Surface and Coatings Technology 172 (2003) 7278

The effect of MEVVA implanted Cr on the corrosion resistance of CrN coated low alloy steel by cathodic arc plasma deposition
K.L. Changa, S. Hanb, J.H. Lina, J.W. Husa, H.C. Shiha,*
a

Department of Materials Science and Engineering National Tsing Hua University, Hsinchu 300, Taiwan, ROC b National Taichung Institute Technology, Taichung, Taiwan, ROC Received 16 September 2002; accepted in revised form 3 February 2003

Abstract Metal vapor vacuum arc (MEVVA) source implantation is a novel and profitable surface modification process. Cathodic arc plasma deposition of CrN coating has been applied on an industrial scale to improve the corrosion resistance of AISI 4140 steel. The effect of the Cr implanted by MEVVA (Crysteel) on the corrosion behavior of CrNysteel through the surface modification was investigated. Both AISI 4140 steel and its coated assemblies of Crysteel, CrNysteel and CrNyCrysteel were evaluated in aerated 0.1 N HCl solution. The composition and structure of the MEVVA implanted Cr and cathodic arc plasma deposited CrN on steel were studied by X-ray diffraction and secondary ion mass spectrometer. The polarization resistance (Rp ) of all samples was measured and compared with d.c. polarization resistance and electrochemical impedance spectroscopy. The microstructure of corroded samples was also examined by scanning electronic microscopy and electron probe X-ray microanalyser. The results indicated that the corrosion resistance of CrN coated steel was significantly enhanced by the MEVVA implanted Cr in CrNyCry steel. 2003 Elsevier Science B.V. All rights reserved.
Keywords: Metal vapor vacuum arc; CrN ysteel; CrN yCrysteel; Electrochemical impedance spectroscopy; Corrosion resistance

1. Introduction Ion implantation has been used to improve surface properties, such as corrosion, wear and oxidation resistance. The final surface microstructures of the ionimplanted steels are from stable to metastable or to amorphous states on the surface w1x. Metal vapor vacuum arc (MEVVA) ion source is an attractive ion implantation technique for surface modification w2,3x, which may have advantages in improving surface hardness, wear and corrosion performance w46x. Transition metal nitride coatings have been widely used for the corrosion protection of steels. In aggressive environments, the major corrosion problem of coated steels is the defects in the coating, e.g. porosity, cracks, pinholes that may form during the deposition process. These defects may form direct paths between the substrate and the exposed environment. The application of
*Corresponding author. Tel.: q886-3-571-5131, ext. 3845; fax: q 886-3-571-0290. E-mail address: hcshih@mse.nthu.edu.tw (H.C. Shih).

an intermediate layer between the substrate and coating is used to limit the effect of the defects and to improve the corrosion resistance of the substrate w7,8x. The intermediate layer can be prepared by several techniques, such as electroplating, electroless plating and PVD methods w9x. A duplex coating of (CrN y Cr y steel) with the electroplate chromium as the intermediate layer has been investigated w10,11x. The MEVVA ion implantation was used to modify the steel surface. One of the main ideas is to introduce surface elements with a high affinity for oxygen in reducing corrosion of steels using ion implantation. This makes the passivation easier to produce better corrosion resistance w12x. This study focused on the effect of MEVVA Cr ion implantation on the corrosion resistance of Cr y steel. The corrosion resistance of CrN y Cr y steel was compared with that of CrN y steel by electrochemical approaches. 2. Experimental AISI 4140 was used as the substrate with the following chemical composition in weight percentage: 0.39 C,

0257-8972/03/$ - see front matter 2003 Elsevier Science B.V. All rights reserved. doi:10.1016/S0257-8972(03)00318-9

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Fig. 1. XRD pattern of steel, Crysteel, CrNysteel and CrNyCrysteel.

0.24 Si, 0.71 Mn, 0.029 P, 0.04 Ni, 0.18 Mo, 1.06 Cr and Fe bal. Disk-shaped specimens 3 mm thick and 15 mm in diameter were machined for electrochemical measurements, including electrochemical impedance spectroscopy (EIS) and d.c. polarization resistance measurement (Rp). All specimens were ground with a series of emery papers of 120, 400, 800, 1000 and 1200 grit. Contamination on the surface was first ultrasonically cleaned with acetone and ethanol, and then the sample was stored in a desiccator prior to the coating operation. An implanted chromium layer was applied using a MEVVA ion implanter at an extraction voltage of 50 kV. The Cr ion energy, ion doses and current density were 100 keV, 2=1017 ions y cm2 and 6 mA y cm2, respectively. The substrate temperature was measured by a Ktype thermocouple, and the substrate was heated from room temperature up to 100 8C after implantation. Subsequent deposition of the CrN film was conducted in a cathodic arc plasma deposition system. A Cr interlayer prior to the CrN deposition in order to provide better adhesion between the substrate and its coating. During the deposition process, the substrate was biased with a d.c. voltage of y150 V at an arc current of 60 A, which gave a substrate temperature of 350 8C under the N2 partial pressure of 2.7 Pa for a deposition time of 70 min. The microstructure was observed by scanning electronic microscopy (SEM), and the crystallographic phases were determined by X-ray diffraction (XRD) Cu Ka radiation (MAC Sci., model MXP-18). The specimens were investigated using u y 2u diffraction mode ranging from 30 to 908. The Cr atom distributions were determined by secondary ion mass spectrometer (SIMS Cameca IMS4F). The electrochemical corrosion analysis was controlled by an EG&G 273 potentiostat, using a three-electrode cell configuration. A saturated calomel electrode was used as the reference and a platinum sheet as the counter electrode. AISI 4140 steel and the three

Fig. 2. SIMS depth profiles of Cr, Fe, O and N for (a) CrNysteel (b) CrNyCrysteel.

coated assemblies (i.e. Cr y steel, CrN y steel and CrN y Cr y steel) were immersed in 400 ml aerated 0.1 N HCl solution for corrosion tests. The corrosion current and

Fig. 3. Rp values for the steel, Crysteel, CrNysteel and CrNyCrysteel as a function of immersion time.

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mode, as shown in Fig. 1, the presence of the (2 2 0) and (2 0 0) peaks, and a preferred orientation of CrN (2 2 0) of the CrN structure can be clearly observed. However, the XRD spectrum of Cr y steel, i.e. Fig. 1(2) which is similar to that of substrate, i.e. in Fig. 1(1), does not provide any information related to the Cr phase. The results of SIMS measurements are used on CrN y Cr (implanted) y steel shows the depth profiles of 54 Cr, 57Fe, 16O and 14N in Fig. 2a. It is evident that the composition of Cr and N is uniform along the thickness (;2 mm) of the coatings. The coating y substrate interface indicates the thickness of CrN coatings is approximately 2 mm. The contribution of implanted chromium can be seen more clearly at the coating y substrate interface of Cr distribution (Fig. 2b) when compared with that in Fig. 2a. The distribution of Cr implanted layer

Fig. 4. (a) Corrosion potential and (b) corrosion current density of the CrNyCrysteel in 0.1 N HCl solution with immersion time.

the polarization resistance Rp were evaluated based on the linear polarization method over a small potential range of "15 mV with respect to the corrosion potential (Ecorr). For the polarization resistance determination, a sweep rate of 10 mV y min was employed. The EIS measurements were analyzed using a frequency analyzer (EG&G 5301). The impedance spectra were recorded in a frequency range between 100 kHz and 10 mHz. The amplitude of sinusoidal signals was 10 mV around the free corrosion potential Ecorr. The X-ray mapping of corroded specimens was performed by electron probe X-ray microanalyser (EPMA JXA-8800M). 3. Results and discussion 3.1. Crystallographic analysis The XRD spectra of CrN y steel and CrN y Cr y steel have been compared and consistent with the JCPDS database of CrN phase (No. 11-0065). In the u y 2u

Fig. 5. Cross-sectional SEM images after EIS tests (a) CrNyCrysteel and (b) CrNysteel.

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effective in reducing the corrosion. The variation in Ecorr and icorr of CrN y steel and CrN y Cr y steel in 0.1 N HCl solution with immersion time is shown in Fig. 4. The icorr is an important parameter to understand the kinetic mechanism of corrosion reactions. The icorr of the CrN y steel is higher than that of CrN y Cr y steel (Fig. 4b) and the Ecorr of the CrN y steel decreases for the first 12 h of immersion, and approaches a steady state value of y0.55 V thereafter, as compared to y0.54 V for the

Fig. 6. Nyquist plots as a function of immersion time in a 0.1 N HCl solution: (a) CrNysteel and (b) CrNyCrysteel.

varies with the implantation depth. From the depth profile the maximum implantation depth is ;200 nm. 3.2. Electrochemical behavior 3.2.1. Polarization resistance The polarization resistances (Rp) of steel, Cr y steel, CrN y steel and CrN y Cr y steel resulting from linear polarization measured in 0.1 N HCl as function of immersion time are presented in Fig. 3. The Rp value of Cr y steel is obviously higher than that of bare steel, indicating that the corrosion resistance has been improved by the Cr implanted steel surface. The Rp of CrN y steel decreases more rapidly than that of CrN y Cr y steel as immersion time increases, showing that CrN y Cr y steel possesses a better capability for preventing the localized galvanic attack between the coating and the substrate. The Rp of CrN y Cr y steel indicates that the Cr implanted layer is

Fig. 7. Bode plots as a function of immersion time in a 0.1 N HCl solution: (a) CrNysteel and (b) CrNyCrysteel.

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CrN y Cr y steel (Fig. 4a). It is apparent CrN y steel suffers more corrosion than CrN y Cr y steel coatings w13x. The cross-sectional SEM images after the immersion tests show the appearance of corrosion products at the coating y substrate interface, as shown in Fig. 5. A part of CrN coating has been spilled off due to the local expansion of the corrosion products in a pit (;400 mm) on CrN y steel. The corrosion mechanism of the CrN coated steel may be comprehended by the generation of pits on the substrate, resulting from the dissolved anodes that were produced due to the coating defects on the exposed substrate steel. During a progressive corrosion process, new pits initiated and existing pits may spread laterally. Finally, these pits link up together to form a large pit w14x. The corrosion of steel takes place inside the coating, where a higher icorr of CrN y steel is produced w15x. It may be concluded from these observations that the Cr layer in CrN y Cr y steel provides a beneficial effect on the corrosion resistance of the steel.

3.2.2. Electrochemical impedance spectroscopy behavior EIS can provide useful information on the corrosion process of the PVD coated steel exposed in an aggressive environment w8,16x. The Nyquist impedance diagrams at the free corrosion potential for CrN y steel and CrN y Cr y steel are presented in Fig. 6. The polarization resistance (Rp) values were also evaluated by the EIS behavior. The solution resistance (Rs) was estimated from the impedance in a high frequency range, while the sum of Rp and the Rs was estimated from the impedance in the low frequency range. The difference between these two impedance values results in Rp, which is inversely proportional to the corrosion rate. The Rp values from EIS confirm the trends of results from linear polarization. The impedance values of CrN y steel and CrN y Cr y steel decrease with the immersion time. Fig. 7 shows the bode plots of CrN y steel and CrN y Cr y steel as a function of immersion time. A second time constant can be clearly resolved at lower frequen-

Fig. 8. SEM micrograph and its X-ray mappings of Cr, Cl and Fe: (a) CrNysteel and (b) CrNyCrysteel.

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Fig. 8 (Continued).

cies of CrN y steel Bode-phase plot after 108 h immersion (Fig. 7a). The different shape of Bode-phase plot after longer time of immersion is associated with the presence of local detachment of the coating due to the accumulation of corrosion products at the coating y substrate interface w17,18x. The Bode-phase plot of CrN y Cr y steel (Fig. 7b) shows a much less resolved time constant at lower frequencies after longer time of immersion. The X-ray mapping of the elements Cr, Fe and Cl of the corroded CrN y steel and CrN y Cr y steel are illustrated in Fig. 8a and b, respectively. From the EPMA observation on CrN y steel, the corrosion products plugged the defects in CrN y steel to detach the coating of CrN (Fig. 8a). Such mechanism is in agreement with the EIS behavior. When compared with the CrN y steel, the CrN coating of CrN y Cr y steel degrades more slowly (Fig. 8b). The implanted Cr in the CrN y Cr y steel assembly is apparently more efficient in reducing the corrosion of the CrN y steel assembly. The performance of the coated

steels against corrosion is strongly affected by the coating defects w17,19,20x. The Cr implanted layer promotes the surface passivity of the steel substrate and physically to isolate the structure defects of the CrN coatings. 4. Conclusions Cr implantation using MEVVA is an effective method to improve the surface passivity of the steel substrate and to physically cut off the paths originating from the defect structure of the CrN coating. The Rp values evaluated either from d.c. polarization or from EIS showed that the Cr implanted steel provided a better protection against corrosion of steels in 0.1 N HCl solution. References
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