of non-diamond phases and complex Co carbides that are highly undesirable. mainly because of their excellent toughness. film roughness. diamond coatings can easily be removed from the cutting edges. Hypereutectic Al-Si alloys are increasingly being used in this industrial sector. concrete. especially when forced in the direction of relatively weak columnar grains. Diamond coatings are often deposited at high temperatures. Most of the methods involve selective etching of Co by chemical means. and they must be considered along with the residual stresses whenever the quality of a diamond coating is evaluated. and substrate grain size. fiberglass composites. Trava-Airoldi et al. In principle.. long wear life. during cooling. Currently. a low Co content (<5%) in cemented carbide is highly desired. hence. the selection of the correct types of WC-Co material is a must for achieving strong bonding and. In one case.. wheels and chassis. relatively high strength. Lux and Haubner. Keipke et al.e. Cu. otherwise. Komanduri and Nandyal. 1998. or blister and thus destroy the entire structure. In addition to strict process control during deposition. If bonding is not intimate and strong... premature delamination of the diamond film in early trials represented the biggest challenge and most common mode of tool failure.. and high resistance to wear (Deuerler et al. Two other problems can occur when diamond films are used in machining operations. When these stresses are combined with the stresses associated with cutting action. the need for diamond-coated tools will increase. The presence of a high stress in the coating can lead to various undesirable failure modes that can cause the film to delaminate. Despite its extreme hardness. Specifically. Briefly. substrate preparation. Interfaces with a high proportion of non-diamond phases and low nucleation density suffer from poor adhesion. and metal-matrix composites). 1998. also affect film/substrate adhesion. Prengel et al. 1998. 1996. Too much Co can also increase the difference in thermal expansion coefficient between diamond and substrate. and CH3COOH. and high-temperature durability. Gunnars and Alahelisten. Another key application for diamond coatings is in woodworking tools. 1998. 1996).. In fact. the other is fracture or chipping.. C-C composites. One is oxidation. and some transmission parts. Residual stresses are inherent in all CVD-diamond coatings. crack. They are then rinsed and ultrasonically cleaned in ultrapure water for 5 min.. hence. 1998.. 1998. 1996. hardness. which thus lose their cutting performance and effectiveness. it is important to use carbide substrates with low Co content or to etch the Co out completely from the near surface.. The most important factor that governs the success of a diamond-coated tool insert in cutting operations is strong bonding between diamond coating and substrate insert (i. tool inserts are dipped in a nitric acid and water solution (mixed 1:1 by volume) and ultrasonically agitated for 15 min. In another case. 1996.. and a large mismatch in thermal-mechanical properties between the diamond coating and the underlying substrate leads to large compressive stresses. Toenshoff et al. and Mn.

Mitsubishi. Sjostrand. As discussed above. Increased surface roughness provides better mechanical interlocking between diamond and WC grains. Greater improvements in tool life are reported when cutting Al-Si alloys. 1994. green ceramics. J.12 Cutting performance of an uncoated and CVD diamond-coated insert while machining a cast aluminum alloy containing 7% Si (cutting conditions: speed. A209..8 mm/rev). 1994). If too much Co is removed from the surface. 0. depending on the material cut and cutting conditions. Few other procedures have been developed by industry to achieve strong adhesion. the tool will become weakened and its integrity near the surface will be impaired. and fiberreinforced composites. Norton.13 demonstrates the effectiveness of a nanocrystalline diamond-coated carbide insert in preventing edge wear and loss of sharpness after machining of a high-Si-content Al alloy. cost less. DeBeers. and Sumitomo are the major firms.E. M. tools coated with CVD diamond can exhibit tool life improvements that range from 25% to more than a factor of 40. Sandvik. Published case studies indicate that. Reineck. Kennametal and Sandvik provide diamond-coated tools commercially. Several companies are engaged in the production of CVD diamond-coated tool inserts. Sci. The market share of coated tools is expected to increase steadily because prices are declining while performance and reliability are improving.FIGURE 24. 150 to 2500 m/min. Kennametal. CVD diamondcoated tools were proven to be as good as or better than the PCD tool inserts when used during turning of Al-Si alloys and graphite. whereas the absence of Co ensures higher nucleation density and better adhesive bonding. CVD diamond-coated inserts are primarily targeted for machining applications that involve high-Si-Al alloys. and increase productivity. SiC.. The effectiveness of bond layers is very much dependent on the exact composition and thickness of the bond layer material.. very little is known about them. feed rate. Si.. I. 405-413. W.25 to 0.e.. Figure 24. Better quality and reliability will certainly result in diamondcoated tools that last longer. The projected growth of Al use in automobiles indicates © 2001 by CRC Press LLC . Eng.. CVD diamond-coated cemented carbide cutting tools. M. Nachi-Fujikoshi.) environment.. With permission. Co removal must be done with great care. (From Karner.12 shows the performance of uncoated and CVD-diamond-coated carbide inserts during machining of an Al-Si alloy for a truck wheel application. Because Co is the binder that holds the tool’s WC grains together. depth of cut. Kubelka et al. (1996). but they are considered highly proprietary. Pedrazzini. and Si3N4) have also been tried on tool inserts to achieve strong bonding. Formation of stable Co borides and silicides that can endure the high deposition temperatures of diamond has also been used in the past to prevent Co-associated problems (Kupp et al. 0. E. Figure 24. and Bergmann. it also evaporates Co and thus reduces the amount of Co at or near the surface. Mater.5 to 3 mm. hence. Various bond layers (i. Heat treatment causes grain growth in WC and hence roughens the surface..

a diamond-coated seal can also be very useful in applications where a liquid lubricant is not permissible.b) have demonstrated that smooth diamond films can result in substantial reductions in frictional torque and wear rates of shaft seals.3 Other Applications Microelectromechanical systems represent a new class of moving mechanical assemblies that can be used for a wide range of applications. when rubbed against rough diamond. actuators. Coated seals would be especially attractive in applications where high chemical stability and resistance to corrosion. Polished or smooth nanocrystalline diamond coatings will be more desirable for seal applications. (1998a. that the growth of the diamond-coated tool insert market will be significant. for example.2. they offer an excellent business opportunity. in pharmaceutical and food processing plants. © 2001 by CRC Press LLC . Total energy losses due to high friction and wear can be very high. Over 3 million higher-end pumps rely on the tribological performance of SiC seals. CVD tools may displace PCD in some applications. mechanical seals represent the next best application possibility for CVD diamond films.4.4. Recent studies by Hollman et al. they too suffer major wear losses. these inserts wear out rather quickly. Tungsten carbide blades already comprise a large part of the woodworking tool market.FIGURE 24. erosion. Because properly applied diamond coatings afford very low friction to the sliding surfaces of seal components. and abrasion is needed. CVD diamond-coated tools have yet to be used in woodworking and.13 Extent of wear damage on (a) uncoated and (b) nanocrystalline diamond-coated tool inserts after machining of a hypereutectic aluminum-silicon alloy. One of the sealing faces (inserts) is made of soft graphite or C composite. Improper use of or leakage in mechanical pump systems can be very costly and may lead to environmental disasters. 24. 24. Rough diamond coatings cannot be used in seal applications. Woodworking tools represent another major market segment for diamond coatings. high-precision positioning devices. they can extend the useful life of these components and also reduce energy losses. including sensors. Hard SiC inserts can also be used.2. When the performance and price of CVD tools compare favorably with those of PCD tools. When rubbed against a rough and superhard surface. ranging from the very simple seals used in automotive water pumps to higher-end seals that are used at high temperatures and in aggressive environments. and SiC is an ideal substrate for diamond film growth.2 Mechanical Seals After cutting tools. The mechanical-seals market is rather large. Because of its low friction. thus. but they are much more expensive and.

hence. and attractive mechanical.1 Background on DLC Films 24. The tribological behavior of these films strongly depends on the deposition technique. Consequently. Phases with an H content that is too high. and tribological properties. MEMS devices such as gear assemblies and micromotors have been largely fabricated by Si micromachining technology. mainly Si. With these films. The most common type of DLC is the hydrogenated a-CH film.. and nanometer scales.14. However.e.3. Because of its excellent properties. surgical blades. chemical. 10 to 30 nm). the film structure. 24. © 2001 by CRC Press LLC . 1995. However. removing midgap defect states. The second part summarizes the tribological behavior of DLC films. Si3N4. Researchers have developed alternative fabrication methods that allow production of MEMS devices from SiO2.g. the first part of this discussion is dedicated to a background on DLC. stabilizing the random network. or as tetragonal amorphous C (ta-C). with only moderate sp3 content and a rather high H content of up to ≈50 at%. electrical. and preventing its collapse into a graphitic phase.3. the sp1 C hybridization being negligible. termed ta-CH (Weiler et al. highlighting the relationships between the deposition process. or SiC-type materials. is also shown.1. 24. researchers have recently been exploring possible uses of diamond coatings for MEMS applications (Bjorkman et al. there have been some difficulties in fabricating diamond coatings and/or components with a morphology suitable for MEMS. F. tab tools. Other tribological applications for CVD diamond coatings include woodworking tools. successively at the macroscopic.5 to 10 µm may not achieve complete coverage on the surface of Si-based MEMS devices. Aslam and Schulz. A lightly hydrogenated analogue of ta-C. Donnet (1998) attempted to modify some DLC properties by the addition of alloying elements. etc. 1996). The general term “DLC” describes hydrogenated and hydrogen-free metastable amorphous carbon materials. it will be possible to attain film coverage at very small thicknesses (as thin as 50 nm) and hence preserve the fine structural features of MEMS devices.. high-precision microdrills. 1999). The nonhydrogenated films are classified either as sputtered amorphous C (Sputtered C) with a predominance of the sp2 hybridization.. 1998. As proposed by Robertson (1998).1 Classification of DLC Films Diamond-like carbon coatings have been the subject of intensive studies for the last 20 years. and various metals. jet nozzles). Conventional CVD films with thicknesses of 0.microelectronics. The film structure and properties are determined by the H content and the relative ratio of the two sp2 and sp3 carbon hybridizations. the tribological performance of these materials is also very poor. 1999. 1998.. the wide range of DLCs is conveniently displayed on a ternary phase diagram in Figure 24. wire-drawing dies. The NCD films discussed previously appear to be better suited because of their very small grain size (i. and various wear parts that are used against erosion and abrasion (e. through a description of the friction and wear mechanisms. The sp2-bonded amorphous C lies in the lower left corner. and some film properties. lying at the far right of the diagram. 1995. Gardos. microscopic. Si exhibits very poor mechanical and tribological properties. composition. When these microdevices are used in very high-speed applications. push pins. Cagin et al. N. however. they suffer from unacceptably high friction and wear losses and thus are unsuitable for applications that involve high speeds and realistic loads. cannot form an interconnected network and form gas or liquid molecules. Mao et al. prepared by a wide variety of PVD and CVD techniques. Hydrogen in DLC is important for obtaining a wide optical gap and a high electrical resistivity. with a predominance of the sp3 hybridization of up to 85%. optical. they may not function well in a dynamic MEMS application. The films exhibit a wide range of structure.. Ramesham..3 Diamond-like Carbon (DLC) Films DLC films represent a noteworthy example of thin films whose properties can be varied over a wide range of structures and compositions.

Singapore. DLC films are generally smooth to the level of tenths of a nanometer and are therefore referred to as nanosmooth. Deposition mechanism of diamond-like carbon. The study of hydrogenated DLC and the state of our knowledge concerning its properties and practical applications have apparently matured. and laser plasma. (Eds. the fraction of sp3 bonding is maximized for ion-dominated processes with ion energies ≈100 eV. S..) Such a wide range of film structures and composition and the diversity of methods used for DLC film deposition provide the flexibility to tailor their properties according to specific needs and applications. 1997). Whatever the deposition conditions. 32-45. the main processes used to deposit nonhydrogenated DLC films are magnetron sputtering.. 24. cathodic vacuum arc. Adhesion can be affected by the deposition method. by multiplex processes that minimize the introduction of defects and impurities between the superimposed layers and allow precise control of the entire deposition methodology. The adhesion of DLC coatings to silicide-forming metals can be improved by depositing a 2.2 Influence of Deposition Methods on Film Microstructure and Composition From the point of view of optimizing the routine production of DLC films. thus forming an interfacial silicide layer promoted by the plasma. Robertson. 1994). J.1. To be used as tribological coatings.FIGURE 24. (From Robertson. Today. J. in Amorphous Carbon: State of the Art. The roughness thus conforms to the underlying topography. the primary need is for effective process control. with film growth governed by © 2001 by CRC Press LLC . The deposition of adhesion and interface layers is ideally achieved in the same reactor as the deposition of the DLC films. With permission.. the adhesion of DLC films varies widely. The use of Ti-based.and silicide-forming substrates. in combination with the nature of the substrate. and Amaratunga. depending on the nature of the substrate. World Scientific Publishing. even at relatively low substrate temperatures. The specific properties of ta-C films are achieved by the high energies of the impinging particles.J. Whatever the technique.14 Ternary “phase diagram” showing the various forms of diamond-like carbon. W.. Milne. Indeed. A wide literature survey on the deposition procedures has been assembled by Grill and Meyerson (1994). The following discussion is limited to the techniques that are most commonly used to deposit DLC films. primarily the tailoring of adhesion properties. the latter exerting dominant control.3.A. and the adhesive forces must overcome the high internal stresses that would otherwise cause film delamination (Holmberg and Matthews. functionally gradient films intercalated between the substrate and the DLC top layer has also been studied (Voevodin et al.P.).to 4-nm-thick interfacial layer of amorphous Si between the metal and the C film. The study of hydrogen-free DLCs has not yet reached this state and practical applications for it have yet to be found. The deposition of ta-C films is summarized prior to a discussion of the deposition of a-CH films. The growth and properties of DLC films are controlled by the substrate temperature and the energy of the species impinging on the surface during the deposition process. (1998). DLC films must adhere well to the substrate material. All methods for the deposition of DLC are nonequilibrium processes characterized by the interaction of energetic species with the surface of the growing film. mass-selected ion beam. with emphasis on the relationships between deposition conditions and film structure. G.R.I. Good adhesion of DLC films is observed on carbide. Silva.

is probably the most popular means to deposit a-CH films. 1992). However. Ar/H mixtures allow the production of hydrogenated DLC films. thus increasing the sp3 content of the films. is increased. The sp3 content can reach a maximum near 80% and H content in the range of 25 to 30%. including insulators. 1999). at the lowest impact energies. and polymer-like C films with a predominance of ෇CH2 groups are generally obtained. it is possible to obtain ta-C films that contain up to 80% sp3-hybridized C by varying the acceleration. by introducing into the reactor species or precursors that contain the modifying elements. the nature of the precursor plays a direct role in the fraction of H bonded to C. Free H fraction increases when the impact energy. ta-C films can also be obtained by a cathodic vacuum process on both the laboratory and industrial scales.. RF power can be capacitively coupled to retain the ability to deposit the films on a wide variety of substrates. it is widely used for DLC film deposition by creating a plasma plume similar to the cathodic arc produced by UV laser ablation of a graphite target.. with the substrate attached to the cathode to maximize ion bombardment. Metal. As with ta-C films. This free H. the temperature during the deposition process is also a crucial parameter. Parallel plate reactors are preferred because they allow the deposition of uniform films over large areas. With the massselected ion-beam technique. 30%-ionized plasma that expands through the deposition chamber and condenses onto the substrate. This also leads to higher C network crosslinking. Above a transition temperature of 250°C. The chamber is configured with cathode and anode plates. The sp3 and H content are strongly controlled by the average impact energy. based on recent comparisons between FTIR and 13C/1H NMR experiments performed on typical DLC films obtained under various conditions (Donnet et al. In the unbalanced configuration. 1998). a noticeable decrease in the high sp3 content and density is generally observed. and energy selection of a C ion beam that is condensing onto the substrate. with an effect of deposition temperature that is more complex than that for ta-C films. The bias is indirectly controlled by the RF power and the gas pressure in the RF configuration. Consequently. At intermediate impact energies. © 2001 by CRC Press LLC . the H content has declined sufficiently so the C–C sp3 bonding has reached a maximum. this ability depends on several plasma parameters — primarily the bias and the gas pressure. This transition temperature. Deposition should be carried out below 250°C to stabilize a significant sp3 content. should be trapped in some voids of the carbonaceous network. mass. thus leading to the so-called diamond-like qualities. if the impact energies become too high. the absolute quantification of the fraction of H that is bonded to C remains ambiguous. a significant amount of H in a-CH films has been unbound to C (Grill and Patel. which is much lower than the thermal stability temperature of ta-C films (which can reach relatively high values approaching 600°C). optically inactive by FTIR. Laser plasma deposition is a versatile method used to deposit many materials. creating an intense. Because the film structure is a strong function of the energy of the impacting species. Consequently. More precisely.a subplantation process instead of conventional condensation as in a-CH films (Robertson. the substrate is bombarded with Ar ions. Magnetron sputtering is probably the most commonly used industrial method for depositing DLC films. From characterization by Fourier transform infrared (FTIR) combined with forward recoil elastic scattering experiments. However. at the expense of a decline of C–C sp3 bonding. decreases with increasing ion energy. The resultant films are called ta-CH. and by operating at lower gas pressure to increase plasma ionization (Weiler et al. The filtered cathodic vacuum arc configuration avoids degradation of the growing film by particulates produced in the arc along with the desired reactive species. and hence the dissociation of precursor. temperature during deposition is another parameter that generally affects the DLC structure. Plasma-enhanced CVD. the gaseous precursor is not sufficiently decomposed. in which any gaseous hydrocarbon species is used as precursor.and/or nonmetal-doped diamond-like films are deposited by the same techniques as the regular films. The increase of diamond-like qualities of a-CH films has been achieved using a plasma beam source with acetylene to reduce the amount of incorporated H. graphite-like C structures are generally deposited because of an increase of disordered sp2-like bonding. An arc is struck on a graphite cathode. by analogy to ta-C. 1996).

0 <600 0. Differing models.3. hydrogenated. Young’s modulus. an increase in H content is generally associated with a decrease in hardness. such as the graphitic cluster. including tribological behavior. 24. a෇CH = amorphous carbon. fraction of H bonded to C. and the experimental difficulties encountered when thin metastable amorphous films are accurately probed. For each category of film. and compressive stress. Young’s modulus. the structure and composition of the films (H content. 24. the random covalent network. resistivity. depending on the nature of the dopant. which remains difficult to investigate for the reasons mentioned previously.1 summarizes the range of various typical properties that depend on the presence or lack of H in the film. making some doped DLCs suitable for various applications — for example.1 Variable Range of DLC Structure. Thus. the tribology of DLC coatings has been discussed extensively in the literature. Grischke et al. density. In hydrogenated DLC films. include elements such as Si. The introduction of dopants generally brings about a decrease in compressive stress.4–1. % Density. constitute interesting guidelines to improve our current knowledge about structure/property relationships. and lower index of refraction. eV Electrical resistivity. The relationships between the structure and the properties of DLC films have been more extensively studied on a-CH than on ta-C films. and may modify various physical properties.2.0 Hydrogen content.9–3. stress. The difficulties in generalizing the structure/property relationships are due to a lack of systematic and unambiguous standardized characterization of DLC films.2 <400 0.2.8–4. and bandgap.3. to improve field emission characteristics. thermal stability. Ω/cm Index of refraction Compressive stress. Nonhydrogenated films exhibit generally higher hardness. similar in structure to a-CH or ta-C. the introduction of alloying elements into DLC affects many properties. GPa a b a–C = amorphous carbon.3. N. and has been summarized in recent © 2001 by CRC Press LLC . Thus. as controlled by the deposition process. nature of bonds. and Properties a-Ca <5 5–90 1.5–5 <80 <900 <60 <300 a-CHb 20–60 20–65 0. density. C hybridizations.1. due to fewer interconnections in the random carbonaceous network.TABLE 24. the property variation is directly related to the structure.3. mainly because of the very low friction coefficients and high wear resistance of these materials. the wide range of structures and compositions. Composition. F. when compared with hydrogenated films. or the defective graphite network reviewed by Grill and Meyerson (1994). and index of refraction. and various metals.9–2. °C Optical gap. alloying elements) are strongly influenced by the average impact energy of the particles that impinge on the growing surface and by the deposition temperature. GPa Young’s modulus. thermal stability.1.4 0. g/cm3 Thermal stability. and an increase in the gap and electrical resistivity. at% sp3. most film properties depend on key structural parameters that are related to specific deposition processes and conditions. As highlighted in Section 24.8–2. Table 24.3 Influence of Film Structure and Composition on Some Typical Properties As described in Section 24.5 102–1016 1. A more accurate discussion remains impossible because most of these properties also depend on the fraction of H that is bonded to C. Various C-based materials.2 Tribology of DLC Films Much effort has been invested in the characterization of the tribological behavior of DLC films. GPa Hardness. (1995) have shown that the specific chemical composition of the modified films strongly influences the surface energy.

. physical parameters (temperature during friction). Friction and wear of DLC coatings are strongly affected by the nature of the films. span the range of 0.reviews such as those of Holmberg and Matthews (1994). and Erdemir (1998). and chemical parameters (nature of the environment).15) when compared with a-CH coatings. under UHV conditions during tribological tests. bias. This finding is consistent with the expected role of H in stabilizing the random covalent network and preventing its collapse into a graphitic network. In ta-C films. and the surface chemistry of the films deposited under differing conditions. can be controlled by the H content of the films. In the case of H-containing films deposited by PECVD. Hydrogen concentrations lower than 34 at% systematically lead to high friction. Extremely low wear rates can be achieved for both ta-C and a-CH coatings. Donnet (1995.01 or less [Erdemir et al. as well as films with normalized wear rates as low as 10–8 mm3/N-m. it is not surprising to observe a decrease in the friction of ta-C films with increasing humidity (Voevodin et al. thus increasing the difficulty of comparing results.5). and pressure). Wear rates are less systematically investigated and are often recorded in nonstandard units. kinematic parameters (nature of motion. as controlled by the deposition process.2 and 24. can be produced.2. Donnet and Grill (1997) have shown that this binary friction behavior. wear resistance performance is not so easy to discuss by simply discriminating between the two previous categories of DLC films. The microscopic scale focuses on the accommodation modes. in which a top-down approach to DLC tribology is used to focus on the various phenomena occurring at three different scales.1 Tribology of DLC at the Macroscopic Scale: Friction and Wear Behavior The friction data on DLC films show that their sliding friction coefficients.003 to 0. with wear rates strongly depending on the nature of the films. An exhaustive presentation of the tribological behavior of DLC is thus impossible. Hydrogen-free films generally exhibit lower friction (<0. transfer film buildup. which probably represents the widest range of friction behavior in any category of coatings. speed). as described in Section 24.b]) or high values (>0. 24. In inert environments. together with the environmental conditions.2. 1996). Polymer-like films obtained at low average impact energy (controlled through low DC bias) are less wear resistant than diamond-like films.3.3.3. in terms of interfacial shearing mechanisms. friction generally ranges between 0.. friction easily causes a local shearinduced graphitization at the microscopic scale. 2000a.2. the current knowledge at these three complementary scales is summarized.2.. friction of a-CH films generally increases with humidity (Franks et al. including material parameters (nature of the substrate). friction coefficients can reach either ultralow values (down to 0.6. A more interesting and useful method of presentation will be used here. 1998).05 and 0. and by the tribotesting conditions. similar to the friction level of diamond or graphite in the same UHV environment. © 2001 by CRC Press LLC . The nanometric scale focuses on the chemical reactivity of the top surface in relationship to the environment that surrounds the contact spot. Below. Thus. µ. On the other hand.3.2. Grill (1997b) has correlated wear resistance (down to 0. primarily by considering the nature of the DLC films. Friction and wear control can be achieved. The effect of H on the friction level is highlighted in the chapter section dedicated to the tribology of DLC at the nanometric scale (Section 24. mechanical parameters (contact pressure).3).1 nm for 1000 rotations in ambient air) with deposition conditions (precursor. including dry N and vacuum. Ultralow friction is achieved with films that contain at least 40 at% H.2. Grill and Meyerson (1994). The role of water vapor at both the microscopic and nanometric scales is highlighted in Sections 24.3.3. 1990). Consequently. DLC films that are easily scratchable with no wear resistance at all. this finding shows that the optimization of the wear resistance of DLC films requires strong attention to the control of the deposition procedure. Grill (1997a). In ambient humid air (typically 20% < Relative Humidity < 60%). and friction-induced wear-particle formation. because water molecules are known to intercalate between graphite layers and ease their slip over each other.3. Unlike friction. based on the accumulated knowledge described in the previous sections on deposition/structure/property relationships. The macroscopic scale allows the establishment of relationships between the nature of the films and friction levels and wear rates under various testing conditions.

1). metal-containing DLC films can exhibit promising tribological properties in terms of steadystate friction levels and wear rates for various applications.3. where compared with that of conventional undoped DLC in ambient humid air. the behavior of ta-C and a-CH is rather similar. precision ball bearings and gears. sliding bearings.4. Interfilm sliding mechanism consecutive to transfer film formation.4) appears to be soft. together with its thickness.15). is in the same range as that in a-CHSi. The reduction of stress. The resultant shear strength is that of the two layers sliding against one another.1) and high wear resistance (<10–7 mm3/N-m) under moderate mechanical conditions.02 to 0. Dimigen and Klages (1991) observed friction coefficients in the range of 0.A compilation of the tribology of doped DLC and C alloy coatings has been recently prepared by Donnet (1998).2) can be controlled by deposition conditions to obtain films with comparable wear resistance and friction levels of conventional a-CH films. strongly depend on the nature of the counterfaces and the environmental conditions. The range of composition and structures attainable with metal-containing DLC coatings appears to be enormous. 24. the reduction of the surface energy is higher with F than with Si. with comparably high wear resistance.2 Tribology of DLC at the Microscopic Scale: Accommodation Modes Most experimental observations indicate that for the low friction and reasonably long life of DLC. and wear does not systematically vary linearly with time. frequently observed with DLC © 2001 by CRC Press LLC . for the protection of low-stress aerospace or automotive components. ta-CHSi films can be used in applications that require both low friction (<0. and magnetic recording media. Less research has been performed on the tribological investigation of N-containing DLC films because of their recent discovery when compared with conventional DLC and other doped DLC. when compared with conventional DLC. Moderate fluorination (F/[F+C] < 0. The interfilm sliding mechanism occurs when the DLC film adheres strongly to both contacting surfaces. Highly fluorinated DLC (F/[F+C] > 0. The kinetics of transfer film formation. Consequently. When optimization is achieved. One should keep in mind that the optimization of the material combination and deposition parameters is a challenging subject for each element or combination of elements. At this scale. Silicon incorporation into the DLC structure is shown to affect most film properties (including a decrease in surface energy and internal stress) and its tribological behavior. However. but with lower stress and surface energy. Friction appears to be significantly reduced (<0.2).2. with no wear resistance. One should keep in mind that the initial formation of a transfer film is associated with significant wear of the initial coated part. conventional ta-C and a-CH films cannot be surpassed. this tribological behavior appears to be observed when the contact pressure remains below 1 GPa. except if the film is completely worn. The incorporation of Si and F into the DLC structure affects the surface properties. However. Consequently. but separates into two distinct layers that slide across one another. and DLC films are generally considered to slide according to this accommodation mode.15 coatings. a transfer film buildup that is followed by an interfilm sliding mechanism is the most frequently observed velocity accommodation mode (Figure 24. Neither of the two original surfaces is in contact. A review of the tribological behavior of C nitride films is presented elsewhere in this chapter (Section 24. At higher contact pressures. this initial running-in wear may be crucial to ensure low friction and wear over long periods. FIGURE 24.04 in ambient air when a significant amount of Ta or W was incorporated in a-CH films.

This effect has been observed in hydrogenated DLC film deposited on an Si substrate and tested against a steel pin counterface in UHV at various pH2O values (Donnet et al. which appears to influence the friction level.20.The nature of the counterfaces can significantly influence the size and nature of the transfer layer (both of which sometimes differ from the initial composition of the film). as frequently observed in a wear-induced graphitization mechanism (Erdemir et al. and friction rises to higher values. and O.2. the environment. and can be attributed to the suppression of temperature rises at hot spot. H. Without the DLC film. Moreover. but this kind of assumption can be checked only by tribological tests under UHV conditions and sliding in situ on fresh surfaces. the chemical composition of the first layers is of paramount importance in understanding the tribochemistry of DLC coatings. 1991. the nature and thickness of contaminant or passivation layers will probably play a role.. A transition between ultralow friction (10–2 range) and higher friction (10–1 range) is observed within a water vapor pressure range between 0. Liu et al. Alumina was transferred to the surface of the disc wear track. because of the low adhesion between PTFE and the DLC coating. 1991. interfacial rheology is associated with exposure of the top surfaces and interfaces (third body) to one another and. this is associated with a drastic decrease in friction coefficient from 0. Tribochemical reactions between the transfer film and the counterface can induce the formation of complex structures and compositions on the top surface of the film. without any transfer film formation. 1991).. A lower wear rate of the pin. Therefore..1 hPa (RH = 0.3. strongly affects the transfer film thickness. 1995. similar mechanisms are generally observed when ceramic materials are used. as described in Section 24. Higher humidity values are associated with a thinner transfer film.. controlled by the partial pressure of pure water vapor (pH2O).3 Tribology of DLC at the Nanometric Scale: Tribochemistry and Molecular Interactions During a sliding process. the nature of the counterface and the tribotesting parameters.02. An exception to this conventional transfer film formation mechanism can be found when DLC-coated steel slides slowly against PTFE (Yang et al. so that AES detects the substrate elements that underlie this transfer. Thus. A decreased graphitization rate is also observed at lower temperatures and higher humidity during friction.. Miyoshi et al. The transfer is thus impeded at high humidity values.3.04.13 to 0. very little PTFE is directly transferred onto the steel counterface and friction remains between 0. This can be explained in terms of tribochemical reactions.2. Lower humidity generally increases the graphitization rate. play a crucial role in the kinetics of formation and composition of the transfer film. © 2001 by CRC Press LLC . 1993). With the DLC film. The thickness of the transfer increases with higher loads and sliding velocities. The transfer layers may become a mixture of the original carbon film and elements from the counterface. associated with a modification of the transfer composition.. 1992). Fe. indicating a strong triboreactivity with the initial pin counterface. 1996. Cr. with Al2O3 pins. Consequently. to the surrounding atmosphere. more than likely because the effect of water molecules is reduced. These results were observed both on H-free and hydrogenated DLC films. the coatings and experimental setup that had been studied earlier with metal counterfaces. The structure of the transfer layer can also be modified by the friction process. Such a mixture has already been observed by secondary ion mass spectroscopy (SIMS) analysis of inside wear tracks of DLC-coated steels (Ronkainen et al. as shown by in situ Auger electron spectroscopy (AES) performed inside the transfer film.15 and 0. with composition strongly depending on the environment during friction (Kim et al. 1998). Transfer layers are also formed on ceramic counterfaces such as Si3N4. 1996). and thus strongly influence the friction levels and wear rates. Ultralow friction at the lowest pH2O values is associated with a homogeneous C-based transfer. friction decreases to 0. 24. 1993. except for UHV tribotests.. together with the nature of the environment. The analysis revealed a transfer film composed of a mixture of C.4% at 23°C) and 1 hPa (RH = 4% at 23°C).3. The authors also investigated. Moreover. was observed by SIMS analysis at high loads and high speeds.

The actual interaction force is somewhere within this range.4 eV (37 kJ/mol) to 0. O.4–0. When transfer film buildup during the running-in period is taken into account. sub-bands of the graphite band structure) overlap at selected sites of the Brillouin zone. steady-state sliding with DLC films is accommodated between the two counterfaces by interfilm sliding of C-covered smooth surfaces.4 to 0. depending on how the band parameters influence the net inter. this mechanism appears to be predominant if the H content is higher than ≈40 at%. Under UHV conditions.2 range..2.2 Friction Mechanism of Carbonaceous Compounds at the Molecular Scale < 0. the UHV friction coefficient is initially in the 0. and experimental friction ranges have been compiled by Donnet (1997.2 Hydrogen 0. as long as the surface sites are saturated by H. they interact with high energies and thus contribute to the high friction. The discussion related to a-CH films is more complex in that it considers the wide distribution of H content and C hybridizations. The role of the H content and sp2/sp3 hybridizations in a-CH films is discussed first. Others have already observed that aliphatic-type hydrocarbon chains with high flexibility undergo easy friction-induced orientation along the sliding direction. Desorption of adsorbates upon rubbing in vacuum creates σ dangling bonds on diamond surfaces. DLC with low H content (UHV) Friction range Nature of the interaction Energy (eV/bond) Schematic of the interaction (environment) Note: Energy values are indicated by Gardos (1994).and intraplanar attraction of a family of imperfect graphitic planes of particles interacting in a solid lubricant layer. as reviewed by Gardos (1994).2). as with poorly hydrogenated a-CH films.8 eV (66 kJ/mol). or H2O molecules. as shown by polarized infrared microscopy performed on inside wear tracks of hydrogenated DLC after a UHV friction test (Sugimoto and Miyaki. The discussions are based on Table 24. graphite. the π-π* orbitals (i. Steady-state friction of diamond and un-intercalated graphite is generally very high (>0. The overlap of these sub-bands can lead to attractive interactions that range from 0.2 a-C:H or a-C (RH > 4%) >0.02 van der Waals 0. As observed by Donnet and Grill (1997). The exact origin of the threshold between ultralow friction and high friction observed with a difference limited to 6 at% is not completely understood. 1990).e.5). 1998b) and Gardos (1994). With this approach. the contaminant topcoats are removed and sliding occurs between the two carbonaceous fresh surfaces.08 a-C:H (UHV) 0. whereas DLC with H content lower than 34 at% behaves in UHV as graphite or diamond. a high friction and wear material. and determines various degrees of C crosslinking. If these free bonds do not reconstruct or are not activated by any adsorbates.1–0.5 σ or π 0. UHV means ultrahigh vacuum.TABLE 24. In the case of diamond/diamond or graphite/graphite. The ultralow friction of highly hydrogenated DLC films in UHV is consistent with the predominance of hydrocarbon polymerlike topcoats mutually interacting through weak van der Waals interactions (Table 24.8 Diamond.8 eV binding energy between the basal planes is enough to render pristine highly oriented graphite. it should be possible to explain the role of the high H content in lowering the friction of DLC in UHV from high values that are in the same range as values related to diamond or graphite under the same environmental conditions. © 2001 by CRC Press LLC .1 to 0. Gardos (1994) indicates that the 0. In the case of un-intercalated graphite.

Video recording or magnetic data storage tapes. but wear was significantly high. dry air. Nonhydrogenated ta-C films have yet to find such widespread application. Improvement of carbon/carbon composite prosthetics by DLC coatings has also been demonstrated. such as polyurethane.1 caused by humidity and oxidation indicates that the increase in bond strength from 0. gears. only conventional DLC films have been used for practical applications (see extensive reviews by Grill and Meyerson. has been found capable of satisfying both the mechanical and biological requirements and improving the performance of these components. The triboreactivity was reduced in dry Ar. DLC is being considered for coating metallic and polymeric-substrate biocomponents. The exploited properties thus far include high wear resistance and low friction coefficients. Currently. However. which are components of artificial heart valves. infrared transparency. Consequently. make them suitable for various applications. in which ferromagnetic metal is a recording medium. and applications are being developed for their use in biological environments. 1999). and moist air conditions. Grill. Humidity caused a tribochemical reaction and led to a transfer film composed of oxidized hydrocarbon and hydrated silica (from the ball). DLC seems also to have found its uses in tribological coatings for metal bearings. © 2001 by CRC Press LLC . DLC and its modifications are being considered as low-dielectric materials for the interconnect structures of ultra-large-scale integrated circuits (ULSI). The announcements of the latest MACH3 razor blades by Gillette underscore the use of DLC as a coating to improve the quality and performance of the blades. such a description fails to account for the modification of the rheology of the contact by triboreactivity between the transfer layer and the counterface. 1997a). with a transfer film and debris whose composition was similar to that of the initial film. 24. DLC coatings could protect biomedical implants against corrosion and serve as diffusion barriers. The most widespread use of DLC films is in wear and corrosion protection of magnetic storage media. Because they are chemically inert and impermeable to liquids. polycarbonate. and the metallic capstans in contact with the tapes are also being protected with DLC coatings to reduce wear and friction.2 eV/bond (H bonding at C෇O sites by water molecules) associated with a progressive friction-induced graphitization should be the main cause of the change in friction (Table 24. and. (1991) by performing FTIR microprobe tests to identify the debris and film structures observed on various interfacial films formed by a Si3N4 ball rubbed against DLC-coated Si in dry Ar. Nanosmooth and very thin (even <5 nm) DLC films are now used as corrosion and wear protective coatings for both magnetic disks and magnetic heads (Bhushan. 1999). Although ta-C has properties similar to or (in some instances) better than those of conventional DLC (i. Its potential use for phase-shift masks for DUV lithography has also been demonstrated. friction was rather low. The low deposition temperature of DLC allows its use as a wear-protective layer on products made of plastic.The tenfold increase in friction from <0.e.. field emission and low dielectric constant. and ZnSe (Grill. a-CH). chemical inertness. A better understanding of the means to control the thermal stability and other integration problems of DLC and its modifications will potentially expand their use in ULSI chips. thus far. and by the formation of friction-induced wear particles. thus lowering both friction and wear.08 eV/bond to 0. Because DLC is IRtransparent. wear-protective coating for IR optics (at wavelengths of 8 to 13 µm) made of Ge. thus extending both the life of the tapes and their reliability. together with the possibility of adjusting the properties by choosing the right deposition parameters. to improve their compatibility with body tissues.02 to >0. and polyethylene. 1994.2). DLC deposited on stainless steel and Ti alloys. and seals. it can be used as an antireflective and scratch-resistant. therefore. high electrical resistivity. The most promising application appears to be for cathodes in field-emission-based flat-panel displays or as pixel elements in large outdoor displays. The opposite tribological behavior was observed in dry air. it is used to protect polycarbonate sunglass lenses from abrasion. potentially.3. where the transfer layer and debris were composed of a carbonyl compound formed by the tribo-oxidation of hydrocarbons in the DLC films. The same properties may make DLC useful as a protective coating for hip joint implants.3 Applications of DLC Films The unique properties of DLC films and their modifications. ZnS. DLC films appear to be biocompatible. This modification of the rheology has been shown by Kim et al.

hence. like diamond. © 2001 by CRC Press LLC . ion energy. Furthermore. Currently. Also. (Murakawa and Watanabe. In one approach.e. and hence reduce the amount of stress buildup at the coating-substrate interface. CBN can also be used in various optical and electrical applications. 1997). pulse laser deposition. the surface finish of CBN films is much smoother. 1990.. 1999). 1996). 1997. 1990). For higher quality CBN films. CBN offers high thermal conductivity and a very large band gap (≈6 eV). it does not dissolve in or interact with Fe-based alloys. CBN exhibits many exceptional properties that render it far superior to other hard nitrides and carbides used by industry today. the formation of an sp3-hybridized CBN phase is largely controlled by the substrate temperature and the energy of N and Ar ions in sputtering and ion-beam deposition. Increases in B above stoichiometry and concomitant formation of vacancies on the N sublattice lead to distortions and significant changes in crystal structure..4. safe film thickness for crystalline CBN films is in the range of 0. The use of a Ti layer or first layer.1 Cubic Boron Nitride (CBN) Like diamond.. hence. The most widely used deposition methods include magnetron sputtering. The deposition temperatures needed for the formation of the CBN phase are substantially lower than those required for diamond films. CBN can also work very well under dry machining conditions. Several factors can affect the synthesis of high-quality CBN films during deposition. Because CBN has a very high melting point. plasma-enhanced CVD. annealing of the CBN films both during and after deposition was tried. Growing CBN films tend to accumulate increasingly high compressive stresses in their microstructures and this represents a major problem in attaining films that are thick enough (at least 3 to 5 µm) for machining operations. During deposition. 1991). achieving and maintaining a 1:1 stoichiometry between B and N atoms tends to be rather difficult. 1997. compressive stress within the film tends to increase with increasing thickness and eventually becomes so high that CBN film delaminates prematurely or fractures severely (Murakawa and Watanabe. approaches have been tried to achieve strong bonding between CBN and various substrate materials. Smeets et al. ion-beam-assisted deposition.2 to 0. Depending on deposition temperature. These changes can adversely affect the mechanical. and other important properties of CBN. Despite some incremental improvements in achieving strong adhesion between CBN and various substrate materials. The presence or absence of H in the plasma can also affect film quality. and current density. was shown to be quite effective in achieving strong adhesion between CBN and several tool materials (i.. are not perfectly crystalline.5 µm. moderate ion energies are needed (Schaffnit et al. high residual stresses in these films still hinder the deposition of very thick films with good adhesion. films thicker than this are needed. The lack of suitable tool substrates with a good lattice and thermal expansion match is a major part of this problem. First. 1990. It can be doped with both pand n-type elements.24. In another approach. and exhibits excellent hot hardness and strength. Like diamond. hence. Chiang et al. but not with CBN. etc. thermal.. In addition to its excellent thermal and chemical stability and high wear resistance. it can provide excellent resistance to wear and oxidation at elevated temperatures. Annealing is thought to relieve some of the residual stresses. Most films are slightly N-deficient and. CBN was produced over a graded Ti interlayer. WC-Co alloy and high-speed steel). Murakawa et al.. It is the second hardest material known. and thus can be used to machine ferrous materials (which account for 80% of all cutting and machining operations). ion plating. In recent years. there is no need for post-deposition polishing (Watanabe et al. a duplex coating of the two hardest materials can be obtained. For example. hence. For most machining and other tribological applications.. CBN can be synthesized by the HPHT method in the powder form and can be deposited in thin films on various metallic and ceramic substrates by both PVD and CVD methods.4 Other Related Films 24. Unlike diamond. resultant films may contain appreciable amounts of amorphous or hexagonal BN phases. it was shown that CBN can be directly grown on diamond films without using a bond or a graded BN layer (Murakawa and Watanabe. followed by a second layer of graded BN. Konyashin et al. Deposition of such thick films is quite possible with diamond. is chemically very stable.

5 under the same test conditions. To test this idea. (1992) and Watanabe et al. wear was almost zero... limited film thickness.4. The results of tribological tests showed that this composite film exhibited significantly lower friction coefficients and much longer wear life than the single-layer CBN film. including wear parts. The unique crystal structure of cubic β-C3N4 is based on the β-Si3N4 structure. Despite its many attractive properties (i. CBN films have not yet been offered for large-scale applications.4. and high-temperature durability. In a search of self-lubricating materials for space applications. Cohen predicted that such compounds based on C and N. and usefulness of CBN for extreme machining operations have been explored. 1990) have predicted a new form of carbon nitride (i. Poor adhesion of hexagonal BN led to premature debonding and hence poor wear performance. and CBN in UHV environments. bearings. cubic beta carbonitride β-C3N4) that exhibits an extremely low compressibility and superhigh hardness that exceed those of natural diamond. high thermal stability. the friction. whereas films with an amorphous structure exhibited good frictional properties but very short wear lives. followed by a second layer of amorphous BN on top of the CBN layer with a gradient interlayer formed between the two BN layers. highly crystalline CBN films provided the best wear resistance and lubrication. these authors concluded that perhaps an ideal film should contain a mixture of CBN (for high wear resistance) and amorphous BN (for good lubricity) phases.3 to 0. In their tests. an initial layer of CBN was deposited onto an Si substrate by ion plating. it has been the subject of several tribological studies in recent years. Tribological studies have indicated that the friction and wear performance of CBN is highly dependent on the test environment and counterface materials. Currently. but in water.e. Large-scale applications of CBN films have not yet been realized. DLC. which have very small atomic radii and the strongest bonds. (1991. low reactivity with ferrous alloys.2 Carbon Nitride Films First-principles calculations by Cohen (1985) and Liu and Cohen (1989. Studies by Miyake et al. Because of their excellent tribological properties. in which C is substituted for Si to achieve an atomic bond configuration that favors extreme hardness and elastic modulus. wear-resistant couple for UHV or space applications. it is high. Accordingly. CBN suffers from poor adhesion. CBN holds significant promise for various tribological applications.24. 24. whereas those of TiC. More specifically. cutting tools. CBN films were deposited on WC-Co drills and tool inserts and subjected to cutting operations.1 Tribology of CBN Films Because of its excellent mechanical properties. 1995) have demonstrated that the friction coefficients of high-quality CBN films are in the range of 0. and poor reproducibility of structure and properties. it was found that CVD diamond films against CBN exhibited the lowest coefficients of friction. wear. high internal stresses. Except for a few case studies where superior machining and lower torque were demonstrated while cutting or drilling steels.1 to 0. researchers are concentrating on overcoming these problems. wear is low. they prepared a duplex film that consisted of both CBN and amorphous BN. CBN coatings reduced torque while drilling 440C steel work pieces. Such impressive results led Miyoshi to the conclusion that a combination of these two hardest materials may serve as an effective self-lubricating. Tribological tests by Watanabe et al. Compared to other hard nitride and carbide coatings. smooth surface finish. CBN provides very low friction coefficients during sliding in air.2. seals. TiN. Miyoshi (1999) performed comprehensive tests with diamond. Sliding CBN against Al led to high friction and wear in air and vacuum. © 2001 by CRC Press LLC . Because hardness is inversely proportional to the bond length and hence to the radii of the atoms that form that bond. When CBN is slid against steel in air or under water. Comprehensive studies by Murakawa (1997) and Watanabe et al. chemical inertness.e. but in high vacuum. excellent resistance to corrosion and high-temperature oxidation. etc. (1991) demonstrated that the crystallinity of CBN coatings strongly affects the friction and wear properties of ion-plated CBN films. Surprisingly. In the end. dies. and low-to-moderate deposition temperatures).1. and TiCN films are 0. (1999) have revealed that CBN exhibited much better wear performance than amorphous BN and TiN or TiC films. Except for partial delamination in a few cases. Specifically.

they still provide excellent tribological performance. researchers have predicted that β-C3N4 will provide excellent thermal conductivity and wide bandgap (Cohen.14 for CNx films produced by a reactively ionized cluster beam technique. and related films. Yu et al.05 to >0. a few researchers have tried to stabilize the crystalline phase in a pseudomorphic state using appropriate structural templates such as TiN or ZrN(111).. with the expectation that this will lead to new possibilities in the fields of superhard and wear-resistant materials. great strides have been made in the deposition. During the past decade. using crystalline ZrN(111) as the structural template. but the progress in implementation has been rather slow.e. Reported friction values range from 0. mainly because of an extremely high bond dissociation energy for N in gas discharge plasmas or ion fluxes. RF and DC magnetron sputtering. several new methods have been developed and used to synthesize crystalline β-C3N4 films. Occasionally. Wang. but this value increases to ≈0.. which represent some of the hardest materials known. deposition methods and conditions. (1997). etc. In addition to their exceptional mechanical properties. the mechanical properties of the films. 1997. Such a large scatter in friction has been mainly attributed to the differences in N content. Frustrated by slow progress in producing β-C3N4 in the bulk or thin-film forms. which can provide the correct unit cell geometry and lattice match. (1998). Carbon nitride coatings can also be used in other tribological fields where conventional DLC films have already been exploited. and. In dry environments or high vacuum. Primarily because of a large variation in their microstructure and chemical stoichiometry (i.5 in steady states. (1998) have found that CNx films deposited with >70% N in the sputtering gas exhibit higher friction and wear coefficients than films grown in the presence of lower N content..). (1997. ion energy. extent of sp3 and/or sp2 hybridization. (1994) have observed that in dry sliding contacts. characterization. As far as tribological applications are concerned. Khurshudov and Kato.e. much higher friction coefficients were observed.1 against a 52100 steel ball. some researchers have reported the presence of small crystallites with electron diffraction patterns that match the pattern of β-C3N4 (Chen et al. within the predominantly amorphous structure of these films. Most research groups have been able to successfully produce amorphous C nitride coatings. 24. 1996. amorphous C nitride films produced by various research groups exhibit large variations in mechanical properties and tribological performance. ion current density. Specifically. CNx gives an initial friction coefficient of 0. and deposition conditions (i. These C nitride coatings also provided ≈3 to 30-times longer wear life than commercial C coatings. and Fendrych et al. (1998) have also found a very close relationship between friction and wear properties of CNx films. especially when used as a protective overcoat for computer hard drive systems (Cutiongco et al. DLC. successful synthesis of crystalline β-C3N4 has not yet been fully realized. many researchers have attempted to synthesize β-C3N4 in both the bulk and thin-film forms by various methods. (1999) reported steady-state friction coefficients of 0. Czyzniewski et al. 1996). these coatings incorporate several other attractive © 2001 by CRC Press LLC . ion implantation. Kusano et al. Khurshudov and Kato (1996) reported that the wear rates of the carbon nitride-coated disks were 10 times lower than those of disks coated with a commercial DLC film of the same thickness. 1997.5 Summary and Future Direction Over the last 2 decades. C:N ratio.. and hot-filament CVD) have produced amorphous carbon nitride films with a relatively low N content (≈20 to 30%). Hajek et al. Although these coatings are much softer than diamond. 1997). 1995. Li et al. UV-assisted chemical synthesis. and tribological utilization of diamond. 1994)... Zou et al. In addition to its extreme mechanical properties. Despite intense research efforts around the world. temperature. ultimately. Li et al. Since these initial theoretical studies. C:N ratio). plasma arc deposition. (1995) and Wu et al. ion-beam deposition. amorphous C nitride films are currently used as protective coatings in magnetic hard disks. 1998) have recently produced a multilayer film that consists of very thin β-C3N4 (1 to 2 nm thick) and ZrN films with a hardness value above 40 GPa and an elastic modulus of 400 GPa. Most PVD and CVD methods (such as laser ablation.will exhibit the highest hardness.5 in air.08 to 0. Yu et al.

The combination of high wear resistance (due to high mechanical hardness) and low friction makes diamond. insufficient thickness. with proper control of their microstructure. It is anticipated that their use in the cutting-tool industry will further increase if and when their reliability is improved and their unit cost is further reduced. and surface topography. and related films very unique and ideal for demanding tribological applications. are now available. the number of publications that deal with them has steadily increased over the years. When compared to diamond. the future of diamond. high fabrication cost (both diamond and CBN). depending on the tribological and environmental constraints. DLC. With recent advances in deposition technology. Office of Energy Research. alternatively. the quality and reliability of these coatings are expected to improve in the near future and. chemistry. nanocrystalline diamond films with a very smooth surface finish can be used to achieve low friction and wear in sliding tribological applications. strong bonding between these films and their substrates is an important prerequisite for long service life in most tribological applications. Poor adhesion. Some of the reasons for the slow progress in the commercialization of diamond and CBN coatings are rough surface finish (in the case of diamond). The high surface roughness of microcrystalline diamond films presents serious problems in many tribological applications. Field and laboratory test results confirm the notion that diamond coatings can afford excellent life improvement to cutting tool inserts when they are used to machine Al-Si alloys and graphite.S. As with other types of hard coatings. these films may live up to their promise. hence. the results of previous studies suggest that. As a true reflection of the growing interest in these films. DLC and C nitride films are more cost-effective and much easier to produce than diamond and CBN. they are now used in various tribological applications. under Contract W-31-109-Eng-38. hence. and related coatings in tribological applications looks promising because the industrial need for materials with unusual properties is constantly increasing. hence. increase their chances for large-scale applications. mechanical seals) with diamond coatings have also been prepared. Although some applications are still in the exploratory stage and require further refinement. DLC. whereas CBN is more suitable for machining ferrous and nonferrous alloys. and difficulties in attaining and maintaining 1:1 stoichiometry between B and N atoms in a cubic crystalline structure during deposition are some of the major problems that hinder further use of CBN in tribological fields. and other related films allows many tribocomponents to be coated with these films and offered for practical applications. Department of Energy. © 2001 by CRC Press LLC . Until now.g. tribochemical and thermomechanical interactions can occur at the sliding interfaces of these films and control their friction and wear performance. Existing data suggest that. but even a simple literature survey will yield several key publications for those who are interested in more in-depth information about these films. have led to their greater utilization by industry.properties that can be very useful for some demanding tribological applications. However. as well as conference proceedings. Acknowledgment This work is supported by the U. These microcrystalline films can be polished by various methods or. and most important. Briefly. prototypes of others have been successfully produced and are currently being evaluated for endurance and reliability. these superhard coatings have much to offer future tribological applications. Although prototypes of other tribological parts (e. These smooth films are particularly suitable for mechanical shaft seals and MEMS applications. DLC. problems with adhesion (CBN).. their large-scale utilization has not yet been realized. high internal stresses. In addition to some archival journals. The current state-ofthe-art in diamond. The relatively high cost of diamond and poor adhesion and reliability of CBN are delaying their wider applications in industry. However. CBN has not yet found large-scale applications in the industrial world. several technical/scientific books and book chapters. only tool inserts and drills have been coated successfully with diamond and CBN and been made available for limited commercial use. These publications have led to a better understanding of the microstructure and chemistry of these films and. It is not possible to refer to all of them in this chapter. insufficient reliability and reproducibility in actual application.

N.. F. London.T. Coat.K. 1992. Sol. B. IL. Proc. F. 1964).. 222-224. D. and Goddard. Stockholm. Butler.. (1951).K. LEOS. P. 526. Proc.C.R. 1-18. Fijany. (Eds.. and Owano. B. 8th Int.. M. Polishing of diamond films. in Low-Pressure Synthetic Diamond. Pulsed laser treatment of Wc-Co tool substrates to improve Co removing and diamond nucleation. S. Elsevier Science. Friction and Lubrication of Solids. Piscataway.. C. 59-80. (1998). 1772-1781. P.C.. mechanical. on Solid-State Sensors and Actuators. D. Diam. Linker. Cappelli. J. Chiang. and Hanwell.. H. (Part I. Bhushan. The friction of diamond sliding on polished cube faces of diamond. Preparation and properties of boron nitride films by sputtering. Mater.J. K. Berlin. 21-39.. and Wilks.. 278-284. IEEE Piscataway.. Bhushan. T. (1998). Development of Low-Pressure Diamond Growth in the United States. Phys. Summer Topical Meeting of the IEEE/LEOS. Hollman.). Springer-Verlag.. Surf. Germany. F. Oxford. Blau. S. J. A. and Eurosensors IX. Cappelli. Comparative evaluation of CVD diamond technologies. 23. (1990). (1998).P. IEEE. 233-243. J. A. ANL-Conf-9202262.. W. J. Nanotechnology. M. Conf. NJ. © 2001 by CRC Press LLC .E. Transparent nanocrystalline diamond films grown by microwave CVD. Mater. D.. Plasma-jet deposition of diamond. New York. Pinzari. (Eds. 1950. CA. Nichols. and Brookes. R. 6. Diamond microstructures for optical MEMS. 1-12.5 nm: recent developments. E. MRS Bull. Proc. and Gupta. Wang. Lin. 75.. Philos.P. (1992)... Spear. V. (1997). 53. England.E. B. Roy. A208.. Banholzer. Roy. Phys. 1998. C. Simulation and experiments on friction and wear of diamond: a material for MEMS and NEMS applications.. Sweden. M.S. and tribological characterization of ultra-thin and hard amorphous carbon coatings as thin as 3.). Proc. Bjorkman. 71-97. Technol. (1992). Tribological properties of polished diamond films. Phys.A. Wear. 107. 399-407. Mag.. Soc.M.. T. and Chen. K.. O. 1985-2015. J. 22-27. S.. 178-185. Bhushan. 117-164.J. H. Clarendon Press. Understanding the mechanism of CVD diamond. A. and Wild. and Windischmann. L. Bowden. C.Y. J. Bowden. 361-365.. C. 48.. E. Amsterdam.A.References Angus. NJ.. Part II. Subramanian. B.. Rel. (1998). Tribol.R. K. on Tribology. 4178-4185. Soc. (1973).). (1994). 4. Bhusari. 13-17.. Argonne National Laboratory. Proc. and Clausing.A. B. Diamond Rel. B. J. and Tabor. Bowden.... 212. graphite. M. and Bhushan. G. The friction of clean crystal surfaces. P..V.V. Diamond Films Technol. 444-455. (1999). J.P.. 77-78. 301-305. (1998).E. Bhushan. Chen. and Ascarelli. Proc. Morphological aspects of the friction of hot-filament-grown diamond thin films. Brookes. Appl.. T.. 79-89. and Schulz.I.K. 74. J. (1993). L.. (Eds. Chandraseka.. B. Friction of diamond. Gupta. Yust. Chen. Workshop on Diamond and Diamondlike Carbon Films. John Wiley & Sons. Cagin. Rangsten. Casey. (1991). (1997). State Commun.P. F.E. Guo. 4-5.G. D: Appl. J. 16th Lees-Lyon Symp. Developments in CVD diamond synthesis during the past decade. Monterey. 10. 153. Micro/nanotribology using atomic force microscopy/friction force microscopy: state of the art. P. Yang. and Meyer. Mater. (1966). The role of environment in the friction of diamond for magnetic recording head applications. (1998). Experimental evidence for alpha. 155-162. Orlando. Aslam.and beta-phases of pure crystalline C3N4 in films deposited on nickel substrates.E. Malshe. MRS Symp. (1995). Diamond on perspective A review of mechanical properties of natural diamond. Che. Chem.A. F. Phys. and Dismukes. in Synthetic Diamond: Emerging CVD Science and Technology. E. Subramanian. Argonne. Proc. (1992). D. T.. Part 2 (of 2). and Moores.H. and carbon and the influence of surface films. Gardos. and Wang. 8. A295. J. and Young. and Ruan. Feb. B. (1994). Eng. Dischler. W. Anthony.. 1.G. A. Chemical. and Hjort. Y. Technology of diamond microelectromechanical systems. (1999). V.

94/95. Surf.F.. Methods Phys. Tribol. Coat. 735-741.. 49. Diamond Films Technol. Rev. (1998). Krauss. and Walkowiak. (Eds. Tribol. A..R. VTT-Helsinki. and Gruen.. Structural. (1996d).. A. and Jahnes. 7988-7993. 118.C. Friction and wear properties of smooth diamond films grown in fullerene+argon plasmas.. Trans. A. V. 559-563.M.. electronic. Krauss.M. Thin Solid Films. J. F. 76/77.. Krauss. Bindal. M...P.. S. G. and Fedoseev. American Chemical Society. Calculation of bulk moduli of diamond and zinc-blende solids. (1996a). C. Pancielejko. Csencsits. Soc. L. Ronkainen. Precht. V. Zuiker.B. The synthesis of diamond at low pressures. Proc. E. 6. and Wilbur. D. and optical properties of carbon nitride. 667-673. Fenske.. (1985)..R. C. A. M. 154. Diamond Rel. J.. 102-109.C. and Jahnes. Czyzniewski. D. A. Y. Krauss. and Wilbur. Erdemir. 39. Sci..P.. Pies. D.. Erdemir. B.S. 537-541..E. Erdemir. and Klages.W.. R. M.. G.V. © 2001 by CRC Press LLC . Csencsits. W.C.R. Homolo. 72-102. Donnet.. Recent progress on the tribology of doped diamond-like and carbon alloy coatings: a review. (1996c). C.L. 233. Eng. 38-56. Deuerler. and Tabor. Fontaine. Erdemir.. P. Belin. A. Surf. Tabersky.. Erdemir. Tribological performance of diamond and diamondlike carbon films at elevated temperatures. A:209.. (1975). Grill. Structure.. composition and tribological properties of carbon nitride films.. C. (1995). Technol. Durability and tribological performance of smooth diamond films produced by Ar-C60 microwave plasmas and by laser polishing.. Friction and wear mechanisms of smooth diamond films during sliding in air and dry nitrogen. 40. ACS Symposium Series 485. Phys. Grill. (1997b). Paga. Patel. Madiba. J. 85. Instrum.. G. 3264-3270.. T. Chung. News.. 94/96. and Grill.. B32. A. A. K. M.. Mater. COST-516 Trib. A. (Eds.. Tribol.. Zuiker.. Technol. and Gruen. Characterization of transfer layers on steel surfaces sliding against diamondlike carbon in dry nitrogen. T.. M. and Konov.E.. and wear behaviour of plasma jet CVD diamond films on hard metal cutting tools.. Donnet. P. G. C. and Gruen. in Surface Science Investigations in Tribology. Donnet. 4. J. Nucl... (1995). A. L... 456-462. (1998). and Sellschop. 923-931. Sci.. 384-387.. Pimenov. A. Erdemir. (1998a). Erdemir. A. A. (1983). H. 9-24.I. Trans. C. (1999).L. V. C. (1997). 543-548. Halter. A. 180-186. G.. Bindal..M. C. 5. Friction control of diamond-like carbon coatings. Peebles. J.P. Coat. Res. Surf.. Myslinski. Surf... Halter. E. Ponsonnet. Coat. Gruen. Trans. 31-47. and Buck.R. Appl.. Dugger. Donnet....R. D. Am. A.R.. C. Zuiker.. C. C. C. The properties of diamond. R. Erdemir. Phys. Tribological properties of hard carbon films on zirconia ceramics.. Tribological characterization of smooth diamond films grown in Ar-C60 and Ar-Ch4 plasmas. Mat. and Pope. 559-562.. Cohen. C. (1996b). and Holmberg. and Fenske.R. G.. Counterface material and ambient atmosphere: role in the tribological performance of diamond films. C. Technol... Oxygen and hydrogen on the surface of diamond.. Deryagin. 787-794.. Tribology of solid lubricant coatings.M. Tribological behavior of amorphous carbon nitride overcoats for magnetic thin-film rigid disks. Lett. Lefèbvre.. G. W.. Le Mogne.-W... Symp. Production. D. D. and Street. Solid state 13C and 1H nuclear magnetic resonance investigations of hydrogenated amorphous carbon. C. Fenske. (1991). Tribol. 218. R.. D. Coat.). M. Li. Experimental Approaches. London. (1996). Condensed Mat. The respective role of oxygen and water vapor on the tribology of hydrogenated diamond-like carbon coatings. Coat. Bindal. (1996).. Tribology of hard carbon films under extreme sliding conditions. 317. R. Y. van den Berg. A.. Fenske. Techno. Tribol. 259-265.M. D. 403-422.... Technol. D. Patel.Cohen. Fenske.. 39. (1997a).. H. 1-4. Proc. C. C. M. Res. Cutiongco. Dimigen. 405-417. (1995). Physica Status Solidi (A) Appl. 543-547.. Enomoto. Washington. Finland. Y. and Bhatia. characterization.). Microstructure and wear behavior of metal-containing diamondlike coatings.B. Derry. Fenske.. F. (1981).R. H. 100/101. A. P. Surf. Chung. Donnet. (1992). V. Bindal. A373. 4. (1998)..

K. O. P. Erz.V. Met. Diamond Films Technol. Doetter. (1992).. D. Technol. J. P.. Silicon and diamond for MEMS bearing applications in extreme environments.. Germann. 121. 50. B. Fenske. 419-504. G. (1993). Fendrych. W..R.. (1993). (1999). K. (1993). and Wilbur.). in Synthetic Diamond: Emerging CVD Science and Technology.E. R.A. U.N. II. 417-421. A. A..187. and Fenske. High-temperature durability and tribological performance of diamond and diamondlike carbon films. and Csencsits. Jastrabik. Eryilmaz. Academic Press. (1962). Field. Erdemir. London. Pan... O. G. Erdemir. Technol. D. Synthesis of diamondlike carbon films with superlow friction and wear properties. J.J. Tribol.P. Phys..R. S. 169.N.. Soukup.E. J. friction noise and wear with silicon and diamond. Switala.A. J. Gardos.. Surface chemistry controlled friction and wear behavior of Si (100) vs. Diamond-like carbon — Properties and applications. Neubauer. Jung. Appl.. Eversole. Tribological properties of nanocrystalline diamond films. Feng. (1994). 4. 41-56. 113. (1999). 449-453. (1994). III. Gardos. and Dismukes.. R. A. M.. Atmospheric effects of friction. Vacuum Sci. Friction and wear performance of ionbeam-deposited diamondlike carbon films on steel substrates. Electrochem. Spear. New York. 103-112.M. Phys. 73. John Wiley & Sons.R. 21. 185-198. Field.S.Erdemir. J. London. Patents 3. 25. Erdemir.. A. Gardos. Erdemir. K. The Properties of Diamond. K.L.030. Wei. Gardos. and Seki. P. Academic Press. Diamond Rel. M.. Coat. Surf. Davis. D. Z. 465-481. in Protective Coatings and Thin Films: Synthesis. 18. Preparation of smooth and nanocrystalline diamond films. (1994). Atomic scale friction of a diamond on diamond (100) and (111) surface. Coat. J.B.. Crystal-structure-controlled tribological behavior of carbon-graphite seal materials in partial pressures of helium and hydrogen. Coat. (1992). 169-184. (1991). Pauleau. 97.. 6. 163-176. J. and Fenske. and Richardt.. 183-200. SEM tribometry. Nilufer. New York. and Gabelich.. Lett.. Feng.. L. (Eds.. Pajasova. Appl. P.. S. 3.R..S. McCauley. Cohen. 3.. 221-29.E. Tribology and wear behavior of diamond. (1997). (1997c).. The friction and wear of diamond sliding on diamond.L.. Characterization and Applications. Technol. Tribological fundamentals of polycrystalline diamond films. Gardos. (2000a). G. 47.E. M. D. and Rusnak. G.N. A.. SEM tribometry of polycrystalline diamond in vacuum and hydrogen. J.P. 7. Fenske. X. A tribological investigation of the graphite-todiamond-like behaviour of amorphous carbon films ion beam deposited on ceramic substrates..G. F. Diamond Rel. Surf.. (1993).. (1998). G.B. Proc. 9. K. and Barna.188. (2000b).E. (1990). M.. Friction of diamond and chemical vapor deposited diamond coatings. 2.. (1999). Kluwer Academic. and Meldrum. A33-A37. 1987-1992. in Synthetic Diamond: Emerging CVD Science and Technology.... (1991).)..).. M. Tribol. Mechanical tribological and optical properties of CN2 coatings prepared by sputtering methods. Wear. A. London. Friction and wear behavior of diamond films against steel and ceramics. M. I. (1979). and 3. The Properties of Natural and Synthetic Diamond.). McClelland. A. F.E. Y. K. 695-700. Wei. Krauss. R. NATO ASI-High Technology Series. Mater.E. Fedoseev. J. Enke. and Field. Gruen. M. (Eds.N. Diamond Rel. and Ehrhardt. G. H. Chvostova. and Field. Technol. W. Diamond Rel. (1998). Field. G. and Dismukes. and Wilbur.K.. Mater.. textured polycrystalline diamond film tribocontacts.. and Tamor. and Ravi.M. John Wiley & Sons. Mater. G. Franks. 281-324. Phys. Gangopadhyay. Nichols. Surf. (Ed. M. L. Erdemir. © 2001 by CRC Press LLC . A. J. Gardos. Mater.. H. Surf.. Coat. 632-637. Technol. Lett. Effect of source gas chemistry on tribological performance of diamondlike carbon films. T. and Wilbur.. 17-23. (Eds. 119-124.A.. L. Soc.. J. 631-645. Mater.. Z. Spear. Vol. A.N.. Summary of Research on Diamond Growth from the Gas Phase in Russia. Eryilmaz.N..030.. 589-593. R. November. 139-165.

(1994). (1998). Gruen.W.Gilbert. 1758-1763. Diamond Rel. Lett.A.J. Chem..). Electrical and optical properties of diamondlike carbon. 356. Fullerenes Photonics. 200. P. and Wild. John Wiley & Sons. I... P. Effects of chemically bound. R... White.P. Thin Solid Films. Grill.-G.A. Am. Harrison. Coat. and Seitzman. Grill.739-745. Conf. Phys..W. An atomic-scale view of the wear of diamond. and Brenner.. 91-141. Pressure-induced phase transformations in diamond. 13. 94/95. L. and Field. (1997). Chem. J.E. 80. 225-232. © 2001 by CRC Press LLC .M.V. (1993).. 49. C. (1996). Liu. Gruen.M. Tribology of diamondlike carbon and related materials. (1997b). Luo. J. Appl. (1995). Gupta. D. and Pan. Molecular-dynamics simulations of atomic-scale friction of diamond surfaces.A. Liu. Coat.. Low temperature diamond deposition. IMechE. Application-oriented modifications of deposition processes for diamond-like-carbon-based coatings.R. 215-227.R..K. Hayward.T. and Alahelisten. C..P. A. 243-253. A. Int.P.). Grill.S. Buckyball microwave plasmas: fragmentation and diamond-film growth. D.. 271. Martinu. and Pan. X. 25/30. A.. K. and Singh. Spear. A. and Hedenqvist. (1995). C.. Springer-Verlag. 103-117.. 1299-1304. 84. 116. New York. (1992).. 116.. Novel in situ production of smooth diamond films. 554-559. 1502-1504. S. in Low-Pressure Synthetic Diamond.G. Gogotsi. and Patel. Harrison.. Malshe. flexible hydrocarbon species on the frictional properties of diamond surfaces. C. J.. Bewilogua. Vlcek. Property control of diamondlike carbon coatings by selection of precursor bias and dilutant. 57-67. 205-209. 1-13. 507-513. 9700-9708. Characterization of diamondlike carbon by infrared spectroscopy.E. Surf. 50 Years on. Tribol. B. A. 2089-2091. Phys. A. New York. A. B. H. Hatta. Hayward. Kluwer Academic. 64. and Brenner.. Diamond growth by hot-filament chemical vapor deposition: state of the art.L. (1992b). 6573-6576. (1998). R. Technol. C. Nucleation. Berlin. Diamond films grown from fullerene precursors. R. Wear. J. A. Wear. B. 23. Appl. Phys. D. Direct current bias applied to hotflame diamond deposition produces smooth low friction coatings. Mater. 445-453.E.W. P. Gunnars.. Colton..M. Kailer.). B. 157. (1994). M.. Harrison. and Nickel. Trojan. K. Friction and wear of diamond. and fracture of diamond (111) surfaces. (1991).R. Simulated tribochemistry.R. Technol. Appl. Effect of roughness on the friction of diamond on CVD diamond coatings. J.. 213. Wear.A. Dischler. J. Development and status of diamondlike carbon. Friction and wear properties of diamonds and diamond coatings. Surf. and Dismukes. in Protective Coatings and Thin Films. Grill. Zuiker. Technol. Dimigen.M. (1987). J. adhesion.J. Grill.M. 32-35. Hayward. J. and Brenner. Coat. V. B... Grischke. and microstructure of nanocrystalline diamond films. K. Gruen. Lee. Soc.. (Eds. R. I. Singer.P.. 2.T. A. (1998).... White. (Eds. Phys. and Lux... A.W. (1994)..J.. Surf. D. (1997a).G. A. J. Haubner. J. J. (Eds. in Synthetic Diamond: Emerging CVD Science and Technology. Coat. S. A. L. I. A. Colton... Krauss. K. 1277-1294. D. R. K.. J. and Brenner. 10399-10402.. S. I. (1996). and Krauss.K. 189-193. Appl. Nanoscale investigation of indentation. and Subramanian. growth. J. Surf. Gruen. Sci. Y. D. 75. and Meyerson. J. Surf. 303-312. and Hiraki.T. (1994). 74/75.. Hollman. Phys.. Y. Harrison. Hogmark. Rusnak. (1992a). Bhushan. C159/87. B. H. A... Lett.. Krauss. V.. Technol. D.. V. MRS Bull. J. D. and Berna.. 97. and Hawthorne. White. 46. D. (1999). Hajek. On Tribol. Pauleau.. Fullerenes as precursors for diamond film growth without hydrogen or oxygen additions. 1735-1737... (1998).. Tribological study of CN2 films prepared by reactive DC magnetron sputtering. Colton. (1994). Alahelisten. Phys..B. Res.. X. Thermal stresses in diamond coatings and their influence on coating wear and failure. Mater. (1993). 80-89. 60. D. Friction and wear properties of chemomechanically polished diamond films. Rev. (1992).

(1991). G. P. 3rd Int. Surf. Ref.R. K. Coatings Tribology. B. Eng. Leyendecker. 603-610. Rev. (1994). 239-255. (1993). Prediction of new low-compressibility solids. 10727-10734.. Low-pressure diamond synthesis of polycrystalline diamond abrasive. (1998). F.. C. Cheng.. B.K.L. Tribological properties of CVD diamond films in various environments. and Aldinger. and Weimer. Rev. Properties of carbon nitride films deposited by magnetron sputtering. (1996)..L. 1360-1369. J. B. (1998b). Lemmer.S. (1998). Karner. M. Holmberg. Higuchi.. Appl. 120. Eng. and Cohen. Buchkremer-Hermanns.. 48. Hollman. 664-671. Wanstrand..H. 378-383. M... (1992). Dravid. and Grasserbauer. 3.. V.. Konyashin.E. Influences of WC-Co hard metal substrate pre-treatments with boron and silicon on low pressure diamond deposition. S. and Sproul. 203-205. (1997).. (1990). Mater. Coating crank up tool performance. 537-542. Tzeng. and Kato..E. Int. L. 245. Conf. Adv. and Farrabaugh. Pedrazzini. M. Kubel. in Low Pressure Synthetic Diamond. (1995). Komplin. R. Yoshikawa. A. Films and Rel.. W. Tribol.R. 15. Tribologia. L. E. Science. R.). 1769-1777..... Coat. Mater..W. (1994).C. 33-62. Wong..E. 49. and Gallois. Y. © 2001 by CRC Press LLC . and Noda. Y. 135-148. 68-69. Mater. S. S. Jahanmir. 12. I. Steiner... Stingeder. Chung. Sci.D. N. Tribological properties of carbon nitride overcoat for thin-film magnetic rigid disks. A.. Technol. S. S... and Ren.. Mat. Surf.P.E. Holmberg. 119-136. Li.. I. A.K. A. (1990). Structural properties and electronic structure of low-compressibility materials: β-Si3N4 and Hypothetical β-C3N4. Elsevier.E. Inspektor. Kim. 3.-W. J. J. Thermogravimetric analysis of the oxidation of CVD diamond films.. Evetts. Diamond Rel. H.E.. Res.D. A. Coat. Kohzaki. 285-296. Wong. Kupp. Thin Solid Films. Komanduri. and Bauer. and Mansur. Drawl. 86/87. D. Int. and Wild. 332.Y. D. Wear. R. X. D. NIST SP-885.. S. 405-413. Plasma-assisted CVD of cubic boron nitride. (1994). Friction properties of smooth nanocrystalline diamond coatings.. (1998). Somekh.. E. Mater. Ives. Coat. 37.Y. on Appl. Johnson. and polymers... Kubelka. Surf.. Lin. Diamond coatings applied to mechanical face seals. Lux. Mater. Phys.. X. Tribological characteristics of synthesized diamond films on silicon carbide. (1998).. Rao.Hollman. Dischler. Berlin... graphite.C. 169-174. Chung. C. (Eds. 13. Alahelisten. Chu. Tribology of diamond and diamond coatings — A review... M. R.. Oles. Diamond Rel. Y.S. M. O. (Eds.. M. Liu.A. Machine Tools Manuf. 40-46.J. 9. Surf. Manufact. B. Kusano.M. Diam.. M.H. 105. G. and Murakawa. 5. D. Y. Trans. and Bergmann. S.. Technol... Haubner.. D. Esser. and Hogmark. Yarhrough.. Sjostrand. R. (1994).S. and Hogmark. (1993). Proc. A. Reineck.. Li. E. Deckman. Weiss.W. Met. and Hutchings. 49-56. P. Bill. Other CVD methods for diamond production.. R.S. A. J.. D... and Matthews. 15540-15551. Liu.. K. Hard Mater. (1996). and Cohen. and Uchida. (1989). The effects of oxygen and humidity on friction and wear of diamond-like carbon films. (1997). (1989). H. Keipke. Theory and practice in diamond coated metal-cutting tools. Coat. Phys. 183-190. M. 56-61. J. W.. CVD diamond-coated cemented carbide cutting tools.A. 479-482. 67. (1994). S. Springer-Verlag. Washington.E. W. Hasting. S. Manufact. Mater. Technol. Diamond Films Technol.G.. (1998a).. K. Res.. T. Nano-indentation and tribological studies of ultrahigh strength carbon nitride thin films..R. C. H.. and Sproul. Lett.J. M. E. Interlayers for diamond-coated cutting tools. Y. 2320-2325. Mater. Synthesis of superhand carbon nitride composite coatings. E.. 1471-1477. M. Feldman. Lee. Bjorkman.. 7. Hembree. H. Machining of hypereutectic AlSi alloy with CVD diamond-coated Si3N4 inserts... Khurshudov. Noda. A209. Phys.. K. W. Tribological characteristics of polycrystalline diamond films produced by chemical vapor deposition.A. 7. (1998).. E. Fischer. and Frank. K.. M. Amsterdam. I... 133. M. M.E. O.. Process.. J. Kohzaki... A. 33. and Hauge. J. Technol. and Nandyal. (1995).. 841-845.). Wear mechanism of diamond coated cutting tools. 41. K. and Spear. Feldman..M. 73-81.. W. Raman scattering from ion-implanted diamond.

.. C.Y.. and Miyazaki. Electron. Self-lubricating Diamond Films and Coatings.L. H.. Friction and wear of diamond and diamondlike carbon coatings. R.N.. 54/55. (1994). (1997). Phys. 15. M... and Meletis..A.L. 102. Blatter. (1998).M. Wear..Y. W. Coat. Anderson. C. Mater.. Res.J.C. H. with emphasis on Ballas. M. K. S.. M.I. V. P.B. and Wild. Mater. A. Forum. Diamond as a wear-resistant coating. 340.. Lett. and Garscadden. Sci. Manufacture of c-BN films with improved adhesion. M. diamond films and coatings.. Int. R. Watanabe. Technol. Surface Design Engineering Toward Wear-Resistant. B. B. Watanabe. Loubnin. Miyamoto. Appl. (1992). Y. Res. K. J. (1996). Ramesham. (1997). M. and Haubner. Possibility of coating cubic BN films on various substrates. J.F. J. Pate. Maillat.. T. 212.C. A.H. (1995). A.T.. S. R. and Miyake. Molian.E. 8. and Haubner. E. 223-227.I.P. Pfouts. Proc.and micro-tribological properties of polished CVD diamond films and trial processing diamond. Wang. 320. Structures and mechanical properties of natural and synthetic diamonds.L. S. 11. Wu. Appl. E78.. E. (1996).. A. A. Thin Solid Films.. T. 82. Murakawa. (1982). Natural and synthetic polycrystalline diamond. S.. H. and Lawler. K. R. Appl.T. Burger. Murakawa..A. Sci. Coat. W. Miyoshi. (1996).J. (1998). Holzer. Fabrication of diamond microstructures for microelectromechanical systems (MEMS) by a surface micromachining process. NOYES Publications Park Ridge. J. Surf. 783-785. Miyake. and Santhanam. 1-6. and Miyamoto. Haubner.. R.. Hecht.. K. 93. T. 1-28. Olson. Pierce. E. Miyoshi. M. T. Wear. U. B. Tribological improvements of polished chemically vapor-deposited diamond film by fluorination. Jupiter. J. 65. Surf. Prengel. Murakawa. Davis. 48-56. Murakawa.G. 223-242. Miyoshi. J.. Technol. H. 153-172. Stefan. J. (1999).. Surface coating of superhard materials for tool applications. Eng. Kaneko. A. Fine patterning of diamond thin films.... Technol. Dischler. 9. Miyoshi. 263-288. Leijala. M. and Dawes. Janvrin.. IEEE Micro Electro Mechanical Systems. IEICE Trans. 180-185. 133-140. Nanotribology studies of carbon surfaces by force microscopy.. and Jackson. 246.. Phys.R.. 17-20. Friction and wear of plasma-deposited diamond films. Tribological properties of smooth diamond films. 1109-1111.. A. Ohta.W.Liu. Diamond Films Technol. B.. 428-434. Sci. Springer-Verlag. and Hintermann. Thin Solid Films. Waclawski.D. M. Surf. P. B. Met. P. Xie.M. Menningen. J. S.. Shek... 4446-4450. Mater. 183-190. Wu. Ramesham.. 145-153.. A.. Examination of the material properties and performance of thindiamond film cutting tool inserts produced by arc-jet and hot-filament chemical vapor deposition. Technol.F.). 165. (1992). Childs. (Ed.. K.. Bogli.. Mate. B. (1998). Toyoda.. Physica B... (1995). NASA TM-208905. (1993). Polishing of polycrystalline diamond by hot nickel surface. Smolin. (1993).. 392-393. M.. 1765-1775. Mao. M. H.E. S. Ref. and Molian. State of the art in hard coatings for carbide cutting tools. ASME-IEEE.L. Hard Mater. (1990).. Berlin. 92. in Low-Pressure Synthetic Diamond. R. Barnes. and Wang. Lux. and Rose. Pimenov. Miyake.. 1-17.. M.J. Coat. and Swanson.. Binns. Laser chemical vapor deposition of fluorinated diamond thin films for solid lubrication. B. R.. 106-114. Diamond (111) surface: a dilemma resolved. © 2001 by CRC Press LLC . R. Surf.. A study of the wear mechanism of diamond-like carbon films. P. and DeVries. Lux. Miyake. (1994).C. T. Erdemir.E.).F.A. N. R. L. Obraztsova... 753-758. (1995)... (1993).N.. Thin Solid Films. D. 262-266. Macro. R. S. 915-920. 168. Garscadden. Konov. Tribological study of cubic boron nitride film. 43. M. 74. (Eds. Evaluation of a substrate pretreatment of hot-filament CVD of diamond. 117/118. Coat. (1999). R.. Lux. Surf. and Watanabe... (1991).. NJ. 184-243. Kaneko.M. CVD diamond for cutting tools. A140. (1993). S. Mater.

. S.P. K. C. (1990). Technol. Yates. III (1997).W. S. Surf. (1996). Likonen... Robertson.. 49. K. and Miyake.. Meneve. (1996). (1997). 86/87. (1995). Coat.). Academic Press. 406-410. Friction-induced phase transformation of pulsed-laser-deposited diamond-like carbon.I.. in The Properties of Diamond. Thin Solid Films. 5. Mater. J. Friction behavior of amorphous-BN-cubic-BN duallayered film. (Eds. 5. in Applications of Diamond Films and Related Materials: 3rd International Conference. V. S. Phys. Diamond chemical vapor deposition: emerging technology for tooling applications. Shen.. E. NASA TM 113163.S. A. and Murakawa. Diamond Rel. Hugon. Lett.. 32-45. Corat. Effect of fluorination of diamond — C4F9 and CF3 photochemistry on diamond (100). K. (1998). Technol. A. Mater.. 416. A.. Wheeler. J. (Eds. 370. in Synthetic Diamond: Emerging CVD Science and Technology.W. K. and Zabinski. D. Surf.. 209-231.E..A. Characterization of wear surfaces in dry sliding of steel and alumina on hydrogenated and hydrogen-free carbon films.E. L. and Tribological Properties of Cubic Boron Nitride Films.A. M. Murakawa. and Donley. Performance and applications of CVD thin film diamond coated tools. Silva. Microstructure.J.. Monograph.. Voevodin. Goddard. New York. Appl.G. The current status of CVD diamond applications and prospects for the future. Robertson.J. J.. Research on carbon nitrides. Thin Solid Films.S. Phelps. 2846-2864. Surf.. 76/77. 56. V.H.. World Scientific Publishing. (1988). and Winkler. J.J. C. Surf. R...). Varjus. Smeets. New York. Thomas. 228. Y. Smentkowski. 241-298.P. Samuels.. (1998). S. Laube. 419-504. 325-350. 1868-1870.. P. Spear... Oriented hydrocarbons transferred from a high-performance lubricative amorphous CHSi film during sliding in vacuum. S... Coat. Sugimoto.. Zabinski.K.Ravi. MRS Symp. Koskinen. Surface Chemistry.S. and Yates. G. Tankala. 600-603.. Dekempeneer. Singapore.. J. Mohlfeld.). Shen. J. 543-550.A. in Amorphous Carbon: State of the Art. W. Mater. 1264-1269. Importance of diamond coated tools for agile manufacturing and dry machining.. J. S. Trava-Airoldi. 293-298. Seal. Watanabe. Street. K. Smentkowski. Technol.). Gey. 195-244. NIST Special Publication #885. Mater. M. Rossi.. Jr.R. Design of a Ti/TiC/DLC functionally gradient coating based on studies of structural transitions in TiC films. amorphous and hexagonal boron nitride films. I. M. Sci.. Toenshoff. 3-12. M. J. Chen. Technological applications of CVD diamond. Res. J. Schaffnit.S. Coat. Key Eng. (Ed.. J.P. Technol.... 41. (1979). F. Electrochem. S. (1996). (Eds.. S.T. V. X. (1994).. (1991). 1329-1336. Wang. Jr. Voevodin.. (1997). Soc.. The friction of diamond sliding on diamond. J. and Murakawa. and De Wilde. J. B. D.. W. Sci. Adhesion and friction. J.. Milne. John Wiley & Sons. Tabor. L. C. Mater.. H. Fluoroalkyl iodide photodecomposition on diamond (100) — An efficient route to the fluorination of diamond surfaces. S. M. 23.. 3.B.R. 672-677.. J.. Field. (1999). and Miyake. A.S. M. (1990). Capano.. S.J. Diamond Rel. et al. Oxidation of diamond films synthesized by hot-flament-assisted chemical vapor deposition. Coat. (1998).. 108/109. 298.. Feldman. Ronkainen. Surf.. 138/140. 2483-2489. A. and Baranauskas. (1993). J. H. Van Den Bergh.J. 86/87. Technol.. E. Miyake.. Sci.. J. 402-408. Prog...A. E. Watanabe. © 2001 by CRC Press LLC . Miyoshi. (1996).T. and Amaratunga. and Wilks.-H.A. 107-115. (1995).. C.. Key Eng. Tribological properties of cubic. 138/140/25-55.. Deposition of wearresistant BN coatings by RF plasma-assisted chemical vapour deposition. Modification of cemented carbide cutting tools for improved adhesion of diamond coatings. (1998). (1997). Miyake. Abel. M. V. Surf.S. J. and Vihersalo. and Dismukes. and Pauleau. Plasma-assisted chemical vapour deposition of BN coatings: effect of the experimental parameters on the structure of the films. Coat. Mater. Deposition mechanism of diamond-like carbon. 272-275. Donley. Watanabe.V. V. Mater.

Zuiker. Han. M. Superhard coatings of CN2/ZrN multilayers prepared by DC magnetron sputtering. J. Bindal. Toivanen. Gluche.. © 2001 by CRC Press LLC . Thermochemical polishing of CVD diamond films.E.. K. S.. Surf. Q. Haller. Res. P. R. Phys. MRS.. McClure. Krauss.H. J. and Yates. Raiko. Wang.L. Hansen..Wei.. Physical and tribological properties of diamond films grown in argon-carbon plasmas. (1999).. Thin Solid Films. smooth diamond films on silicon for electronic devices. Anttila. 111..-C.S. Smentkowski. Job.... and Wu. J.C. 120. Jung.. Zaitsev. B.. Philos..O. Mater. S.. Ebert. and Robertson. Wong.W. 32. (1995)..R. Kosaca. Observation of crystalline C3N4. A.P. Erdemir... 196. Borst.. H. 453-459.. 270. C. Wu. Lett. H. Veerasamy. X. Preparation and properties of highly tetrahedral hydrogenated amorphous carbon..M.S. Crit. Vescan. and Prater. New carbon nitride phase synthesized by ion-beam sputtering. Thin Solid Films.. and Fenske. Ong. Yee. L. Phys..Q. Proc. Chung. 1796-1805.S.. Zou. (1995). Lett. 63-68. 1108-1117. and Fahrner... 5. Gruen. (1994).P. (1995). J. and Kohn. Fries. Giessen. 1594-1608.. A.Y. (1998). M. and Sproul. Z. M. Mater.D. Pan. W. and Chang.-Y.H. 12.T.. T. J.. smooth (100) faceted diamond thin films using microwave plasma chemical vapor deposition.. A. Z. Ong. X. Technol.L.. Proc. Csencsits. Yu. Structural and tribological characteristics of carbon nitride films deposited by the reactive ionized-cluster beam technique.L. E... J. Wolden. Friction and wear of polytetrafluorethylene on diamondlike carbon film. and Feng. (1998). 307-312.. Fabrication of highly oriented.Y. 383.D.. Yu. A... Rev. and Fan. Cohen.. (1996).M.. Z.C. Wong. W.H. Development of flat.. 113-117. Yee. C. Ehrhardt. E. MRS. Qian. Highly oriented diamond deposited using a low pressure flat flame.T. Wu. G.R.. Sitar. Y. Rev. W. J. L. Mater. R. 308/309. T.A.M. K. R. 423.. Surf. (1991).m L25-L29. G. V. Richarz. J. A. Y.-W.C. 49.P.L.. E. Liu. Chem. 9-12...L.D. 154-159. V. and Chang. Li. W. W. A...M.. Coat. M. (1997). (1997). Diamond Rel. A.. Stewart. Xie. Diamond surface chemistry II — Selected bibliography.. Sattel.L... 119-122. Yang. W. Y. 5034-5039. A.. I. M... M. C.K. Xu. B. Rev. (1997). 7. B53(3). Chung. Xu. R. D. (1997). R. J. Synthesis of coatings with hardness exceeding 40 GPa by magnetron sputtering. Mag.W. S. Weiler. and Sproul..-Y..... Yang. X. Tribol.-C.. J... J. 78. M. (1996). and Hirvonen.L. Zhang. Morphological control of diamond thin films: it influence on friction and wear. T. H. Thin Solid Films.... Wolter.. 179-183. 73-248. R.

Sign up to vote on this title
UsefulNot useful