Tribological behavior of nano-undulated surface of diamond-like carbon films

Tribological behavior of nano-undulated diamond-like carbon (DLC) films of the surface roughness ranging from 0.6 to 13.7 nm was investigated in an ambient air of 50% relative humidity. The nano-undulated DLC films were prepared by radio frequency plasma-assisted chemical vapor deposition (r.f.-PACVD) using nanosized Ni dots on a Si (100) substrate. The friction coefficient between the DLC film and the steel ball was characterized by a ball-on-disk type wear rig. Auger and Raman spectroscopy analysis of the debris revealed that the tribochemical reaction with environment was significantly suppressed as the surface roughness increased. Even if the rough surface increased the wear rate of the steel ball and thus the concentration of Fe in the debris, neither the oxidation of Fe nor the graphitization of the carbon in the debris occurred on the rough surface. However, the frictional behavior was affected by several factors: the composition and the size of debris, plowing effect of the rough surface, and the presence of the transfer layer on the wear scar surface.     

Stresses in diamond-like carbon films

Internal stresses have been measured in diamond-like carbon (DLC) films deposited by d.c. plasma assisted chemical vapor deposition from methane, acetylene, or cyclohexane, and in nitrogen containing DLC films deposited from acetylene, or cyclohexane and nitrogen. The total hydrogen content in the films and the fraction of bound hydrogen have been analyzed by forward recoil elastic scattering and Fourier transform infrared spectroscopy respectively. It was found that in pure DLC films the stresses increase with increasing fraction of unbound hydrogen. The highest compressive stresses were obtained in the films deposited from methane and the lowest stresses in films deposited from cyclohexane. In the nitrogen containing DLC films the stresses decrease with increasing nitrogen content in the films. Stresses as low as 0.22 GPa were obtained in the films deposited from cyclohexane and nitrogen at a ratio of 1/15 in the plasma.     

Surface energy of the plasma treated Si incorporated diamond-like carbon films

Surface energy and surface chemical bonds of the plasma treated Si incorporated diamond-like carbon films (Si-DLC) were investigated. The Si-DLC films were prepared by r.f. plasma assisted chemical vapor deposition using benzene and diluted silane (SiH₄/H₂ = 10:90) as the precursor gases. The Si-DLC films were subjected to plasma treatment using various gases like N₂, O₂, H₂ and CF₄. The plasma treated Si-DLC films showed a wide range of water contact angles from 13.4° to 92.1°. The surface energies of the plasma treated Si-DLC films revealed a high polar component for O₂ plasma treated Si-DLC films and a low polar component for CF₄ plasma treated Si-DLC films. The CF₄ plasma treated Si-DLC films indicated the minimum surface energy. X-ray photoelectron spectroscopy (XPS) revealed that the polarizability of the bonds present on the surface explains the hydrophilicity and hydrophobicity of the plasma treated Si-DLC films. We also suggest that the O₂ plasma treated surface can provide an excellent hemocompatible surface from the estimated interfacial energy between the plasma treated Si-DLC surface and human blood.     

Bacterial adhesion on silicon-doped diamond-like carbon films

In this paper the surface properties of silicon-doped diamond-like carbon films with various Si contents on 316 stainless steel substrate by a magnetron sputtering technique were investigated. X-ray photoelectron spectroscopy was applied to determine the surface chemical composition of the films. Atomic force microscopy was used for the determination of surface roughness and topography. The sp² contents in the films were determined with Auger electron spectroscopy, which were 67.1%, 34.2% and 25.0% for silicon contents 1%, 2% and 3.8%. The sp³/sp² ratio increases with increasing the silicon contents in the films. Contact angles of three test liquids on the films were obtained with a Dataphysics OCA-20 contact angle analyzer. Surface free energies of the films and their dispersive and polar components were calculated using van Oss acid–base approach. Staphylococcus aureus was used for bacterial adhesion test. The experimental results showed that bacterial adhesion decreased with increasing the silicon content or with increasing sp³/sp² ratio in the films.     

Nitrogen incorporated diamond-like carbon films by microwave surface wave plasma CVD

Nitrogen incorporated diamond like carbon films have been deposited by microwave surface wave plasma chemical vapor deposition (MW-SWP-CVD), using methane (CH₄) as the source of carbon and with different nitrogen flow rates (N₂ / CH₄ flow ratios between 0 and 3). The influence of the nitrogen incorporation on the optical, structural properties and surface morphology of the carbon films were investigated using different spectroscopic techniques. The nitrogen has been incorporated into DLC:N films which was confirmed by the X-ray photoelectron spectroscopy (XPS) measurement. Moreover, the nitrogen incorporation was accompanied by a variation in the optical gap, which was attributed to the removal or creation of band tail states.     

Lubrication performance of diamond-like carbon and fluorinated diamond-like carbon coatings for intravascular guidewires

Diamond-like carbon (DLC) and fluorinated DLC (F-DLC) films were deposited on SUS316L guidewires using radio frequency (RF) plasma enhanced chemical vapor deposition (CVD), and the lubrication performance of DLC- or F-DLC-coated guidewires was then evaluated under in vitro conditions using a novel friction simulator developed for this study. Scanning electron microscopy (SEM) demonstrated that DLC or F-DLC film completely coated the specimens (SUS316L guidewires) and that polishing scars were substantially reduced. In the torturous vessel model, DLC- or F-DLC-coated guidewires exhibited significantly improved lubrication performance (by approximately 30% over that of uncoated wires). DLC and F-DLC films are thus promising candidates for lubricious coating of intravascular guidewires.     

类金刚石薄膜在橡胶表面改性中的研究进展

介绍了类金刚石薄膜的结构、制备方法及其在橡胶表面改性中的研究进展。     

Characteristics and surface energy of silicon-doped diamond-like carbon films fabricated by plasma immersion ion implantation and deposition

Diamond-like carbon (DLC) films doped with different silicon contents up to 11.48 at.% were fabricated by plasma immersion ion implantation and deposition (PIII-D) using a silicon cathodic arc plasma source. The surface chemical compositions and bonding configurations were determined by X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. The results reveal that the sp³ configuration including Si–C bonds increases with higher silicon content, and oxygen incorporates more readily into the silicon and carbon interlinks on the surface of the more heavily silicon-doped DLC films. Contact angle measurements and calculations show that the Si-DLC films with higher silicon contents tend to be more hydrophilic and possess higher surface energy. The surface states obtained by silicon alloying and oxygen incorporation indicate increased silicon oxycarbide bonding states and sp³ bonding states on the surface, and it can be accounted for by the increased surface energy particularly the polar contribution.     

Low friction and protective diamond-like carbon coatings deposited by asymmetric bipolar pulsed plasma

Diamond-like carbon (DLC) thin films have been prepared at room temperature by plasma-enhanced chemical vapour deposition (PECVD) using pulsed-DC power and CH₄ as precursor. Tribological tests of these DLC films have been carried out with a nanotribometer and a calotest instrument adapted for wear measurements. Friction coefficients ranged from 0.15 to 0.20, which differ from values obtained by other techniques. In this study we have systematically measured the abrasive wear rate and friction coefficient of DLC films deposited at different conditions (pulse frequency and peak voltage), and we have discussed the results in terms of DLC structure and surface morphology. These films could find application as ultrathin anti-friction and anti-wear protective coatings, hydrophobic coatings, gas diffusion barriers and dielectric layers in electronic devices.     

Atmospheric plasma deposition of diamond-like carbon coatings

The atmospheric pressure plasma-enhanced chemical vapor deposition of diamond-like carbon (DLC) has been investigated. The DLC coatings were grown with a mixture of acetylene, hydrogen and helium that was fed through a linear plasma source. The plasma was driven with radio frequency power at 27.12 MHz. Deposition rates exceeded 0.10 µm/min at substrate temperatures between 155 and 200 °C. Solid-state carbon-13 nuclear magnetic resonance revealed that the coatings contained approximately 43% sp²-bonded carbon and 57% sp³-bonded carbon. Coefficient of friction values for the coatings were found to be 0.24 ± 0.02, which is within the range observed for vacuum deposited DLC.     

Protective coatings for carbon bonded carbon fibre composites

Carbon bonded carbon fibre composites (CBCF) were modified by direct reaction with molten silicon in order to obtain a silicon carbide layer on the composite surface. Subsequently, the Si-infiltrated CBCF material was coated with a silica-based glass containing yttria and alumina by means of a slurry-dipping technique. On heat treatment the glass yielded a glass-ceramic layer thus giving a multi-layered oxidation and erosion protection system. The microstructural characterisation of the coating was conducted by standard microscopy techniques and by X-ray diffraction. The controlled crystallization of the glass-produced cristobalite, yttrium silicate (Y₂Si₂O₇, keiviite, β-form) and mullite as main crystalline phases. These are excellent ceramic materials for oxidation and erosion protection of SiC-coated carbon-based composites since their coefficients of thermal expansion (CTE) closely match that of SiC. The possibility of healing (closure) of micro cracks by a thermal treatment at 1375 °C, thus exploiting the viscous flow of the residual glass in the glass-ceramic, was explored in order to extend the service life of the protection system.     

Surface energy,wettability, and blood compatibility phosphorus doped diamond-like carbon films

There is an increasing interest in developing novel coatings to improve the biocompatibility of cardiovascular implants. In this work, we fabricated phosphorus-doped (P-doped) diamond-like carbon (DLC) films by plasma immersion ion implantation and deposition (PIII and D) and the structure, physicochemical characteristics, electrical properties, as well as surface biomedical compatibility, were evaluated using different characterization techniques. Microstructures manifesting as dots are visible under optical microscopy while atomic force micrographs disclose that these round and flat islands are distributed evenly on the film surface. Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS) results show that they are composed of C, P and O while only C and O can be found in the areas away from the islands. Attenuated total-reflection Fourier transform infrared spectroscopy (ATR-FTIR) spectroscopy indicates the presence of many PO_x and CP_xO_x species. In the Raman spectra, the G peak of the P-doped sample shifts to a lower wave-number suggesting that the film is more disordered. The P-doped DLC film exhibits excellent wettability (16.9° water contact angle). In vitro platelet adhesion and coagulation factor experiments were conducted to examine the blood compatibility. Scanning electron microscopy (SEM) and optical microscopy reveal a significant decrease of the number as well as activation of platelets on the P-doped DLC film.     

Large-area uniform hydrogen-free diamond-like carbon films prepared by unbalanced magnetron sputtering for infrared anti-reflection coatings

The hydrogen-free diamond-like carbon (DLC) films are potential materials to be used as infrared anti-reflection protective coatings if their optical absorption can be reduced to get relatively thick films needed. In this study, hydrogen-free DLC films were deposited by the physical vapor deposition (PVD) method in an unbalanced magnetron sputtering (UBMS) system with a rectangle graphite target of 440 × 80 mm in the argon atmosphere. The UBMS system was described in detail and the magnetron field distribution of the target was denoted in this work. The film thickness uniformity was investigated and the results showed that this system is capable of depositing uniform films larger than 150 mm in diameter. The infrared transmission spectra of DLC films were analyzed by a FTIR spectrometer, the results indicating that transparent films were obtained in the infrared region for the single side DLC coated on the silicon and germanium substrates, and about 68.83% and 63.05% transmittance were achieved respectively at the wave number of 2983 /cm, close to theoretical value for non-absorption carbon material. No obvious absorption peaks were found between 5000 and 800 /cm. The refractive index and extinction coefficient of the DLC films deposited under optimized conditions were about 2.08 and 0.067 respectively at the wavelength of 1600 nm. These important optical characteristics showed that the hydrogen-free DLC films prepared in the UBMS system were suitable for infrared transmission enhancement applications.     

Thermal gas effusion from diamond-like carbon films

Good-quality diamond-like carbon films (6 at.% H₂, 2400 kgf/mm² microhardness, 2.7 eV bandgap, higly insulating) have been obtained by the DC glow discharge decomposition of acetylene. Mass spectroscopic thermal effusion measurements were carried out on the films deposited under different deposition conditions. Analyses of hydrogen in conjunction with hydrocarbon effusing species yield information on the microstructure and nature of C---H bonding configurations. It is shown to be a useful analytical tool to study hydrogenated amorphous carbon films of different microstructures varying from polymer-like to diamond-like.     

Iodine doping of amorphous diamond-like carbon films

Amorphous diamond-like carbon (a:DLC) films have been doped by incorporation of iodine during the films deposition. XPS and AES analysis shows the existence of iodine atoms with constant concentration of 0.9% along the iodine doped DLC film (a:I-DLC). The optical and electronic properties of the doped films were studied. Optical measurements in the visible light show that iodine affects the interband absorption of the a:DLC films. Iodine causes decreasing of the optical energy gap, from 1.07 to 0.78 eV and affects the density of states at the conducting band. Like the optical measurements, electrical measurements show that iodine also decreases the activation energy of the films from 0.34 to 0.22 eV. This shows that although both gaps decrease, the optical energy gap remains different from that of electrical gap, also after doping.     

Heat resistance of fluorinated diamond-like carbon films

The heat resistance of fluorinated diamond-like carbon (F-DLC) films produced by Plasma Immersion Ion Processing (PIIP) technique was investigated by annealing F-DLC coatings in a vacuum furnace. The growth rate for the F-DLC films was approximately 0.6 μm/h. In order to see the possible change in the composition and properties of the F-DLC films, Rutherford Backscattering Spectrometry (RBS), nanoindentation and contact angle measurements were performed before and after the heat treatments. The results show that the composition and properties of the F-DLC films were unchanged up to heat treatment at 300°C for up to 30 min. Blistering and film delamination occurred for samples treated at 400°C.     

Fast deposition of diamond-like hydrogenated carbon films

Diamond-like hydrogenated carbon films have been formed at low temperatures using methane and acetylene as precursor gases. The source used was of a cascaded arc type employing Ar and Ar/H₂ as carrier gases. Energies of ion species and ion densities in the plasma were measured with a mass energy probe and a Langmuir probe.The films produced were characterized in terms of sp³ content, refractive index, relative hydrogen content, hardness and adhesion. The variation of these parameters is presented as functions of precursor gas flow, process pressure, and surface temperature.Deposition rates up to 30 nm/s have been achieved using acetylene as precursor gas at substrate temperatures below 100 °C. Experiments with acetylene showed deposition rates seven times greater than with methane. The typical sp³ content of 55–78% in the films was determined by X-ray-Excited Auger Electron Spectroscopy (XAES) technique. The hardness and reduced modulus were determined by nanoindentation. Preliminary Atomic Force Microscopy (AFM) studies of the films showed a roughness below 3 nm (R_a).     

Optical observation of bonded and quasi-free hydrogen in diamond-like carbon

The technique of vacuum UV Raman spectroscopy is applied to diamond-like carbon (a-C:H) films in order to study the state of hydrogen non-bonded with host carbon atoms. Under resonant excitation, a series of Raman bands related to rotational levels of a stretched H₂ molecule is observed. The data are used to estimate the parameters of the H₂ molecule in a-C:H. A model of the reversible transfer of hydrogen between the molecular state and states bonded to carbon is discussed.     

Mechanical and tribological properties of diamond-like carbon coatings films deposited from an electron cyclotron resonance plasma

The friction coefficients have been investigated in amorphous diamond-like carbon (DLC) films deposited by a dual ECR–r.f. method, as a function of r.f. substrate bias in relation with the H content and bonding. Combined infrared absorption, elastic recoil detection analysis and tribological tests are used to characterize fully the films in their as-deposited state. Friction coefficients (μ) of the coatings against sapphire balls are determined in air at room temperature. The results indicate clearly that the samples exhibit high compressive stresses and the friction coefficients are found to be low and are affected by the magnitude of the biaxial stress and the microstructure of the films.     

Characterization of crystalline diamond incorporated diamond-like carbon films

The purpose of this paper is to show the production and characterization of diamond-like carbon (DLC) films with incorporated crystalline diamond (CD), produced by plasma enhanced chemical vapor deposition. CD-DLC films were characterized by scanning electron microscopy, X-ray diffraction, atomic force microscopy and Raman scattering spectroscopy. Wetting contact angle, stress and friction coefficient were also evaluated. Our results demonstrated CD-DLC films are more hydrogenated and hydrophobic, with higher fiction coefficient. The stress values kept almost constantly.