ICMCTF2010 Session E3-2: Tribology of Nanostructured and Amorphous Films

Monday, April 26, 2010 1:30 PM in Room Pacific Salon 1

Monday Afternoon

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1:30 PM E3-2-1 Friction, Wear and Solid Lubrication Mechanisms of MoS2/Sb2O3/Au Composite Coatings
Thomas Scharf (The University of North Texas); Paul Kotula, Somuri Prasad (Sandia National Laboratories)

Amorphous MoS2/Sb2O3/Au composite sputtered coatings are well known for their solid lubricating behavior and environmental robustness. In the current study, we have investigated the fundamental mechanisms of friction and interfacial shear strength, and the role of contact stress and environment on their tribological behavior. Friction and wear measurements were made from 0.3 to 1.1 GPa contact pressures in dry (<1% RH) nitrogen or humid (50% RH) air, with precise control of dew point and oxygen content. The friction coefficient of MoS2/Sb2O3/Au in dry nitrogen was extremely low, ~0.007, whereas in humid air it increased to ~0.16, with minimal amount of wear in both environments with wear factors of 1.2-1.4 x 10-7 mm3/Nm. The coatings also exhibited non-Amontonian friction behavior, with friction coefficient decreasing with an increase in Hertzian contact stress. The main mechanism responsible for low friction and wear in both dry and humid environments is governed by the interfacial sliding between the wear track and the friction-induced transfer film on the counterface ball. The interfacial shear strength, computed from friction coefficient - inverse Hertzian contact stress plots, was found to be 20 MPa in dry nitrogen and 38 MPa in humid air (both very low values for solid lubricant coatings). Cross-sectional transmission electron microscopy (XTEM) with Automated eXpert Spectral Image Analysis (AXSIA) software for X-ray spectral images and high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM) were used to study the solid lubrication mechanisms of the wear tracks and corresponding transfer films. It was determined that that in dry nitrogen, frictional contact transformed the amorphous coating into crystalline 2H-MoS2 basal (0002) planes oriented parallel to the sliding direction inside the wear track. This amorphous to crystalline transformation resulted in a continuous MoS2 film across the entire wear track, while in the humid air, the wear track was also enriched with Au islands leading to the slightly higher friction coefficient and interfacial shear strength. In both environments, the transfer films also exhibit (0002)-orientated basal planes along their entire section resulting in predominantly self-mated ‘basal-on-basal’ interfacial sliding, and thus low wear. This presentation will also discuss the interrelationships between interfacial structure/tribochemsitry and the pressure-induced transfer film shear strength to explain the observed friction and wear behaviors in the two environments.

1:50 PM E3-2-2 Friction Behaviour of Fullerene-Like WS2 Nanoparticles in Ni-Matrix Coating Compared to PVD WS2 and MoS2 Coatings
Fredrik Gustavsson, Staffan Jacobson (Uppsala University, Sweden)

MoS2 and WS2 are widely used as solid lubricants in coatings for tribological applications and have shown super-low friction in non-humid atmospheres and vacuum. They are known for their non-Amontonian behaviour, meaning a decreased coefficient of friction μ with increasing load. The big drawback is their sensitivity to humidity, leading to tribo-induced oxidation of WO3 and MoO3, respectively. These oxides are much harder to shear, thus resulting in higher μ. Inorganic Fullerene like nanoparticles (IFLs) of WS2 and MoS2 have been proposed to perform better, based on that their closed structure would make them more stable against oxidization.

This paper compares the friction behaviour of three MeS2 based coatings in various atmospheres under different loads and sliding velocities against ball bearing steel balls.

A novel electrodeposited composite coating with IFL-WS2 in a Ni-P-matrix is compared with a PVD coating with a columnar WS2 structure and with a commercial MoS2 PVD coating. The tests were performed in a pin-on-disc setup. Wear tracks and the transfer films were analysed with EDX, XPS and TEM.

In dry nitrogen atmosphere the IFL-WS2 coating shows μ below 0.01, which is as good as the commercial PVD coating. The IFL-WS2 coating shows very little wear under these conditions. In more humid atmospheres the IFL-coating performs better then the planar WS2 coating but not as good as the commercial MoS2 coating. Tests at elevated temperature, when no water is adsorbed to the surface, show some very promising results for the IFL-WS2 coating. It has also been observed that the IFL-WS2 coating performs better under higher normal load. Transfer films were observed for all contacts and their characteristics were investigated and are believed to have an important role for the friction behaviour.

The results clearly show that coatings containing IFL-nanoparticles can become an attractive alternative for specific tribological situations.

2:10 PM E3-2-3 High-Power Ion Beam Deposition of Nanocomposite and Nanolaminate Multilayer Coatings: Synthesis and Characterization*
Timothy Renk, Thomas Buchheit, Paul Kotula, Somuri Prasad (Sandia National Laboratories)
We have formed self-assembled nanocomposite thin-films using ablation/redeposition by high-power ion beams. The films were formed using the the Repetitive High Energy Pulse Power (RHEPP-1) facility at Sandia National Laboratories with deposited energy densities up to 10 J/cm2 energy per pulse. Individual deposited layers are ~ 10 nm thick, and hundreds of layers have been assembled to form films of up to several microns thickness. Films of alternating bi-metal composition (e.g. Mo-Ti or Mo-Ir), exhibit a well-delineated multi-layer structure of up to 20 GPa hardness. When a third element is added (in the form of MoS2 instead of pure Mo), the growth of smooth individual layers was disrupted and the resultant structure comprised of 100 nm-sized single-crystal Mo spheres periodically spaced through the film thickness. Characterization of the films was performed on cross-sections of wear scars suitable for TEM analyses prepared using focused ion beam (FIB) microscopy. Friction and wear measurements were performed using a Si3N4 ball in dry nitrogen and air with 50% relative humidity (RH). The MoS2 film with self-assembled spheres was found to exhibit both low friction and low wear, even in humid air with 50% RH. The spheres seem to provide a hard wear-resistant surface, while the MoS2 contributes low friction. The formation of MoO3 is inhibited in this structure. The latter is mechanically unstable, and contributes to the breakdown of MoS2 in humid conditions. Sulphur appears to catalyze the sphere formation in an as-yet unknown way. Sphere growth occurs only under specific conditions, e.g. when the depositional substrate is heated to 350°C, MoS2 and Ti layers are deposited separately, and a relatively high amount of Ti is deposited, more than the 20 at% mentioned by most researchers who have investigated Ti additions to MoS2. Substitution of vanadium in place of the Ti leads to the same Mo sphere formation. This is significant, as Mo and Ti are immiscible, whereas Mo and V are fully miscible. We have also formed nanocomposites using WS2 and Zr in place of MoS2 and Ti (or V). The WS2-Zr layer exhibits the same sphere microstructure, with single-crystal W spheres in place of the Ti spheres. This suggests that there are other examples of self-assembled nanocomposites possible. Analysis is continuing, and latest results will be presented.

*Sandia is a multiprogram laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the United States Department of Energy’s National Nuclear Security Administration under Contract DE-AC04-94AL85000.

2:30 PM E3-2-4 Mapping Tribocorrosion Behaviour of ZrNxOy Nano-Structured Thin for Decorative Applications
Mathew Mathew (Rush University Medical Center); Edith Ariza, Luis Rocha, P Carvalho, Filipe Vaz (Universidade do Minho, Portugal)
Recently, there is a large growth in the nanotechnology research focused on the fabrication and evaluation of nano-structured devices and system, having several novel properties and applications including the decorative commodities. High surface area to volume ratio, tunable optical properties and enhanced mechanical properties are some of the key characteristics. However during the practical usage, such surfaces are also exposed to movements (For example: holding door handles) in diverse chemical environment (For example: human sweat). In such situations the wear and corrosion resistance of the surfaces are significant and influences the durability/performance of the component itself. Tribocorrosion is a new laboratory testing method, where prior evaluation of the surfaces can be made. This testing method represents a powerful and unique tool that can give precious information about the future in-service behavior of several tolls and machine parts and, most important, parts that are coated with a certain functional thin film system.

Among the different examples that one can imagine, decorative thin film systems are certainly among the most important examples, since this kind of materials are subjected to simultaneous wear and corrosion environments whenever they are put in service. In order to gain further knowledge, both in the test method itself,, as well as in the study of the future behavior of a particular decorative-like system, ZrNxOy thin films were tested for their tribocorrosion properties on a standard reciprocating sliding tribometer (TE 67/E) in an environment of artificial sweat solution. The study was conducted as a function of load (3-6-9N) and electrode potential (-0.5, 0, +0.5 V (E vs SCE)). The evolutions of the friction coefficient and current have been measured during the test. Electrochemical impedance test were used to comprehend the changes in the surface chemistry before and after the sliding test. For the in-depth understanding of the tribocorrosion process, wastage map, mechanisms map and synergism map were constructed as a function of electrode potentials and load.

2:50 PM E3-2-5 Microstructures and Mechanical Properties Evaluation of TiAlN/CrSiN Multilayered Thin Films with Different Bilayer Thickness
Chien-Ming Kao (Tungnan University, Taiwan); Jyh-Wei Lee, Li-Chun Chang (Mingchi University of Technology, Taiwan)
Nanostructured TiAlN/CrSiN multilayer coatings were deposited periodically by a bipolar asymmetric pulsed DC reactive magnetron sputtering technique. The structures of multilayer coatings were characterized by an X-ray diffractometer. The surface and cross sectional morphologies of thin films were examined by a scanning electron microscopy (SEM) and transmission electron microscopy (TEM), respectively. The surface roughness of thin films was explored by an atomic force microscopy (AFM). The nanohardness and elastic modulus of multilayer coatings were investigated by means of a nanoindenter . The scratch and wear testers were used to evaluate the tribological properties of thin films. It is observed that coatings with bilayer thickness ranges from 5 nm to 40 nm were produced in this work. The surface roughness of the multilayered coating decreased with increasing bilayer thickness. An optimal hardness and tribological behaviors were found on the coating with a critical bilayer thickness of 12 nm.
3:10 PM E3-2-6 Nanostructured Hard Coatings Deposited by Cathodic Arc Evaporation: from Concepts to Applications
Frederic Sanchette, Cedric Ducros (CEA, France); Thomas Schmitt (Ecole Centrale de Lyon, France); Philippe Steyer (INSA de Lyon, France)

The vacuum cathodic arc evaporation (CAE) process is now widely used on an industrial scale essentially to prepare protective hard coatings on cutting tools, metal molds etc… It has been recognized that high ionization levels of cathodic arc discharges and high ions energy can provide advantages as, for example, enhanced adhesion which is required for mechanical applications involving high loads. CAE allows deposition of a wide range of hard compounds as nitrides or carbonitrides. However, CAE generates macrodroplets that lead to degrade the surface roughness of coatings. The recent trend is to develop advanced nanostructured hard coatings in order to enhance properties as hardness, toughness, oxidation resistance etc…

This paper deals with the recent developments in both CAE technology and nanostructured thin films synthesis. Technological progresses on macrodroplets filtering or new cathodes are discussed. Elaboration and characterization of both nanocomposite and nanolayered hard coatings are described. Thus, relationships are established between deposition parameters, nanostructure and tribological behaviours of the coatings.

3:50 PM E3-2-8 High-Temperature Sliding-Wear Performance of Nanomultilayer PVD Coatings
Frank Kustas, Demetri Falsone (Engineered Coatings, Inc.); Ronghua Wei (Southwest Research Institute); Andrew Kustas, John Williams (Colorado State University)

High performance turbine engines, aircraft-engine control components, and air-foil bearings are required to operate at increasing temperatures, which increases system efficiency. Liquid lubrication systems have limited temperature capability and reaction with steel surfaces can result in corrosion. Development of wide-temperature-range solid lubrication that offers low coefficient of friction (COF) and low wear factor (WF) is a key technology for future mechanical systems. Engineered Coatings and Southwest Research Institute deposited nanomultilayer coatings, adopted from the dry-machining industry, for tribological-property characterization at room temperature (RT), 260°C (M50 steel substrates vs. M50 balls), 485°C (Pyrowear substrates vs. Si3N4 balls), and 648°C (Pyrowear substrates vs. Si3N4 balls). From the sliding-wear tests conducted in air on coated Pyrowear substrates, nanomultilayer coatings consisting of TiAlCrN / (Ti-W-Ti)N exhibited the best combination of low COF (~0.4 at RT and ~0.37 at 485° C) and low ball WF at RT and 485° C, while a nanomultilayer coating of TiAlCrN / TiN exhibited the best performance at 648°C (COF ~0.37). A TiAlCrN / (Ti-W-Ti)N multilayer coating with a WS2 cap layer exhibited lowest COF at RT on Pyrowear, but the low COF (~0.2) lasted for only about 50% of the test duration; at 485°C the COF was ~0.4. At lower temperatures on M50 steel substrates, the best performing coating was a monolayer of AlTiCrSiCN at RT, while at 260°C the best performer was the nanomultilayer coating TiAlCrN / TiN. However in both cases COF on coated M50 steel was higher than for coatings on Pyrowear. Photographs of the ball wear scars were taken to characterize the wear behavior.

4:10 PM E3-2-9 Application of Thick and Thin Film Coatings in Oil & Gas Drilling
Chih Lin (Baker Hughes)

Oil and gas drilling represents a unique industry that demands innovation and efficiency and where many physical limitations and technological challenges exist. The materials used in drilling oil and gas wells have to balance between different opposing attributes and are usually pushed to their maximum mechanical capability. This presentation will discuss the applications of various thick and thin film coatings in drill bits that are used to make the well for extracting oil and gas. The drilling environment can be corrosive or abrasive or both. Thus, keeping a rock bit drilling in the hole for an extended period of time with a desirable penetration rate requires substantial protection on the exterior surface and sustaining wear resistance of the internal components. Functional coatings, such as tungsten carbide hardfacing, silver plating, thermally sprayed coating, and diamond-like carbon coating, have been attractive engineering solutions as they can be applied to almost any geometry without adding substantial dimensions. Careful material selection, testing, and application of the coating can not only enhance the performance but also extend the life of a rock bit. A comprehensive test program will be demonstrated to show how tungsten carbide hardfacing and diamond-like carbon coating were successfully brought to commercialization in oil and gas drilling.

4:50 PM E3-2-11 Comparative Analysis on Structure and Tribo-Mechanical Properties of Ti-B-C Nanocomposite Coatings Prepared by Magnetron Sputtering
Juan Carlos Sánchez-Lopéz, Manuel David Abad, Angel Justo (Instituto de Ciencia de Materiales de Sevilla (CSIC-US), Spain); Marta Brizuela, Alberto García-Luis (Fundación Inasmet-Tecnalia, Spain)
Protective coatings based on hard ceramic phases (TiC, TiB2) combined with amorphous carbon (a-C) at a nanometric scale are of interest because of the adequate balance between mechanical and tribological properties. In this work, two series of Ti-B-C nanocomposite coatings were prepared by sputtering of a graphite target and a second one composed of either TiB2:TiC (mixed) or pure TiB2 (single). Varying the sputtering power ratio, the a-C content could be tuned inside the coatings as observed by means of Raman and X-ray photoelectron spectroscopy (XPS). The microstructural characterization demonstrated that the set of coatings differ significantly in the crystal size and its dependence with the carbon content. The analysis of the carbon bonding by XPS and Raman revealed the differences in terms of relative amount of a-C and carbide components (TiC and TiBxCy). The hardness values decreased by half when the carbon addition leads to the formation of an amorphous carbon matrix. However, in the case of the mixed-target series the carbon content can be increased maintaining almost invariable the hardness because it is incorporated in the form of non-stoichiometric TiBxCy compound. The friction properties are correlated with the detected phases displaying a sharp transition from 0.6-0.9 to <0.3 when the fraction of a-C is above 50 at. %. Raman observation of the wear tracks determined the presence of disordered sp2-bonded carbon phase associated to the diminution of the friction level.
5:10 PM E3-2-12 Particle Erosion Characteristics of Super-Elastic Hard Ti-Si-C Films Prepared by PECVD
Salim Hassani, Jolanta Klemberg-Sapieha, Ludvik Martinu (Ecole Polytechnique de Montreal, Canada)

Titaniun carbide (TiC) thin films are widely used for tribological applications due to their high hardness (H) and wear resistance. TiC films prepared by low temperature Plasma Enhanced Chemical Vapor Deposition (PECVD) exhibit an unusual simultaneous combination of properties such as very high H, low Young’s modulus (E), and low friction coefficient (µ). Tailoring such properties is well suited for a wide range of tribological applications, particularly for the protection against solid particle erosion in different components of aircraft and helicopters. In order to further improve the properties of TiC, in the present work, we incorporated silicon (Si) as an alloying element to obtain ternary nanostructured Ti-Si-C films. Si addition into the base Ti-C resulted in significant microstructural, mechanical and tribological modifications. By controlling the Si content in the films, we succeeded to obtain transition from films consisting of fine nano-sized TiC crystallites embedded in a an amorphous SiC/a-C:H matrix to a microstructure formed by nano-sized SiC crystallites encapsulated in a TiC/a-C:H matrix. This allowed one to control the main mechanical characteristics, namely H, E, and µ, in the range of 14-32 GPa, 140-240 GPa, and 0.16-0.6, respectively. For films prepared under optimized conditions, high resistance to elastic and plastic deformation of the Ti-Si-C films, expressed by high values of H/E and H3/E2 ratios, respectively, resulted in 8 times higher erosion resistance at 90° compared to bare steel substrate. At the same time, erosion resistance at 30° impact angle increased by a factor of 22 due to a simultaneous combination of high H and low µ. Taking into consideration the severe erosion test conditions and the Ti-Si-C film thickness of only 2.5 µm in this work, further improvement is expected for thicker films.

5:30 PM E3-2-13 Tribological Properties of Nanoporous Anodic Aluminum Oxide Film
H.S. Kim, Hyo-Sok Ahn, Dae-Hyun Kim (Seoul National University of Technology, Korea); Junhee Hahn, Woo Lee, Seong Jai Cho (Korea Research Institute of Standards and Science, Korea)
Friction and wear properties of nanostructured anodic aluminum oxide (AAO) films were studied in relation to contact load and pore density (pore size and inter-pore distance). Uniformly arrayed nanoporous aluminum oxide films (pores of 28 nm, 45 nm and 200 nm dia. and 2 μm thick) were synthesized by mild anodization. Reciprocating wear tests using 1 mm diameter steel balls as counterpart were carried out for a wide range of load ( from 1 mN to 1 N) at ambient environment. The friction coefficient significantly reduced with the increase of load. The pore density marginally affected the frictional properties of AAO films. The friction coefficient was decreased by approximately 10% when the pore density decreased 60 times. The worn surface of AAO films tested at low loads (1 mN and 10 mN) did not experience tribochemical reaction and exhibited only mild plastic deformation. Dispersed thick smooth films were formed on the worn surface of all samples at relatively high loads (100 mN and 1 N) whereas only extremely thin smooth film patches were rarely formed at low loads (1 mN and 10 mN). These thick smooth films were generated by combined influence of tribochenmical reaction at the contact interface and plastic deformation of compacted debris particles as evidenced by energy-dispersive spectroscopy and X-ray photoelectron spectroscopy analyses. We suggest that these thick films mainly contributed to the decrease of friction regardless of the pore density.
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