ICMCTF2011 Session E3-2: Tribology of Nanostructured and Amorphous Films

Monday, May 2, 2011 1:30 PM in Room California

Monday Afternoon

Time Period MoA2 Sessions | Abstract Timeline | Topic E Sessions | Time Periods | Topics | ICMCTF2011 Schedule

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1:30 PM E3-2-1 Prediction of the Friction Behavior of Lubricated Tribological Systems Containing Amorphous Carbon Coatings using an Artificial Neural Network
Edgar Schulz, Sebastian Roehner, Stephan Tremmel (Friedrich-Alexander-University Erlangen-Nuremberg, Germany); Yashar Musayev, Tim Hosenfeldt (Schaeffler Technologies GmbH & Co. KG, Germany); Harald Meerkamm, Sandro Wartzack (Friedrich-Alexander-University Erlangen-Nuremberg, Germany)
Amorphous carbon coatings are more and more used in combustion engine applications to reduce friction and wear in highly stressed tribological systems to fulfill legislative guidelines concerning energy efficiency and CO2 emissions. In oil-lubricated tribological systems working under mixed friction conditions, e.g. in the valve train, the performance of coated components like bucket tappets depends on the interaction between all elements of the tribological system. Engine lubricants and additives are actually still optimized for polar metal surfaces. In combination with non-polar and inert carbon surfaces, the effectiveness of these additives is reduced or prevented. Even undesirable effects may occur by the changed conversion of the additives. Up to now these interactions are not sufficiently understood. In literature, the impact of some additives on amorphous carbon coatings is described isolated. To handle the complexity of the tribological processes these works are always limited to the variation of a few influencing variables and the use of one specific tribological test. Therefore, the transferability of these results to applications is restricted. As well an analytical prediction of friction and wear is not possible since the friction and wear mechanisms are overlapping in the temporal and local undetectable real contact area. Thus always empirical studies are needed to determine the tribological behavior. In such studies as many influencing variables as possible should be varied to obtain a better understanding of the friction and wear behavior. Especially the high complexity of these systems and the large experimental effort show the need for a specific prediction of the friction and wear behavior. This article presents the development of a multilayer artificial neural network (ANN) to predict the friction behavior of such tribological systems. Using an ANN with its learning capability reduces the experimental effort significantly. Precondition for the modeling with such a network is the availability of empirical test data. In this article a total amount of 400 experiments were carried out by using various tribological test equipments, such as model, component and unit tests to assess the transferability between the different tests. Input parameters like type of coating, base oil, additives, temperature, pressure, etc. were varied systematically. The predictive capabilities of the ANN model were validated with experimental results. A satisfactory agreement between the predicted friction values and experimental observations was found. Furthermore the influence of the input parameters on the friction coefficient could be quantified.
1:50 PM E3-2-2 Fatigue Properties of a 21MnCr5 Steel Coated with an Amorphous Carbon Coating
Stephan Tremmel (Friedrich-Alexander-University Erlangen-Nuremberg, Germany); Berthold von Großmann (Georg Simon Ohm University of Applied Sciences Nuremberg, Germany); Sandro Wartzack (Friedrich-Alexander-University Erlangen-Nuremberg, Germany)

A lot of components in technical applications, for example bucket tappets or piston pins, are both mechanical and tribological highly loaded. To enhance their tribological properties they often get coated with amorphous carbon by PVD or PACVD. Although it is known, that surface treatment may strongly influence the fatigue properties of steels, there are only a few investigations about the influence of amorphous carbon coatings up to now. Besides that, there is a lack of methods for dimensioning such coated parts, not least because there do not exist adequate stress limits for coatings. Motivated by the described situation this article presents results of fatigue tests of 21MnCr5 specimens similar to ASTM 606 and coated with an a-C:H:W coating under zero-to-tension cyclic loading. It is discussed, how strong the coating influences the fatigue properties of the substrate and if it is possible to identify fatigue limits of coatings under defined stress conditions using conventional fatigue tests on resonant testing machines. First results from a set of fatigue tests indicates, that the amorphous carbon coating does not influence the static strength, in particular the tensile strength, but decreases the fatigue limit with increasing cycle number. This effect is not understood up to now, although there are some presumptions, which should be discussed and compared to other works, which studies the influence of different hard coatings on the fatigue limits of different substrates, too. Furthermore, in this article a method is suggested, which allows in a quite simple way the detection of fatigue limits of the coating using microsections of the fatigue specimens and their investigation by light microscopy. Compared to other known methods, for example cyclic impact tests, the suggested method provides fatigue limits under quite well defined stress conditions.

2:10 PM E3-2-3 The Effect of Coating Properties on the Fracture Characteristics and Tribological Performance of a-C:H and ta-C Films
Helena Ronkainen, Kenneth Holmberg, Anssi Laukkanen, Tom Andersson (VTT Technical Research Centre of Finland); Masao Kumagai, Makoto Kano, Takahiro Horiuchi (Kanagawa Industrial Technology Center, Japan); Tetsuya Suzuki (Keio University, Japan); M. Taki (Onward Ceramic Coating Co, Ltd., Japan)
DLC films cover a wide range of different carbon based coatings, starting from soft to extremely hard diamond-like carbon films. In this case two different types of DLC films have been studied in respect of their fracture characteristics and tribological performance. The coatings are a-C:H deposited by PECVD and ta-C coating deposited by filtered arc technique. In order to evaluate the stress and strain behaviour of the coatings under load, 3D FE modelling was carried out in combination with scratch testing. Also the tribological performance was evaluated with static load as well as with continuously increasing normal load pin-on-disc tests.

The 3D FEM model was developed for calculating the stress and strain distributions. The simulation model was applied to the scratch test contact conditions, when the spherical diamond tip was moving with increased load on a coated surface. The crack propagation during the empirical scratch testing was detected. It was observed that the first crack appeared for the both coatings as an angular crack representing the maximum stress experienced on the scratch groove edge. When combining the simulated stress values with empirical observation of coating fracture patterns the coating fracture toughness was determined. A major effect of the coating elastic modulus on the stress and fracture behaviour of the coatings was observed.

In the tribological testing the both coatings had a low friction performance. In the tribological testing with continuously increasing load, the critical load for coating delamination was higher for the a-C:H coating. This is in accordance with the results of FE modelling of stress accumulation and the fracture toughness evaluation of the coatings. The influence of coating characteristics on the performance properties in real applications will be discussed.

2:30 PM E3-2-4 Stress Reduction in Hard a-C:N DLC Coatings
Sascha Louring, NisDam Madsen, AndersNørløv Berthelsen (Aarhus University, Denmark); Bjarke Holl Christensen, Klaus Pagh Almtoft, Lars Pleth Nielsen (Danish Technological Institute, Tribology Centre, Denmark); Jørgen Bøttiger (Aarhus University, Denmark)
Nitrogen-doped amorphous carbon (a-C:N) coatings were deposited by use of reactive DC magnetron sputtering with an industrial-scale deposition system. The reactive gas N2 was used in combination with graphite targets, and the compositions of carbon, nitrogen and impurity atoms were measured by X-ray Photoelectron Spectroscopy (XPS). The mechanical properties of the coatings – hardness and elastic modulus – were extracted from nanoindentation data, and from the elastic modulus and the G-peak position measured by Raman-spectroscopy the compressive stress was calculated. High resolution XPS spectra were also recorded for the C 1s and N 1s spectra in attempt to link the microstructure of the coatings to their mechanical properties. The tribological performance of the films was investigated with a pin-on-disc setup using Al2O3 as counter-parts. The tests were carried out at room temperature in both ambient and controlled atmospheres and information about both wear rates and friction coefficients of the coatings were obtained. A number of process parameters – substrate bias, N2 flow and deposition temperature - were systematically varied to optimize the mechanical and tribological performance of the coatings. An increased temperature during the deposition process led to a more than 50 % reduction in the compressive stress from above 3 GPa to 1.4 GPa. Increasing the deposition temperature caused a slight decrease in the N/C atomic ratio from 0.34 to 0.29, while the hardness was approximately constant at 15 GPa.
2:50 PM E3-2-5 2.5 nm Thick TiSiN Protection Layer for HDD Magnetic Media
Franck Rose, Daryl Pocker, Qi-Fan Xiao, Bruno Marchon (Hitachi Global Storage Technologies Inc.)

To achieve HDD areal densities of 1 Tb/sq.inch it is required that the magnetic spacing between the head sensor and the disk media is reduced to 6 nm. Especially, the overcoat (OC) film that protects the disk has to be as thin as 2.5 nm. Within this spacing budget the OC has to retain excellent tribological properties, lubricant compatibility, and anticorrosion protection of the Co-containing media.

TiSiN [1] and SiNx [2] ultra-thin films are prospective materials for high density HDD disk OC. SiNx films are denser than conventional diamond like carbon OC and can act as barriers that prevent migration and corrosion of Co. Unfortunately, SiNx OC are unstable under high humidity and temperature. Water hydrolysis leads to SiOx growth on the surface of SiNx OC resulting in HDD failures such as head crashes and irreversible disk damages.

Here, we show that adding Ti into SiNx induces the formation of a TiOx surface protection layer that allows reducing SiOx growth and Co corrosion while concomitantly decreasing the OC surface energy. We present an extensive spectroscopy and microscopy study (XPS, XRR, FTIR, AFM, SEM, TEM, OSA) of 2.5 nm thick TiSiN OC, with focus on their composition and nanostructure, stability against hydrolysis, and anticorrosion protection.

OC were deposited by reactive magnetron sputtering on top of magnetic media on glass disks using different TixSiy targets to vary their content ratio R=Ti/(Ti+Si). These films were found to be different in nature than previously reported nanocomposite TiSiN [3]. They are completely amorphous with mass densities increasing with R (0 to 1) from 3.14 to 4.34 g/cc. These values are comprised between those of stoichiometric Si3N4 (3.2 g/cc) and TiN (5.4 g/cc). Moreover, angle-resolved XPS and FTIR showed that TiSiN OC are actually oxynitrides terminated with a native surface layer of TiOx.

Overcoat stability against hydrolysis was studied in function of films Ti content. It was found that 4 at. % of Ti is enough to reduce SiOx formation by half, and that higher Ti contents can block SiOx surface growth. To reduce surface chemical reactivity and contaminant attraction it is desirable that disk OC have low surface energy. Surface energy of disks lubed with 1.2 nm of ZTMD, a perfluorinated lubricant, was measured by using the droplet contact angle method. TiSiN OC have much lower surface energy (16-19 mN/m) than SiNx OC (31 mN/m). For comparison, we measured 17 mN/m for both TiNx and TiOx OC, which is consistent with TiSiN OC being capped with TiOx.

[1] Q.Dai et al., US Pat. 6586070 B1 7/2003

[2] B.K.Yen et al., Vac. Sci. Technol. A 21(6), 1895, 2003

[3] S.Veprek et al., Surf. Coat. Technol. 202, 5063, 2008

3:10 PM E3-2-6 Tribology Behavior of Nanocrystallite Carbon Film Prepared by ECR Sputtering Method
Chao Wang, Dongfeng Diao (Xian Jiaotong University, China)

Nanocrystallite carbon film has drawn much interests since it has not only high hardness and good wear performances comparable to those of diamond but also wonderful conductivity close to that of graphite. It has a brightly future as a new coating material in modern industry. Among the methods which are introduced to prepare carbon film, Electron Cyclotron Resonance (ECR) method has some exclusive advantages such as high energy efficiency, flexible working condition and simple facility. Therefore, ECR method is a very promising way to produce nanocrystallite carbon film in large scale.

In this study, we have prepared amorphous carbon films with different content of sp2 bonded nanocrystallite by ECR sputtering method. By controlling ECR plasma condition, either electron sheath or ion sheath was formed, and the film surface would be etched by either electron or ion during the film growth process, namely electron etching mode and ion etching mode. Carbon films with different nanocrystallite content were prepared under different etching mode and etching energy. The film's binding configurations and nano-structures were characterized by XPS spectrums and TEM pictures respectively. Friction coefficients and wear lives of the films were tested with a Pin-on-Disk tribometer, and super-low-friction phenomena were observed in certain films' wear tests.

3:30 PM E3-2-7 Tribological Behaviour of Aluminum Against Tungsten Doped DLC at Elevated Temperatures
Ahmed Abou Gharam (University of Windsor, Canada); Michael. Lukitsch (General Motors Research and Development Center); Ahmet Alpas (University of Windsor, Canada)

Diamond-like carbon (DLC) coatings are particularly suited for applications that require minimum adhesion, low coefficient of frication (COF) and good wear properties against aluminum alloys. These properties however deteriorate rapidly at elevated temperatures. In this study, friction and wear behaviour of W doped DLC (W-DLC) was studied as a function of testing temperature to investigate the coating’s surface and subsurface damage at temperatures up to 400ºC. Pin-on-disk tests of 319 Al ran against W-DLC showed that the lowest COF was observed at 25ºC (0.20). While at 100ºC, 200ºC and 300ºC, high average steady state COF values of 0.59 were recorded and as the temperature reached 400 ºC, the COF reduced again to 0.18. Cross sections of the wear tracks prepared by focused ion beam (FIB) milling showed that at 100ºC the coating was spalled and aluminum was adhered to the exposed substrate and hence resulting in the observed high COF. However, at 400ºC, FIB cross sections of the wear track showed no evidence of coating failure or aluminum adhesion. Additional analyses illustrated that at 25ºC and 400ºC, a transfer layer was formed on aluminum contact surface, which prevented aluminum/DLC interactions, and reduced the friction by eliminating aluminum adhesion. Further chemical investigations of the transfer layer using micro Raman, X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) were conducted to elucidate details of the mechanisms responsible for the low COF at elevated temperatures.

3:50 PM E3-2-8 Identification of the Wear Mechanism on WC/C Nanostructured Coatings
Said El Mrabet, Manue David Abad, JuanCarlos Sanchez-Lopez (Instituto de Ciencia de Materiales de Sevilla, Spain)

A series of WC/C nanostructured films with carbon contents ranging from 30 to 70 at.% was deposited on M2 steel substrates by magnetron sputtering of WC and graphite targets in argon. Depending on the amorphous carbon (a-C) incorporated in the coatings, nanocrystalline coatings (formed mainly by WC1-x and W2C phases) or nanocomposites (WC1-x/a-C) were obtained with tunable mechanical and tribological properties. Ultrahardness values of 35-40 GPa were measured for the nanocrystalline samples whilst values between 16 to 23 GPa were obtained in the nanocomposite ones depending on the a-C content. The tribological properties were studied using a pin-on-disk tester versus steel (100Cr6) balls at 5N of applied load in dry sliding conditions. Three different zones were identified according to the observed tribological behaviour: I (μ>0.8; adhesive wear); II (μ:0.3-0.6; abrasive wear) and III (μ~0.2; self-lubricated). The wear tracks and the ball scars were observed by scanning electron microscopy (SEM) and Raman spectroscopy in order to elucidate the tribochemical reactions appearing at the contact and to determine the wear mechanism present in each type. A correlation among mechanical properties, crystal phases, a-C content and wear modes could be established for the series of WC/C coatings.

4:10 PM E3-2-9 Advanced Applied Technology of DLC Coatings
Makoto Kano (Kanagawa Industrial Technology Center, Japan)
Reduction of the mechanical friction especially for automotive engine has been strongly required in recent years for improving fuel economy. Reducing the friction between the cam and follower is effective in this regard in the low engine speed range. A diamond-like carbon (DLC)-coated cam follower of the bucket type has been applied to the gasoline engines to reduce engine friction. This low friction property is obtained by the hydrogen free DLC, ta-C lubricated with the ester containing oil. The main experimental results of this applied technology are explained briefly. The recent topic of the applied DLC coating technology is the advanced technique of DLC coating on aluminum alloy with the high adhesive strength and wear resistance. The DLC coated aluminum engine piston showed the excellent wear resistance after the actual motor cycle 4h race. The second one is the potentiality of the super low friction property by DLC-DLC combination under the environmentally friendly fluid lubrication. The super low friction coefficient below 0.01 was obtained by the ta-C coating using the filtered arc deposition process under oleic acid lubrication. The material technology using DLC coating with the environmentally friendly lubricant has much potentiality to improve the environment problem in various kinds of the industries.
4:50 PM E3-2-11 Superlow Friction of SiOx-Doped DLC Coatings under Oxygen and Hydrogen Ambients
Julien Fontaine (Ecole Centrale de Lyon - LTDS, France); Robert Carpick (University of Pennsylvania); Somuri Prasad (Sandia National Laboratories); Thierry Le Mogne, Sandrine Bec (Ecole Centrale de Lyon - LTDS, France)
Although diamond-like carbon films exhibit remarkable mechanical and tribological performance under a range of conditions, the addition of dopants is of interest for further improving properties, especially thermal stability. SiOx-doped DLC’s, also referred to as “diamond-like nanocomposite” films, exhibit lower surface energy, higher sp3 bonding, higher hardness, and better thermal stability than typical hydrogenated DLC’s. These properties are particularly advantageous for space applications of the coating. To investigate both the fundamental mechanisms of the tribological behavior of this material as well as to assess its behavior in environments with relevance to aerospace applications, the tribological behavior of a commercial SiOx-doped DLC coating was investigated against a 52100 steel pin on an ultra-high vacuum tribometer. Linear reciprocating motion under a residual pressure lower than 10-7 Pa and a speed of 2 mm/s was used. The coefficient of friction increases very quickly from 0.2 to more than 0.7 within the first few cycles, exhibiting significant transfer of steel onto the coating surface, and then producing heavy coating damage. The tribological behavior under vacuum thus appears to be governed by adhesive phenomena. Experiments were also performed under different partial pressures of molecular oxygen and hydrogen. Under 1 kPa of O2, or 6 kPa of H2, coefficients of friction down to 0.005 were observed, with clear evidence of tribofilm build-up on the steel counterface. Investigations of the rubbed surfaces were then conducted by surface analysis (XPS, AES) and Atomic Force Microscopy. The involved solid lubrication processes will thus be discussed in light of tribochemical interactions as well as of surface topography evolution.

5:10 PM E3-2-12 Mechanical and Tribological Properties of a-C:H Thin Films Prepared by an Unbalanced Magnetron Sputtering System
Bao Feng, Steven Taylor, Lucy Davies (Caterpillar Inc)
Hydrogenated amorphous carbon (a-C:H) thin films were deposited in an industrial scale unbalance magnetron sputtering (UBMS) system. Coating microstructure was studied with Raman spectroscopy. Nanoindentation tests were performed to characterize coating mechanical properties. Coating friction and wear behavior were evaluated using micro scale abrasion test (MSAT), high frequency reciprocating rig (HFRR) test, block on ring (BoR) test and impact test. BoR test was performed at different temperatures and in different fuels to simulate the operational condition of a diesel application. Comparison was made with tungsten containing hydrocarbon (W-C:H) and tetrahedral amorphous carbon (Ta-C) coatings. Coating selection considerations for potential industrial applications were discussed.
Time Period MoA2 Sessions | Abstract Timeline | Topic E Sessions | Time Periods | Topics | ICMCTF2011 Schedule