ICMCTF2010 Session D2-2: Diamond and Diamond-Like Carbon Materials

Thursday, April 29, 2010 1:30 PM in Room Pacific Salon 3

Thursday Afternoon

Time Period ThA Sessions | Abstract Timeline | Topic D Sessions | Time Periods | Topics | ICMCTF2010 Schedule

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1:30 PM D2-2-1 Comparison of DLC Deposited by Different Techniques
Vladimir Gorokhovsky, Kent Coulter, Michael Miller, Ronghua Wei, Carol Ellis (Southwest Research Institute)
Diamond like carbon (DLC) samples were prepared by different techniques: filtered cathodic arc deposition, vacuum arc source with hot evaporating cathode (VAHEC), plasma assisted low pressure chemical vapor deposition (PACVD) and ion beam assisted deposition (IBAD). The VAHEC source utilized a graphite cathode heated by an electron beam. The influence of characteristic processing parameters, reactive gas environment (H2, CO2, O2) and substrate temperature on the properties of DLC films were investigated. The structure and morphology of the coatings was studied by optical and scanning electron microscopy, Raman spectroscopy, and X-ray and electron diffraction methods. The mechanical properties of DLC coatings on different substrates (diamond, cemented carbide, steel, copper and aluminum) were investigated by indentation and acoustic emission methods. The correlation between the interlayer thickness and the adhesion of the DLC films deposited by different techniques vs. substrate bias was studied. In addition, the resistance of DLC to etching by low energy ion beams (Ar+, H+, or O+) in comparison to other carbon materials was studied. Results of Raman scattering show that the DLC films are amorphous, with a mixed sp2 and sp3 bonding. The ratio of sp3 to sp2 bonds varied from some units up to 20-30% and, in some cases, to more than 50% depending on the bias potential and concentration of hydrogen atoms in the plasma. It was found that most DLC films exhibit an elastic response to low loads. When the load met certain critical values, catastrophic delamination of the films occurred. The critical load depends on the substrate material, bias and deposition technique. Films with a high concentration of sp3 bonds and high ion etching resistance typically also exhibit good mechanical properties.
1:50 PM D2-2-2 Surface and Structural Properties of DLC Coatings and their Influence on Protein Adsorption
Wolfgang Waldhauser, Markus Kahn, Birgit Pointner (Joanneum Research Forschungsgesellschaft GmbH, Austria); Rupert Kargl (Karl-Franzens University Graz, Austria); Martin Reischl, Stefan Köstler, Volker Ribitsch, Elmar Brandstätter (Joanneum Research Forschungsgesellschaft GmbH, Austria)

Diamond-like carbon ( DLC), also known as amorphous hydrogenated or non-hydrogenated carbon (a-C:H, a-C), is a class of coating materials with excellent mechanical, tribological and biological properties. Depending on the deposition conditions and by the addition of other elements into the DLC these properties can be varied within a certain range. In the present work DLC coatings were deposited by employing DC magnetron sputtering of graphite targets, rf magnetron sputtering of titanium and silicon targets, respectively, in an argon/acetylene atmosphere and by the use of a special ion gun (anode layer source (ALS)) working with acetylene as carbon precursor. The structure and the topography of the coatings deposited onto silicon, glass and PET substrates were investigated by Raman spectroscopy and atomic force microscopy. The surface energy and the contact angle of the different coatings were determined by the sessile drop technique. Protein adsorption was investigated by fluorescence spectroscopy, fluorescence microscopy and a quartz crystal micro-balance method (QCM) using a bovine serum albumin.

For a-C:H coatings deposited by the ALS the discharge voltage varied from 1 kV to 3 kV was found to be the critical parameter to control the bonding structure and sp3 content in the coatings. The metal content of the doped DLC coatings was adjusted by varying the sputtering power density and the C2H2/Ar ratio.

The bonding structure in the a-C:H coatings showed a slight influence on the surface properties and on the protein adsorption. For metal doped DLC a higher protein adsorption was found whereas a-C:H:Si coatings showed the highest values very closed to the glass reference substrate.
2:10 PM D2-2-3 Industrial Filtered Laser-Arc Film Deposition, New Quality of ta-C Films
Hans-Joachim Scheibe (Fraunhofer Institute for Materialsand Beam Technology IWS, Germany); Carl-Friedrich Meyer, Michael Leonhardt, Andreas Leson, Volker Weihnacht (Fraunhofer Institute for Material and Beam Technology, IWS, Germany)
Hydrogen-free tetrahedral amorphous carbon (ta-C) coatings are known to have extraordinary low-wear and low-friction properties. Therefore they are of increasing interest for sliding automotive and machinery components as well as for tool applications. An efficient deposition of ta-C coatings within a series production is only possible by vacuum-arc technologies, e.g. arc ion plating or pulsed arc deposition. Especially the laser controlled pulsed arc deposition (Laser-Arc) was successfully implemented as a module source (Laser-Arc-Module / LAM) on industrial batch coaters, due to its excellent long-term stability of the pulsed graphite cathode erosion process. A disadvantage of all these processes for ta-C deposition is the high surface roughness resulting from the particle emission during the plasma creation from the solid graphite cathode. Therefore, most of the coated components and tools have to be surface smoothened in order to reach an optimized sliding behavior with very low-wear loss in a tribological system. For the deposition of smooth films by arc technologies, magnetic filter equipment has been successfully applied. However, for the industrial usage of such techniques for the deposition of thicker films they are not productive enough due to their high loss in deposition rate.

A newly developed filter module will be presented which was successfully developed from the laboratory state into an industrially usable LAM source. The principle of this filter for the separation of the charged plasma from macro- and micro-particles will be demonstrated. The advantages of this kind of filtering are the unlimited linear extension of the deposition area, a simple construction as well as the high efficiency. The transparency of the filter has been measured to be more than 60% in the case of super hard carbon (ta-C) film deposition. It is shown that the starting surface quality of components will be hardly changed by coating with ta-C up to a film thickness of more than 2 µm.

2:50 PM D2-2-5 Tetrahedral Amorphous Carbon (t-aC) Deposited by Filtered Cathodic Vacuum Arc (FCVA) Bombarded by Argon Ions
Francisco Marques, Myriano Oliveira, Edison Motta (Universidade Estadual de Campinas, Brazil)

Structural properties of tetrahedral amorphous carbon (t-aC) deposited by the filtered cathodic vacuum arc (FCVA) technique is investigated. The films were prepared with 5 ms current pulses of 180 A and frequency of 3 Hz. The deposition substrate was polarized in a range of 0 to - 500 V bias voltage. Argon gas was incorporated in a series of films using an ion gun source to simultaneously bombard the films with a beam of argon ions with energy in the 0-180 eV range. Argon concentration in the films was determined by RBS measurements. A study of argon effusion, realized in the range from room temperature up to about 1000°C, shows that the structure of the films depends on the argon ion bombardment energy. The density of the films, also determined by RBS, was in the 2.5 to 3.0 g/cm3 range, depending on the substrate bias voltage. The films are extremely stressed (up to about 10 Gpa) as determined using the bending beam technique, which limited the deposition of films to about 50-70 nm. It was observed that the stress reduces significantly as a function of annealing temperature. Nanohardness measurements show that the hardness of the films prepared in the 100-200 V bias voltage is about 30 Gpa. This value is underestimated since the films are very thin. Raman measurements were used to investigate the structure of the films as a function of the bias voltage and annealing temperature.

3:10 PM D2-2-6 Multı-Pass Scratch Test of DLC Coatings Deposited by CFUBMS on Anodized-CP-Ti at the Different Temperatures and Potentials
Cıgdem Albayrak, Ozlem Baran (Erzincan University, Turkey); Akgün Alsaran, Ihsan Efeoglu, Ayhan Celik (Atatürk University, Turkey)
Diamond-like carbon(DLC) coatings have a great deal properties such as high microhardness, high adhesion, high chemical stability and low friction coefficient. But ,the DLC films adhesion becomes poor if the hardness and the termal expansion difference between the substrate and the coating is considerable. Therefore, the DLC film seperates rapidly under loading. In this work, with a anodizing process was formed oxide layer on the Ti specimen surface at the varios temperatures and potentials to increase adhesion between DLC film and substrate. After anodizing treatment on CP-Ti substrates were deposited DLC films at the 2 μm thickness by Closed-Field Unbalanced Magnetron Sputtering. Structural and mechanical properties of this films are analyzed by XRD, SEM and microhardness tester. To determination adhesion properties of this coatings have been multi-pass scratched in the same track at different fractions of critical load. Consequently, anodization process effected morphology of DLC films and this process improved adhesion and wear properties.
3:30 PM D2-2-7 In Situ Real-Time Ellipsometry Study of Diamond-Like Carbon Films on Metal Substrates
David Escaich, Marwan Azzi, Oleg Zabeida, Jolanta Klemberg-Sapieha, Ludvik Martinu (Ecole Polytechnique de Montreal, Canada)
Hydrogenated amorphous carbon (a-C:H, or diamond-like carbon, DLC) films containing significant amounts of sp3 bonding are of great interest in different areas, especially in the biomedical field. Widespread applications are, however, frequently hampered by insufficient adhesion of DLC to metal substrates such as stainless steel or titanium alloys in medical instrumentation, implants and others. In the present work, we investigate the kinetics of DLC film growth on 316L stainless steel, Ti-6Al-4V titanium and c-Si substrates using UV-VIS-NIR in situ real-time spectroscopic ellipsometry (SE). In particular, we focus on the substrate/film interface at the early stage of growth, and on the effect of substrate characteristics on the growth mechanisms. DLC films were prepared in radio-frequency powered plasma-enhanced chemical vapor deposition (RF-PECVD) system. In addition to SE measurements, complementary polarization modulated infrared spectroscopy (PM-IRRAS), Raman spectroscopy, atomic force microscopy (AFM), and scanning electron microscopy (SEM) analyses have been performed. We found that the early stages of deposition on c-Si exhibit an island growth mode, followed by a layer-by-layer mode, while on metal substrates, the DLC films directly grow in the layer-by-layer mode since the very beginning. Optical properties (refractive index, n, and the extinction coefficient, k) of the growing films were constantly evolving at the first moments of the deposition, but they stabilized after 4 minutes (140 nm thick films) and 2.5 minutes (85 nm thick films) on c-Si and metal substrates, respectively. The difference during the initial steps of growth was found to affect the properties of the final (300 nm) DLC deposits. While on both metals the films are quite similar, their counterparts on c-Si possess lower roughness, lower amount of sp3 bonds, reduced index of refraction, and higher extinction coefficient. The growth mechanisms are discussed with respect to the substrate surface characteristics including roughness, surface energy, temperature, and ion bombardment energy.
3:50 PM D2-2-8 Anisotropic Texturing of Diamond-Like Carbon Films by Colloidal Lithography with Sub-Micron Spheres
Carles Corbella, Sabine Portal, Miguel Rubio-Roy, MªÀngels Vallvé, Jordi Ignés-Mullol, Enric Bertran, José-Luis Andújar (University of Barcelona, Spain)

Diamond-like amorphous carbon (DLC) surfaces have been patterned by a combination of colloidal lithography and pulsed-DC plasma-enhanced chemical vapour deposition. A self-assembled monolayer of silica sub-micron particles (~ 300 nm) was deposited on monocrystalline silicon (~5 cm2) by Langmuir-Blodgett, in order to act as sacrificial template for hole-mask lithography. A sub-micrometric pattern was generated on the substrate via ion beam etching (argon) of the colloid samples (550 eV), which was held at different incidence angles. As a result, in-plane anisotropy in the sub-micron range was generated. The fabrication was completed by plasma deposition of DLC thin film on the textured substrates. The samples were morphologically characterized by SEM and AFM. The surface properties evidenced the formed anisotropy, as shown by the directional dependences of friction coefficient (nanotribometer) and wettability (water contact angle). This fabrication technique finds applications in the industry of micromechanical devices, anisotropic tribological coatings, nanoimprint lithography, microfluidics, photonic crystals, and patterned surfaces for biomedicine.

4:10 PM D2-2-9 High Temperature Tribological Behaviour of Carbon Based (B4C and WC-DLC) Coatings Against Aluminum
Ahmed Abougharam (University of Windsor, Canada); Michael Lukitsch (GM Research & Development Center); Ahmet Alpas (University of Windsor, Canada)

Carbon based coatings, particularly diamond like carbon (DLC) surface films are known to mitigate aluminum adhesion and reduce friction at room temperature. This attractive tribological behaviour is useful for applications such as tool coatings for aluminum forming and machining. However, for those operations that are performed at elevated temperatures (e.g., hot forming) or generate frictional heat during the contact (e.g., dry machining) coatings are expected to maintain their tribological properties at high temperatures. The candidates for these demanding applications include boron carbide (B4C) and DLC coatings reinforced with nanoparticles. An understanding of the micromechanisms of friction, wear and adhesion of carbon based coatings against aluminum alloys at high temperatures will help designing coatings with improved high temperature tribological properties. With this goal in mind, this study was focused on B4C and DLC reinforced with WC nanoparticles coatings sliding against a 319 grade cast aluminum alloy by performing pin-on-disk experiments at temperatures up to 400°C. Experimental results have shown that the 319 Al/B4C tribosystem generated coefficient of friction (COF) values ranging between 0.51 and 0.65, independent of the testing temperature However, increased amounts of aluminum adhesion was detected inside the B4C coating’s wear tracks at elevated temperatures. Focussed ion beam (FIB) milled cross-sections of the wear tracks revealed that the coating failed due to shearing along the columnar grains. The 319 Al/WC-DLC tribosystem generated much lower COFs; in fact, the room temperature COF of 0.15 decreased to 0.06 at 200°C, in contrast WC-DLC wear increased slightly with the temperature. The wear and adhesion mechanisms of these coatings were further assessed using FIB, HRTEM and FTIR analyses and will be discussed in the meeting.

4:30 PM D2-2-10 Synthesis of Ultra-Smooth and Ultra-Low Friction DLC Based Nanocomposite Films on Rough Substrates
Kalpak Shaha, Yutao Pei, Changqiang Chen, Jeff De Hosson (University of Groningen, The Netherlands)

Surface roughness and dynamic growth behavior of TiC/a-C nanocomposite films, deposited by non-reactive pulsed-DC (p-DC) sputtering of graphite-targets, were studied using atomic force microscopy, cross-sectional scanning and transmission electron microscopy. Upon increasing the intensity of concurrent ion impingement by raising the frequency of p-DC sputtering, a transition from dynamic roughening to dynamic smoothing was revealed. Rough TiC/a-C films were intentionally grown on smooth surface at low pulse frequency (100 kHz) to simulate a rough finishing of industrial substrates and then rapid smoothening of such initial rough films at higher pulse frequency (350 kHz) was observed. From detailed analyses of surface morphology and growth conditions it was concluded that a transition in dominating growth mechanism from geometric shadowing at p-DC 100 kHz to surface diffusion driven by impact-induced atomistic downhill flow process due to enhanced impingement of Ar+ ions at 350 kHz occurs. It was shown that rapid smoothing of initially rough surfaces with RMS roughness ~ 6 nm to < 1 nm can be effectively achieved with p-DC sputtering at 350 kHz pulse frequency, leading to a transition from a strong columnar to a columnar-free microstructure. The observed dynamic smoothing phenomenon was applied to obtain ultra-smooth (RMS roughness ~ 0.19 nm) and ultra-low friction (µ~0.05) TiC/a-C:H nanocomposite films on rough steel substrates by p-DC sputtering of Ti-targets in an argon/acetylene atmosphere.

Time Period ThA Sessions | Abstract Timeline | Topic D Sessions | Time Periods | Topics | ICMCTF2010 Schedule