Investigation of nanostructured TiSiC-Zr and TiSiC-Cr hard coatings for industrial applications C. Vitelaru, M. Balaceanu, A. Parau, C.R.

Luculescu, A. Vladescu PII: DOI: Reference: To appear in: Received date: Revised date: Accepted date: S0257-8972(14)00290-4 doi: 10.1016/j.surfcoat.2014.04.001 SCT 19320 Surface & Coatings Technology 28 October 2013 31 March 2014 1 April 2014

Please cite this article as: C. Vitelaru, M. Balaceanu, A. Parau, C.R. Luculescu, A. Vladescu, Investigation of nanostructured TiSiC-Zr and TiSiC-Cr hard coatings for industrial applications, Surface & Coatings Technology (2014), doi: 10.1016/j.surfcoat.2014.04.001

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Investigation of nanostructured TiSiC-Zr and TiSiC-Cr hard coatings for industrial applications

National Institute for Laser, Plasma and Radiation Physics, 409 Atomistilor Str., Magurele-

Abstract

TiSiC, TiSiC-Zr and TiSiC-Cr coatings, with Zr and Cr added to TiSiC base coating system, have been prepared by cathodic arc method in a CH4 reactive atmosphere. All the coatings exhibited nanocomposite structures, mainly consisting of a mixture of crystalline facecentered cubic (FCC) carbide solid solutions, with a preferential (220) texture, and amorphous

microstructures.

Cr and Zr incorporation in TiSiC resulted in lattice distortion (from a lattice parameter of 0.4358 nm for TiSiC, to 0.4536 nm and 0.4320 nm for TiSiC-Zr and TiSiC-Cr, respectively) and grain refinement. Also, alloying TiSiC led to a reduction of stress in the films, from -3.12 GPa (TiSiC) to -2.37 GPa (TiSiC-Cr) and -2.58 GPa (TiSiC-Zr), and to film hardness changes (TiSiC: 35.2 GPa; TiSiC-Zr: 42.1 GPa; TiSiC-Cr: 31.4 GPa). Of the investigated coatings, TiSiC-Zr exhibited the lower dry friction coefficient (~ 0.3) and the lowest wear rate (~ 2*10-6 mm3N-1m-1).

Keywords: TiSiC, TiSiC-Zr and TiSiC-Cr coatings; cathodic arc; structure; friction and wear

Corresponding author: Alina Vladescu, E-mail alinava@inoe.ro, Tel./Fax: +4021-457 57 59.

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carbon phases. The coatings showed compact, homogeneous and featureless cross-sectional

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Bucharest, Romania

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National Institute for Optoelectronics, 409 Atomistilor Str., Magurele-Bucharest, Romania

C.Vitelarua, M. Balaceanua, A. Paraua, C.R. Luculescub, A. Vladescua1

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1. Introduction Over the past two decades, there has been an increasing interest to produce Si containing

resistance. Many types of nitrides (TiSiN, ZrSiN, CrSiN, MoSiN, VSiN, TaSiN, WSiN 19

CrSiCN) 1823 have been widely investigated as potential candidates for use as protective coatings against wear, corrosion and high-temperature oxidation. Their superior

nanocrystalline grains of metal nitride, carbonitride or carbide in an amorphous matrix (Si3N4,

high cohesive strength, were considered as the main factor responsible for the high hardness

residual stress, adhesion, friction performance, resistance to oxidation and corrosion) could be further improved by adding small amounts of certain elements in the compositions of Si containing coatings. This has become recently a common method to modify the structure and properties of binary or ternary coatings based on transition metal compounds. For example, it was shown that Al increases thermal stability and oxidation resistance, Zr and V improve wear behavior, Nb enhances hardness and corrosion resistance, Y provides extensive grain refinement, increased hardness and stabilization of coating - substrate interface, Cr improves oxidation resistance and reduces friction, W increases wear performance 2430. In a recent review [31], Jansson and Lewin discussed the effects of metal and non-metal addition to binary transition-metal carbide films. For TiSiN and TiSiCN coatings the addition of various alloying elements led to complex nanocomposite coatings such as TiAlSiN, TiCrSiN, TiSiBN, CrAlSiN, TiAlSiBN, TiAlVSiN and CrTiAlSiN 3235 or TiCrSiCN and TiAlSiCN 2

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and thermal stability of these coating types 1, 5. Nevertheless, some film characteristics (e.g.

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SiCxNy or SiC). The presence of nanometer-scale grains, having well-defined boundaries of

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characteristics were attributed to the formation of nanocomposite structures consisting of

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carbides (TiSiC, HfSiC, WSiC, ZrSiC, MoSiC) 1017 or carbonitrides (TiSiCN, ZrSiCN,

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excess of 40 GPa), superior fracture toughness, high thermal stability and good oxidation

nanocomposite hard coatings due to their remarkable properties such as very high hardness (in

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23, 36, 37, with high hardness and thermal stability, superior friction and wear behavior, and high cutting performance. Up to now TiSiC coatings were investigated mainly as protective coatings for tribological applications and also for electrical sliding contacts [1013], [15],

composition, chemical bonds, microstructure, morphology, mechanical and tribological

TiSiCN, much less attention was devoted to TiSiC alloying. So far, it was examined only the addition of Ag to TiSiC, which proved to improve their electrical conductivity [38].

coatings. We selected as alloying elements Zr and Cr, which are strong carbide-forming metals. Zr- containing coatings, in monolithic [39] or multilayered structures [40], showed superior mechanical characteristics and tribological performance, while Cr-doped hard

37, 41, 42]. The coatings prepared in the present work are envisaged to be used for the protection of irrigation water pump components, working under wear and corrosion conditions. According to the considered application, the tribological tests were carried out on uncoated and coated C45 steel substrates. To accommodate the harsh working environment, only coatings with relatively high carbon content (in excess of 50 at %) were synthesized because such coatings were found to exhibit superior structural, mechanical and tribological characteristics as a result of the formation of a free carbon phase [15, 43, 44]. The coatings were produced by the cathodic arc technique in a CH4 reactive atmosphere. Film characterization was performed in terms of elemental and phase composition, chemical bonds, morphology, residual stress, hardness, adhesion, corrosion resistance, friction and wear performance. The properties of the coatings with either Cr or Zr addition were assessed in comparison to those of the TiSiC coatings. 3

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coatings exhibited superior thermal stability and high-temperature oxidation resistance [31,

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The present study reports the effects of additions of different metallic elements into TiSiC

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characteristics, erosion resistance and electrical properties. But, in contrast with TiSiN or

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chemical vapour deposition was also employed. The coatings were analyzed for elemental

[16]. Most of the coatings were prepared by magnetron sputtering, but plasma enhanced

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2. Materials and methods Experiments were conducted on coatings deposited by reactive cathodic arc evaporation,

shown in Fig 1. The deposition chamber (700x700x700) mm3 was equipped with two

99.9 % purity) and another of either Zr or Cr (99.9 % purity). The composition of the TiSi alloy was selected to correspond to the eutectic composition, because the preparation of such

controlled. Also, a cathode with this composition was expected to provide a Si content in the film between 2 and 9 at %, which was found to determine improved characteristics of other Si containing hard coatings. Before deposition all samples were ultrasonically cleaned in

using a rotary pump and a turbomolecular pump. Prior to deposition, the substrates were placed on a rotating substrate holder and sputter-cleaned by Ar+ ion bombardment for 10 min, by applying a substrate bias of -1000 V in an Ar atmosphere at a pressure of 0.7 Pa. Preliminary experiments were conducted to select the optimum process parameters (CH4 flow rate, substrate bias voltage) to prepare TiSiC coatings with high hardness. In order to keep constant the carbon/metal ratio for all the prepared coatings, the CH4 flow rate was increased with about 15% when Zr or Cr were added. As a result, the main deposition parameters were as follows. The CH4 flow rates (FRCH4) and the related working pressure were of 130 sccm and 8x10-2 Pa, respectively, for TiSiC deposition, and of 150 sccm and 9.2x10-2 Pa, respectively, for TiSiC-Zr and TiSiC-Cr deposition. The coatings were grown using a substrate bias of -200V and arc currents of 110 A, 130 A and 100 A at TiSi, Zr and Cr cathodes, respectively. The substrate temperature 4

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isopropanol for 10 min. The deposition chamber was evacuated to a base pressure of 6x10-4 Pa

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an alloy, as well as its characteristics (microstructure, morphology), are easier to be

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cathodes (16 mm thick discs with =120 mm), one of TiSi alloy (84 at. % Ti; 16 at. % Si;

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the analyses and tests to be made. A schematic representation of the deposition chamber is

using an industrial deposition unit. Si and C 45 steel were used as substrates, depending on

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(measured with a thermocouple) was in the range of 290310 C, and resulted from substrate ion bombardment during deposition (no additional heating source was used), while the substrate current density was of about 4.8 mA/cm2. The ~1h deposition time was chosen for

temperature of 850 C for 4h. The effects of thermal annealing on the structural and

hardness) were also investigated.

The chemical bonds close to the film surface were determined by XPS, using a VG ESCA

were similar to those given in Ref 45. The depth profiles of atomic concentrations were obtained by GDOES, by means of a SPECTRUMA GDA-750 HP spectrometer. The phase composition and the crystalline structure of the films were assessed by XRD, using a Rigaku

examined by a Nano SAM Lab S Scanning Auger Microscopy System (Omicron), while the worn surfaces were investigated by scanning electron microscopy coupled with energydispersive X-ray spectroscopy (EDS) using a FEI InspectS equipment. Film characterization in terms of thickness, surface roughness and residual stress was done by a Dektak 150 surface profiler. For residual stress measurements, the radii of curvature of the Si wafer substrates were determined prior and after coatings deposition. The film hardness was measured with a Vickers microhardness tester (0.05 N load). The scratch tests were carried out according to ASTM C1624 - 05(2010) for measuring the coating adhesion of the coatings (critical load, Lc). The testing conditions were: indenter 0.2 mm radius diamond tip, load continuous increase from 0 to 100 N, scratching speed 10 mm/min, scratching distance 10 mm.

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MiniFlex II diffractometer (Cu K radiation). The fracture cross-sections of films were

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3MK II spectrometer with AlK radiation. The sample preparation and the spectra processing

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mechanical properties of the coatings (lattice parameter, crystallite size, residual stress,

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After deposition, the coated Si samples were annealed under a vacuum of ~10-4 Pa at a

producing coatings of 3.63.8 m thickness.

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Experiments on friction and wear performance of the coatings in dry atmosphere were conducted using a CSEM pin-on-disc tribometer (sapphire ball of 6 mm in diameter, 0.15 m/s, 400 m sliding distance, 5N load). To determine the worn volume, the cross-sectional areas of

3. Results and discussion

Chemical binding state in the top layer of the deposited films was examined by XPS. The Ti 2p, Zr 3d, Cr 2p, Si 2p, C 1s and O 1s XPS spectra were taken after 3 min sputtering time. Assuming a sputter rate of about 0.1 nm/s for 4 keV Ar+ ion bombardment 46, the investigated zone was situated at ~18 nm below the film surface. The peak assignment was done according to Ref. 47.

Fig. 2 shows, as an example, the Ti 2p, Si 2p and C1p XPS spectra of the TiSiC coating.

show the presence of both metal-carbon and metal-oxygen compounds. The formation of an oxide rich layer is a typical contamination phenomenon when coatings are exposed in open atmosphere, being frequently reported for coatings of transition metal compounds, particularly for metal-Si-C coatings 12, 14, 38. For these latest coatings, oxygen concentrations of up to 2226 at. % were measured in the vicinity of surface. From the deconvolution of the Si peak (Fig. 2), the peaks at binding energies of 99.2, 100.6 and 102.3 eV were assigned to Si, SiC and SiO2 phases, respectively. The examination of the carbon bonding was of particular interest because, as noted above, the presence in the film composition of a carbon amorphous phase is expected to have beneficial effects on film properties. The peak deconvolution gives evidence of different carbon binding: C-Ti bonds (281.6 eV), C-Si (282.8 eV), C-C sp2 graphitic carbon (285.0 eV) and C-O (286.4

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The Ti 2p3/2 peaks at 454.7 and 455.9 eV (assigned to Ti-C and Ti-C-O bonds, respectively)

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3.1. Chemical bonds and chemical composition depth profiles

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the wear tracks were measured on 8 points on each track, using the surface profiler.

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eV and 287.7 e V).When Cr or Zr were added to the TiSiC film, similar spectra were recorded. Summarizing the XPS data, it can be concluded that in the vicinity of the surface, the coatings

an example, the GDOES depth profile of the TiSiC sample is presented in Fig. 3. It can be

elemental compositions of the TiSiC, TiSiC-Zr and TiSiC-Cr coatings at a depth of 2 m, considered representative for the compositions in the films bulks, are listed in Table 1. It is to note the overstoichiometric compositions of the coatings, with C/(metal + Si) ratio in the range 1.81.9, and the added metal/Ti ratio of about 0.4. 3.2. X-ray structural analysis

The diffraction patterns of the TiSiC, TiSiC-Zr and TiSiC-Cr coatings are given in Fig.4. For

solid solutions. The absence of the Si peaks, or of its compounds (e.g. SiC or metallic silicides) is probably due to their amorphous structures or/and low concentrations. It should be noticed that all coatings exhibit (220) preferred orientations. This particular texture is rather unusual for the coatings deposited by cathodic arc method, which commonly exhibit an (111) orientation 48, 49. Nevertheless, under the conditions of a highly energetic ion bombardment of the substrate, as is the case of our deposition conditions (substrate bias and current density: -200 V and ~ 4.8 mA/cm2, respectively), the preferred orientation tends to change from (111) to (200) or (220), as reported in Refs. 50] and [51. Beside the ion bombardment conditions, the texture of carbon containing coatings could be also affected by their composition. For example, in the case of arc plasma deposited TiCN films, it was reported a texture change from (111) to (220) for high carbon contents 52.

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all the coatings, the X-ray diffraction results show the formation of only FCC nanocrystalline

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seen that the equilibrium atomic concentrations are reached at depths exceeding 1 m. The

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GDOES analysis was used to determine the elemental compositions of the deposited film. As

consist of mixtures of metal carbide, metal oxide (or oxi-carbide) and free carbon phases.

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In order to clarify the effects of ion bombardment and carbon concentration on film texture, additional X-ray analyses were performed for the reference TiSiC coating (Vs = -200 V, FRCH4 = 150 sccm; Fig. 5a) prepared at lower substrate bias Vs (Vs = -100 V, FRCH4 = 150

from -200V to -100V resulted in the decrease of the (220) peak intensity, while the decrease

(111). To conclude, the XRD results clearly demonstrated the important role of both ion bombardment and film composition on the preferred orientations of arc plasma deposited TiSiC.

From the XRD data, the lattice parameters a0 of the deposited coatings were determined (Table 2). As expected, the metal additions modified the value of the lattice parameter of TiSiC film. As currently admitted (e.g. [53]), the value of the lattice parameter, as calculated

in the film. For example, a compressive residual stress induces a lattice expansion, while the presence of atoms with different radii and/or changes in stoichiometry determines specific modifications of the lattice constant. To separate the chemical and stress contribution to lattice distortion, X-ray analysis was also performed for the annealed samples, since for such samples a drastically stress relaxation is expected (see below). The lattice parameters before and after annealing are given in Table 2. Considering the chemical contribution, as reflected in a0 values for the annealed samples, it can be seen that addition of Cr atoms, with smaller atomic radii (0.1249 nm) than Ti (0.1462 nm), lowered the lattice parameter from 0.4324 nm to 0.4281 nm, while Zr atoms, with larger atomic radii (0.1603 nm), led to its increase to 0.4495 nm. Comparing a0 values for the as- grown and annealed samples of the same coating type, it results that stress determines, as expected, an increase of the lattice constants for all the coatings. 8

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from the position of diffraction peaks, is influenced by both chemical composition and stress

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of CH4 flow rate from 150 sccm to 110 sccm induced a change in film texture from (220) to

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the diffractograms, one can observe notable differences. Thus the decrease of bias voltage

sccm; Fig. 5b) or lower CH4 flow rate (Vs = -200 V, FRCH4 = 110 sccm; Fig. 5c). Comparing

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As seen in Fig.4, when adding Zr and Cr in the TiSiC coating system, the crystallinity becomes poorer and the (220) texture less pronounced. As a rough approximation, the crystallite size d was estimated from the XRD peak broadening of (220) orientation, using the

formation of finer morphologies.

reported for thermal annealed hard coatings (e. g. [2],[54]). This effect is considered to result from the recrystallization process during the thermal annealing. 3.3. Cross-sectional morphology and mechanical characteristics The cross-sectional morphologies were observed by scanning electron microscopy (SEM). The investigations revealed dense and compact structures for all the coatings, with no significant differences between them. Fig. 6 shows a typical SEM cross-sectional fracture

coatings investigated), illustrating the glass-like microstructure of the film. The main mechanical properties of the investigated coatings (residual stress, hardness, adhesion) are summarized in Table 2. The residual stress and hardness values after samples annealing are also given.

The as-deposited coatings were found to be in a highly compressive stress state, with stress values in the range from -2.37 GPa to -3.12 GPa (Table 2). This result is typically for the cathodic arc deposited coatings, being attributed to the highly energetic ion bombardment of the films during growth, causing ion-induced point defects 21, 55. The maximum stress value was measured for the TiSiC coating (-3.12 GPa). Incorporation of alloying elements in TiSiC resulted in a slight reduction of residual stress to -2.37 GPa for TiSiC-Cr and to -2.58 GPa for TiSiC-Zr coatings. One possible explanation of the decrease in residual stress with Zr and Cr addition to TiSiC could be the reduction of defect concentration for the doped TiSiC 9

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micrograph of the TiSiC-Zr coating deposited on Si substrate (representative for all the

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After annealing, an increase in the crystallite size in all the coatings is noticed, as commonly

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were found for TiSiC-Zr (d = 4.2 nm) and TiSiC-Cr (d = 5.6 nm) coatings, indicating the

Scherrer formula (Table 2). As compared with the TiSiC coating (d = 7.5 nm), lower values

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coatings. As currently admitted (e.g. [56]), the intrinsic stress, is mainly related to the morphology of films, particularly to the presence of ingrown defects (interstitials, vacancies). For the annealed samples, a significant decrease in stress is observed, down to values ranging

All the deposited coatings exhibited high hardness levels (Table 2). Metal addition to TiSiC

42.1 GPa, while Cr addition resulted in a slight hardness reduction (31.4 GPa). Several factors have been considered to influence the hardness of complex hard coatings: lattice distortion, solid solution formation, preferred orientation, crystallite size, residual stress, coating compactness etc 1, 5, 30, 57]. Since both Zr and Cr additions were found to determine the lattice deformation, reduction of crystallite size and residual stress values, and did not significantly modify the texture, the aforementioned factors are not able to account for the

differences can be related to the higher strength of Zr-C chemical bonding compared to Cr-C 57. It can also be seen that the annealed samples exhibit hardness values with about 1112 GPa lower than those of the as-grown films, as often reported for PVD deposited hard coatings (e. g. [2, 54]), being attributed to the residual stress relaxation. Scratch tests were performed in order to assess the coating adhesion on C45 steel substrate. The critical load values for the investigated coatings were ranging from about 33 to 38 N (Table 2), with no significant differences between the coatings. Examination of scratch tracks (not shown) indicated mainly a cohesive failure mode of the coatings (conformal cracking evidenced by numerous semicircular cracks, typical for brittle, stressed and hard coatings 58, 59), but also chipping or spallation at the edges of the track. Also, local failures and partial delamination of the coatings were observed as the load increased beyond 4050 N.

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differences in hardness between the TiSiC-Zr and TiSiC-Cr coatings. More probably, these

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(hardness of 35.2 GPa) had different effects on film hardness: Zr led to an enhancement at

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for by relief of growth-defects caused by the high substrate temperature (e. g. [54]).

from -0.3 to -0.4 GPa. The stress relaxation as a result of thermal annealing can be accounted

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3.4. Friction and wear performance The tribological tests were performed on coatings prepared on C45 steel discs (30 mm diameter). The obtained results were summarized as the variation of the friction coefficient

tests (Fig. 8). For comparison, data on tribological characteristics of the uncoated substrate are

In Fig. 7, the friction coefficient of the TiSiC coating is observed to initially increase to a maximum of about 0.5 for a sliding distance of approximately 100 m, beyond which it slightly decreases to a stable value of ~ 0.38. Noticeable modifications in friction behaviour of TiSiC coatings were observed at Zr or Cr addition. The friction coefficient of the TiSiC-Zr coating decreased during the first stage of the test, reaching a steady-state value of ~ 0.3 as the test advanced, at about 70 m sliding distance. The relative low level of the friction for TiSiC and

by XPS analysis) which acts as a lubricant phase, as it was reported for overstoichiometric metallic carbides on carbonitrides (e.g. [15, 60, 61]). In contrast, a poor friction behaviour can be observed for the TiSiC-Cr coating (the friction coefficient continuously increased during the wear test up to a value of about 0.7 at ~ 230 m sliding distance, followed by a relative steady state stage). In this case it appears that the beneficial effect of the C-based lubricated phase on the tribological characteristics is hidden by other phenomena. Particularly, this poor friction behaviour can be related to the presence on the film surface of embedded nodular defects and high asperities which can be easily removed during the wear process. The resulting hard debris and craters on surface can have a significant influence on friction and wear. The role of these modular defects in friction and wear behaviour was previously taken into account by Zheng et al. [36] and Li et al. [23] to explain the tribological performance of other CrSi containing coatings: CrSiCN, TiCrSiCN and TiCrSiCON. The presence of such 11

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TiSiC-Zr coatings can be explained by the formation of a carbon-rich surface layer (detected

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also presented.

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the wear track divided by the load and by the sliding distance) at the end of the ball-on-disc

vs. sliding distance (Fig. 7), and as the values of the wear rate K (the worn-out volume from

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defects in the case of TiSiC-Cr coatings was evidenced by optical microscope examination of the coating surface (not shown), and also by the higher measured Ra roughness (Ra 0.85 m), as compared to the values for TiSiC (Ra 0.40 m) and TiSiC-Zr (Ra 0.45 m)

best wear performance was obtained for the TiSiC-Zr coating, followed by TiSiC and TiSiC-

the coatings. A hard surface determines a reduced adhesive contact area so that adhesive wear is diminished as well. According to the Archard's law [62], the worn volume is inversely proportional to the hardness of the material, so that the hardest coating (TiSiC-Zr) exhibits the smallest volume loss. The higher wear rate of the TiSiC-Cr coating can be also construed by the existence of a significant amount of hard debris detached from the film, also responsible for its high friction coefficient.

shown in Fig. 9. In the case of TiSiC coating, the semi-circular cracks clearly visible on the observed within the scratch tracks, as already mentioned. This feature is much less visible for the other coatings. The TiSiC-Zr coating appears to be much less affected by the wear process, a polishing wear being observed on the worn surface. It should be noted that the wear track is contaminated by some adhesive material. A local failure in the film is also visible in the wear track. In contrast to the TiSiC and TiSiC-Zr coatings, the TiSiC-Cr sample was subjected to a severe wear, the coatings being almost completely worn. The presence of wear debris is apparent on both sides of the wear tracks. The cross-sectional profiles of the wear tracks (Fig. 9) show that the TiSiC-Zr coating exhibits the smallest wear cross-sectional area, followed by the TiSiC and TiSiC-Cr samples.

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Optical micrographs and surface profiles of the wear tracks at the end of the sliding test are

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Cr. These results can be explained by the differences in hardness and friction coefficient of

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Fig. 8 compares the values of the wear rate K for all the investigated coatings. As seen, the

coatings.

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In order to clarify the wear mechanisms and to account for the difference in wear performance between the TiSiC-Zr and TiSiC-Cr coatings, the wear tracks for these films were examined using an electron microscope equipped with EDS.

EDS (in the central area, marked as zone C on the SEM images) and on the both sides of the

A close look to the worn tracks of both coating types shows the lack of grooves parallel to the sliding direction, suggesting that abrasion does not play an important role in the wear mechanism. On the other hand, it can be seen that the wear track is contaminated by wear debris (black stains), which appear as plastically deformed adhering material, attached to the coating surface. In the case of TiSiC-Cr, the debris is mainly present along the two edges of the wear track. Comparing the SEM images of the two investigated coatings, it should be

coating was much less affected or damaged by the wear, with a very superficial trail, showing a much better wear resistance. For the TiSiC-Zr coating, the film composition in the central zone does not differ much from that of the as-deposited coatings (except for an increase in oxygen content, from about 4 to 16 at. %), showing a relatively slight wear damage, which confirms the optical and SEM examinations. For the same film, the adhesion material in the A and B zones consists of highly oxidized particles. It should also be noted the presence of aluminum in these regions, indicating the material transfer from the sapphire (Al2O3) ball counterbody to the coating. Though sapphire is commonly considered a chemical inert slider material, it has been shown [63] that it adheres quite strong to some types of coatings (e.g. TiC:H), due to the formation of intermetallic Al-Ti or hydrogen bonds. The formation of the transfer film is a process closely related to adhesive wear (e.g. [64]). 13

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noted a marked and deep wear track for the TiSiC-Cr coating. In contrast, the TiSiC-Zr

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wear track (zones A and B).

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coatings, the atomic concentrations on the worn surfaces (see Table 3) were determined by

Wear track SEM images of the TiSiC-Zr and TiSiC-Cr coatings are given in Fig. 10. For both

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In the case of the TiSiC-Cr coating, similarly to TiSiC-Zr, highly oxidized particles were observed in zones A and B, but an Al containing transfer layer was not detected. Instead, some amounts of material arising from the substrate (Fe) were found. In the central area, the

proceeded, more and more oxidized wear particles were pushed to the vicinity of the wear

their low adhesion.

To summarize, for the TiSiC-Zr and TiSiC-Cr coatings, the wear was characterized by adhesive phenomena, oxidation process, material transfer and film polishing. The dominant wear mechanism was a combined adhesive and oxidative wear, also considered to be responsible for wear behaviour of some TiSiC and TiSiCN coatings [16, 37].

TiSiC, TiSiC-Zr and TiSiC-Cr nanocomposite coatings, with Zr and Cr as alloying elements, were produced by cathodic arc technique. The coatings, with relatively high carbon/(metal+ Si) ratio (1.81.9), were found to consist mainly of a mixture of nanocrystalline carbide solid solution (FCC structure, (220) texture), and a free amorphous carbon phase. The grain size, as determined from X-ray peak broadening, was on order of 48 nm. The coatings exhibited compact and dense morphologies, high compressive stress (from -2.37 GPa to -3.12 GPa), high hardness levels (35-42 GPa) and satisfactory adhesion to C45 steel substrates (critical loads of 33-38 N). Both types of alloying elements led to the lattice distortion, reduction in grain size and diminishment of residual stress of the TiSiC reference coatings. Among TiSiC, TiSiC-Cr and TiSiC-Zr coatings, the latest showed the highest hardness (~ 42 GPa). Under dry sliding conditions, the main wear mechanisms were found to be adhesive and oxidative wear. Cr 14

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4. Conclusions

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scar, forming a consistent adhering layer. These particles cannot withstand fretting, due to

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severe damage of the coating, worn down close to the substrate. As the wear process

Fe content is dominant in comparison with the elements composing the film, indicating a

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addition to TiSiC did not result in any improvement of tribological behaviour. In contrast, the TiSiC-Zr coating exhibited good wear and friction performance in dry conditions (wear rate 2x10-6 mm3 N-1m-1 and friction coefficient 0.3). Therefore, the TiSiC-Zr coating could be a

Acknowledgements

(CNCS UEFISCDI), project no. PN-II-PT-PCCA-2011-3.2-1453.

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Work supported under the grant of the Romanian National Authority for Scientific Research

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potential candidate for tribological applications.

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Table 1. Elemental compositions of the coatings, as obtained by GDOES Coating Ti TiSiC TiSiC-Zr TiSiC-Cr 31.1 23.1 23.6 Elemental composition (at. %) Zr 9.2 Cr 8.8 Si 3.2 2.9 3.0 C 63.2 62.0 61.3 O C/(metal+Si) Added metal/Ti

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Table 2. Structural and mechanical characteristics of TiSiC, TiSiC-Zr and TiSiC-Cr coatings: lattice parameter a0, crystallite size d, residual stress , hardness H, critical load Lc Coating as-grown TiSiC annealed as-grown TiSiC-Zr annealed as-grown TiSiC-Cr annealed a0 (nm) 0.4358 0.4324 0.4536 0.4495 0.4320 0.4281 d (nm) 7.5 12.6 4.2 5.1 5.6 15.9 (GPa) -3.12 -0.43 -2.58 -0.31 -2.37 -0.33 H (GPa) 35.2 23.3 42.1 31.5 31.4 19.6 Lc (N) 38 36 33

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Table 3. EDS compositions of the wear tracks Coating Ti Zone A TiSiC-Zr Zone B Zone C Zone A TiSiC-Cr Zone B Zone C 15.1 12.9 23.9 12.7 13.5 2.3 Zr 7.0 6.6 10.7 Elemental composition (at. %) Cr Si 2.1 1.8 2.6 1.5 1.7 0.5

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Fe 13.8 14.6 51.4

C 17.2 16.3 46.1 13.5 14.3 28.5

O 53.7 56.9 16.1 53.6 51.8 16.2

4.9 5.5 0.6

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Fig. 1. Schematic representation of the deposition chamber in the cathodic arc unit.

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Fig. 2. XPS Ti 2p, Si 2p and C1s spectra of the TiSiC coating

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Fig. 3. GDOES depth profiles of the TiSiC coating

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Fig. 4. X-ray diffraction patterns of coatings deposited at Vs = -200 V substrate bias: (a) TiSiC, FRCH4 = 130 sccm, (b) TiSiC-Zr, 150 sccm and (c) TiSiC-Cr, 150 sccm (s = substrate)

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Fig. 5. X-ray diffraction patterns of TiSiC coatings obtained in different conditions: (a) FRCH4 = 130 sccm, Vs = -200 V; (b) FRCH4 = 130 sccm, Vs = -100 V. (c) FRCH4 = 110 sccm, Vs = -200 V (s = substrate)

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Fig. 6. SEM cross-section image of the TiSiC-Zr coating

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Fig. 7. Friction coefficients vs. sliding distance for the substrate and the TiSiC, TiSiC-Zr and TiSiC-Cr coatings (dry testing conditions; sapphire ball, 0.15 m/s, 400 m sliding distance, 5 N load)

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Fig. 8. Wear rate K for the substrate and the TiSiC, TiSiC-Zr and TiSIC-Cr coated samples

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Fig. 9. Optical images and cross-sectional wear profiles of the wear tracks for the TiSiC

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(a), TiSiC-Zr (b) and TiSiC-Cr (c) coatings

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Fig. 10. SEM micrographs of the wear tracks for the TiSiC-Zr and TiSiC-Cr coatings

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Highlights TiSiC, Zr- and Cr-doped TiSiC coatings were prepared by cathodic arc method. Coatings were composed of FCC carbide solutions and amorphous carbon.

The Zr-doped coating exhibited high hardness (~ 42 GPa) and good adhesion (Lc = 36 N). Zr alloying improved the coating friction and wear performance of TiSiC coating.

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Zr and Cr additions led to grain refinement and reduction in residual stress state.

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