Amorphous hydrogenated carbon films for tribological applications I. Development of moisture insensitive films having reduced compressive stress

Although earlier investigations on the tribological behaviour of amcrphous hydrogenated carbon (AHC) films in sliding contact with steel showed encouraging results, four open issues were identified. They were: (a) dependence of friction and wear on humidity (i.e., the friction coefficient and the wear increased with humidity), (b) limitations on film thickness (i.e., films greater than 2 μm thick delaminated due to large compressive stress), (c) deposition of films on substrates other than silicon and (d) lubricant compatibility (i.e., formation of lubricant-derived antiwear films on AHC film surfaces). Steps were taken to address some of these open issues by incorporating silicon in AHC films. Friction and wear tests were conducted on AHC films containing various amounts of silicon. Incorporation of silicon in AHC films rendered the friction coefficients and the wear of a steel counterface insensitive to moisture. Silicon incorporation in AHC films also significantly reduced compressive stress. This allowed deposition of 10 μm thick films. These effects were achieved without any compromise with the friction coefficient and the film wear if the amount of silicon in the film was kept within a certain concentration range. In addition, silicon-containing AHC films were thermally more stable than silicon-free films. Experiments conducted with two lubricants resulted in significantly lower wear of the silicon-free AHC films than that obtained for unlubricated sliding. Similar friction coefficients were obtained for AHC film/steel and steel/steel combinations in lubricated sliding.     

Mechanical and tribological properties of amorphous carbon films

The mechanical and tribological properties of amorphous carbon films have been studied in more detail in recent years because these films (a) can be deposited near room temperature, thus allowing film deposition on common engineering alloys (i.e., aluminum and steel) without altering their mechanical properties, and (b) are smooth and conform to surface roughness of the substrate, thus requiring no post deposition processing. In addition, amorphous carbon films exhibit low unlubricated sliding friction in contact with steel and ceramics which is comparable to that of steel against steel in a lubricated contact. The wear resistance of these films is also better than Ti‐based hard coatings. Further improvement in film tribological properties can be achieved by modifying film chemical composition. Because of these attractive features, amorphous carbon films have been evaluated in several applications including automotive, electronic and biomedical engineering. However, environmental factors such as oxygen and humidity have been found to influence tribological properties significantly. This paper reviews the current understanding of the tribological properties of both hydrogenated and non‐hydrogenated amorphous carbon films, the mechanisms responsible for low friction coefficient and identifies areas that require further research. This revised version was published online in June 2006 with corrections to the Cover Date.     

Adhesion and friction properties of hydrogenated amorphous carbon films measured by atomic force microscopy

Atomic force microscopy has been used to measure adhesion and friction forces at the interface between an oxidized metal probe tip and amorphous carbon films of varying hydrogen contents (12.3–39.0 atomic percent hydrogen). The interface of an oxide surface and a hard carbon coating models the unlubricated head-disk interface of current hard disk products. Adhesion forces normalized by the radius of curvature of the contacting tip range from 1.09 to 8.53 N/m. Coefficients of friction values, measured as the slope of the friction versus load plot, range from 0.33 to 0.87. A trend of increasing adhesion forces and coefficients of friction is observed for increasing hydrogen content in the films. We attribute the increase in adhesion and friction to increases in the surface free energy of the carbon films with the incorporation of hydrogen.     

Multilayer composite ceramicmetal-DLC coatings for sliding wear applications

The design of anti-friction coatings able to perform well in different wear conditions without lubricants requires a combination of adequate hardness and toughness, good adhesion, a low friction coefficient and a low wear rate. Recently introduced metaldiamond like carbon (DLC) coatings produced by magnetron sputtering of metals from targets, which are to a controlled extent covered with carbon from the chamber atmosphere, can be a step towards the achievement of such a combination. These coatings consist of an amorphous a:CH matrix with the possible incorporation of metal (Ta, W, Nb, Ti), metal carbide and/or graphite grains. Previous studies of Ti_x%-DLC coatings showed their good protective properties against abrasive, impact and single scratch wear, as well as a requirement for supporting interlayers to successfully apply such coatings to low-cost steels. In the present work an example of the selection of metal-ceramic Ti-TiN-TiCN supporting interlayers is given based on studies of their morphology, structure and mechanical properties. This resulted in the development of Ti-TiN-TiCN-[TiC-(Ti_x%-DLC)] multilayer composite coatings. Several coatings were prepared with the same supporting interlayer and a variation in the preparation of the Ti_x%-DLC layer. Ball-on-disc experiments were carried out to investigate these coatings in conditions of sliding wear against steel and cemented tungsten carbide balls. CrN, TiN and TiCN coatings were also deposited and tested in the same conditions to provide a reference. Low friction coefficients (below 0.2 at an air humidity of 50% RH) in combination with low normalized wear rates were found for multilayer coatings with upper Ti_20%-DLC and Ti_35%-DLC layers.     

A comparative study on the microstructure and tribological properties of Si3N4 and TiN films produced by the IBED method

The tribological properties of Si₃N₄ and TiN thin films produced by ion beam enhanced deposition (IBED) were compared on a SRV friction and wear testing machine. The friction coefficient of all thin films shows a descending tendency with increase in load, and is lower than that of 52100 steel. All the IBED films show a much better wear resistance than 52100 steel, especially in the higher load and frequency ranges; it can reach six times that of the latter. In order to understand the reasons for their excellent properties, the microstructure, microhardness and bonding strength with the substrate were analysed by SEM, X-ray diffraction, Knoop hardness and scratching test methods separately. The results show that the TiN(1) film exhibits the best tribological properties, which are closely related with its greater hardness and bonding strength.     

Dependence of the friction process on the molecular structure and architecture of thin polymer films

The frictional properties of a homologous series of poly(n-alkyl methacrylates) (PnAMA) and a series of poly(methyl methacrylate) (PMMA) films, cast from a variety of solvents, are characterized. The choice of polymer film was driven by the consideration of the possible mechanisms for the accommodation of a macroscopically applied shear stress by molecular entities. Two possible mechanisms are proposed: (i) the relative flexibility of the polymer backbone chain. For this purpose the PnAMAs have been chosen. By varying the length of the substituent chain, the relative molecular freedom around the backbone chain is altered. These molecular differences are sensed in the frictional properties at the macroscopic level, and (ii) the molecular organization is also proposed to be a factor in determining the friction response of a particular polymer film. For this purpose, the frictional properties of PMMA films cast from different solvents are investigated. There is observed to be a strong influence of the molecular organization on the frictional properties of the solvent cast PMMA films. The molecular probe employed to characterize the molecular environment is vibrational spectroscopy. Conformationally sensitive vibrational modes are used to determine the relative flexibility of the backbone chain and the organization of the chain network.     

Tribological properties of nickel-base nanocrystalline coatings sputter-deposited on austenitic stainless steel

500 nm-thick films are deposited on austenitic stainless steel by neutral (Ar⁺) or reactive (N⁺) ion beam sputtering of Ni or NiTi targets, with (or without) high energy 160 keV-Ar⁺ ion beam assistance. Most of the time the coatings are nanocrystalline and induce a large (excellent in some conditions) increase of the wear resistance. Only Ar⁺ ion beam sputtering of a NiTi target gives an amorphous deposit which does not improve the substrate tribological properties. The hardness and wear resistance of ion beam assisted films are larger than those obtained with non-ion beam assisted coatings. The presence of a hard TiN phase inside a ductile Ni phase, of grains with preferential orientation beneficial to slip, as well as film densification are the main factors which increase the wear resistance. The best results are obtained when the structure is composed of two phases, Ni and TiN. The TiN phase strengthens the already good tribological Ni properties and the Ni ductility induces mechanical accommodation during the friction process.     

The composition of lubricant-derived surface layers formed in a lubricated cam/tappet contact II. Effects of adding overbased detergent and dispersant to a simple ZDTP solution

The surface films formed by a set of oils of related additive chemistry, but with differing detergent and dispersant contents, have been chemically characterized using a combination of surface analysis techniques. The films were formed in a cam/tappet friction apparatus with a direct acting bucket tappet geometry. In the absence of overbased detergent, the amorphous films were composed essentially of inorganic zinc phosphates formed by the ZDTP anti-wear additive, and evidence of higher molecular weight phosphates (e.g. metaphosphates) was found. Adding overbased detergent and dispersant resulted in partial replacement of zinc by the detergent metal and loss of the higher molecular weight phosphates in favour of ortho- and pyro-phosphates.     

Comparative studies of perfluorinated lubricants adsorbed on hydrogenated amorphous carbon and amorphous carbon nitride

Temperature-programmed desorption and scanning force microscopy have been used to probe the interaction of a perfluorinated lubricant (Fomblin ZDOL) with hydrogenated amorphous carbon (a:C-H _x ) and amorphous carbon nitride (a:C-N _x ) substrates, two materials used as hard coatings in disk drive products. Temperature-programmed desorption measurements indicate that the nitride surfaces are more reactive toward this perfluorinated lubricant and, as a result, the thin lubricant film is more tightly bound to this substrate. Frictional force microscopy has been used to measure the coefficient of friction of the lubricated surfaces, 0.18 ± 0.02 for both substrate materials, and finds that frictional properties of these interfaces in the low load regime are influenced more by the presence of the lubricant rather than the adsorbed state of the film. Likewise, similar disjoining pressures were measured for the lubricant adsorbed on the different coating materials and suggest that the ultrathin nature of the adsorbed lubricant film dominates this property rather than adsorption states.     

Small amplitude reciprocating wear performance of diamond-like carbon films: dependence of film composition and counterface material

Small amplitude (50 μm) reciprocating wear of hydrogen-containing diamond-like carbon (DLC) films of different compositions has been examined against silicon nitride and polymethyl-methacrylate (PMMA) counter-surfaces, and compared with the performance of an uncoated steel substrate. Three films were studied: a DLC film of conventional composition, a fluorine-containing DLC film (F-DLC), and silicon-containing DLC film. The films were deposited on steel substrates from plasmas of organic precursor gases using the Plasma Immersion Ion Implantation and Deposition (PIIID) process, which allows for the non-line-of-sight deposition of films with tailored compositions. The amplitude of the resistive frictional force during the reciprocating wear experiments was monitored in situ, and the magnitude of film damage due to wear was evaluated using optical microscopy, optical profilometry, and atomic force microscopy. Wear debris was analyzed using scanning electron microscopy and energy dispersive spectroscopy. In terms of friction, the DLC and silicon-containing DLC films performed exceptionally well, showing friction coefficients less than 0.1 for both PMMA and silicon nitride counter-surfaces. DLC and silicon-containing DLC films also showed significant reductions in transfer of PMMA compared with the uncoated steel. The softer F-DLC film performed similarly well against PMMA, but against silicon nitride, friction displayed nearly periodic variations indicative of cyclic adhesion and release of worn film material during the wear process. The results demonstrate that the PIIID films achieve the well-known advantageous performance of other DLC films, and furthermore that the film performance can be significantly affected by the addition of dopants. In addition to the well-established reduction of friction and wear that DLC films generally provide, we show here that another property, low adhesiveness with PMMA, is another significant benefit in the use of DLC films.     

Influence of surface roughness on friction and scuffing behaviour of cast iron under sparse lubrication

Friction and scuffing behaviour of grey cast iron as influenced by the surface roughness under sparse lubrication conditions is studied. The studies are carried out on a three-shoe-on-disc machine under the conditions of parallel sliding. The experiments were conducted at three oil supply rates of 0.10, 0.22 and 0.36 μg/cm² per contact obtained through a mist oiling system and with specimens of cast iron shoes of different roughness values, Ra, between 0.04 and 2.0 μm against a 0.55% C steel disc. In a step load procedure, the friction torque at the end of each load step and the scuffing load are the major parameters measured. Results of friction and scuffing behaviour as a function of roughness and oil supply rates have been discussed.     

Effects of film thickness and contact load on nanotribological properties of sputtered amorphous carbon thin films

The nanotribological properties of amorphous carbon (a-C) films of thickness in the range of 5-85 nm sputtered on Si(1 0 0) substrates were investigated with a surface force microscope (SFM), using a Berkovich diamond tip of nominal radius of curvature approximately equal to 200 nm and contact (normal) loads between 10 and 1200 μN. The dependence of the friction and wear behaviors of the a-C films on normal load and film thickness was studied in terms of nanomechanical properties, images of scratched surfaces, and numerical results obtained from a previous analytical friction model. The increase of the contact load caused the coefficient of friction to decrease initially to a minimum value and, subsequently, to increase to a maximum value, after which, it either remained constant or decreased slightly. The dominant friction mechanism in the low-load range was adhesion, while both adhesion and plowing mechanisms contributed to the friction behavior in the intermediate- and high-load ranges. Thinner (thicker) a-C films yielded higher (lower) friction coefficients for normal loads less than 50 μN (low-load range) and lower (higher) friction coefficients for normal loads greater than 150 μN (high-load range). Elastic and plastic deformation, microcracking, and delamination of the a-C films occurred, depending on the contact load and film thickness ranges. The reduced load-carrying capacity, relatively low effective hardness (strength) obtained with thinner films, and dominant friction and wear mechanisms at each load range illustrate the film thickness and contact load dependence of the nanotribological properties of the sputtered a-C films.     

Thermal Stability of Fomblin Z and Fomblin Zdol Thin Films on Amorphous Hydrogenated Carbon

Thermal desorption spectroscopy has been used to monitor the decomposition kinetics of Fomblin Zdol and Fomblin Z lubricant films adsorbed to the amorphous carbon overcoats of hard disk media. Comparisons have been made between Fomblin Z and Zdol with vastly different molecular weights (MW = 4000 and 50000), and films of Fomblin Z with different thickness (20 and 60 Å). Several species have been observed desorbing from the surface during heating. In all cases decomposition occurs over roughly the same temperature range of 600–750 K. This suggests that the desorption process is the result of decomposition and that the end groups of the Fomblin lubricants are not involved in determining the kinetics of this decomposition reaction. The activation barrier to the decomposition process has been estimated at 114±6 kJ/mol.     

Effects of lubricant-additives on the kinetics and mechanisms of ZDDP adsorption on steel surfaces

The influence of temperature, co-additive type, and basestock on the rates of adsorption of zinc di-isopropyldithiophosphate on SKF-3 steel have been measured. Adsorption behaviour is more complex than previously observed on the similar EN-31 steel and Langmuir kinetics may apply only in the early stages of the process. All co-additives cause reductions in ZDDP adsorption as also does the change from hydrocarbon to diester basestock. Reasons for the observed behaviour are discussed.     

Effects of lubricants on friction and wear of Ti(CN)/1045 steel sliding pairs

The friction and wear properties of Ti(CN)/1045 steel rubbing pairs were investigated under dry and lubricated conditions by using a pin-on-disk tribometer. The selected speed range was 0.8 to 3.2 m/s and the load range was 58.8 to 235.2 N. Distilled water and a mineral oil (no additives) were used for lubrication, respectively. The wear of Ti(CN) ceramic under dry conditions was caused mainly by adhesion between the rubbing surfaces and the microfracture of Ti(CN). With the load and speed increasing, the adhesion and diffusion between rubbing surfaces increased and resulted in wear increasement of Ti(CN). Because of the brittleness of ceramics, the microfracture wear of Ti(CN) increased rapidly when the load was raised to some high values. The lubricating and cooling effects of the lubricants could improve the frict on and wear. Compared with water, oil was much better in improving the tribological properties. The analysis results obtained from XPS and AES examinations showed that ferrous oxide was produced on the wear scars, which could reduce the adhesion between the rubbing surfaces to some extent. The lubricating effects of the oil under boundary lubrication conditions were attributed to the formation of carbon films on the rubbing surfaces.     

A study on mechanical and tribological properties of silicone rubber reinforced with white carbon black

This paper analysed the effect of different white carbon black (fumed silica and precipitated silica) on the mechanics and friction property of silicone rubber. The tensile strength, tearing strength, elongation rate and shore hardness of silicone rubber reinforced with different kinds or dosages of white carbon black were investigated in detail. The wear morphology, worn surface analysis and chemical compositions of the rubber sample after the friction test were analysed by means of scanning electron microscopy, three-dimensional profile metre and energy dispersive spectrometer, respectively. Results showed that the mechanics properties of silicone rubber were obviously enhanced with the increase in white carbon black content. Moreover, after the friction test, the vulcanised rubber reinforced with fumed silica has less wear surface protrusions and grinding than that of precipitated silica. The wear rubber filled with fumed silica surface is quite smooth and shows few furrows and grooves, which well corresponds to good anti-wear ability of the reinforcing fillers. In the course of practical application, it is necessary to take into account of the mechanical properties, wear resistance of rubber and the adding amount of filler to achieve the optimum coordination for the best mechanical and friction properties of silicone rubber.     

Lubrication of Si3N4 and Al2O3 in water with and without addition of silane coupling agents in the range of 0.05–0.10 mol/l

To improve water lubrication of ceramics at a lower sliding velocity, the effect of the addition of silane coupling agents was investigated. Si₃N₄ and Al₂O₃ were slid against themselves in water with and without the addition of silane coupling agents in amounts ranging from 0.05 to 0.10 mol/l. Silane coupling agents containing one or more amino groups were effective in reducing the friction of Si₃N₄ and Al₂O₃ in water. Si₃N₄ also showed significant wear reduction but not Al₂O₃. However, the addition of a silane coupling agent containing an epoxy group increased both friction and wear of Si₃N₄. Improved lubricative characteristics of Si₃N₄ in water and in silane coupling agent solutions were obtained when Si₃N₄ contained smaller amounts of sintering additives. The adsorption behaviour of a silane coupling agent on ceramics was examined using both Fourier transform infrared spectroscopy and thin layer chromatography to clarify the interaction between the silane coupling agent and the ceramics. The role of polysiloxane film formation on ceramics is discussed to demonstrate the lubrication properties of ceramics.     

Thin layer activation for measuring fretting wear and material transfer in iron alloys

An important difference between fretting wear and macroscopic wear processes lies in the amounts of wear volume. Because of the small relative displacements in fretting wear the wear volumes are much smaller than in (classical) macroscopic wear processes. Classical wear measuring techniques such as weighing and 2D-profilometry often fail to determine the fretting wear volumes. Their sensitivity as well as their accuracy are inadequate. 3D-profilometry partially solves this problem but the obtained wear results do not take eventual material transfer between the test specimens into account. In this work thin layer activation (TLA) is presented as a potentially powerful tool for quantitative fretting studies, especially in relation to material transfer. In contrast with the other mentioned wear measuring technique TLA allows measurements of very small amounts of wear as well as material transfer between the test specimens. Preliminary results are reported for steel specimens. A surface zone of 7 mm² of one test specimen, in which the wearing zone during the fretting experiment is situated, is irradiated with protons from a cyclotron. As a result of a nuclear reaction the iron in the irradiated test specimen forms radionuclides, mainly cobalt-56, in a surface layer of 260 μm depth. The amount of cobalt-56 as compared to iron is negligible so that the physical and chemical properties of the irradiated zone remain unaffected. Measuring the gamma rays of cobalt-56 in the wear debris gives quantitative information about the wear volume and measuring the mating surface gives information on the transfer volume.     

Load-carrying capacity evaluation of coating/substrate systems for hydrogen-free and hydrogenated diamond-like carbon films

Diamond-like carbon (DLC) coatings have shown excellent tribological properties in laboratory tests. The coatings have also been introduced to several practical applications. However, the functional reliability of the coatings is often weakened by adhesion and load-carrying capacity related problems. In this study the load-carrying capacity of the coating/substrate system has been evaluated. The DLC coatings were deposited on stainless steel, alumina and cemented carbide with two different deposition techniques: the tetrahedral amorphous carbon (ta-C) coatings were deposited by a pulsed vacuum arc discharge deposition method and the hydrogenated carbon (a-C:H) films by radio frequency (r.f.) plasma deposition method. The load-carrying capacity of the coated systems was evaluated using a scratch test, Rockwell C-indentation test and ball-on-disc test. The effect of substrate material, substrate hardness, coating type and coating thickness was studied. An increase in substrate hardness increased the load-carrying capacity for the coated systems, as expected. The two coating types exhibited different performance under load due to their different physical and mechanical properties. For the load-carrying capacity evaluations the ball-on-disc configuration was found to be most suitable. This revised version was published online in July 2006 with corrections to the Cover Date.     

The lubricated wear of ceramics : Part II: The wear and friction of silicon nitride and steel in the presence of mineral oil or an ester based lubricant

The friction and wear characteristics of combinations of silicon nitride, alumina and AISI 52100 steel in the presence of mineral oil containing anti-wear, dispersant and detergent additives have been investigated in a tri-pin-on-disc machine. The tests were carried out at a nominal temperature of 100°C for a range of sliding speeds, loads and total sliding distances. In Part II of this two-part paper a comparison will be made between the tribological performance of these sliding pairs of materials in mineral oil and ester based lubricant environments. The results of the investigation showed that the alumina performed relatively poorly under these test conditions, whereas silicon nitride showed good potential as an improved wear resisting material compared with 52100 steel. Wear factors of the order of 10⁻¹⁰ mm³/Nm were deduced for the alumina, while values as low as 10⁻¹¹ mm³/Nm were typical of the silicon nitride sliding against 52100 steel discs. The alumina pins wore by a process of brittle fracture at the surface, whereas the silicon nitride pins wore primarily by a tribochemical polishing mechanism. The rate of tribo-chemical wear was found to be proportional to the nominal contact area.