Thin Solid Films 519 (2011) 31283134

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Thin Solid Films

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Effect of Cr interlayer on the adhesion and corrosion enhancement of nanocomposite TiN-based coatings deposited on stainless steel 410
D. Li a,b, S. Guruvenket b, S. Hassani b, E. Bousser b, M. Azzi b, J.A. Szpunar a, J.E. Klemberg-Sapieha b,
a b

Department of Mining and Materials Engineering, McGill University, 3610 University Street, Montreal, Quebec, Canada, H3A 2B2 Department of Engineering Physics, Ecole Polytechnique, C.P. 6079, Succ. Centre Ville, Montreal, Quebec, Canada, H3C 3A7

a r t i c l e

i n f o

a b s t r a c t
Applications of hard protective nanocomposite coatings are frequently limited by insufcient adhesion related to high stress. In the present work, we study the effect of an intermediate Cr layer on top of the stainless steel 410 (SS410) substrate on the performance of the nanocomposite (nc) TiN-based coatings prepared by plasma enhanced chemical vapor deposition. The Cr layer was found to enhance the corrosion resistance of the SS410 substrate by a factor of 280 in terms of corrosion current, and to increase adhesion of the TiN coating by a factor of 4. We show that for the nc-TiN/a-SiNx and nc-TiCN/a-SiCN coatings, the substantial improvement of the corrosion resistance can be attributed to the combination of the inertness of the Cr layer, and of the densely packed homogeneous nc structure of the nc coatings containing Si and/or C in comparison to columnar crystalline TiN coatings. 2010 Elsevier B.V. All rights reserved.

Article history: Received 8 May 2010 Received in revised form 30 September 2010 Accepted 7 December 2010 Keywords: Nanocomposite Interface Adhesion Corrosion resistance Plasma enhanced chemical vapor deposition

1. Introduction The combination of good tribological properties and chemical stability makes TiN an attractive candidate in a wide variety of industrial applications including coatings for cutting tools, diffusion barriers in microelectronic devices, decorative lms and protective layers for aircraft components and numerous others [17]. Alloying TiN with other elements (e.g. C, Si, B, Al, etc.) can lead to the formation of ternary or quaternary nanocomposite (nc) compounds, giving rise to further enhancement of both mechanical and tribological characteristics [812]. In general, nc coatings are composed of a matrix formed by a polycrystalline or amorphous material in which nanometer-size grains are embedded [13,14]. Specically, adding silicon and/or carbon to TiN leads to the formation of nc-TiN/amorphous (a)-SiNx and nc-TiCN/amorphous (a)-SiCN systems. Under optimum deposition conditions, the hardness could be substantially increased from ~ 25 GPa (TiN) to ~45 and 55 GPa, respectively, and the corresponding wear rate was found to decrease by a factor of ~5 and ~ 56 [9,15,16]. Although the TiN-based nc coatings possess numerous advantageous properties, a signicant problem arises when applying them as protective layers on metals. In such cases, large external forces applied to the coating may result in coating cracks or even delamination, due to the low bearing capacity of the metallic substrate [17]. Therefore, appropriate interface engineering approaches are necessary to fabricate a coating-substrate system with reliable adhesion and

enhanced mechanical properties. Among different methods to solve this problem, a duplex process consisting of surface nitriding of the steel prior to deposition has been applied [1821]. However, although nitriding can increase hardness of the stainless steel as well as its wear resistance and coating adhesion, such a treatment may lead to reduced corrosion and tribo-corrosion resistance of the coatingsubstrate system [22]. In the present work, we investigate a double-layer coating by applying a chromium interlayer between the TiN-based lms and the stainless steel 410 (SS410) substrate. We show that the Cr interlayer not only improves the adhesion of the TiN-based nc coatings to the SS410 substrate, but it also substantially enhances corrosion resistance. A further property improvement of the nc coatings can be related to enhanced packing density with the presence of silicon and carbon. 2. Experimental details 2.1. Coating deposition Prior to deposition, the SS410 substrates (25 mm25 mm1.2 mm) were mechanically polished to 1 m rms (root mean square) surface nish by alumina suspension, followed by ultrasonic cleaning in acetone and alcohol baths for 10 min and argon sputter cleaning for 10 min. The Cr layer was then deposited by a pulsed dual magnetron sputtering system, with a 15 sccm argon ow, a bias voltage, VB, of 200 V, and a substrate temperature, Ts, of 523 K. The TiN, nc-TiN/a-SiNx and nc-TiCN/a-SiCN coatings were deposited using radio frequency (RF, 13.56 MHz) plasma enhanced chemical vapor deposition (PECVD). The deposition chamber was

Corresponding author. Tel.: +1 514 340 5747; fax: +1 514 340 3218. E-mail address: jsapieha@polymtl.ca (J.E. Klemberg-Sapieha). 0040-6090/$ see front matter 2010 Elsevier B.V. All rights reserved. doi:10.1016/j.tsf.2010.12.020

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evacuated to a base pressure of 1.3 10 4 Pa by rotary and turbomolecular pumps. The samples were sputter-cleaned in argon/ hydrogen plasma for 5 min at VB = 600 V and Ts = 773 K. During deposition, the working pressure, VB and Ts were maintained at 26.7 Pa, 600 V and 773 K, respectively. The gas ows applied for the fabrication of TiN, nc-TiN/a-SiNx and nc-TiCN/a-SiCN coatings are presented in Table 1. Complete duration of the deposition cycle was 2 h. The thickness of the Cr interlayer was about 2 m, while that of the TiN-based coatings was about 2.5 m as determined by crosssectional scanning electron microscopy (SEM) (see Fig. 1) combined with the energy dispersive X-ray (EDS) analysis. 2.2. Sample characterizations Chemical composition in the coatings was determined by means of wavelength dispersive X-ray spectroscopy (WDS) with an acceleration voltage of 10 kV. The microstructure was studied by X-ray diffraction (XRD) with the Rigaku Rotaex Ru-200B X-ray diffractometer (Cu K line = 0.154 nm) at an incidence angle of 1.5. The grain size was calculated using the DebyeScherrer formula [23]. Field emission transmission electron microscopy (FETEM, Jeol JEM-2100 F) with acceleration potential of 200 kV and resolution of up to 0.1 nm was applied for microstructural characterization of the coating, which was prepared cross-sectionally using focused ion beam technique (FIB, HITACHI FB2000A). Morphology of the coatings was examined by atomic force microscopy (AFM, Nanoscope III) as well as by eld emission scanning electron microscopy (FESEM, PHILIPS XL30) equipped with EDS. Hardness, H, and reduced Young's modulus, Er of the coatings were measured by a triboindenter (Hysitron Inc.) system equipped with a Berkovich pyramidal tip with loads ranging from 1 to 10 mN. A microscratch tester (CSEM) equipped with an integrated optical microscope was employed to determine the adhesion of the coatings to the substrate using a Rockwell C diamond stylus (200 m radius), a loading rate of 30 N/min, and a scratch length of 10 mm. Three identical scratches were performed for each sample to verify test reproducibility. 2.3. Electrochemical testing The electrochemical measurements were conducted in a 1 wt.% NaCl aqueous solution at room temperature by Autolab PGSTAT302 potentiostat. For more details about the setup schematic, see reference [24]. With an area of 0.79 cm2 inside an O-ring exposed to the electrolyte, the sample acted as a working electrode, while a standard calomel electrode and a graphite rod served as reference and counter electrodes, respectively. The sample was immersed in the solution for 1 h until a stable open circuit potential (OCP) was reached. It was followed by electrochemical impedance spectroscopy (EIS) measurement performed at OCP with the frequency ranging from 105 Hz to 10 2 Hz. Potentiodynamic polarization test was then carried out with a scan rate of 5 mV/s, starting from a potential of 0.2 V with respect to the OCP, to a potential at which a current of 1 mA/cm2 was reached.
Table 1 Gas ows and corresponding elemental compositions of the TiN, nc-TiN/a-SiNx and ncTiCN/a-SiCN coatings determined by WDS. Coating Gas ows (sccm) TiCl4 TiN nc-TiN/a-SiNx nc-TiCN/a-SiCN 11 11 11 N2 34 34 34 SiH4 0.6 0.6 CH4 16 H2 70 70 70 Ar 100 100 100 Elemental composition (at.%) Ti 48.7 34.8 32.3 N 48.5 49.7 28.3 Si 0.0 13.5 12.5 C 0.0 0.0 25.9 Cl 2.8 2.0 1.0

Fig. 1. Cross-sectional SEM images of (a) TiN, (b) nc-TiN/a-SiNx and (c) nc-TiCN/a-SiCN coatings deposited on the Cr interlayer.

3. Results and discussion In this section, we rst present the microstructural and mechanical characteristics of the as-deposited coatings, and we then discuss the effect of the Cr interlayer on the adhesion and corrosion enhancement of the TiN-based coatings on steel substrates. 3.1. Microstructure and mechanical properties of the as-deposited coatings In the rst part of this work, we assess the effect of added Si and/or C on the microstructure of the TiN-based coatings deposited on the Cr interlayer. Table 1 presents the elemental compositions of TiN, ncTiN/a-SiNx and nc-TiCN/a-SiCN lms as a function of the working gas composition. The TiN coating exhibits a 1:1 Ti/N stoichiometric ratio, which is frequently correlated with its good tribological properties

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and chemical stability [25,26]. With a ow of 0.6 sccm of SiH4 introduced during the deposition, the resulting nc-TiN/a-SiNx coating exhibits a decrease of [Ti] by 13.9 at.% (from 48.7 at.% to 34.8 at.%). In this case, Ti is replaced by 13.5 at.% of Si that accounts for the amorphous SiNx matrix. Meanwhile, [N] remains approximately constant, with values of 48.5 and 49.7 at.% for TiN and nc-TiN/aSiNx, respectively. The nc-TiCN/a-SiCN coating contains 25.9 at.% of C. Here, carbon is mainly responsible for replacing nitrogen, as documented by a decrease of [N] from 49.7 at.% for nc-TiN/a-SiNx to 28.3 at.% for nc-TiCN/a-SiCN. One can observe that adding Si and/or C to the TiN-based coatings leads to a reduction of the residual [Cl] from 2.8 at.% for TiN to 2.0 at.% and 1.0 at.% for nc-TiN/a-SiNx and nc-TiCN/ a-SiCN, respectively. In general, chlorine in the coating is considered to affect the coating stability against corrosive environment [27]; therefore, reduction of chlorine leads to improved corrosion resistance as it will be discussed in the following sections. The microstructure of the coatings was studied by XRD and the results are presented in Fig. 2. For all coatings, the XRD patterns reveal face-centered cubic (FCC) crystalline structure. The strain-free peak positions from the JCPDS powder diffraction database are represented by the vertical lines for the TiN (dotted lines) and TiC (solid lines) phases. The (200)/(111) peak height ratio is ~4.2 and ~4.4 for TiN and nc-TiN/a-SiNx coatings, respectively, compared to ~1.3 for the strainfree TiN powder, indicating a (200) preferred orientation for these two coatings. As discussed by Greene et al. [28] and Gall et al. [29], TiN (200) plane has the lowest surface energy. This preferred orientation is formed with the introduction of abundant energy supplied by ion bombardment. This allows adatoms to gain sufcient mobility and move to the sites with the lowest surface energy, and it in turn leads to a densication of the coatings compared to traditional CVD TiN coatings. With the incorporation of Si and/or C, all XRD peaks are expanded and shifted towards lower 2 values. As calculated using the Debye Scherrer formula [23], the grain size of 13.2 nm for TiN was reduced to 9.5 nm for nc-TiN/a-SiNx, and to 7.1 nm for nc-TiCN/a-SiCN coatings. Such a grain size reduction is related to the phase segregation between the crystalline and amorphous phases [16]. The amorphous phase surrounding the crystalline grains can retain the grain growth and formation of columnar structure, as further discussed later in the article. Additional C in the nc-TiCN/a-SiCN coating leads to a shift of all peaks from the TiN to the TiC positions and it gives rise to a larger full width at half maximum. Taking into account the fact that N was mainly replaced by C in the nc-TiCN/a-SiCN coating (according to WDS analysis), this peak shift is possibly due to the transition from the TiN phase to the nc-TiCN/a-SiCN nanocomposite structure [9,15].

The microstructure of the nc-coatings was further investigated using FETEM analysis. Fig. 3 shows a representative bright eld TEM image and the electron diffraction patterns of the nc-TiN/a-SiNx coating. As highlighted in the high resolution TEM image, the equiaxial TiN grains have a grain size of ~10 nm, in agreement with XRD analysis, with our previous study and results published in the literature [19,38]. The electron diffraction patterns conrm the FCC structure of the TiN nc-grains. No evidence of formation of other crystalline phases was observed. Surface morphology of the coatings was analyzed by AFM and the results are shown in Fig. 4. The TiN coating exhibits cauliower morphology as a consequence of the columnar lm growth [30]. With the incorporation of Si and/or C, the columnar TiN structure transformed into a densely packed nanocomposite structure [9], as also conrmed by the cross-sectional SEM observation in Fig. 1. The microstructure of the TiN coating deposited on the Cr interlayer is composed of columnar grains. This structure changed and became more dense and featureless as Si and C were introduced into the TiNbased coatings. As presented in the 3-D AFM images (Fig. 4), the size of the surface features on the TiN-based coatings is also reduced by Si and/or C incorporation, and the rms roughness consequently decreased from ~ 50 nm for TiN down to ~33 nm for nc-TiN/a-SiNx and to ~28 nm for nc-TiCN/a-SiCN. The H and Er values of the TiN-based coatings, of the SS410 substrate and of the Cr interlayer are summarized in Fig. 5. Compared to the SS410 (H = ~5 GPa), the H of TiN is substantially increased to ~29 GPa. Due to Si and/or C incorporation, the H is further increased to ~38 and 42 GPa, for the nc-TiN/a-SiNx and nc-TiCN/a-SiCN coatings, respectively. With an intermediate H of ~ 11 GPa, the Cr interlayer appears to substantially improve the adhesion of the hard TiN coating to the SS410 substrate, as will be discussed in the following section. 3.2. Effect of the Cr interlayer on adhesion The inuence of the Cr layer on the adhesion enhancement of the TiN coating to the SS410 substrate was assessed by micro-scratch test measurement. The scratch tracks of the TiN samples without and with the Cr interlayer are displayed in Fig. 6. Here, we determine the level of adhesion in terms of three critical loads, Lc: Lc1 the load at which the rst crack appears; Lc2 the load creating regular cracks across

Fig. 2. XRD patterns of (a) TiN, (b) nc-TiN/a-SiNx and (c) nc-TiCN/a-SiCN coatings deposited on the Cr interlayer.

Fig. 3. Bright eld TEM image and electron diffraction patterns of the nc-TiN/a-SiNx coating.

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Fig. 5. Mechanical properties of the SS410 substrate, Cr interlayer and the TiN-based coatings.

indenter. This leads to a strong plastic deformation in the pile-up substrate, and hence to high shear stress and interfacial cracking [31]. For thin hard coatings, the coating-substrate deformation under the sliding indenter mainly depends on the substrate hardness; for a harder substrate, a larger load is required to induce the same level of plastic deformation, which results in an increased Lc [32]. Therefore, harder substrates are favorable candidates to reduce susceptibility of the coating-substrate system to buckling failure. With H twice as high and with similar Er compared to SS410, Cr has a higher H3/E2 r ratio; this indicates a higher resistance to plastic deformation as discussed by Leyland and Matthews [33]. In addition, as also displayed in Fig. 5, the Cr interlayer possesses an intermediate hardness between SS410 and the TiN-based coatings; such a system then exhibits a gradual change of the hardness from the substrate toward the protective coating surface. This hard Cr layer can thus provide a higher load bearing capacity than SS410, and hence improve the tribological properties. Zhang et al. [34] developed an interesting concept to assess the coating toughness and its adhesion to the substrate. The authors claimed that Lc1 represents the resistance to crack initiation, while (Lc3 Lc1), with the denition of Lc3 and Lc1 as used in the present paper, represents the resistance to crack propagation. They dened a parameter assigned as scratch crack propagation resistance (CPR) to simultaneously account for crack initiation and propagation: CPR = Lc1 Lc3 Lc1 :
Fig. 4. AFM images of (a) TiN, (b) nc-TiN/a-SiNx and (c) nc-TiCN/a-SiCN coatings deposited on the Cr interlayer.

Applying the Lci values for TiN coatings without and with the Cr layer, one can conclude that the presence of Cr increased the CPR by a factor of ~4; this is a fairly good representation of the experimental outcome presented above. 3.3. Effect of the Cr layer on the enhancement of corrosion resistance In order to investigate the effect of the Cr interlayer on the improvement of the corrosion resistance of SS410, we performed potentiodynamic polarization tests for all coating-substrate combinations. The resulting polarization curves are presented in Fig. 7 and Table 2. The sharp increase of the current at the breakdown voltage, EBD, in the upper polarization curves in Fig. 7 indicates the initiation of localized pitting corrosion caused by the penetration of Cl ions through the defects in the protective layer [35]. It is seen that the Cr layer substantially enhances the corrosion resistance of the SS410 substrate; its presence reduces the corrosion current, icorr, by approximately a factor of 280 (from 3.1 10 6 to 1.1 10 8 A/cm2), and increases the EBD from ~0.2 to ~0.7 V. In

the scratch track; and Lc3 the load causing complete delamination of the coating. As shown in Fig. 6 a, cracking started at Lc1 = 5.3 N for the SS410/ TiN sample. As the load was gradually increased, regular buckling occurred at Lc2 = 10.6 N, and the TiN coating was completely delaminated at Lc3 = 15.8 N. When the Cr interlayer was applied, the Lc1 and Lc2 values increased to 10.2 N and 15.5 N, respectively (Fig. 6). Even at the maximum load (30 N) in this scratch test and partial buckling spallation [31], the TiN coating was not completely delaminated from the Cr interlayer, and traces of the coating inside the scratch track could be observed. Buckling, typically appearing as transverse curved cracks extending to the edges of or beyond the scratch track, dominates adhesion failure modes for thin hard coatings on a ductile substrate. It generally occurs due to the compressive stress generated in front of the

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Fig. 6. Optical images of the scratch track of (a) SS410/TiN and (b) SS410/Cr/TiN samples.

Fig. 7. Potentiodynamic polarization curves of the bare SS410, SS410/Cr, SS410/TiN, SS410/Cr/TiN, SS410/Cr//nc-TiN/a-SiNx and SS410/Cr//nc-TiCN/a-SiCN samples.

order to obtain a better insight into such notable improvement, we performed SEM observations of the two samples before and after corrosion tests as shown in Fig. 8. The bare SS410 substrate surface was well polished before the corrosion test (Fig. 8 a1); following the attacks by Cl ions in the potentiodynamic polarization test, the resulting morphology bore witness of severe intergranular and transgranular etching (Fig. 8 a2). This corrosion behavior doesn't

reveal a mechanism of pitting formation, resulting in the steady increase of the current at the anodic polarization and difculty to clearly dene EBD. The as-deposited Cr layer showed a relatively rough morphology, which may enhance adhesion of the TiN-based coatings as discussed in the previous section. After the corrosion test, only few pits could be detected in the whole electrolyte-exposed area, while the intact region still exhibited identical feature as before the test. This indicates that the Cr layer well protects the SS410 substrate against corrosion attack until the EBD has been reached. With such a good corrosion resistant of Cr interlayer, the corrosion resistance of the SS410/Cr/TiN coating system was signicantly enhanced (see Fig. 7). The icorr decreased from 1.2 10 6 to 2.8 10 7 A/cm2, and the EBD increased from ~ 0.2 V to ~1 V (see Table 2). Compared with the bare SS410 substrate (EBD = 0.23 V), the TiN, nc-TiN/a-SiNx and nc-TiCN/a-SiCN coatings with the Cr interlayer showed a large range of passivation effectiveness, retaining the current at a relatively low value until an EBD value of ~1 V has been reached. Moreover, the coatings substantially reduced the icorr of the bare SS410 substrate from 3.1 10 6 A/cm2 to 2.8 10 7, 1.4 10 8 and 1.7 10 8 A/cm2 for TiN, nc-TiN/a-SiNx and nc-TiCN/a-SiCN coatings, respectively. Such reduction of the icorr and increase of the EBD demonstrated a signicant enhancement of the corrosion resistance by applying the TiN-based coatings with a Cr interlayer. 3.4. Electrochemical behaviors of the TiN-based coatings The EIS test has been applied to further quantitatively investigate the effect of microstructure of the TiN-based coatings on the corrosion

Table 2 The icorr, Ecorr and EBD values obtained from potentiodynamic polarization tests and corresponding characteristics of the Randle circuit obtained from the best-t curves of the EIS spectra (the results have been normalized by the exposed area with a size of 0.79 cm2). Sample Polarization test results icorr (A/cm2) SS410/Cr/TiN SS410/Cr//nc-TiN/a-SiNx SS410/Cr//nc-TiCN/a-SiCN SS410 SS410/Cr SS410/TiN 2.8 10 1.4 10 8 1.7 10 8 3.1 10 6 1.1 10 8 1.2 10 6
7

EIS results EBD (V) 0.97 1.01 1.01 0.23 0.72 0.18 Rs ( cm2) 67 66 59 56 Qdl Y0 (F/cm2) 7.22 10 6.95 10 5 3.36 10 5 1.12 10 4
5

Ecorr (V) 0.21 0.28 0.12 0.47 0.06 0.22

Qdl n 0.817 0.892 0.932 0.798

Rct ( cm2) 7.3 104 1.5 106 1.4 106 8.1 103

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Fig. 8. SEM images of the bare SS410 substrate before (a1) and after corrosion test (a2) and of the Cr-coated SS410 substrate before (b1) and after corrosion test (b2). Note: (b2) uses different magnication to exhibit larger electrolyte-exposed area.

resistance. In order to ensure a complete characterization of the electrode/electrolyte interface and the corresponding charge transfer processes, EIS tests were carried out over a broad frequency range from 105 to 10 2 Hz. Bode plots were used to present the EIS results, and Randle equivalent circuit was used to t the EIS curves as shown in Fig. 9. The Randle electric equivalent circuit is composed of the following elements: Rs uncompensated solution resistance; Rct charge transfer resistance; and Qdl constant phase element corresponding to the double layer capacitor. Qdl is used to replace the capacitor Cdl, since the deviation of the impedance from the pure capacitor behavior is often induced due to surface inhomogeneities, such as roughness, adsorption or diffusion [36]. The impedance can then be represented using the following equation: n ZQ = 1 = Y0 j ; 2

compared to the TiN coating. Such a signicant improvement can be attributed to the transition from columnar TiN structure, which may induce penetration of Cl ions and hence be vulnerable to the corrosion attacks (see Fig. 1 a), into the homogeneous dense nc structure with high packing density and homogenous featureless characteristics (see Fig. 1 b and c). The amorphous phase surrounding

where Y0 is the admittance of Qdl, n is an empirical exponent that represents the degree of deviation of Qdl from a pure capacitor, and is the angular frequency [37]. The experimental (dotted lines) and corresponding best-t (solid lines) data using the Randle circuit are presented in Fig. 9. The best-t values of the EIS spectra, as listed in Table 2, show that the Rct of the bare SS410 substrate (8.1 103 cm2) was increased to 7.3 104, 1.5 106 and 1.4 106 cm2, for the TiN, nc-TiN/a-SiNx and nc-TiCN/ a-SiCN coatings, respectively. With the addition of Si and/or C, the corrosion resistance (in terms of Rct) of the nc-TiN/a-SiNx and ncTiCN/a-SiCN coatings was substantially enhanced by a factor of ~20,

Fig. 9. Randle circuit, Bode plots and the best-t curves (solid lines) of the TiN, nc-TiN/ a-SiNx and nc-TiCN/a-SiCN coatings with a Cr interlayer, and of the bare SS410 substrate.

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nanocrystalline grains increases corrosion resistance. In our previous study [39] we show that a-SiNx and a-SiCN lms acts as a barrier against corrosion decreasing the icorr of SS301 from 2.5 10 8 to 7.5 10 12 and 6.6 10 12 A/cm2 respectively. Furthermore, the ncTiN/a-SiNx and nc-TiCN/a-SiCN coatings display lower roughness compared to the TiN coating (see Fig. 4), which also contributed to their enhanced corrosion resistance by increasing the surface homogeneity and reducing the surface area exposed to the solution [8]. 4. Conclusions In the present work, the effect of the Cr interlayer on the enhancement of the adhesion and of the corrosion resistance of TiN, nc-TiN/a-SiNx and nc-TiCN/a-SiCN coatings on SS410 was systematically investigated. The Cr layer substantially enhanced the corrosion resistance of the SS410 substrate. It not only drastically reduced the corrosion current by a factor of ~280, but it also increased the breakdown voltage from ~ 0.2 V to ~ 0.7 V. With a two-time higher hardness compared with SS410, the Cr interlayer signicantly improved the adhesion of the TiN-based coatings to the SS410 substrate. The combination of simultaneous adhesion and corrosion enhancements makes Cr an attractive candidate to be applied as an interlayer between the hard coatings and steel substrates. With the incorporation of Si and/or C, the columnar structure of TiN transformed into a densely packed homogeneous nanocomposite structure of the nc-TiN/a-SiNx and nc-TiCN/a-SiCN coatings. This gave rise to a further improvement of the corrosion resistance by a factor of ~ 20 compared to TiN. Acknowledgements The authors acknowledge the nancial support of NSERC and CRIAQ under the project no. CRDPJ328038-05. References
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