Low temperature Si-DLC coatings on fluoro rubber by a bipolar pulse type PBII system

Diamond-like carbon (DLC) films have been attractive materials because of their excellent mechanical properties such as high hardness, low friction coefficient, high wear resistance and more. In order to spread the application of the DLC coatings for polymer materials, it is necessary to make the temperature go down during the coating process.Our group has been studying DLC coatings on several materials with bipolar pulse type PBII (plasma based ion implantation) systems, which consist of positive and negative (or bipolar) pulse generators and a timing controller. Recently we have introduced a new bipolar pulse generator, whose slew-rate is several times larger than that of previous generators, and a controller which can make a very short pulse less than 1 μs. Using the pulse generator and controller, we have tried to make Si incorporated DLC (Si-DLC) coatings on fluoro rubber, which is widely used in many industries, at low temperature.Using the new pulse generator and controller, we can make very short width positive pulse of about 1 μs, and reduce the temperature during Si-DLC coating to about 30 K. The lower temperature makes fewer folds on the sample surface. By using optical indentation microscope system, Meyer hardness (H_M) of uncoated and Si-DLC coated fluoro rubber was obtained and the value of H_M for Si-DLC coated rubber is about 1.4 times larger than that of uncoated rubber. Coefficient of friction of Si-DLC coated rubber was 0.2 to 0.25 and drastically decreased from 1.3 to 1.9 of uncoated rubber. Wear of uncoated fluoro rubber is apparent, however, wear of Si-DLC coated rubber cannot be observed, except for the creep effect of fluoro rubber substrate. The counter SUJ2 ball surfaces also showed almost no wear. Si-DLC coating can make the tribological property of fluoro rubber to low friction and less wear. Si-DLC coatings are very useful in many applications.     

Cathodic arc plasma deposition of nano-multilayered ZrN/AlSiN thin films

Thin films of ZrN/AlSiN were deposited on SKD 11 tool steel substrate using Zr and AlSi cathodes in an Ar/N₂ gas mixture in a cathodic arc plasma deposition system. The influence of the AlSi cathode arc current and the substrate bias voltage on the mechanical and structural properties of the films was investigated. X-ray diffraction, electron probe micro-analysis, high resolution transmission electron microscopy, nanoindentation and profilometry were used to characterize the films. The ZrN/AlSiN thin films had a multilayered structure by rotating the substrate in which nano-crystalline ZrN layers alternated with amorphous AlSiN layers. The hardness of the films increased as the AlSi cathode arc current was raised from 35 to 40 A, and then decreased with a further increase of the current. The hardness of the films increased with the increase of the bias voltage from − 50 to − 100 V. Further increase in the bias voltage decreased the hardness. The films exhibited a maximum hardness of 38 GPa. With the increase of bias voltage, the residual stress of the films correlated well with the hardness.     

The effect of applied substrate negative bias voltage on the structure and properties of Al-containing a-C:H thin films

Al-containing hydrogenated amorphous carbon (Al-C:H) films were prepared using a magnetron sputtering Al target in the CH₄ and Ar mixture atmosphere with various applied substrate pulse negative bias voltages. The hydrogen content and internal stress of the film decrease dramatically with the substrate pulse bias voltage increase. However, the hardness values of the films keep at high level (∼ 20 GPa) without any obvious changes with the increase of the applied substrate pulse bias voltages. The Al-C:H film prepared at applied substrate high bias voltage shows a long wear life and low friction coefficient.     

Influence of the C content on the mechanical and tribological properties of the TiCN coatings deposited by LAFAD technique

TiCN coatings with different C content were deposited using a large area filtered arc deposition (LAFAD) technique from Ti targets in a mixture of N₂ and CH₄ gases. Scanning electron microscopy (SEM), nano-indentation, and pin-on-disc tribometer were used to characterize the cross-sectional microstructure, hardness, modulus, wear rate, and friction coefficient of the TiCN coatings. The increase in the CH₄ fraction in the gases leads to a continuous increase in the deposition rate of the TiCN coatings as well as an increase in the defect density in the coatings. Nano-indentation results indicate that with an increase of the C content in the coatings, the hardness and elastic modulus increase to a maximum at a C content of 2.8 at.%, then decreases rapidly, which results from the increase in the defect density in the coatings. Tribological test results show that when tested against Al₂O₃ balls, there is no significant change in the friction coefficient (0.78-0.88) of the TiCN coatings with a C content of below 4.6 at.%, but the friction coefficient decreases rapidly to 0.21 with a further increase in the C content to 9.3 at.%. In addition, with increasing C content in the coatings from 0 to 9.3 at.%, the wear rate decreases remarkably from 2.5 × 10⁻⁶ mm³/Nm to 5.3 × 10⁻⁷ mm³/Nm. The low friction coefficient and the formation of a transfer layer correspond to the low wear rate for the TiCN coatings with high C content.     

Adhesion and composite micro-hardness of DLC and Si-DLC films deposited on nitrile rubber

Thin films of hydrogenated diamond-like carbon (DLC) and silicon (Si) doped diamond-like carbon (Si-DLC) have been deposited on acrylonitrile butadiene rubber (NBR) using a closed field unbalanced magnetron sputtering ion plating system. A sputter cleaning process was integrated into the deposition process so as to reduce the likelihood of re-contamination between the cleaning and deposition stages. The deposited coatings showed excellent adherence with an adhesion rating of 4 A for films with a Si-C interlayer. The composite micro-hardness was highest for DLC films at 15.5 GPa for indentation load of 147.1 mN using a Vickers micro-hardness tester. Tribological tests undertaken under normal load of 5 N using a pin-on-disc tribometer for all of the samples of DLC and Si-DLC films, with and without Si-C interlayer, show a friction increase between 0.25 and 0.4 to between 0.45 and 0.6. This friction increase has been related to the micro-hardness of the films.     

Effect of bias voltage on microstructure and properties of Ti-doped graphite-like carbon films synthesized by magnetron sputtering

Ti-doped graphite-like carbon (GLC) films with different microstructures and compositions were fabricated using magnetron sputtering technique. The influence of bias voltages on microstructure, hardness, internal stress, adhesion strength and tribological properties of the as-deposited GLC films were systemically investigated. The results showed that with increasing bias voltage, the graphite-like structure component (sp² bond) in the GLC films increased, and the films gradually became much smoother and denser. The nanohardness and compressive internal stress increased significantly with the increase of bias voltage up to −300 V and were constant after −400 V. GLC films deposited with bias voltages in the range of -300--400 V exhibited optimum adhesion strength with the substrates. Both the friction coefficients and the wear rates of GLC films in ambient air and water decreased with increasing voltages in the lower bias range (0--300 V), however, they were constant for higher bias values (beyond −300 V) . In addition, the wear rate of GLC films under water-lubricated condition was significantly higher for voltages below −300 V but lower at high voltage than that under dry friction condition. The excellent tribological performance of Ti-doped GLC films prepared at higher bias voltages of −300--400 V are attributed to their high hardness, tribo-induced lubricating top-layers and planar (2D) graphite-like structure.     

Characteristics and tribological performance of DLC and Si-DLC films deposited on nitrile rubber

The characteristics and tribological performance of DLC and Si-DLC films with and without Si–C interlayers were studied in this paper. The films were deposited on nitrile rubber using a closed field unbalanced magnetron sputtering ion plating system. The film properties and characteristics were determined by scanning electron microscopy (SEM), hydrophobicity studies, Raman spectroscopy and tribological investigations. Tribological performance of these films was investigated using a pin-on-disc tribometer under applied loads of 1 N and 5 N under conditions of dry and wet sliding. The effect of immersing the films in water on tribological performance was also examined. The results show that the morphology of the films had a crack-like network. At a substrate bias of − 30 V, the coatings were characterised by a very dense non-columnar microstructure. The highest value of the ratio of intensities of the D and G peaks (I_D/I_G) was 1.2 for Si-DLC film with Si–C interlayer. The lowest value of 0.7 was observed for DLC film. The contact angle (CA) of water droplets showed that the films were hydrophobic. These results are interpreted in terms of hybridisation of carbon in these coatings. The tribological investigation showed a dependence on both the tribological condition under investigation and the atomic percentage of Si in the films. At 5 N normal load the lowest wear depth was observed for DLC films.     

Investigation of cytocompatibility of surface-treated cellulose nitrate films by using plasma immersion ion implantation

The alpha-particle sensitive colorless cellulose nitrate films (commercially available as LR 115 films from DOSIRAD, France) have been proposed as cell-culture substrates for alpha-particle radiobiological experiments. Cytocompatibility of the substrate is a key factor to the success of such experiments. The present work aims to investigate the cytocompatibility of surface-treated cellulose nitrate films by using plasma immersion ion implantation-deposition. The films were placed in a vacuum chamber, into which nitrogen gas was continuously bled and where the pressure was kept at 2 × 10^− 3 Torr. Implantation was carried out by igniting the nitrogen plasma at 100 W radio-frequency and applying high bias voltage in pulse with 20 μs pulse width and 50 Hz (with 20 kV or no voltage). HeLa cervix cancer cells were then cultured on both the plasma-treated and untreated cellulose nitrate films. Our tests showed that the plasma-treated films are in general more cytologically compatible.     

Characteristics of copper oxide films deposited by PBII&D

Copper oxide films were deposited by plasma based ion implantation and deposition using a copper antenna as rf sputtering ion source. A gas mixture of Ar + O₂ was used as working gas. During the process, copper that was sputtered from the rf antenna reacted with oxygen and was deposited on a silicon substrate. The composition and the chemical state of the deposited films were analyzed by XPS. The structure of the films was detected by XRD. It is observed that Cu₂O film has been prepared on the Si substrate. It is found that the microstructure of the deposited film is amorphous for the applied voltage of − 5 kV. The surface layer of the deposited films is CuO. This is because the surface layer absorbs the oxygen from ambient air after the treated sample was removed from the vacuum chamber. An appropriate applied voltage, 2 kV under the present conditions, brings the lowest resistance. It is also seen that the maximum absorbance of the deposited films moves to a lower wavelength with increased applied voltage.     

Fabrication, microstructure and tribological behavior of pulsed laser deposited a-CNx/TiN multilayer films

a-CN_x/TiN multilayer films were deposited onto high-speed steel substrates by pulsed laser ablation of graphite and Ti target alternately in nitrogen gas. The composition, morphology and microstructure of the films were characterized by energy dispersive X-ray spectroscopy (EDS), scanning electron microscopy (SEM), X-ray diffraction (XRD) and Raman spectroscopy. The tribological properties of the films in humid air were investigated using a ball-on-disk tribometer. The multilayer films consist of crystalline TiN, metallic Ti and amorphous CN_x (a-CN_x). With an increase in thickness ratio of CN_x to bilayer, the hardness of multilayer film decreases, friction coefficient decreases from 0.26 to 0.135, and wear rate increases. The film with thickness ratio of CN_x to bilayer of 0.47 exhibits a maximum hardness of 30 GPa and excellent wear rate of 2.5 × 10^− 7 mm³ N^− 1 m^− 1. The formation of tribo-layer was observed at contact area of Si₃N₄ ball. The film undergoes the combined wear mechanism of abrasion wear and adhesion wear.     

Growth, stress and hardness of reactively sputtered tungsten nitride thin films

Tungsten nitride (WN_x) thin films were deposited on Si(100) substrates using direct current reactive magnetron sputtering in discharging a mixture of N₂ and Ar gas. The effects of nitrogen flow rate (F_N2) and substrate bias voltage (V_b) on the composition, phase structure, and mechanical properties for the obtained films were evaluated by means of X-ray photoelectron spectroscopy, X-ray diffraction, high-resolution transmission electron microscopy and nanoindentation. The evolution of phase structure is found closely correlated to N concentration in the films. When V_b = −40 V, with increasing F_N2, the N/W atomic ratio gradually increases in the film, accompanied by a phase transition from cubic β-W to hexagonal WN through face centered-cubic (fcc)-W₂N. At F_N2 = 15 sccm, the N/W atomic ratio gradually decreases with increasing the absolute value of V_b, resulting in a transition from fcc-W₂N to cubic β-W(N) through a mixture of fcc-W₂N + β-W(N). In addition, the increase in implanted nitrogen causes the increase in the compressive stress with increasing F_N2. In contrast, although with increasing the absolute value of V_b from 80 to 160 V the N/W atomic ratio decreases, the increase of the defects caused by increasing ion bombarding energy, dominates the increase of the compressive stress. Furthermore, the maximum hardness value for the films arrives at 38.9 GPa, which is obtained at V_b = −120 V when fcc-W₂N + β-W(N) mixed structure is formed.     

Study on nanocrystalline Cr2O3 films deposited by arc ion plating: II. Mechanical and tribological properties

In this work, the influence of substrate bias voltage on the microhardness, adhesive strength, friction coefficient, and wear rate of AIP Cr₂O₃ films deposited on AISI 304 stainless steel substrates was investigated systematically. In the meantime, the wear failure mechanism of AIP Cr₂O₃ films in dry sliding contact was also analyzed and discussed. The results showed that the mechanical properties, adhesive behaviors, and tribological performance of AIP Cr₂O₃ films were greatly altered by applying a negative bias voltage. With increasing the bias voltage, the hardness, critical load, and tribological performance of AIP Cr₂O₃ films first were improved gradually, and then were impaired slightly again. When the bias voltage is − 100 V, the Cr₂O₃ film possessed the highest hardness, the strongest adhesion, and the best wear resistance. The essence of above phenomena was attributed to the variations of microstructure and defect density in the films induced by the substrate bias voltage increase. The main wear failure mechanism of AIP Cr₂O₃ films is crack initiation and propagation under the high contact stresses, inducing the local film with small area to flake off gradually, and eventually leading to the formation of a wear scar.     

Mechanical and tribological properties of coatings sputtered from SiC target in the presence of CH4 gas

Amorphous hydrogen-free silicon carbide (a-SiC) coatings demonstrate good adhesion to different steel substrates, low intrinsic stress and high hardness however show quite high coefficient of friction in comparison with carbon-based coatings. Some addition of carbon to SiC can promote the decrease of friction coefficient.In the present work the amorphous hydrogenated silicon-carbide (a-SiC:H) films with different C/Si ratio were prepared at room temperature using DC magnetron sputtering in two ways: (i) sputtering of silicon target; (ii) sputtering of SiC target, both in the gas mixture of Ar and CH₄. In the latter case the films contained less hydrogen at the same C/Si ratio. The mechanical and tribological properties of these films were studied to find their optimum combination.The hardness, elastic modulus (nanoindentation), intrinsic stress (Stoney's formula) and coefficient of friction (pin on disc tribometer) were examined in dependence on the technological parameters, film structure and composition (Raman spectra, electron probe microanalysis). An increase of carbon in the films from 50 to 70 at.% resulted in decrease of hardness and friction coefficient. In the first case (i) the hardness decreased from 13 to10 GPa and in the second case (ii) from 23 to 16 GPa. Thus sputtering of SiC target in the gas mixture of Ar and CH₄ allows obtaining at room temperature the films with C/Si > 1 in which relatively high hardness (16-18 GPa) and low friction coefficient (~ 0.15) are combined.     

Deposition of titanium oxide films by reactive High Power Impulse Magnetron Sputtering (HiPIMS): Influence of the peak current value on the transition from metallic to poisoned regimes

In this study, reactive High Power Impulse Magnetron Sputtering (HiPIMS) experiments were carried out to synthesize titanium oxide films, using a 45 × 15 cm² titanium target in Ar/O₂ gas mixtures. The deposition process was studied as a function of the peak current (i_peak) at constant voltage during the pulse (1 kV) and constant average power (P_av). As the oxygen flow was increased, i_peak was kept constant (160, 300 or 400A) by adjusting the pulse duration and the average power (2 or 4 kW) by adjusting the pulse repetition frequency. For all experimental conditions, an abrupt transition from metallic towards poisoned regimes was observed. The transition curves exhibit hysteresis. As i_peak is increased from 160 A to 450 A, for P_av = 4 kW, the oxygen content (Ω) in the Ar/O₂ mixture needed to poison the target surface was reduced from Ω = 11.5% to Ω = 8.5%. These values are much smaller than those recorded for DC magnetron sputtering (DCMS) (Ω = 42%) and pulsed DCMS (Ω = 36%) experiments carried out at the same power. These results are explained by the enhancement of the ionization and dissociation rates of oxygen molecules with the increase of i_peak.     

Electrical and optical properties of tantalum oxide thin films prepared by reactive magnetron sputtering

Tantalum oxide thin films were prepared by using reactive dc magnetron sputtering in the mixed atmosphere of Ar and O₂ with various flow ratios. The structure and O/Ta atom ratio of the thin films were analyzed by X-ray diffraction and X-ray photoelectron spectroscopy (XPS). The optical and dielectric properties of the Ta₂O₅ thin films were investigated by using ultraviolet-visible spectra, spectral ellipsometry and dielectric spectra. The results reveal that the structure of the samples changes from the amorphous phase to the β-Ta₂O₅ phase after annealing at 900 °C. The XPS analysis showed that the atomic ratio of O and Ta atom is a stoichiometric ratio of 2.50 for the sample deposited at Ar:O₂ = 4:1. The refractive index of the thin films is 2.11 within the wavelength range 300-1000 nm. The dielectric constants and loss tangents of the Ta₂O₅ thin films decrease with the increase of measurement frequency. The leakage current density of the Ta₂O₅ thin films decreases and the breakdown strength increases with the increase of Ar:O₂ flow ratios during deposition.     

Mechanical and tribological properties of multi-element (AlCrTaTiZr)N coatings

Multi-element (AlCrTaTiZr)N coatings are deposited onto Si and cemented carbide substrates by reactive RF magnetron sputtering in an Ar + N₂ mixture. The influence of substrate bias voltage, ranging from 0 to − 200 V, on the microstructural, mechanical and tribological properties of these nitride coatings is studied. A reduction in concentration of N and Al is observed with increasing substrate biases. The (AlCrTaTiZr)N coatings show the face-centered-cubic crystal structure (B1-NaCl type). The use of substrate bias changes the microstructure of the (AlCrTaTiZr)N coating from the columns with microvoids in boundaries to the dense and less identified columns. The compressive macrostress increases from − 0.9 GPa to − 3.6 GPa with an increase of substrate bias. The hardness and adhesion increase to peak values of 36.9 GPa and 60.7 N at the bias voltage of − 150 V, respectively. The tribological properties of the (AlCrTaTiZr)N coatings against 100Cr6 steel balls are evaluated by a ball-on-disc tribometer with a 10 N applied load. With an increase of substrate bias, the wear rate reduces while the friction coefficient almost keeps constant at 0.75. The lowest wear rate of 3.65 × 10^− 6 mm³/Nm is obtained for the (AlCrTaTiZr)N coating deposited at the bias voltage of − 150 V.     

Performance of W-TI-(N) coated pins in lubricated pin-on-disk tests

W-Ti-(N) thin films were deposited on polished bearing steel balls by dc magnetron sputtering varying the partial pressure ratio, pN₂/pAr. The tribological behaviour was accessed by pin-on-disk testing with contact geometry of uncoated and coated 100Cr6 balls sliding against uncoated different disk materials used as stamping sheet. Different types and amounts of lubricants were used in the tests.In non-lubricated tests, friction coefficients (μ) as high as 0.8 were achieved. For the more ductile sheet materials (Al alloy and Zn-coated steel) strong adhesion was observed. The best compromise between low wear rate and low friction coefficient was achieved for N-containing coatings deposited without ion gun assistance.In lubricated conditions, a significant decrease of the friction coefficient down to 0.05 and a reduction of the wear coefficient in more than one order of magnitude down to < 10^− 16 m²N^− 1 were reached in relation to non-lubricated tests. Very good tribological results were achieved using the corrosion protection oil as lubricant, with amounts usually applied for protection of sheet materials (2 g/m²). It was found that the wear coefficient of the coated ball decreased linearly with increasing hardness of the coating, being the best that deposited with N contents in the range from 35 at.% to 40 at.%. The tribological performance of the coated samples was approximately constant even when the amount of used lubricant was reduced to only 25% of the initial value (0.5 g/m²).     

Effects of thickness and cycle parameters on fretting wear behavior of CVD diamond coatings on steel substrates

Diamond films have been grown on carbon steel substrates by hot filament chemical vapour deposition (CVD) methods. A Co-containing tungsten-carbide coating prepared by high velocity oxy-fuel spraying was used as an intermediate layer on the steel substrates to minimize the early formation of graphite (and thus growth of low quality diamond films) and to enhance the diamond film adhesion. The effects of thickness and cycle parameters on adhesion, tribological behaviour and electrochemical treatment of the diamond film were investigated. The diamond films exhibit excellent adhesion under Rockwell indentation testing (1500 N load) and in high-speed, high-load, long-time reciprocating dry sliding ball-on-flat wear tests against a Si₃N₄ counterface in ambient air (500 rpm, 200 N, 300000 cycles). Time modulated CVD (wherein the CH₄ fraction in the process gas mixture is cycled in time) is shown to yield diamond films offering an exceptional combination of low friction, high hardness, high wear resistance, as well as promising corrosion resistance.     

Microstructural, mechanical and tribological properties of tungsten-gradually doped diamond-like carbon films with functionally graded interlayers

A series of tungsten-gradually doped diamond-like carbon (DLC) films with functionally graded interlayer were prepared using a hybrid technique of vacuum cathodic arc/magnetron sputtering/ion beam deposition. With ‘compositionally graded coating’ concept, the deposition of wear-resistant carbon-based films with excellent adhesion to metallic substrate was realized. In the films, a functionally graded interlayer with layer sequence of Cr/CrN/CrNC/CrC/WC was first deposited onto the substrate, and then, a DLC layer doped with gradually decreasing content of W was coated on. The W concentration gradient along depth of the film was tailored by adjusting the W target current and deposition time. The characterized results indicate that the microstructural, mechanical and tribological properties of these films show a significant dependence on the W concentration gradient. A high fraction of W atom in carbon matrix can promote the formation of sp² sites and WC_1 − x nanoparticles. Applying this coating concept, strongly adherent carbon films with critical load exceeding 100 N in scratch test were obtained, and no fractures or delaminations were observed at the end of the scratched trace. The hardness was found to vary from 13.28 to 32.13 GPa with increasing W concentration. These films also presented excellent tribological properties, especially significantly low wear rate under dry sliding condition against Si₃N₄ ball. The optimum wear performance with friction coefficient of 0.19 and wear rate of 8.36 × 10⁻⁷ mm³/Nm was achieved for the tungsten-gradually doped DLC film with a graded W concentration ranging from 52.5% to 17.8%. This compositionally graded coating system might be a potentially promising candidate for wear-resistant carbon-based films in the demanding tribological applications.     

Deposition of nanolayered CrN/AlBN thin films by cathodic arc deposition: Influence of cathode arc current and bias voltage on the mechanical properties

Thin films of CrAlBN were deposited on SKD 11 tool steel substrate using Cr and AlB cathodes in a cathodic arc plasma deposition system. The influence of AlB cathode arc current and substrate bias voltage on the mechanical and the structural properties of the films was investigated. The CrAlBN thin films had a multilayered structure in which the nano-crystalline CrN layer alternated with the amorphous AlBN layer. The hardness of the films increased as the AlB cathode arc current was raised from 35 to 45 A, and then decreased with further increase of the current. The hardness of the films increased rapidly with the increase of the bias voltage from − 50 to − 150 V. Further increase in the bias voltage decreased the hardness. The maximum hardness of 48 GPa was obtained at the bias voltage of − 150 V. With the increase of bias voltage, a good correlation between the residual stress and the hardness of the films was observed.