The tribological performance of fullerene‐like hydrogenated carbon films under ionic liquid lubrication

Fullerene‐like hydrogenated carbon films were deposited on Si substrate by plasma‐enhanced chemical vapor deposition. The microstructures of films were characterized by high‐resolution transmission electron microscopy and Raman spectrum. The tribological performance of films was tested by reciprocating ball‐on‐disc tester under 1‐ethyl‐3‐methylimidazolium tetrafluoroborate ionic liquid. The surface morphology and chemical composition of wear tracks and wear rates were investigated by optical microscope, X‐ray photoelectron spectroscopy, and 3D surface profiler. The results indicated that the film with a typical fullerene‐like structure embedded into the amorphous sp² and sp³ carbon networks could be prepared successfully, and the film shows a higher hardness (26.7 GPa) and elastic recovery (89.9%) compared with the amorphous carbon film. Furthermore, the film shows a lower friction coefficient at low contact load and friction frequency, and excellent wear‐resistance performance at high load and frequency under ionic liquid lubrication. Meanwhile, the wear life of fullerene‐like hydrogenated carbon films could be improved significantly using ionic liquid as a lubrication material. Copyright © 2015 John Wiley & Sons, Ltd.     

Influence of deposition pressure on hydrogenated amorphous carbon films prepared by d.c.‐pulse plasma chemical vapor deposition

Hydrogenated amorphous carbon films (a‐C : H) were prepared by d.c.‐pulse plasma chemical vapor deposition using CH₄ and H₂ gases. The microstructure and hardness of the resulting films were investigated at different deposition pressures (6, 8, 11, 15, and 20 Pa). The growth rate increased sharply from 3.2 to 10.3 nm/min with increasing the pressure from 6 to 20 Pa. According to Raman spectra, XPS, and Fourier transform infrared analysis, the films deposited at the pressure of 6 and 8 Pa have high sp³ content and show typical diamond‐like character. However, the microstructures and bond configuration of the films deposited at 11, 15, and 20 Pa have high sp² content and favored fullerene‐like nanostructure. The hardness and sp² content were shown to reach their minimum values simultaneously at a deposition pressure of 8 Pa and then increased continuously. The film with fullerene‐like nanostructure obtained at 20 Pa displays a high Raman I_D/I_G ratio (~1.6), and low XPS C 1s binding energy (284.4 eV). The microstructural analysis indicates that the films are composed of a hard and locally dense fullerene‐like network, i.e. a predominantly sp²‐bonded material. The rigidity of the films is basically provided by a matrix of dispersed cross‐linked sp² sites. Copyright © 2012 John Wiley & Sons, Ltd.     

Effects of Ar/H/N‐ion bombardment on the surface free energy and friction behavior of the fullerene‐like hydrogenated carbon (FL‐C:H) film

The surface modification of the fullerene‐like hydrogenated carbon (FL‐C:H) film was achieved by bombardment using Ar, H, and N ions, respectively. A systematic comparison of X‐ray photoelectron spectroscopy (XPS) and Fourier transformation infrared(FTIR) spectra was made between the FL‐C:H film and ion‐bombarded films. The results show that ion bombardment resulted in the increase of sp³ C content, specially, new C? N bonds were formed for N‐ion‐bombarded film. The contact angle (CA) and friction coefficient of those films were measured. The surface free energy evaluated from the contact angle increased for ion‐bombarded films, and the most obvious increase was obtained for N‐ion‐bombarded film. The friction coefficient decreased for H‐ion‐bombarded film whereas it increased for N‐ion‐bombarded film, and the friction coefficient of Ar‐ion‐bombarded film was close to that of the FL‐C:H film. Copyright © 2008 John Wiley & Sons, Ltd.     

The influence of anti‐wear additive ZDDP on doped and undoped diamond‐like carbon coatings

Diamond‐like carbon (DLC) coatings are recognised as a promising way to reduce friction and improve wear performance of automotive engine components. DLC coatings provide new possibilities in the improvement of the tribological performance of automotive components beyond what can be achieved with lubricant design alone. Lubricants are currently designed for metallic surfaces, the tribology of which is well defined and documented. DLC does not share this depth of tribological knowledge; thus, its practical implementation is stymied. In this work, three DLC coatings are tested: an amorphous hydrogenated DLC, a silicone‐doped amorphous hydrogenated DLC and a tungsten‐doped amorphous hydrogenated DLC. The three coatings are tested tribologically on a pin‐on‐reciprocating plate tribometer against a cast iron pin in a group III base oil, and a fully formulated oil that consists of a group III base oil and contains ZDDP, at 100 °C for 6 h and for 20 h in order to determine whether a phosphor‐based tribofilm is formed at the contact. The formation of a tribofilm is characterised using atomic force microscopy and X‐ray photoelectron spectroscopy techniques. The main findings of this study are the formation of a transfer film at the undoped, amorphous hydrogenated DLC surface, and also the tungsten amorphous hydrogenated DLC having a significant wear removal during the testing. The three coatings were found to have differing levels of wear, with the tungsten‐doped DLC showing the highest, the silicon‐doped DLC showing some coating removal and the amorphous hydrogenated DLC showing only minimal signs of wear. Copyright © 2015 John Wiley & Sons, Ltd.     

The high‐temperature tribological properties of Si‐DLC films

The tribological properties of Silicon‐containing diamond‐like‐carbon (Si‐DLC) films, deposited by magnetron sputtering Si target in methane/argon atmosphere, were studied in comparison with diamond‐like‐carbon (DLC) films. The DLC films disappeared because of the oxidation in the air at 500 °C, whereas the Si‐DLC films still remained, implying that the addition of Si improved significantly the thermal stability of DLC films. Retarded hydrogen release from DLC film at high temperature and silicon oxide on the surface might have contributed to lower friction coefficient of the Si‐DLC films both after annealing treatment and in situ high‐temperature environment. Copyright © 2012 John Wiley & Sons, Ltd.     

Lower friction and higher wear resistance of fluorine‐incorporated amorphous carbon films

Plasma‐enhanced chemical vapor deposition was employed to fabricate hydrogenated amorphous carbon (a‐C:H) films and fluorine‐doped hydrogenated amorphous (a‐C:H:F) carbon films. For comparison purpose, the a‐C:H films were treated with CF₄ plasma. The bonding structure and tribological behavior of the films were investigated. The results indicate that the F presented mainly in the forms of C–F₃, C–F and C–F₂ groups in both the a‐C:H:F film and the surface CF₄ plasma processed hydrogenated amorphous carbon (F‐P‐a‐C:H) films. Moreover, the a‐C:H:F films, because of the transformation of sp³ to sp², possess a lower friction coefficient than that of the F‐P‐a‐C:H films. Copyright © 2013 John Wiley & Sons, Ltd.     

Study on the anti‐reflection and structure evolution of hydrogenated amorphous carbon grown by plasma chemical vapor deposition

In this work, the interrelation between the anti‐reflective property and the component, especially the sp² content, was studied. The results showed that the refraction index n increased from 2.2 to 3.3 with the direct current negative bias increasing. The reflection result R successful fall by 11.9% because of the existence of hydrogenated amorphous carbon anti‐reflective coatings. Both the refraction index and reflectivity decreasing correspond to a more graphitic microstructure character. Moreover, the optical property evolution of the films was explained by the chemical vapor deposition mechanism based on the ion sub‐plantation model and two‐phase model. Copyright © 2014 John Wiley & Sons, Ltd.     

Diamond like carbon films for enzyme electrodes; characterisation of novel overlying permselective barriers

Diamond like carbon (DLC) coated microporous polycarbonate membranes have been studied for use as novel composite permselective barriers membranes for a glucose enzyme electrode. Permeability coefficients, P, for key electrochemically active interferents across uncoated and DLC coated polycarbonate membranes has been compared. Interferent responses have then been assessed for sensors incorporating such membranes, and their relationship to differing DLC depositions assessed. Membranes with smaller pore sizes (0.03 and 0.01 μm) and extended DLC depositions (up to 7 min coating), while imparting some enhanced selectivity towards glucose, failed to show major discrimination for glucose over interferents as shown by P values: maximum glucose-to-interferent P ratios being 1.36 and 1.25 for ascorbate and urate, respectively. The implications of these findings are discussed.     

Diamond like carbon coated films for enzyme electrodes; characterization of biocompatibility and substrate diffusion limiting properties

The biocompatibility and substrate diffusion limiting properties for a range of diamond like carbon (DLC) coated microporous polycarbonate and DLC coated dialysis (haemodialysis) membranes have been studied. This characterisation builds upon previous findings where DLC coated membranes imparted enhanced enzyme electrode performance. In this study electrode linear ranges have been extended from 10 mM glucose for a 0.01 μm pore size membrane to 160 mM. These findings correlated with the duration of DLC deposition and associated reductions in permeability for glucose. Permeability coefficient ratios for both microporous and dialysis membranes were also found to be important with low glucose/O₂ permeability ratios imparting extensions in glucose linear response range. DLC coated membranes employed within enzyme electrodes have also been shown to exhibit enhanced haemocompatibility as determined by both sensitivity change and surface deposition of blood components examined by scanning electron microscopy. Correlations are made between the reduced losses in sensor response to biofouling/ working electrode passivation processes, and extended linear ranges that DLC coated membranes may impart to enzyme electrode performance. Particular reference is made to the determination of glucose levels within whole blood.     

Bioactivity and mechanical properties of nickel‐incorporated hydrogenated carbon nanocomposite thin films

In this paper, the influence of nickel incorporation on the mechanical properties and the in vitro bioactivity of hydrogenated carbon thin films were investigated in detail. Amorphous hydrogenated carbon (a‐C:H) and nickel‐incorporated hydrogenated carbon (Ni/a‐C:H) thin films were deposited onto the Si substrates by using reactive biased target ion beam deposition technique. The films' chemical composition, surface roughness, microstructure and mechanical properties were investigated by using XPS, AFM, TEM, nanoindentation and nanoscratch test, respectively. XPS results have shown that the film surface is mainly composed of nickel, nickel oxide and nickel hydroxide, whereas at the core is nickel carbide (Ni₃C) only. The presence of Ni₃C has increased the sp² carbon content and as a result, the mechanical hardness of the film was decreased. However, Ni/a‐C:H films shows very low friction coefficient with higher scratch‐resistance behavior than that of pure a‐C:H film. In addition, in vitro bioactivity study has confirmed that it is possible to grow dense bone‐like apatite layer on Ni/a‐C:H films. Thus, the results have indicated the suitability of the films for bone‐related implant coating applications. Copyright © 2011 John Wiley & Sons, Ltd.     

In‐situ stress suppression of hydrogenated a‐CNx film prepared via Ar gas introduction

Evolution of hydrogenated amorphous carbon nitride films was investigated with an introduction of Ar gas in the deposition. The results showed that compressive stress of the films decreased versus an increase of Ar flow rate. Especially, at an Ar flow rate of 5 sccm the film exhibited lower compressive stress, higher hardness and lower root‐mean‐square (rms) roughness than the films deposited without Ar gas introduction. Structural analysis showed that the films with higher hardness, low compressive stress and lower rms roughness had relatively high sp² and nitrogen content. It was attributed to the assistance of Ar plasma, which can cause N atom to enter graphite ring easily and form curved graphite microstructure. Copyright © 2016 John Wiley & Sons, Ltd.     

Fast deposition of amorphous hydrogenated carbon films using a supersonically expanding arc plasma

Experiments concerning the growth rate and quality of an amorphous hydrogenated carbon film deposited in a reactor based on the supersonic expansion of an arc plasma are reported. In order to be able to calculate the deposition rate, an existing flow model has been completed with chernical reaction rate equations. The methane gas that is injected in the arc appears to be dissociated and ionized completely. The calculated deposition rates agree well with the experimental values obtained within-situ ellipsometry. The growth rates are an order of magnitude larger than those reported in the literature. Still, the film quality, expressed in terms of refractive index, optical bandgap, and hardness, is similar to those obtained by other authors.     

The effect of thermal annealing on the microstructure and mechanical properties of magnetron sputtered hydrogenated amorphous carbon films

Hydrogenated amorphous carbon films were deposited by magnetron sputtering of a carbon target in a methane/argon atmosphere. A postdeposition annealing at 300 °C was performed and the microstructure, bonding structure and mechanical properties of the as‐deposited and annealed films were analyzed and compared directly by high‐resolution transmission electron microscopy, micro‐Raman spectroscopy, XPS, and nanoindentation. The results showed that the carbon films are quite stable upon annealing, since there are only minor changes in microstructure and chemical bonding in the amorphous matrix. The hardness of the films remained unaffected, but the elastic properties were somewhat deteriorated. In comparison to the outcomes of our previous work on the growth of fullerene‐like hydrogenated carbon films, we can state that the formation of fullerene‐like carbon structures requires different sputtering process conditions, such as a higher ion energy and/or different sputtering target. Copyright © 2011 John Wiley & Sons, Ltd.     

Effects of negative bias on the structural,topological and tribological properties of amorphous carbon films prepared by magnetron sputtering

Amorphous carbon films were prepared in a magnetron sputtering system at different d.c. negative substrate biases (?50, ? 100, ? 150, ? 200 and ? 250 V). The surface roughness, hardness and tribological properties of as‐deposited films were investigated based on the films' structural evolution. Compared with the films deposited at the negative bias of ? 50 and ? 250 V, the microstructure and bond configuration of the films deposited at negative bias of ? 150 V favored a more graphite‐like structure, which had the maximum of graphiticclusters and ordering structures; meanwhile, the films deposited at bias of ? 150 V showed the minimum coefficient of friction (COF) in air, while the wear rate showed a decrease of two orders of magnitude. The tribotesting results were attributed to the increase of graphitic domains of amorphous carbon films which decreased the interfacial shear force and lowered the COF. The uniform and ordering structure induced steady and smooth friction curves. Copyright © 2010 John Wiley & Sons, Ltd.     

X‐ray photoelectron analysis of surface functional groups on diamond‐like carbon films by gas‐phase chemical derivatization method

Oxygen‐related surface functional groups on diamond‐like carbon (DLC) films were derivatized with fluorine‐ and nitrogen‐related groups by the gas‐phase chemical derivatization (GCD) method, and the groups were analyzed quantitatively by X‐ray photoelectron spectroscopy (XPS). It is desirable that a derivatization reaction is unique to the target group; however, it usually causes undesirable side reactions which affect other groups. This diversity of the reactions has complicated the analysis. In this report, we have overcome the problem by applying a mathematical treatment which takes the side reactions into account. This improved analysis shows that it is no longer necessary to have derivatization reactions unique to the target groups. As a result, it is demonstrated that the carbonyl (C?O) group is the dominant surface functional group on both the DLC and its wet‐oxidized films, the carboxyl (COOH) group plays a minor role, and the presence of the hydroxyl (OH) group is logically denied. Considering the oxidation steps of these oxygen‐related surface functional groups, it is suggested that the C?O group on the DLC films requires the cleavage of the carbon–carbon bond with a relatively high activation energy barrier to change into the COOH group. Copyright © 2010 John Wiley & Sons, Ltd.     

One‐step electrodeposition of amorphous carbon films containing WO3 with high conductivity and good wettability

Tungsten trioxide‐incorporated hydrogenated amorphous carbon (WO₃/a‐C:H) films have been fabricated on a single‐crystal silicon wafer by liquid phase electrodeposition using methanol as carbon source and tungsten carbonyl as incorporated reagent. The morphology, composition and structure of the films have been investigated by SEM, XPS, Raman scattering spectroscopy, Fourier transform infrared spectroscopy (FTIR) and Transmission electron microscope (TEM), respectively. The effects of WO₃ incorporation on the electrical and wetting properties were studied in detail. The characterization results showed that tungsten trioxide nanocrystalline particles with diameters in the range of 10–20 nm were homogenously embedded in the amorphous carbon films. Also, the electrical conductivity and wetting ability of the films were strongly improved due to the contribution of the tungsten trioxide. Copyright © 2010 John Wiley & Sons, Ltd.     

Corrosion and tribocorrosion behaviour of super‐thick diamond‐like carbon films deposited on stainless steel in NaCl solution

Super‐thick diamond‐like carbon (DLC) film is a potential protective coating in corrosive environments. In the present work, three kinds of DLC films whose thickness and modulation periods are 4 µm and 3, 21 µm and 17 and 21 µm and 7, respectively, were fabricated on stainless steel. The effect of different thickness and modulation periods on corrosion and tribocorrosion behaviour of the DLC‐coating stainless steel was investigated in 3.5 wt% NaCl aqueous solution by a ball‐on‐flat tribometer equipped with a three‐electrode electrochemical cell. The DLC‐coating stainless steel served as a working electrode, and its OCP and potentiodynamic polarization were monitored before and during rubbing. The wear–corrosion mechanism of the DLC films was investigated by SEM. The results showed that the increasing thickness can prolong significantly lifetime of DLC films in NaCl aqueous solution. In particular, the modulation period has a significant impact on the tribocorrosion resistance of the DLC super‐thick films. The study suggested that the increasing thickness of compressive stress layer could suppress film damage by reducing crack propagation rate. Thus, the super‐thick DLC film with thickness of 21 µm and 7 periods presented the best tribocorrosion resistance among all studied films. Copyright © 2016 John Wiley & Sons, Ltd.     

On the use of elastic peak electron spectroscopy (EPES) to measure the H content of hydrogenated amorphous carbon films

Quasi‐elastic scattering of 1–2 keV electrons is considered with respect to measuring the H content in hydrogenated amorphous carbon (a‐C:H) materials. Interest in the technique lies in the fact that H cannot be typically detected by electron spectroscopic means (AES or XPS for instance). The feasibility of the approach is demonstrated and a quantification procedure is proposed. At the same time however, limitations of the technique (electron stimulated H desorption, low intensity of the H related signal and its spectral interference with the π‐plasmon peak) are discussed. Copyright © 2008 John Wiley & Sons, Ltd.     

Microstructure and surface roughness of graphite‐like carbon films deposited on silicon substrate by molecular dynamic simulation

Molecular dynamics simulations are performed on the atomic origin of the growth process of graphite‐like carbon film on silicon substrate. The microstructure, mass density, and internal stress of as‐deposited films are investigated systematically. A strong energy dependence of microstructure and stress is revealed by varying the impact energy of the incident atoms (in the range 1–120 eV). As the impact energy is increased, the film internal stress converts from tensile stress to compressive stress, which is in agreement with the experimental results, and the bonding of C‐Si in the film is also increased for more substrate atoms are sputtered into the grown film. At the incident energy 40 eV, a densification of the deposited material is observed and the properties such as density, sp³ fraction, and compressive stress all reach their maximums. In addition, the effect of impact energy on the surface roughness is also studied. The surface morphology of the film exhibits different characteristics with different incident energy. When the energy is low (<40 eV), the surface roughness is reduced with the increasing of incident energy, and it reaches the minimum at 50 eV. Copyright © 2012 John Wiley & Sons, Ltd.     

Electrodeposition and characterization of Pd nanoparticles doped amorphous hydrogenated carbon films

Palladium (0) nanoparticles incorporated hydrogenated amorphous carbon (Pd/a-C:H) films were synthesized on single crystal silicon (100) substrates by electrochemical deposition route using methanol and camphor as carbon source, and Pd nanoparticles as dopant. The characterization results indicate that Pd nanocrystalline particles with diameter in the range of 1–5 nm dispersed in the amorphous carbon matrix. Compared with pure a-C:H films, the introduction of Pd nanoparticles didn't change the structure of carbon films. At the end, the growth mechanism of the Pd/a-C:H composite films was discussed.