Superlow Friction of Diamond-Like Carbon Films: A Relation to Viscoplastic Properties

Composition, structure, electrical, optical, mechanical properties and tribological behavior of diamond-like carbon films (DLC) are strongly dependent on the deposition system. Some hydrogenated amorphous carbon films (a-C:H) may exhibit superlow friction properties in ultra-high vacuum (UHV). The present paper compares tribological and mechanical properties of several DLC films prepared under different conditions. Friction coefficients were measured in an analytical ultra-high vacuum tribometer. The mechanical properties were evaluated from force-displacement curves using a nanoindentation instrument. Making use of continuous stiffness mode, Young's modulus and hardness were determined as a function of indentation depth. The measurements were performed at constant strain rates by special control of the load during indentation. We were, thus, able to determine the dependence of hardness on strain rate, characterizing a viscoplastic behavior. Many of the hydrogenated amorphous carbon films studied were significantly viscoplastic. The aim of this paper is to highlight the correlation between superlow friction and viscoplastic behavior.     

Microfriction and macrofriction of metal containing amorphous hydrocarbon hard coatings determined by AFM and pin‐on‐disk tests

Metal containing amorphous hydrocarbon films (Me‐C:H) have excellent tribological properties and an adjustable electrical conductivity. Friction force microscopy investigations on gold‐ and tungsten‐C:H films show a non‐linear dependence of friction on the load in the nanonewton‐range which can be explained by Hertz model of elastic contact. The effective friction coefficient and the interfacial shear stress strongly depend on the type of metal and the metal concentration inside the film. Microfriction and macrofriction (pin‐on‐disk) show a high qualitative correspondence. This revised version was published online in June 2006 with corrections to the Cover Date.     

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.     

Boundary Lubrication by Pure Crystalline Zinc Orthophosphate Powder in Oil

The aim of this study is to assess the tribological behavior of pure crystalline zinc orthophosphate under boundary lubrication in order to model zinc phosphate-based anti-wear additives. Boundary films were generated from α-Zn₃(PO₄)₂ powder dispersed in poly-alpha-olefin oil, at ambient temperature, by means of a steel sphere-on-flat contact in reciprocating motion. Electrical contact resistance and friction coefficient evolutions enable an understanding of the tribological behavior of crystalline zinc orthophosphate at the sliding interface. A conductive atomic force microscope (C-AFM) equipped with a current sensing setup, Raman spectroscopy, and nano-indentation were used to characterize the resulting film. When involved in a tribological contact, zinc orthophosphate powder forms a continuous patchy adherent film, changing its structure to amorphous orthophosphate, on both sliding steel surfaces. Morphological and mechanical properties of the film are discussed with respect to the ZDTP tribofilm models.     

Tribochemical interactions of Si-doped DLC film against steel in sliding contact

This study concerns the effects of tribochemical interactions at the interface of Si-DLC (silicon-doped diamond-like carbon) film and steel ball in sliding contact on tribological properties of the film. The Si-DLC film was over-coated on pure DLC coating by radio frequency plasma-assisted chemical vapor deposition (r.f. PACVD) with different Si concentration. Friction tests against steel ball using a reciprocating type tribotester were performed in ambient environment. X-Ray photoelectron spectroscopy (XPS) and auger electron spectroscopy (AES) were used to study the chemical characteristics and elemental composition of the films and mating balls after tests. Results showed a darkgray film consisting of carbon, oxygen and silicon on the worn steel ball surface with different thickness. On the contrary, such film was not observed on the surface of the ball slid against pure DLC coating. The oxidation of Si-DLC surface and steel ball was also found at particular regions of contact area. This demonstrates that tribochemical interactions occurred at the contact area of Si-DLC and steel ball during sliding to form a tribofilm (so called transfer film) on the ball specimen. While the pure DLC coating exhibited high coefficient of friction (∼0.06), the Si-DLC film showed a significant lower coefficient of friction (∼0.022) with the presence of tribofilm on mating ball surface. However, the Si-DLC film possesses a very high wear rate in comparison with the pure DLC. It was found that the tribochemical interactions strongly affected tribological properties of the Si-DLC film in sliding against steel.     

Friction of diamond-like carbon films in different atmospheres

Diamond-like carbon (DLC) films constitute a class of new materials with a wide range of compositions, properties, and performance. In particular, the tribological properties of these films are rather intriguing and can be strongly influenced by the test conditions and environment. In this paper, a series of model experiments are performed in high vacuum and with various added gases to elucidate the influence of different test environments on the tribological behavior of three DLC films. Specifically, the behavior of a hydrogen-free film produced by a cathodic arc process and two highly hydrogenated films produced by plasma-enhanced chemical-vapor deposition were studied. Flats and balls used in these experiments were coated with DLC and tested in a pin-on-disc machine under a load of 1 N and at constant rotational frequency. With a low background pressure, in the 10⁻⁶ Pa range, the highly hydrogenated films exhibited a friction coefficient of less than 0.01, whereas the hydrogen-free film gave a friction coefficient of approximately 0.6. Adding oxygen or hydrogen to the experimental environment changed the friction to some extent. However, admission of water vapor into the test chamber caused large changes: the friction coefficient decreased drastically for the hydrogen-free DLC film, whereas it increased slightly for one of the highly hydrogenated films. These results indicate that water molecules play a prominent role in the frictional behavior of DLC films—most notably for hydrogen-free films but also for highly hydrogenated films.     

Ultra-High Tribological Performance of Magnetron Sputtered a-C:H Films in Sand-Dust Environment

The hydrogenated amorphous carbon (a-C:H) films were prepared on AISI 440C steel substrates using a RF magnetron sputtering graphite target in the CH₄ and Ar mixture atmosphere. The friction and wear behavior of a-C:H films were comparatively investigated by pin-on-disc tester under dry sliding and simulated sand-dust wear conditions. In addition, the effects of applied load, amount of sand and sand particle sizes on the tribological performance of a-C:H films were systemically studied. Results show that a-C:H films exhibited ultra-high tribological performance with low friction coefficient and ultra-low wear rate under sand-dust environments. It is very interesting to observe that the friction coefficient of a-C:H film under sand-dust conditions was relatively lower when compared with dry sliding condition, and the wear rate under sand-dust conditions kept at the same order of magnitude (×10⁻¹⁹ m³/N m) with the increase of applied load and particle size as a comparison with the dry sliding condition. Based on the formation of “ridge” layer (composite transfer layer), a transfer layer-hardening composite model was established to explain the anti-wear mechanisms and friction-reducing capacity of a-C:H solid lubrication films under sand-dust conditions.     

Tribological behavior of plasma-enhanced CVD a-C:H films. Part I: effect of processing parameters

A systematic study was conducted on the effect of plasma-enhanced CVD processing parameters, namely bias voltage, pressure and CH₄/Ar flow ratio, on the characteristics and tribological response of amorphous hydrogenated carbon (a-C:H) films. Film hardness, intrinsic stress, structure, composition and tribological response were characterized. Variation of processing parameters was found to produce a-C:H films with a range of characteristics with the CH₄/Ar ratio exercising a dominant effect. A low ratio produced harder films with more sp³ bonding, low hydrogen content and low wear rate; whereas a high ratio produced softer films, with more sp² bonding, higher hydrogen content and low friction. Film characteristics were found to affect the wear mechanism with softer films showing a layer-by-layer removal and harder films involving formation of fine debris. These two diverse types of films offer the opportunity to synthesize multilayered films combining desirable properties from each component.     

The role of hydrogen on the friction mechanism of diamond-like carbon films

The structure, properties and tribological behavior of DLC films are dependent on the deposition process, the hydrogen concentration and chemical bondings in the films. The present paper reports selected tribological experiments on model DLC films with different hydrogen contents. The experiments were performed in ultrahigh vacuum or in an atmosphere of pure hydrogen or argon in order to elucidate various friction mechanisms. Two typical friction regimes are identified. High steady-state friction in UHV (friction coefficient of 0.6) is observed for the lowest hydrogenated and mostly sp²-bonded DLC film. Superlow steady-state friction (friction coefficient in the millirange) is observed both for the highest hydrogenated film in UHV, and for the lowest hydrogenated film in an atmosphere of hydrogen (10 hPa). The high steady-state friction in UHV, observed for the lowest hydrogenated film with a dominant sp² carbon hybridization, is associated with a –^* sub-band overlap responsible for an increased across-the-plane chemical bonding with a high shear strength similar to what is observed with unintercalated graphite in the same UHV conditions. Superlow friction is correlated with a hydrogen saturation across the shearing plane through weak van der Waals interactions between the polymer-like hydrocarbon top layers. This regime is observed during the steady-state period if the film contains enough hydrogen incorporated during deposition. If this condition is not satisfied (i.e., for the film with the lowest hydrogen content), the limited diffusion of hydrogen from the film network towards the sliding surfaces seems to be responsible for a superlow running-in period. The superlow friction level can be reached over longer time periods by suitable combinations of temperature and molecular hydrogen present in the surrounding atmosphere during friction.     

Ultralow Friction Behaviors of Hydrogenated Fullerene-Like Carbon Films: Effect of Normal Load and Surface Tribochemistry

Friction and wear behaviors of hydrogenated fullerene-like (H-FLC) carbon films sliding against Si₃N₄ ceramic balls were performed at different contact loads from 1 to 20 N on a reciprocating sliding tribometer in air. It was found that the films exhibited non-Amontonian friction behaviors, the coefficient of friction (COF) decreased with normal contact load increasing: the COF was ~0.112 at 1 N contact load, and deceased to ultralow value (~0.009) at 20 N load. The main mechanism responsible for low friction and wear under varying contact pressure is governed by hydrogenated carbon transfer film that formed and resided at the sliding interfaces. In addition, the unique fullerene-like structures induce well elastic property of the H-FLC films (elastic recovery 78%), which benefits the high load tolerance and induces the low wear rate in air condition. For the film with an ultralow COF of 0.009 tested under 20 N load in air, time of flight secondary ion mass spectrometry (ToF-SIMS) signals collected inside and outside the wear tracks indicated the presence of C₂H₃ ⁻ and C₂H₅ ⁻ fragments after tribological tests on the H-FLC films surface. We think that the tribochemistry and elastic property of the H-FLC films is responsible for the observed friction behaviors, the high load tolerance, and chemical inertness of hydrogenated carbon-containing transfer films instead of the graphitization of transfer films is responsible for the steady-state low coefficients of friction, wear, and interfacial shear stress.     

Carbon Nanotube Reinforced Polyimide Thin-film for High Wear Durability

In this paper, the influence of single walled carbon nano tubes (SWCNTs) addition on the tribological properties of the polyimide (PI) films on silicon substrate was studied. PI films, with and without SWCNTs, were spin coated onto the Si surface. Coefficient of friction and wear durability were characterized using a ball-on-disk tribometer by employing a 4 mm diameter Si₃N₄ ball sliding against the film, at a contact pressure of ∼370 MPa, and a sliding velocity of 0.042 ms⁻¹. Water contact angle, AFM topography, and nano-indentation tests were conducted to study the physical and mechanical properties of the films. SWCNTs marginally increased the water contact angle of PI film. The addition of SWCNTs to PI has increased the hardness and elastic modulus of pristine PI films by 60–70%. The coefficient of friction of PI films increased slightly (∼20%) after the addition of SWCNTs, whereas, there was at least two-fold increase in the wear life of the film based on the film failure condition of coefficient of friction higher than 0.3. However, the film did not show any sign of wear even after 100,000 cycles of rotation indicating its robustness. This increase in the wear durability due to the addition of the SWCNTs is believed to be because of the improvement in the load-bearing capacity of the composite film and sliding induced microstructural changes of the composite film.     

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.     

Grey theory applied to evaluate the tribological performances of the a-C:H(N) coating films prepared by differing the nitrogen content and the film thickness

The purpose of this paper is to study the tribology performances of the aC:H(N) films by using a nanotester under different scratch loads and velocities. From the measurements of the friction coefficient and wear volume, the tribological performances including wear resistance and friction coefficients were evaluated for the hydrogenated amorphous carbon films prepared by differing film thickness and nitrogen volume friction in the gas mixture of (C₂H₂+N₂). Taguchi experimental design and the grey relational analysis were used to investigate the influence of specimen parameters (film’s thickness, nitrogen content in the film), and operating conditions in tribological tests (scratch load and scratch velocity) on the friction coefficients and the wear volume arising in the specimens with different coating films. It is found that the wear volume of thin film is increased by increasing either the nitrogen volume fraction or film thickness. Moreover, the optimal combination of the testing parameters was also determined in the use of the present model.     

Investigation of the Tribological Behaviors of Polymer Molecular Deposition Films by Tribometer Based on Interferometer

The polymer molecular deposition films including polyelectrolyte molecular deposition (PEMD) film and nanoparticles composite molecular deposition (NPs/MD) film have been prepared using the molecular deposition method and the in situ synthesize method. The polymer molecular deposition films were characterized by atomic force microscope (AFM) and X-ray photoelectron spectroscopy (XPS). The tribological behaviors of the substrate and polymer molecular deposition films were investigated by a tribometer based on interferometer. It is found that the NPs/MD film has a lower friction force and a better anti-wear property than the PEMD film under the dry friction. The poly alpha olefin (PAO2) and water films confined between samples and steel ball surfaces have been investigated using thin film interferometry. The friction force of substrate was lower than the polymer molecular deposition films under PAO2 lubrication. The friction forces alteration of PEMD film and NPs/MD film were similar and consistent, and lower than that for substrate under water lubrication.     

Influence of CH4 Flow Rate on Microstructure and Properties of Ti-C:H Films Deposited by DC Reactive Magnetron Sputtering

Nanocomposite Ti-containing hydrogenated carbon films (Ti-C:H) were prepared using a DC reactive magnetron sputtering system. The relationship between CH₄ flow rate and the film characterization and tribological behaviors in both ambient air and deionized water conditions were investigated. Results showed that the Ti content in the as-deposited Ti-C:H films decreased and the sp³ content increased with an increase in CH₄ flow rate. TiC nanocrystallites can be formed at a relatively low CH₄ flow rate, whereas there was almost no formation of TiC in the amorphous carbon matrix at the highest CH₄ flow rate. The hardness, elastic modulus, and internal stress of the films were decreased firstly and then increased as the CH₄ flow rate increased, whereas their adhesion presented an inversely changing trend. The friction coefficients and wear rates of Ti-C:H films in both ambient air and deionized water conditions decreased with increasing CH₄ flow rate from 8 to 12 sccm and then increased as the CH₄ flow rate continually increased. In particular, the nanocomposite Ti-C:H film deposited with a CH₄ flow rate of 12 sccm could achieve superior combining mechanical properties and low friction and high antiwear behaviors in both ambient air and deionized water conditions, indicating potential applications as a protective and lubricating film for mechanical components.     

Evidence for and role of boron carbide icosahedra in the hardness of amorphous hydrogenated boron carbide

We report both infrared absorption and ¹¹B nuclear magnetic resonance measurements that provide evidence for the presence of boron carbide icosahedra in amorphous hydrogenated boron carbide (a‐B:C:H) thin films. The infrared absorption spectra are dominated by a broad line at 1280 cm^-1 with a FWHM of 320 cm^-1, and the ¹¹B nuclear magnetic resonance spectra are dominated by a line with a chemical shift of 4 ppm and FWHM of 35 ppm; similar features have been previously reported in polycrystalline boron carbide, where boron carbide icosahedra make up the unit cell. We also suggest that it is these icosahedra that increase the hardness of these films over those films without boron, by playing the role of nanocrystals in a nanocrystal/amorphous matrix composite system. This revised version was published online in July 2006 with corrections to the Cover Date.     

Design criteria for superlubricity in carbon films and related microstructures

Carbon offers the kind of flexibility that one needs in the design and production of chemically unique microstructures with properties ranging from superlubricity to super-hardness and/or -softness. This flexibility can be exploited for numerous tribological applications, ranging in sizes from nano-scale electromechanical systems to meso-scale engine parts and components. Recently, carbon was used in our laboratory to produce nearly frictionless carbon (NFC) films having friction coefficients as low as 0.001 and wear rates of 10⁻¹¹–10⁻¹⁰ mm³/N m even under dry sliding conditions and at very high contact pressures. Using advanced fabrication and chemical vapor deposition methods, our research team has pioneered the development of other unique microstructures possessing exceptional physical, chemical, mechanical, electrical, and tribological properties. The combination of such exceptional properties in one material is rather rare, but urgently needed by the industry to meet the increasingly multifunctional needs of advanced mechanical systems and devices. This paper provides an overview of recent progress in the study and understanding of the tribological properties of carbon-based coatings. The design and surface engineering aspects of such coatings are discussed and the principles of superlubricity in these films are presented. Examples of current and future applications for two- and three-dimensional carbon-based structures are also provided.     

Tribofilm formation and tribological properties of TiC and nanocomposite TiAlC coatings

In a recent work a concept for self lubricating low friction TiC and nanocomposite TiAlC coatings was developed. Here we further investigate the mechanical and tribological properties of these coatings. Under identical deposition conditions, the addition of Al initiates the formation of a nanocomposite consisting of (Ti,Al)C grains in an amorphous carbon matrix. The coefficient of friction is lowered from ～0.2 to below 0.1 in a pin-on-disc test against steel with unaffected coating wear rate. The lower friction is attributed to a more extensive formation of amorphous carbon and graphitisation on both the counter surface and in the coating wear track. The addition of Al also reduces coating hardness, Young's modulus and the residual stress, which can be explained by the weak carbide-forming ability of Al and the formation of a nanocomposite microstructure.     

Tribological behaviour of carbon and low alloy steels: effect of mechanical properties and test conditions

Abstract

In this paper, the effects of mechanical properties and test conditions on the tribological behaviour of ISO C45 carbon steel and ISO 42CrMo4 low alloy steel were studied. The tribological tests were carried out, without lubrication, on a reciprocating friction tester. Cylinder on flat contact configuration was adopted. The results showed that there is no obvious relationship between the mechanical properties and the friction ones. However, the variation in the coefficient of friction depends on the test conditions. In contrary to normal load, the effect of sliding speed on the coefficient of friction is not the same for the two steel nuances. The tribological properties are dependent, however, on the nature of wear debris.     

Tribology and surface mechanical properties of the oxide film formed by excimer laser surface treatment of AISI 304 stainless steel

The surface hardness and tribological properties of the surface oxide formed by excimer laser surface processing of AISI 304 stainless steel have been examined. It is found that laser processing initially anneals the stress-induced martensite on the surface of the stainless steel, resulting in a softening of the surface. After more than 100 cycles of melting and resolidification, a surface oxide film develops which is harder than the austenite of the annealed substrate and comparable in hardness to the stress-induced martensite. The thickness of the oxide film is dependent on the number of laser pulses, so that arbitrarily thick films can be produced. The dry-sliding friction of the oxide film against a steel pin is substantially lower than that of the untreated polished surface with only the native oxide film and there is substantially less damage in both the wear track and the pin. The hard surface oxide is underlain by relatively soft austenite. The tribological behavior is thus not obviously the result of the surface mechanical properties of the film-substrate combination but is ascribed to changes in the chemical interaction between the pin and the disk.