The respective role of oxygen and water vapor on the tribology of hydrogenated diamond-like carbon coatings

The tribological behavior of diamond-like carbon coatings (DLC) strongly depends on the chemical nature of the test environment. The present study proposes to explore the influence of water vapor and oxygen on the friction behavior of a hydrogenated DLC coating exhibiting ultralow friction in ultrahigh vacuum (friction coefficient below 0.01). Using a UHV tribometer, reciprocating pin-on-flat friction tests were performed in progressively increasing or decreasing partial pressures of pure oxygen and pure water vapor. The maximum gaseous pressures of oxygen and water vapor were 60 hPa and 25 hPa (1 hPa = 100 Pa), respectively, the second value corresponding to a relative humidity (RH) of 100% at room temperature. It was found that, for the pressure range explored, oxygen does not change the ultralow friction behavior of DLC observed in UHV. Conversely, water vapor drastically changes the friction coefficient at pressures above 0.5 hPa (RH = 2%), from about 0.01 to more than 0.1. Electron energy loss spectroscopy and in situ Auger electron spectroscopy have been performed to elucidate the friction mechanisms responsible for the tribological behaviors observed with the two different gaseous environments. In all cases no significant oxidation has been observed either inside the wear scars or in the wear debris particles. Ultralow friction is systematically associated with a homogeneous carbon-based transfer film. The higher friction observed at partial pressure of water vapor higher than 0.5 hPa, is associated with a thinner transfer film. Consequently friction seems to be controlled by the transfer film whose kinetics of formation strongly depends on the partial pressure of water vapor. This revised version was published online in August 2006 with corrections to the Cover Date.     

类金刚石薄膜的光学性能的研究

利用脉冲真空电弧镀的方法,在硅基底上沉积类金刚石薄膜,研究薄膜的光学性能、光学常数和离子能量关系。结果表明:不同的离子能量可以得到不同折射率的薄膜,无氢类金刚石薄膜的折射率在2.5～2.7之间变化;通过改变工艺条件来制备不同折射率的薄膜,和不同折射率的基底材料相互匹配;折射率和光学能隙随离子能量具有相反的变化趋势,和理论预测的趋势相一致;对于硅、锗等红外材料,要求的薄膜应具有1.8～2.1左右的折射率,因此提出一种基于物理汽相沉积和化学汽相沉积两种相互结合的方法,来降低薄膜的折射率,以达到和硅、锗等材料的折射率匹配。     

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.     

Environmental effects on the friction of hydrogenated DLC films

We have investigated environmental effects on hydrogenated diamond-like carbon (H-DLC) films under various pressures of H₂O, O₂, and N₂ by ultrahigh vacuum (UHV) tribometry. The H-DLC film exhibits an ultralow coefficient of friction (μ = 0.004 in UHV). The μ value increases with increasing pressure of H₂O and O₂. Specifically, μ increases up to 0.07 under 10 Torr of H₂O, and up to 0.03 under 150 Torr of O₂; these are typical H₂O and O₂ contents respectively in ambient air. Our results are consistent with similar environmental effects previously reported. But, we have also discovered that these friction changes are reversible, returning to the ultralow value when UHV is restored. The reversibility of the friction behavior in both environments, coupled with the lack of evidence of tribochemical changes by Auger electron spectroscopy, suggest that the observed friction changes are due to the weakly adsorbed gas molecules that influence the friction property by physically separating the H-DLC interface. Speed-dependent tribometry also supports this argument. In addition, two DLC films with different hydrogen contents and with widely different friction coefficients in UHV are shown to exhibit identical μ values under humid environments, further demonstrating that the frictional properties of these DLC films are essentially determined by the surface layer of adsorbed gas molecules.     

Wear of metal-containing diamond-like carbon coatings

Four commercial metal-containing DLC coatings were tested with a ball-on-disk tribomete to examine their modes of wear. Although all were sputter-deposited, the coatings differed in their compositions, thicknesses, and surface finish. The tests showed certain common wear modes. In each case the films wore away at constant rates until they were worn through. In this sense, interface adhesion was not an important issue. Since the nominal contact areas increased significantly during the course of the test, while the wear rates were constant, the wear rate was not controlled by the nominal average contact stress. Our data are consistent with the model of Greenwood and Williamson.     

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.     

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.     

Tunable friction behavior of oriented carbon nanotube films

Measured friction coefficients of carbon nanotubes vary widely from μ < 0.1–μ > 1.0 [1–6], while theoretical studies suggest intrinsically high friction coefficients, approaching unity [7]. Here we report that measured friction coefficients of MWNT films are strong functions of surface chemistry and temperature, but are not dependent on the presence of water vapor. We hypothesize that the origin of the temperature dependence arises from the interaction of the surface chemical groups on the nanotubes [8–12] and rubbing counterface. The friction coefficient of individual films can be easily tuned by changing the surface temperature and chemistry of either the countersurface or the nanotubes, we have demonstrated the ability to create and control high and low friction pairs through plasma treatments of the nanotube films with argon, hydrogen, nitrogen, and oxygen. This behavior is completely reversible, and when coupled with the superior strength, thermal, and electrical properties of nanotubes, provides a versatile tunable, multifunctional tribological system.     

飞秒脉冲激光沉积类金刚石膜实验研究

期望用类金刚石膜作为硅的红外保护/增透膜,采用波长为800nm,脉宽50fs,重复频率1KH z的T i:Sapph ire飞秒激光器及石墨靶材在单晶S i片上沉积了约0.7μm~1μm厚的类金刚石膜(d iam ond-like carbon film s,DLC),获得了光滑致密,硬度显著提高,红外透过率有一定增加的样品。通过对薄膜拉曼光谱和X射线光电子能谱等的测试,发现单脉冲能量在0.4m J~1.6m J范围内变动时,单脉冲能量0.8m J获得的类金刚石膜综合性能最佳,其对应的焦斑功率密度计算值为1.4×1014W/cm2。     

Functional mechanism of formation of friction polymer with dihydroxydocosanoic acid

The results of wear tests with a four-ball machine showed that dihydroxydocosanoic acid has good antiwear properties, comparatively approaching those of zinc dialkyldithiophosphate (ZDDP): the four-ball wear-scar diameters, d 30 min/294 N, with dihydroxydocosanoic acid, ZDDP, and 400 neutral base oil are 0.36, 0.35, and 0.62 mm, respectively. In order of effectiveness the antiwear ability of the C₂₂ acids is: 13,14-dihydroxydo-cosanoic acid (I) 13(14)-mono-hydroxydocosanoic acid (II) docosanoic acid (III), showing that their antiwear properties are remarkably improved after introduction of the hydroxy group into fatty acids. Work on dihydroxy acid as an antiwear agent is not much reported in the literature up to now. In the present work, it was verified with infrared spectroscopy that polyester is formed on the rubbing surfaces with I and II by tribochemical reaction. An oxygen-rich protective film on the rubbing surfaces was identified with Auger Electron Spectroscopy analysis. These results are identical to the high oxygen-containing polyester film shown by IR analysis. It is preliminarily confirmed that the functional antiwear mechanism is, principally, the formation of a polymeric friction film on the rubbing surfaces.     

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.     

Influence of humidity on the friction of diamond and diamond-like carbon materials

The friction of diamond and diamond-like carbon (DLC) materials was evaluated in reciprocating sliding wear testing under controlled relative humidity. The testing conditions were a displacement stroke of 100 μm, an oscillatory frequency of 8 Hz and a normal load of 2 N. The coefficient of friction of diamond and hydrogen-free DLC (a-C) coatings against a corundum sphere in the steady regime decreased with an increase in relative humidity. A water layer physisorbed at the interface between the mating surfaces played two major roles: acting as a lubricant and increasing the true area of contact. However, it was noticed that the friction coefficient of the hydrogenated DLC (a-C:H) coatings first increased and then decreased with increasing relative humidity in the steady state. There appeared to be a critical relative humidity for the a-C:H coatings, at which the steady-state friction reached the maximum value. The frictional behaviour of the a-C:H coatings also showed dependence on the wear test duration. The interaction between hydrogen and oxygen at the interface between the a-C:H coating and water layer was mainly responsible for such behaviour.     

XPS表征类金刚石膜探讨

介绍X射线光电子能谱(XPS)分析类金刚石(DLC)膜的原理与方法,探讨分峰拟合计算时参量设定对分析结果的影响,改进拟合方法,拟合结果更准确,结果的一致性好。     

Tribochemical effects on the friction and wear behaviors of diamond-like carbon film under high relative humidity condition

Friction and wear behaviors of diamond-like carbon (DLC) film in humid N₂ (RH-100%) sliding against different counterpart ball (Si₃N₄ ball, Al₂O₃ ball and steel ball) were investigated. It was found that the friction and wear behaviors of DLC film were dependent on the friction-induced tribochemical interactions in the presence of the DLC film, water molecules and counterpart balls. When sliding against Si₃N₄ ball, a tribochemical film that mainly consisted of silica gel was formed on the worn surface due to the oxidation and hydrolysis of the Si₃N₄ ball, and resulted in the lowest friction coefficient and wear rate of the DLC film. The degradation of the DLC film catalyzed by Al₂O₃ ball caused the highest wear rate of DLC film when sliding against Al₂O₃ ball, while the tribochemical reactions between DLC film and steel ball led to the highest friction coefficient when sliding against steel ball.     

The Tribological Properties of Low-friction Hydrogenated Diamond-like Carbon Measured in Ultrahigh Vacuum

In this paper, we investigate the sliding friction and wear behavior of a hydrogenated diamond-like carbon (DLC) film in ultrahigh vacuum (UHV) and under partial pressures of water vapor, oxygen, nitrogen and hydrogen. The initial friction coefficient of the film in UHV was ~0.15, but decreased steadily to values as low as 0.03 after about 30 sliding passes. During longer duration tests, the friction coefficient increased again to values as high as ~0.15 and such an increase in friction coincided with hydrogen desorption from the contacting surfaces (as detected by a mass spectrometer). Heating DLC to temperatures higher than 360 K also caused desorption of hydrogen and a resulting marked increase in friction. The presence of molecular nitrogen, oxygen and hydrogen in the test chamber did not have any noticeable effect on friction, but the presence of thermally dissociated or ionized hydrogen within the close proximity of sliding surfaces had a beneficial effect by restoring the low friction behavior of the DLC films. The introduction of water vapor into test chamber had an adverse effect on friction. The results of this study confirm that hydrogen is key to low friction behavior of hydrogenated DLC films and that the presence of water molecules has an adverse effect on their friction behavior.     

Initiation of lubricant catalytic decomposition by hydrogen evolution from contact sliding on CHx and CNx overcoats

Tribochemical studies of the head/disk interface (HDI) were conducted using hydrogenated (CHx) and nitrogenated (CNx) carbon disk samples coated with perfluoropolyether ZDOL lubricant. The studies involved drag tests with uncoated and carbon-coated Al₂O₃–TiC sliders and thermal desorption experiments in an ultrahigh vacuum (UHV) tribochamber. We observed that the hydrogen evolution from CHx overcoats initiates lubricant catalytic decomposition with uncoated Al₂O₃/TiC sliders, forming CF₃ (69) and C₂F₅ (119). The generation of hydrofluoric acid (HF) during thermal desorption experiments provides the formation mechanism of Lewis acid, which is the necessary component for catalytic reaction causing Z-DOL lube degradation. On the other hand, for CNx films, lubricant catalytic decomposition was prevented due to less hydrogen evolution from the CNx overcoat. This revised version was published online in July 2006 with corrections to the Cover Date.     

Ultralow friction of DLC in presence of glycerol mono-oleate (GNO)

This paper presents a unique tribological system that is able to produce no measurable wear of material combination and that reduces friction markedly in the ultralow regime under boundary lubrication. Ultralow friction (0.03) was obtained by sliding hydrogen-free Diamond-Like-Carbon ta-C against ta-C lubricated with Poly-alpha Olefin base oil containing Glycerol Mono-Oleate (GMO) additive. The origin of ultralow friction in these conditions has been investigated by surface analysis techniques. Results are in agreement with the formation of a OH-terminated carbon surface. This new surface chemistry might be formed by the tribochemical reaction of alcohol function groups with the friction-activated ta-C atoms. The origin of low friction could be due to the very low-energy interaction between OH-terminated surfaces.     

Preparation,characterization and investigation of molecular films coated on diamond-like carbon substrate

For the successful application of boundary lubrication, detailed investigations about the influence of preparation process on molecular films are needed. In this paper, a specially designed device was used for the film preparation. The scanning electron microscope (SEM) combined with atomic force microscope (AFM) was employed to characterize the surface morphology and nanotribological behavior of molecular films. After the liquid phase deposition, molecular films are randomly and densely distributed over Ti-doped diamond-like carbon (Ti-DLC) substrates. Through rigorous surface treatments, island-like molecular films were finally achieved on substrate surfaces. The surface friction of molecular films is obviously lower than that of Ti-DLC surfaces. Then, pin-on-disk tribotests were performed to study the macrofriction behavior of molecular films under different preparation parameters. Based on the orthogonal experiment, the effect of five preparation parameters (solution weight percent, smearing force and processing time of three smearing steps) on initial friction coefficient of molecular films was investigated. The results indicated that the order of significance levels is as follows: processing time of the second smearing step > solution weight percent > processing time of step 1 > processing time of step 3 > smearing force. For the purpose of friction reduction, the appropriate level ranges are 0.75% (Solution), 2.5 N–15 N (Force), 1 min–10 min (Step 1), 1 min–2 min (Step 2) and 1 min, 2 min, 5 min and 15 min (Step 3). The initial friction coefficient under the optimized conditions is around 0.112, and the equilibrium friction coefficient is around 0.162, which is lower than that of unlubricated Ti-DLC substrates.     

Triboemission as a basic part of the boundary friction regime: A review

This paper reviews selected phenomena related to the boundary friction process. The central thrust is on triboemission, defined as emission of electrons, charged particles, photons, etc., under conditions of boundary friction and/or surface damage caused by fracture processes. Low‐energy electrons are one of the most important particle components in triboemission. Accordingly, the triboemission process is of particular significance for (i) the boundary friction process as such, and (ii) the tribochemistry of the boundary lubrication process. This review considers all the major issues of triboemission and related phenomena/processes. It is shown that, in the boundary lubrication regime with hydrocarbon lubricants, charge intensities decrease with an increase in lubricant molecular weight. The paper also includes some recent information concerning research on triboemission along with a newly developed apparatus.     

Microfrictional properties of diamond-like carbon films sliding against silicon, sapphire and steel

The low contact pressure characteristic of the microtribological regime relative to macro and nanosystems is suited for testing the microfrictional properties of different types of thin films. Motivated by macro as well as microsystem applications, this study investigates the microfrictional properties of different types of diamond-like carbon (DLC) films, prepared using low- and high-frequency plasma-assisted chemical vapor deposition (HF-PACVD) and the vacuum arc method. Testing was performed with a reciprocating precision microtribometer. Silicon, sapphire and steel balls were used as counterbodies. Friction-load curves suggest that, for applied forces in the μN to mN regime, two properties have a strong influence on the microfriction: first, the chemical composition plays a dominant role and second, the film roughness. With silicon and steel balls, the microfriction of hydrogen-free DLC films was greater than the hydrogen-containing films. With sapphire counterbodies, the results indicate that microfriction is inversely proportional to the film roughness. Also, for the films tested, microfriction was determined to be independent of the sliding velocity. For the force (pressure) regimes tested, mild wear was observed on silicon and some steel counterbodies, while no wear could be detected on any of the DLC films. These results illustrate the utility of implementing microtribological testing in comparative coating studies.