ICMCTF2011 Session B4-2: Properties and Characterization of Hard Coatings and Surfaces

Monday, May 2, 2011 1:30 PM in Room Golden West

Monday Afternoon

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

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1:30 PM B4-2-2 Al- and Cr-Doped TiSiCN Coatings with High Thermal Stability and Oxidation Resistance
Dmitry Shtansky, Konstantin Kuptsov, Philip Kiruykhantsev-Korneev, Alexander Sheveiko (National University of Science and Technology "MISIS", Russia); Asuncion Fernandez (Instituto de Ciencia de Materiales de Sevilla, Spain)

Multicomponent coatings based on refractory transition metal carbides and nitrides attract a great attention as protective layers on the surface of cutting and stamping tools, as well as various mechanical components working under load-bearing conditions at evaluated temperatures. Important coating properties for such applications are high hardness, stiffness, wear-, corrosion-, and oxidation resistance, as well as high thermal stability and low friction. The desired properties can be achieved by complex alloying with other elements such as Al, Cr, Si, etc. The aim of this work was a comparative investigation of the structure and properties of Al- and Cr-doped TiSiCN coatings deposited by sputtering of composite TiAlSiCN and TiCrSiCN targets produced by self-propagating high-temperature synthesis method. Particular attention was paid to the investigation of thermal stability, high-temperature oxidation resistance and tribological characteristics. In addition, the comparison of lifetimes of coated and uncoated WC-Co end mills in dry milling of chromium steel (X12BF brand mark, 52-53 HRC) was fulfilled. The results obtained show that the Ti(Al,Si)SiCN coatings with hardness of 30 GPa showed thermal stability up to 1200oC. The TiAlSiCN coating was more oxidation resistant than the TiCrSiCN coating. After 1 h exposure at 1000oC the TiCrSiCN and TiAlSiCN coatings, 2.7 mm thick, were only partly oxidized with oxidation depth of 0.7 (TiAlSiCN) and 1.1 mm (TiCrSiCN). The end mills with TCrSiCN coatings showed superior dry cutting performance against high-chromium steel compared to the TiAlCN, Cr- and Si-doped TiAlCN coatings. This can be attributed to its better mechanical (high hardness and elasticity) and tribological (low friction and wear) properties.

1:50 PM B4-2-3 Transition Metal Oxynitride Coatings: Enhancing Performance by Adding Oxygen
Lorenzo Castaldi (Oerlikon Balzers AG, Liechtenstein)
The different way nitrogen and oxygen bond with transition metals often results in completely different crystallographic and electronic properties between nitrides and oxides. This translates in divergent functionalities for various technological applications. Interestingly, by varying the O/(N+O) atomic ratio in several transition metal oxynitride coatings, it is possible to tune their electronic, optical and crystallographic properties and also enhance their hardness, thermal stability and oxidation resistance. Therefore, the understanding of the role of oxygen and nitrogen in such compounds is of great interest for a wide range of applications such as microelectronics, heterogeneous catalysis, magnetism and protective coatings. As a model example, it will be shown how the crystal structure and electronic properties of Cr-O-N and Cr-Si-O-N thin films change by varying the oxygen content, and how this variation may result in an enhancement of their mechanical properties, phase stability and oxidation resistance. Although Cr-Si and Cr oxynitride coatings exhibit similar crystallographic, electronic structure and mechanical properties, the Cr-Si-O-N films are superior in terms of phase, nanocrystalline stability and oxidation resistance. The cubic/rhombohedral transition occurs in the O/(N+O) range between 70 and 80%. The oxygen is substitutionally incorporated into the nitride cubic structure resulting in a decrease of the lattice parameter and the development of a strong (002) crystallographic preferred orientation as the oxygen concentration increases. According to SEM, all the coatings have dense and smooth microstructure. The maximum hardness is obtained for a oxygen concentration of 97% (28 Gpa) and 44 % (27 Gpa) for the Cr-O-N and Cr-Si-O-N coatings, respectively. Both Cr-based oxynitride coatings with the cubic structure exhibit an excellent phase stability and oxidation resistance in vacuum and in air, which is higher than 1000 °C for the Cr-Si-O-N coatings with a O/(N+O) ratio of 44%.
2:30 PM B4-2-5 Impact of Nb and Ta on the Phase Stability of Ti-Al-N Thin Films
Richard Rachbauer, David Holec, Paul Mayrhofer (University of Leoben, Austria)

Due to their outstanding mechanical properties at temperatures < 1000°C, ternary Ti1-xAlxN thin films attract a huge industrial interest. At temperatures around and above 900°C the thermally induced spinodal decomposition of metastable cubic Ti1-xAlxN results in an age-hardening effect during the first stages of decomposition. The advent of the stable wurtzite AlN phase, after forming c-AlN-rich domains, goes along with reduced mechanical properties.

In the present study, we highlight the influence of two refractory elements, Nb and Ta, on the thermal stability of magnetron sputtered Ti1-xAlxN thin films. We thereby investigate the development of structure and mechanical properties from a single phase cubic coating after deposition towards their stable constituents as a function of annealing temperature. It is shown, that apart from a solid solution hardening effect in the as-deposited state, vacuum annealing to 900°C initiates a decomposition of the c-(Ti1-xAlx)1-yNbyN coatings, akin to Ti1-xAlxN, to form a dual phase structure of w-AlN and c-Ti1-yNbyN. However, the formation of w-AlN and c-Ti1-yTayN during the thermally induced decomposition of quaternary c-(Ti1-xAlx)1-yTayN thin films is effectively retarded to higher temperatures with increasing amount of Ta.

This combined approach, implementing structural information, mechanical properties and comparison to ab initio calculations emphasizes the underlying structure-property relationships in Nb and Ta alloyed quaternary Ti1-xAlxN based thin films.

2:50 PM B4-2-6 Improved Thermal Stability of TiAlN Through Cr Additions
Rikard Forsén, Hans Lind (Linköping University, Sweden); Mats Johansson (Seco Tools AB Fagersta, Sweden); Ferenc Tasnádi, Igor Abrikosov, Naureen Ghafoor, Magnus Odén (Linköping University, Sweden)

Thermal stability of protective tool coatings is a crucial factor for high speed and dry cutting during which the temperature can exceed 1000°C. Coatings retaining their mechanical properties at elevated temperatures is therefore of interest. This study reports an improved thermal stability of TiAlN when Cr is added. Cubic Ti(1-x-y)AlyCrxN (x<0.4, 0.45<y<0.6) PVD layers were deposited by cathodic arc evaporation using compound TiAlCr cathodes in a N2 atmosphere onto WC-Co substrates. After post deposition annealing at temperatures up to 1400°C the phase evolution and the mechanical properties of the coatings were investigated using nanoindentation, X-ray diffraction and analytical transmission electron microscopy. In-situ investigations of the thermal response of the coatings were investigated with differential scanning calorimetry.

Additionally, first principle calculations are reported. The disorder problem is, on the basis of previous work [1], treated as a coherent potential approximation with local relaxation implemented by means of the independent sublattice model, yielding the mixing free energy of the cubic TiAlCrN system. The mixing enthalpies are positive, giving a driving force for decomposition, except for systems with high contents of Cr.

The crystal structure of the as deposited coatings is cubic (B1). The hardness of the TiAlCrN coatings is maintained or even increased up to annealing temperatures of 1000°C, indicating an age hardening process, which is affected by the Cr-content. This is supported by transmission electron microscopy observations showing compositional modulations similar to what have previously been reported for TiAlN [2], however strongly affected by the Cr-content in accordance with our theoretical predictions. Results from differential scanning calorimetry demonstrate that the thermal stability of TiAlN can be increased by several hundreds degrees through Cr alloying.

[1] B. Alling, et al., Phys. Rev. B 75, 045123 (2007)

[2] A. Knutsson, et al., Appl. Phys.Lett. 93 (2008) 143110

3:10 PM B4-2-7 Quantification of the Hydrogen Content of a-C and a-C:H-Coatings Produced at Various Bias Voltages and their Tribological Behavior under Different Humid Conditions
Wolfgang Tillmann, Fabian Hoffmann, Siavash Momeni (Technische Universität Dortmund, Germany); René Heller (Forschungszentrum Dresden-Rossendorf (FDZ) e.V., Germany)

DLC (diamond-like carbon)-coatings stand for excellent wear and friction properties. Due to their good tribological properties these coatings increase the tool life, reduce the power consumption and improve the surface finish of the work piece. However, under different humid conditions DLC-coatings react very differently. Hydrogen-free a-C-coatings show excellent frictions properties under wet conditions because of the thin water film which is formed between the coating surface and the counter part. Under dry conditions the free C-atoms at the surface bond to the counter body material which deteriorates the frictions coefficient. The hydrogenated a-C:H films act contrary to this and have extraordinary tribological properties under dry conditions since the C-atoms at the surface are hydratized and not available for any bonding with the oppositional material. Under wet conditions water molecules are weakly absorbed by the a-C:H-coatings so the interaction between the coating surface and the tribological counter part changes to a dipole-like interaction which is disadvantageous or the tribological performance. According to this, the hydrogen-content plays an important role for the wear and friction behavior of DLC coatings under different humid conditions. This work focuses on the quantification of the hydrogen content of differently bias a-C and a-C:H top layered coating systems and their influence on the tribological behavior under dry and wet conditions.

By means of a magnetron sputter device two different DLC-coating systems, one with an a-C-top layer and the other one with an a-C:H-top layer have been deposited . In order to quantify the hydrogen content within the layers GDOES (Glow Discharge Optical Emission Spectroscopy) was used. In combination with the results of the tribological tests under different humid conditions using a Ball-on-disc-tester, correlations between the hydrogen content, the bias voltage and the wear and friction performance were made.

3:30 PM B4-2-10 Bonding Structures and Mechanical Properties of Silicon Doped Carbon Nitride Films
Songbo Wei, Tianmin Shao (Tsinghua University, China)
Silicon doped carbon nitride (CNx-Si) films with various silicon contents were prepared by ion beam assisted deposition. X-ray photoelectron spectroscopy (XPS) was used to characterize the bonding structures of the films. Surface topography and nanohardness were investigated by using an atomic force microscope (AFM) and a nanoindenter, respectively. The results show that adequate dope of Si in CNx films could significantly increase the nanohardness of the films. As the increase of silicon content in CNx films, nanohardness of the films increased. The nanohardness reached to a maximum value of 66GPa when silicon content increased up to about 40 at.%, and then rapidly decreased as the silicon content further increased. XPS spectra indicated an increasing proportion of single bonds (N-Si, N-C, et al.) and a decreasing proportion of double and triple bonds (N=C, N≡C et al.) with increasing silicon content of the films. It is suggested that the formations of N-Si and N-C led to the strengthening of the sp3 network, and increased nanohardness of the films. However, the formation of redundant Si-Si bonds due to the continuous increase of Si content in the films, caused the decrease of nanohardness of the films.
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