Effect of Chromium on Structure and Tribological Properties of Hydrogenated Cr/a-C:H Films Prepared via a Reactive Magnetron Sputtering System

Hydrogenated Cr-incorporated carbon films(Cr/a-C:H) are deposited successfully by using a dc reactive magnetron sputtering system.The structure and mechanical properties of the as-deposited Cr/a-C:H films are characterized systematically by field-emission scanning electron microscope,x-ray diffraction,Raman spectra,nanoindentation and scratch.It is shown that optimal Cr metal forms nanocrystalline carbide to improve the hardness,toughness and adhesion strength in the amorphous carbon matrix,which possesses relatively higher nano-hardness of 15.7GPa,elastic modulus of 126.8 GPa and best adhesion strength with critical load(L_c) of36 N for the Cr/a-C:H film deposited at CH_4 flow rate of 20 sccm.The friction and wear behaviors of as-deposited Cr/a-C:H films are evaluated under both the ambient air and deionized water conditions.The results reveal that it can achieve superior low friction and anti-wear performance for the Cr/a-C:H film deposited at CH_4 flow rate of 20 sccm under the ambient air condition,and the friction coefficient and wear rate tested in deionized water condition are relatively lower compared with those tested under the ambient air condition for each film.Superior combination of mechanical and tribological properties for the Cr/a-C:H film should be a good candidate for engineering applications.     

Nanocomposite TiC/a-C：H film prepared on titanium aluminium alloy substrates by PSII assistant MW-ECRCVD

Thin films of titanium carbide and amorphous hydrogenated carbon have been synthesized on titanium aluminium alloy substrates by PSII assisted MW-ECRCVD with a mirror field. The microstructure, chemical composition and mechanical property were investigated. Using XPS and TEM, the films were identified to be a-C：H film containing TiC nanometre grains （namely, the so-called nanocomposite structure）. The size of TiC grains of nanocomposite TiC/DLC film is about 5 nm. The nanocomposite structure has obvious improvement in the mechanical properties of DLC film. The hardness of a-C：H film with Ti is enhanced to 34 G Pa~ while that of a-C：H film without Ti is about 12 G Pa, and the coherent strength is also obviously enhanced at the critical load of about 35N.     

Structure and elastic recovery of Cr-C:H films deposited by a reactive magnetron sputtering technique

Cr-containing hydrogenated amorphous carbon (Cr-C:H) films were deposited on silicon substrates using a DC reactive magnetron sputtering with Cr target in an Ar and C₂H₂ gas mixture. The composition, bond structure, mechanical hardness and elastic recovery of the films were characterized using energy dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, Raman spectroscopy and nano-indentation. The film tribological behavior was also studied by a ball-on-disc tribo-tester. The results showed that the films deposited at low C₂H₂ flow rate (<10 sccm) presented a feature of composite Cr-C:H structure, which consisted of hard brittle chromium carbide phases and amorphous hydrocarbon phase, and thus led to the observed low elastic recovery and poor wear resistance of the films. However, the film deposited at high C₂H₂ flow rate (40 sccm) was found to present a typical feature of polymer-like a-C:H structure containing a large amount of sp³ C-H bonds. As a result, the film revealed a high elastic recovery, and thus exhibited an excellent wear resistance.     

The electrochemical and mechanical properties of Ti incorporated amorphous carbon films in Hanks’ solution

Ti incorporated amorphous carbon (a-C) films with variant Ti contents were prepared by the unbalanced magnetron sputtering process. Scanning electron microscopy, ultraviolet Raman spectroscopy, X-ray photoelectron spectroscopy and transmission electron microscopy were used to characterize the microstructure of a-C films. The hardness and lubricated tribological properties were assessed using nanoindentation and ball-on-disk tribometer. As the Ti content in a-C films increases from 0 to 15.2 at.%, the sp³ volume fraction, the internal stress and the hardness of the films decreases gradually, while the disorder of sp² bond increases. The electrochemical tests reveal that the a-C films with lower than 1.5 at.% Ti possess good corrosion resistance in Hanks’ solution, while the a-C film with 15.2 at.% Ti is susceptible to crevice corrosion. The reduced friction of the a-C films is due to the sp² bonded film surface and boundary lubrication of the Hanks’ solution. The a-C film with 3.1 at.% Ti exhibits the best wear resistance in Hanks’ solution among the studied films.     

Structural and tribological properties of nitrogen doped amorphous carbon thin films synthesized by CFUBM sputtering method for protective coatings

Nitrogen doped amorphous carbon (a-C:N) films are a material that may successfully compete with DLC coatings, which have high hardness, high wear resistance, and a low friction coefficient. The a-C:N films were prepared on silicon substrate by a closed-field unbalanced magnetron sputtering method with a graphite target and using the Ar/N₂ mixture gases. And, we investigated the effects of various DC bias voltages from 0 to −300 V on the structural and tribological properties of the a-C:N films. This study was focused on improving physical properties of the a-C:N film by controlling process parameters like negative substrate DC bias voltage. The maximum hardness of the a-C:N film was 23 GPa, the friction coefficient was 0.08, and the critical load was 25 N on a Si wafer. Consequently, the structural and tribological properties of the a-C:N film showed a clear dependence on the energy of ions bombardment and the density of the sputtering and the reaction gases during film growth.     

(Ti,Al,Si,C)N nanocomposite coatings synthesized by plasma-enhanced magnetron sputtering

Materials’ surface service property could be enhanced by transition metal nitride hard coatings due to their high hardness, wear and high temperature oxidation resistance, but the higher friction coefficient (0.4-0.9) of which aroused terrible abrasion. In this work, quinternary (Ti,Al,Si,C)N hard coating 3-4 μm was synthesized at 300 °C using plasma enhanced magnetron sputtering system. It was found that the coating's columnar crystals structure was restrained obviously with the increase of C content and a non-columnar crystals growth mode was indicated at the C content of 33.5 at.%. Both the XRD and TEM showed that the (Ti,Al,Si,C)N hard coatings had unique nanocomposite structures composed of nanocrystalline and amorphous nc-(Ti,Al)(C,N)/nc-AlN/a-Si₃N₄/a-Si/a-C. However, the coatings were still super hard with the highest hardness of 41 GPa in spite of the carbon incorporation. That a-C could facilitate the graphitization process during the friction process which could improve the coating's tribological performance. Therefore, that nanocomposite (Ti,Al,Si,C)N coatings with higher hardness (>36 GPa) and a lower friction coefficient (<0.2) could be synthesized and enhance the tribological performance and surface properties profoundly.     

Amorphous hydrogenated carbon coatings on IC packaging mold by ECR-CVD system

The surface properties of IC packaging molds such as anti-sticking, wear, and corrosion resistances can be improved by hard surface coating. In this study, Ti/TiN/TiCN/a-C:H thin film coatings were deposited on IC cavity bar molds in a hybrid PVD-ECR-CVD coating system. The structure of the a-C:H films was delineated by a function of bias voltages by Raman spectroscopy. Excellent adhesion and lower friction coefficients of a-C:H films were also assessed. According to the normal adhesion force measurement, a-C:H coating was superior to that of typical electroplated hard chromium (Ep-Cr). Performance evaluation showed that the a-C:H coating could increase the number of molding injections in IC package production lines by 216%.     

Improving the tribological performances of graphite-like carbon films on Si3N4 and SiC by using Si interlayers

Si interlayers were used to obtain the excellent tribological performances of graphite-like carbon (GLC) film on silicon nitride (Si₃N₄) and silicon carbide (SiC). The microstructure and mechanical characteristics of the as-prepared GLC films with Si interlayers were investigated by scanning electron microscopy, Raman spectroscopy, nanoindention and scratch test. The tribological behaviors of GLC-coated and uncoated Si₃N₄ and SiC were comparatively studied by a ball-on-disc tribo-meter in both dry and water environments. Results showed that the Si interlayers were dense and bonded well with both the substrates and GLC layers. The as-prepared GLC films exhibited excellent tribological performances in both dry and water environments. More importantly, the stably mild wear without any delamination was obtained in water by using Si interlayer. The mechanisms of friction reduction and anti-wear performances of GLC films on the two ceramics with Si interlayers under different environmental conditions were discussed, as well as the corresponding models were deduced.     

Comparison of tribological properties of CrN, TiCN and TiAlN coatings sliding against SiC balls in water

CrN, TiCN and TiAlN coatings were deposited on WC cemented carbide disks using enhanced cathodic arc magnetron sputtering and their topographies and structures were observed and analyzed using scanning electron microscopy (SEM) and X-ray diffraction (XRD), respectively. The friction and wear properties of CrN, TiCN and TiAlN coatings sliding against SiC balls in water were investigated and compared synthetically using ball-on-disk tribometer. The results showed that the CrN/SiC tribopairs showed the lowest friction coefficient of 0.076, while the TiCN/SiC tribopairs displayed the highest friction coefficient of 0.264. For the CrN/SiC tribopairs the specific wear rate of CrN coatings was lowest while that of SiC balls became highest. But for the TiAlN(TiCN)/SiC tribopairs, the specific wear rate of TiAlN coatings was highest while that of SiC balls for the TiCN/SiC tribopairs became lowest. This indicated that the friction and wear behaviors of nitride coatings/SiC balls tribo-systems in water were more strongly influenced by the anti-oxidative ability of tribomaterials in water than by their mechanical properties.     

Superhard nanocomposite nc-TiC/a-C:H film fabricated by filtered cathodic vacuum arc technique

Superhard nanocomposite nc-TiC/a-C:H films, with an excellent combination of high elastic recovery, low friction coefficient and good H/E ratio, were prepared by filtered cathodic vacuum arc technique using the C₂H₂ gas as the precursor. The effect of C₂H₂ flow rate on the microstructure, phase composition, mechanical and tribological properties of nanocomposite nc-TiC/a-C:H films have been investigated by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), energy disperse spectroscopy (EDS), microindentation and tribotester measurements. It was observed that the C₂H₂ flow rate significantly affected the Ti content and hardness of films. Furthermore, by selecting the proper value for C₂H₂ flow rate, 20 sccm, one can deposit the nanocomposite film nc-TiC/a-C:H with excellent properties such as superhardness (66.4 GPa), high elastic recovery (83.3%) and high H/E ratio (0.13).     

Comparison of the X-ray photoelectron and electron-energy-loss spectra of the nitrogen-doped hydrogenated amorphous carbon bond

The composition of nitrogen-doped hydrogenated amorphous carbon (a-C : H : N) films grown in a magnetically confined rf plasma-enhanced chemical vapour deposition system has been determined by X-ray photoelectron spectroscopy (XPS) and compared with that determined using a combination of elastic recoil detection analysis, Rutherford back-scattering and nuclear reaction analysis. The importance of nitrogen doping or 'incorporation' in hydrogenated amorphous carbon (a-C : H) films is discussed in relation to the significant variation in the sp 2 -to-sp 3 ratio that takes place. At 7 at.% N in the a-C : H matrix, a critical change in the microstructure is observed, which governs the resulting mechanical, optical and electronic properties. Finally, the correlation between the sp 2 and sp 3 fractions determined by a non-destructive method of obtaining the bond fractions (XPS) and by electron-energy-loss spectroscopy is discussed, with a view to evaluating accurately the sp 2 fraction in a-C : H : N films.     

Vacuum current-carrying tribological behavior of MoS2-Ti films with different conductivities

Current-carrying sliding is widely applied in aerospace equipment, but it is limited by the poor lubricity of the present materials and the unclear tribological mechanism. This study demonstrated the potential of MoS₂-based materials with excellent lubricity as space sliding electrical contact materials by doping Ti to improve its conductivity. The tribological behavior of MoS₂-Ti films under current-carrying sliding in vacuum was studied by establishing a simulation evaluating device. Moreover, the noncurrent-carrying sliding and static current-carrying experiments in vacuum were carried out for comparison to understand the tribological mechanism. In addition to mechanical wear, the current-induced arc erosion and thermal effect take important roles in accelerating the wear. Arc erosion is caused by the accumulation of electric charge, which is related to the conductivity of the film. While the current-thermal effect softens the film, causing strong adhesive wear, and good conductivity and the large contact area are beneficial for minimizing the thermal effect. So the moderate hardness and good conductivity of MoS₂-Ti film contribute to its excellent current-carrying tribological behavior in vacuum, showing a significant advantage compared with the traditional ones.     

Structure and phase composition of thin a-C:H films modified by Ag and Ti

The structure and phase composition of thin a-C:H and a-C:H〈M〉 films (M = Ag, Ti, or Ag + Ti) have been studied by Raman and X-ray photoelectron spectroscopy. The a-C:H〈M〉 films were prepared by ion-plasma magnetron sputtering of a combined target of graphite and metal in an Ar–CH₄ gas mixture. The Raman spectra of these films indicate that their structure is amorphous. The a-C:H〈Ag + Ti〉 films have a more graphitized structure in comparison with pure a-C:H films and films containing only one metal. It is established that carbon in the a-C:H〈Ag + Ti〉 films is in the sp ², sp ³, and C=O states, which are characteristic of the a-C:H, a-C:H〈Ag〉, and a-C:H〈Ti〉 films. In addition, there are also ether (–C–O–C–) or epoxy (?C?O–) carbon groups in the a-C:H〈Ag + Ti〉 films. It has been revealed that silver atoms in the a-C:H〈Ag〉 and a-C:H〈Ag + Ti〉 films form no chemical bonds with carbon, oxygen, and titanium. Titanium in the a-C:H〈Ti〉 and a-C:H〈Ag + Ti〉 films exists in the form of titanium IV oxide (TiO₂).     

Deposition of a-C:H films on UHMWPE substrate and its wear-resistance

In prosthetic hip replacements, ultrahigh molecular weight polyethylene (UHMWPE) wear debris is identified as the main factor limiting the lifetime of the artificial joints. Especially UHMWPE debris from the joint can induce tissue reactions and bone resorption that may lead to the joint loosening. The diamond like carbon (DLC) film has attracted a great deal of interest in recent years mainly because of its excellent tribological property, biocompatibility and chemically inert property. In order to improve the wear-resistance of UHMWPE, a-C:H films were deposited on UHMWPE substrate by electron cyclotron resonance microwave plasma chemical vapor deposition (ECR-PECVD) technology. During deposition, the working gases were argon and acetylene, the microwave power was set to 800 W, the biased pulsed voltage was set to −200 V (frequency 15 kHz, duty ratio 20%), the pressure in vacuum chamber was set to 0.5 Pa, and the process time was 60 min. The films were analysed by X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, nano-indentation, anti-scratch and wear test. The results showed that a typical amorphous hydrogenated carbon (a-C:H) film was successfully deposited on UHMWPE with thickness up to 2 μm. The nano-hardness of the UHMWPE coated with a-C:H films, measured at an applied load of 200 μN, was increased from 10 MPa (untreated UHMWPE) to 139 MPa. The wear test was carried out using a ball (Ø 6 mm, SiC) on disk tribometer with an applied load of 1 N for 10000 cycles, and the results showed a reduction of worn cross-sectional area from 193 μm² of untreated UHMWPE to 26 μm² of DLC coated sample. In addition the influence of argon/acetylene gas flow ratio on the growth of a-C:H films was studied.     

Amorphous hydrogenated carbon films on semiconductors

The adhesion quality of amorphous hydrogenated carbon films (a-C:H) on semiconductor substrates depends to a large degree on the properties of the interface. The present work complements the photoemission results of the preceding paper with a detailed investigation of the atomic structure of the a-C:H/Si and a-C:H/GaAs interfaces. We show that the method of substrate cleaning and the deposition parameters affect the thickness of the interfacial layer and the interface roughness. The carbide compounds that form in the interfacial layer are found to be amorphous and we present evidence for the precipitation of metallic Ga at the a-C:H/GaAs interface. Finally, we have determined the extent of atomic intermixing in the interfacial region and compare our results with different mechanisms of adhesion.     

Ti6Al4V合金表面激光沉积复合涂层的组织和性能

为了增强Ti6Al4V钛合金的耐磨性,采用激光沉积制造方法在其表面上制备了以原位生成的TiC颗粒和直接添加的WC颗粒为增强相的耐磨涂层,观察了各涂层的微观组织,并测量了涂层的显微硬度和涂层在室温大气条件下的摩擦磨损性能。结果表明各涂层和基体呈现冶金结合,原位自生的TiC和部分熔化的WC颗粒均能够均匀弥散分布于基体上,由于增强相颗粒的弥散强化及激光沉积组织的细晶强化作用,基材的硬度和耐磨性均得到了提高。原位自生的TiC涂层比WC涂层硬度梯度分布平缓,但耐磨性稍差。     

Incorporation of nitrogen into amorphous-hydrogenated carbon (diamond-like) films

Nitrogen-doped amorphous hydrogenated carbon films (a-C:H) were prepared by mixing nitrogen gas and benzene during dc plasma discharge deposition. The growth rate of the film decreases strongly with increasing nitrogen content in the mixture. The nitrogen concentration in the films was determined by nuclear reaction analysis (NRA) and Auger electron spectroscopy (AES) using suitable calibration samples. The results of AES measurements are generally consistent with NRA values. Nitrogen incorporation in the a-C:H films shows pronounced doping effects as reflected in their optical and electrical properties.Dedicated to Professor J. P. F. Sellschop for his 60^th birthday     

Substrate effects on the microstructure of hydrogenated amorphous carbon films

In this work, plasma enhanced chemical vapour deposition was used to prepare hydrogenated amorphous carbon films (a-C:H) on different substrates over a wide range of thickness. In order to observe clear substrate effect the films were produced under identical growth conditions. Raman and near edge X-ray absorption fine structure (NEXAFS) spectroscopies were employed to probe the chemical bonding of the films. For the films deposited on silicon substrates, the Raman I_D/I_G ratio and G-peak positions were constant for most thickness. For metallic and polymeric substrates, these parameters increased with film thickness, suggesting a change from a sp³-bonded hydrogenated structure to a more sp² network, NEXAFS results also indicate a higher sp² content of a-C:H films grown on metals than silicon. The metals, which are poor carbide precursors, gave carbon films with low adhesion, easily delaminated from the substrate. The delamination can be decreased/eliminated by deposition of a thin (∼10 nm) silicon layer on stainless steel substrates prior to a-C:H coatings. Additionally we noted the electrical resistivity decreased with thickness and higher dielectric breakdown strength for a-C:H on silicon substrate.     

Synthesis and evaluation of TiN–WC/TiN nanocomposite by the hybrid technique with arc ion plating and magnetron sputtering

By adjusting the power of WC target, novel TiN–WC films with different proportions of WC phase were prepared on TiN interlayer using the hybrid technique of arc ion plating (AIP) and magnetron sputtering (MS). The TiN–WC films were characterized by XRD, XPS, AFM, FESEM, Nano-indenter, and UMT-2MT tribometer. The TiN–WC film that is composed with TiN and WC phases was grown by 15–25 nm nanodotes along the primarily growth direction TiN (1 1 1) in AIP interlayer. Among the three TiN–WC films deposited at various powers of WC target, the TiN–WC2 (500 W) has the highest deposition rate of 1.4 nm/min. The content of WC phase increases as WC target power increases in the TiN–WC films. However, the deposition rate of TiN–WC film gains at first and then declines when WC target power exceeds 500 W because of the addictive poisoning of Ti target. In the present case, the incorporation of WC into TiN is found to result in a slight decrease in friction coefficient. Furthermore, the wear mechanism of multilayer AIP TiN films and MS TiN–WC/AIP TiN films was transformed from “severe wear” to “mild wear”. As a result, the 48TiN52WC film of 35 GPa hardness exhibits better tribological performance.     

Transport and optical properties of amorphous carbon and hydrogenated amorphous carbon films

In this paper we report on the electrical and optical properties of amorphous carbon (a-C) and hydrogenated amorphous carbon (a-C:H) films. Resistivity of both types of films decreases with increase in temperature. At lower temperatures (60-250 K) the electron transport is due to variable range hopping for the a-C films. At higher temperatures (300-430 K) it is thermally activated for both types of films. Analysis of the heterojunction between diamond-like carbon (DLC) and bulk silicon (Si) leads to the conclusion that our a-C films are of n-type and our a-C:H films are of p-type. The optical measurements with DLC revealed a Tauc bandgap of 0.6 eV for the a-C films and 1-1.2 eV for the a-C:H films. An Urbach energy around 170 meV could be determined for the a-C:H films. Strain versus resistance plots were measured resulting in piezoresistive gauge factors around 50 for the a-C films and in between 100 and 1200 for the a-C:H films.