Advanced TiC/a-C:H nanocomposite coatings deposited by magnetron sputtering

TiC/a-C:H nanocomposite coatings have been deposited by magnetron sputtering. They consist of 2–5 nm TiC nanocrystallites embedded in the amorphous hydrocarbon (a-C:H) matrix. A transition from a columnar to a glassy microstructure has been observed in the nanocomposite coatings with increasing substrate bias or carbon content. Micro-cracks induced by nanoindentation or wear tests readily propagate through the column boundaries whereas the coatings without a columnar microstructure exhibit substantial toughness. The nanocomposite coatings exhibit hardness of 5–20 GPa, superior wear resistance and strong self-lubrication effects with a friction coefficient of 0.05 in air and 0.01 in nitrogen, under dry sliding against uncoated bearing steel balls. Especially, reversible transitions from low to ultra-low friction are observed if the atmosphere is cycled between ambient air and nitrogen. The lowest wear rate is obtained at high humidity.     

Optimized a-C coatings by doping with zirconium for tribological properties and machining performance

In this study, a-C:Zr_x% coatings with various levels of zirconium (Zr) addition are deposited on cemented tungsten carbide (WC-Co) substrates using a medium frequency twin magnetron sputtering and unbalanced magnetron sputtering system. The tribological properties of the coatings are investigated by conducting wear tests against an AISI 1045 steel counterbody under a cylinder-on-disk line contact wear mode using an oscillating friction and wear tester system. The machining performance of coated turning cutters and micro-drills is then evaluated by performing turning tests and high-speed through-hole drilling tests using AISI 1045 steel counterbodies and printed circuit board workpieces, respectively. The experimental results reveal that the fabricated a-C:Zr_x% coatings not only have improved tribological properties, but also yield an enhanced machining performance. For sliding against the AISI 1045 steel counterbody under loads of 10 N and 100 N, respectively, the optimal tribological properties are provided by the a-C:Zr_13%coating. However, the optimal turning and drilling performance is obtained using the a-C: Zr_45% coating.     

高硬度、低应力类金刚石薄膜的制备及其摩擦学行为

采用直流磁控溅射金属Al和C石墨组合靶,在单晶硅和不锈钢基底上成功制备出含Al的非氢类金刚石a-C（Al）薄膜。采用XPS、Raman、纳米压痕仪和摩擦磨损试验机等手段分析和研究了a-C（Al）薄膜的结构、力学以及摩擦磨损性能。结构表征显示,引入到类金刚石碳膜中的金属以原子或纳米团簇的形式存在,且一定程度上促进碳网络中sp2杂化键的形成。力学性能测试表明,a-C（Al）薄膜获得较低内应力同时,仍具有高硬度特性。摩擦学性能表明,a-C（Al）薄膜干摩擦时其摩擦系数约为0.07,磨损率仅为4.6×10–16 m3 N-1 m-1左右。良好的综合力学性能以及致密、连续的石墨化碳转移膜是a-C（Al）碳膜获得较好摩擦、磨损性能的关键因素。     

Mechanical and tribological assessment of composite AlCrN or a-C:Ag-based thin films for implant application

The present study focuses on the comparison of cathodic arc deposited AlCrN (ternary coating) and Ag alloyed a-C (amorphous carbon base coating) on chrome nitride (CrN) medical grade 316 LVM stainless steel. The work comprises of morphological, structural, nanomechanical and tribological evaluation in physiological simulated body fluid (SBF) lubrication following conditions pertaining to simulated hip joint. According to the findings, H/E, H³/E² and E_coating/E_substrate significantly effect the nanomechanical and tribological properties of the coatings. While a-C:Ag/CrN exhibited better L_y value compared to AlCrN/CrN due to better surface quality, the later has shown higher L_c2 value during nanoscratch test attributed to lower H³/E² and higher plastic work done. Inspite of lower friction coefficient, a-C:Ag/CrN observed higher wear rate during simulated tribotest attributed to low hardness, separate graphitic structure due to Ag doping and sudden increase of friction coefficient ascribed to severe abrasive delamination of a-C:Ag top layer. The wear mechanism observed under SEM microscopy indicate severe adhesion of Ti6Al4V counterbody on AlCrN/CrN coated surface. The size of wear debris obtained with AlCrN/CrN-Ti6Al4V tribopair was larger in size compared to a-C:Ag/CrN-Ti6Al4V tribopair. Nevertheless, despite inferior surface quality and lower L_y value and larger wear debris size, AlCrN/CrN coating performed better in nanoscratch (at L_c2 value) and demonstrated lower wear in simulated tribotest in physiological SBF condition.     

Hydrogen content influence on tribological properties of nc-WC/a-C:H coatings

Hydrogen content has high influence on low-friction properties of an amorphous carbon coating a-C with or without transition metal additions. In the paper the nanocrystalline nc-WC/a-C:H coatings deposited by means of magnetron sputtering were investigated. Hydrogen content up to 37% was obtained by the use of different flows of pure hydrogen or methane mixed with pure argon. The coatings were investigated by means of SEM, EDS, and SAED HR TEM in order to obtain thickness, sufrace morphology, chemical composition as well as nanostructure. Moreover, these were investigated: type of bonds between carbon atoms by means of Raman Shift Spectroscopy and hydrogen content by means of SIMS and inert gas fusion crucible method. Tribological properties were elaborated by means of ‘pin-on-disc’ method. It was stated that coefficient of friction, microstructure and type of bonds between carbon atoms are highly dependent from the hydrogen content. It is the main parameter for achieving of low friction coefficient (below 0.1) as well as very low wear rate (in a range of 10⁻¹⁷ m³·N⁻¹·m⁻¹. Obtained results confirmed that proposed nc-WC/a-C:H coatings can be used for improving tribological properties of hard steels and hardened titanium alloys.     

Characterization of thick and soft DLC coatings deposited on plasma nitrided austenitic stainless steel

Thick and soft a-C:H:Si coatings containing more than 45% hydrogen (thickness: 25–27 μm, hardness: 6 GPa, Young's Modulus 38 GPa and low ratio of sp³ bonds) were deposited by PACVD with a DC pulsed discharge on nitrided (duplex sample) and non-nitrided austenitic stainless steel (coated sample). After deposition, the chemical, microstructural and tribological properties were studied. Finally, the adhesion and the atmospheric corrosion resistance of a-C:H:Si coatings were also investigated.In pin-on-disk tests, the friction coefficient using an alumina pin of 6 mm in diameter as counterpart, under 0.59 GPa Hertzian pressure was 0.05 for the coated samples and 0.076 for the duplex samples. These values were more than one order of magnitude smaller than the friction coefficient of the nitrided sample without coating, which was around 0.65. In the coated samples, the wear loss could not be measured. In ball-on-disk tests under dry sliding conditions, the coatings were tested under different Hertzian pressures (1.29, 1.44 and 1.57 GPa) using a steel ball with a diameter of 1.5 mm as counterpart. Using a normal load of 9 N, the a-C:H:Si coating of the coated samples was broken and detached thus leading to a coefficient of friction of around 0.429. However, in contrast to that, the friction coefficient of the duplex samples remained stable and reached as maximum a value of 0.208.In abrasive tests, mass loss was undetectable in both duplex and coated samples. Furthermore it could be seen that the a-C:H:Si film showed only some smaller grooves and no severe damage or deformation. On the contrary, severe damage was observed in the only nitrided sample. With respect to adhesion, the critical load to break the coating was higher in the duplex sample (27 N) than in the only coated sample (16.3 N). By chemical analysis using the salt spray fog test, the duplex sample remained clean, but the coated sample failed and presented film delamination as well as general corrosion.     

Ni-P复合镀层摩擦磨损性能的研究

采用化学复合镀在碳钢基体上共沉积（Ni-P）-SiC和（Ni-P）-PTFE两种复合镀层,重点研究了两种复合镀层在相同对磨条件下的摩擦磨损性能及磨损机理表现形式,并与化学镀镍磷层进行对比。结果表明,本实验条件下所制备的（Ni-P）-SiC和（Ni-P）-PTFE两类复合镀层分别具有优异的耐磨和减磨性能,均能对所镀覆基体材料起到良好的保护作用;对磨实验过程中主要出现磨料磨损、粘着磨损和氧化磨损三种磨损方式,而且磨损方式不同,镀层的摩擦磨损性能表现也不尽相同。     

Tribological study of hydrogenated amorphous carbon films with tailored microstructure and composition produced by bias-enhanced plasma chemical vapour deposition

We investigated the mechanical and tribological properties of hydrogenated amorphous carbon (a-C:H) films on silicon substrates by nanoindentation, ball-on-disc tribotesting and scratch testing. The a-C:H films were deposited from an argon/methane gas mixture by bias-enhanced electron cyclotron resonance chemical vapour deposition (ECR-CVD). We found that substrate biasing directly influences the hardness, friction and wear resistance of the a-C:H films. An abrupt change in these properties is observed at a substrate bias of about ?100 V, which is attributed to the bias-controlled transition from polymer- to fullerenelike carbon coatings. Friction coefficients in the range of 0.28–0.39 and wear rates of about 7 × 10^?5 mm³/Nm are derived for the polymeric films when tested against WC–Co balls at atmospheric test conditions. On the other hand, the fullerenelike hydrogenated carbon films produced at ion energies > 100 eV display a nanohardness of about 17 GPa, a strong reduction in the friction coefficient (～ 0.10) and a severe increase in the wear resistance (～ 1 × 10^?7 mm³/Nm). For these films, relative humidity has a detrimental effect on friction but no correlation with the wear rate was found.     

Microstructure and tribological properties of multilayered ZrCrW(C)N coatings fabricated by cathodic vacuum-arc deposition

In this study, a series of ZrCrW(C)N multilayer coatings with various transition layers were deposited on AISI304 stainless steel using cathodic vacuum-arc deposition in N₂–C₂H₂ gas mixture. The tribological behaviors of sliding against Al₂O₃ balls under dry friction and lubricant conditions were investigated using a reciprocating tribometer. The results demonstrated that the ZrCrW(C)N coatings comprised (Zr, Cr, W) (C, N) crystallites and an amorphous carbon phase. It possessed a nano-hardness of 35.4 GPa and an elastic modulus of 417.7 GPa. The friction coefficient of the coating was reduced by 14% compared to that of the 304 matrices, and the wear mechanism changed from adhesive wear to slight abrasive wear under the lubrication steady state. Under dry friction conditions, the ZrCrW(C)N coatings with the entire CrWN transition layer exhibited wear rates of 1.27 ± 0.04 × 10^?8 mm³ (N m)^?1, which were one order of magnitude lower than that of the 304 steel. Compared with the untreated AISI304 stainless steel, the ZrCrW(C)N coating exhibits excellent mechanical and tribological properties under lubricated and dry friction conditions, which are crucial for engineering applications.     

Characterization of wear surfaces in dry sliding of steel and alumina on hydrogenated and hydrogen-free carbon films

Hydrogenated amorphous carbon coatings were deposited by r.f. plasma and hydrogen-free carbon films in pulsed arc discharge on stainless steel substrates. The coatings were characterized and evaluated in tribological tests. Pin-on-disc tests were used over a wide range of test parameters: normal load, 5–40 N; sliding velocity, 0.1–3.0 m s⁻¹. The wear of both coatings was of the same order of magnitude (0.7 × 10⁻³−5.1 × 10⁻³ mm³). However, the wear of the counterface was one order of magnitude higher for the hydrogenfree carbon coatings. Increasing the normal load generally caused an increase in coating wear and in most cases also an increase in counterface wear. When the steel pin was sliding against the hydrogenated carbon coating with a high sliding velocity and load, a rather thick tribofilm was formed on the pin wear surface, lowering the coefficient of friction and reducing the pin wear. The tribofilm formed on the alumina pin sliding against the hydrogenated carbon film also seemed to reduce the friction coefficient but could not prevent the pin wear. A tribofilm was also formed on the pin wear surface when the hydrogen-free carbon coating was sliding against the steel and alumina pins, but the layer was not able to protect the pins. The tribofilm did, however, lower the coefficient of friction, which was rather insensitive to the different test parameters used. According to secondary ion mass spectroscopy analyses, material transfer of the pin was detected on the disc (coated) wear surfaces. The tribofilms formed on the pin wear surfaces consisted of pin material, hydrogen, oxygen, and carbon.     

润滑剂对Ti（CN）陶瓷摩擦学性能的影响

在销—盘试验机上考察了干摩擦、水润滑及油润滑条件下Ti(CN)/45钢摩擦副的摩擦磨损性能。Ti(CN)陶瓷的磨损主要由粘着剥落和微断裂引起,水对Ti(CN)/45钢摩擦副的摩擦性能无明显改善,但能较明显地减小陶瓷的磨损。油润滑时,摩擦和磨损均得到了明显改善。水和油润滑介质的存在能有效地抑制金属在陶瓷表面的粘着转移,从而降低陶瓷磨损率。采用SEM,XPS,AES等对陶瓷磨痕的分析结果表明,摩擦面上Fe_2O_3的生成对粘着磨损起到了一定的改善作用。油(不含添加剂的液体石蜡)在极压条件下的减磨作用主要是由于其在陶瓷摩擦面上形成了较厚的碳膜(焦质,石墨复合膜)。     

Improved adhesion and tribological properties of fast-deposited hard graphite-like hydrogenated amorphous carbon films

Graphite-like hard hydrogenated amorphous carbon (a-C:H) was deposited using an Ar-C₂H₂ expanding thermal plasma chemical vapour deposition (ETP-CVD) process. The relatively high hardness of the fast deposited a-C:H material leads to high compressive stress resulting in poor adhesion between the carbon films and common substrates like silicon, glass and steel. A widespread solution to this problem is the use of an adhesion interlayer. Here we report on the changes in adhesion between the graphite-like a-C:H films and M2 steel substrates when different types of interlayers are used. Insignificant to very small improvements in adhesion were observed when using amorphous silicon oxide (a-SiO_x), amorphous organosilicon (a-SiC_xO_y:H_z) and amorphous hydrogenated silicon carbide (a-SiC_x:H_y) as adhesion layers. However, when sputtered Ti was used as an interlayer, the adhesion increased significantly. The dependence of the adhesive properties on the deposition temperature and interlayer thickness, as well as on the thickness of the a-C:H layer is presented and discussed. The low wear rates measured for the a-C:H/Ti/M2 stack suggest that these films are ideal for tribological applications.     

Mechanical stability,corrosion performance and bioresponse of amorphous diamond-like carbon for medical stents and guidewires

Diamond-ike carbon (DLC) coatings have been investigated with respect to biocompatibility, mechanical stability under biofluid exposure, corrosion resistance and the impact of the fabrication or operation of catheter guidewires and stents upon coating integrity. High mechanical tensile and compressive forces, during guidewire winding or stent expansion, pose severe limitations on the use of DLC-coated stainless steel. Doping with silicon and the use of an a-Si:H interlayer can help minimise the risk of adhesion failure or film cracking. The incorporation of Si increased the hydrogen content and the estimated sp³ fraction but reduced the film hardness. Silicon-doped a-C:H coatings exhibit significantly improved corrosion barrier properties, with over two orders of magnitude increase in the charge transfer resistance. Immersion in biofluid, however, reduced the interfacial adhesion strength by up to 75%. Human microvascular endothelial cell attachment was enhanced while platelet attachment was reduced on Si-doped compared to undoped a-C:H. The macrophage response to non-hydrogenated tetragonal (t-aC) carbon show that these coatings stimulate less inflammatory activity than uncoated materials and produce comparable responses to already existing polyurethane coatings.     

Preparing SiC/diamond coatings via chemical vapor deposition of SiC on diamond-coated graphite and their frictional properties

SiC/diamond coatings with excellent frictional properties were successfully prepared using graphite as substrate. Diamond particles with size of 25–38 μm were firstly bonded on graphite substrate through PVA glue, followed by chemical vapor deposition (CVD) of SiC with varied MTS flow on the diamond-coated graphite substrate to enhance the adhesion of diamond particles. The influence of the MTS flow on the SiC coatings was investigated. The results showed that polycrystalline SiC coating with good crystallinity has been obtained. With MTS flow increasing, the SiC grains feature increased surface roughness and greater sizes of the SiC crystallite resulting from the co-deposition of SiC and carbon with increased carbon containing species. Reciprocating sliding wear tests were conducted to investigate the coefficient of friction. With increasing applied load, while the low-flow specimens showed a remarkable increase in the friction coefficient resulting from degradation of the SiC coatings, the high-flow specimens maintained a relatively low friction coefficient during wear tests indicating strong holding force to diamond particles of the SiC coatings. The reason for low friction coefficient of the high-flow specimens was that GCr15 steel ball was wearing by the SiC/diamond coatings with good affinity to the substrate resulting in a flat–flat contact on the contact area.     

Diamond-like a-C:H(:F) films obtained by d.c. magnetron sputtering

Diamond-like a-C:H and a-C:H:F films were obtained by reactive d.c. magnetron sputtering from a glassy carbon target in an argon-hydrogen atmosphere. For the deposition of a-C:H:F layers, hexafluoroethane (C₂F₆) was added to the sputtering atmosphere. The a-C:H(:F) films are transparent and mechanically hard. The films can be used as protective and antireflective coatings on a-Si:H photoreceptors. Electrical, optical and structural properties of the a-C:H(:F) films are examined. Fluorinated films are found to have a more compact structure and exhibit a higher stability to ambient temperatures than unfluorinated material.     

Nanotribological study of PECVD DLC and reactively sputtered Ti containing carbon films

Amorphous carbon film, also known as DLC film, is a promising material for tribological application. It is noted that properties relevant to tribological application change significantly depending on the method of preparation of these films. These properties are also altered by the compositions of these films. DLC films are well known for their self-lubricating properties, as well. In view of this, the objective of the present work is to compare the tribological properties of diamond like carbon (DLC) film obtained by plasma enhanced chemical vapour deposition (PECVD) with the Ti containing nanocrystalline carbon (Ti/a-C:H) film obtained by unbalanced magnetron sputter deposition (UMSD) in nN load range. Towards that purpose, DLC and Ti/a-C:H films are deposited on silicon substrate by PECVD and UMSD processes respectively. The microstructural features and the mechanical properties of these films are determined by scanning electron microscope (SEM), transmission electron microscope (TEM) and nano indenter. The surface topographies and the friction force surfaces of these films are evaluated by means of an atomic force microscope (AFM). The results show that although PECVD DLC film has higher elastic modulus and higher hardness than UMSD Ti/a-C:H film, the surface roughness and the friction coefficient of PECVD film is significantly higher than that of UMSD Ti/a-C:H film.     

Tribological behavior of carbon nanotube and polytetrafluoroethylene filled polyimide composites under different lubricated conditions

The friction and wear behavior of polyimide (PI) composites reinforced with carbon nanotube (CNT) and polytetrafluoroethylene (PTFE) were comparatively evaluated under dry sliding, water‐, oil‐ or alkali‐lubricated condition. The wear mechanisms of the composites were also discussed. Results indicate that, when comparison with the dry friction situation, PI‐based composites results lower friction coefficients and wear rates under oil‐ or alkali‐lubricated condition. The lowest wear rate of the CNT/PTFE/PI composite is recorded as 1.2 × 10⁻⁶ mm³/Nm during the composite sliding in alkali, which is only about 40% of the value sliding under dry friction condition. The worn surface of neat PI under dry sliding is characterized by severe adhesive wear, whereas abrasive wear is the main character for CNT/PTFE/PI composites. The worn surfaces of CNT/PTFE/PI composites sliding in oil or alkali lubricated condition are smoother than those under dry or water condition. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Chemical,mechanical and tribological characterization of ultra-thin and hard amorphous carbon coatings as thin as 3.5 nm: recent developments

Diamond material and its smooth coatings are used for very low wear and relatively low friction. Major limitations of the true diamond coatings are that they need to be deposited at high temperatures, can only be deposited on selected substrates, and require surface finishing. Hard amorphous carbon (a-C), commonly known as diamondlike carbon (DLC), coatings exhibit mechanical, thermal and optical properties close to that of diamond. These can be deposited with a large range of thicknesses by using a variety of deposition processes, on variety of substrates at or near room temperature. The coatings reproduce substrate topography avoiding the need of post finishing. Friction and wear properties of some DLC coatings can be very attractive for tribological applications. The largest industrial application of these coatings is in magnetic storage devices. Recent developments in the chemical, mechanical and tribological characterization of the ultra-thin coatings are reviewed in this paper. The prevailing atomic arrangement in the DLC coatings is amorphous or quasi-amorphous with small diamond (sp³), graphite (sp²) and other unidentifiable micro- or nanocrystallites. The mechanical and tribological properties of the DLC coatings are dependent upon the deposition technique. Thin coatings deposited by filtered cathodic arc, ion beam and ECR-CVD hold a promise for tribological applications. Coatings as thin as 5 nm in thickness provide wear protection.     

Friction and wear studies of polyetherimide composites under oscillating sliding condition against steel cylinder

Tribological properties of neat polyetherimide (PEI), glass, carbon fiber, and solid lubricants filled PEI composites are presented in this article. The aim of this study was to investigate the friction and wear properties of these composites under dry oscillating sliding condition at room temperature (RT) as well as at elevated temperature (120°C). The polymer specimens were made to oscillate against steel cylinder as a counterpart. The friction and wear properties of PEI and composites were strongly influenced by the temperature. Incorporation of carbon fiber in the PEI matrix has increased the wear rate at RT, while at elevated temperature this trend was opposite. Abrasive action of carbon fibers has severely damaged the counterpart and resulted in accelerated wear of the composite at RT. Solid lubricants filled (PTFE, MoS₂, graphite) along with glass fiber is beneficial in improving the friction and wear performance of the PEI composite at RT, whereas at elevated temperature wear performance was deteriorated. Tribological performance of neat PEI and glass fiber composite was similar with each other at RT. Scanning electron micrographs and optical micrographs of the worn polymer specimens and the steel cylinders was used to study the possible wear mechanisms. The present test results were also compared with data available on the reciprocating wear of PEI and composites in the literature and trends have been reported. POLYM. COMPOS., 38:48–60, 2017. © 2015 Society of Plastics Engineers     

Surface and Corrosion Characteristics of a-C:H/Fluorocarbon Films

Fluorocarbon films were deposited on type 301 stainless steel substrates from mixtures of hexafluoroethane (HFE) or hexafluoroacetone (HFA) and acetylene and argon in a radio-frequency (13.56 MHz) plasma discharge. A 10 nm thick polysilicon interlayer was deposited prior to fluorocarbon film deposition to obtain good adhesion. To prevent film failure. a-C:H layer was deposited on the polysilicon layer prior to fluorocarbon film deposition, resulting in a-C:H/fluorocarbon composite film structures. The influence of the feed gas composition on the properties of the layered structure was investigated. Surface energies of the films were calculated from the film contact angle values obtained with water and diiodomethane. The composition of the surface layer of these films was characterized using X-ray photoelectron spectroscopy (XPS). The resistance offered by these a-C:H/fluorocarbon film structures to anodic breakdown in an electrolyte containing 0.1 M NaCl and 0.1 M Na₂SO₄ was studied using a potentiostatic technique. The anodic current density for the coated type 301 stainless steel samples was at least 3 orders of magnitude smaller than that for the bare sample and more than an order of magnitude smaller than that observed with samples coated with only the (equally thick) a-C:H layer. The resistance offered by the layered coatings to solution penetration increased with increasing fluorine content in the films.