Accepted Manuscript

Facile chromaticity approach for the inspection of passive films on austenitic stainless steel Cong Qian Cheng, Jie Zhao, Tie Shan Cao, Qin Qin Fu, Ming Kai Lei, De Wei Deng PII: DOI: Reference: To appear in: Received Date: Accepted Date: S0010-938X(13)00041-3 http://dx.doi.org/10.1016/j.corsci.2013.01.035 CS 5253 Corrosion Science 23 November 2012 19 January 2013

Please cite this article as: C.Q. Cheng, J. Zhao, T.S. Cao, Q.Q. Fu, M.K. Lei, D.W. Deng, Facile chromaticity approach for the inspection of passive films on austenitic stainless steel, Corrosion Science (2013), doi: http:// dx.doi.org/10.1016/j.corsci.2013.01.035

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Facile chromaticity approach for the inspection of passive films on austenitic stainless steel Cong Qian Cheng, Jie Zhao*, Tie Shan Cao, Qin Qin Fu, Ming Kai Lei, De Wei Deng (School of Materials Science and Engineering, Dalian University of Technology, Dalian, 116085, China) Corresponding author: Jie Zhao, Email: jiezhao@dlut.edu.cn, Tel: 86 411 84709076, Fax: 86 411 84709284 Abstract A chromaticity approach for the inspection of passive films on 304 stainless steel is explored by measuring the redness degree of the colouration reaction product of phenanthroline. The measurement exhibits good capability in evaluating film quality. The measured values are dependent on the structural integrity of the passive films. Based on the electrochemical examination and XPS spectra, this approach is discussed from the view point of the inhibition of the passive films on the release of ferrous from the matrix during its reaction with phenanthroline. The preferential dissolution of Fe-rich oxides in the films can affect the measurement. Keywords: A. stainless steel; B. cyclic voltammetry; B. XPS; B. polarisation; C. passive films.

1. Introduction Austenitic stainless steel (ASS) is widely used as a construction material. The bilayer structure of passive films with outer Fe-rich oxides and inner Cr-rich oxides on ASS has attracted considerable attention because of its barrier properties in corrosion environment [13]. The quality of passive films in ASS manufacturing is important for the safe application of ASS facilities in nuclear reactors and chemical industries. For example, surface rust or corrosion resistance degradation occurs if passive films are damaged by an unsuitable manufacturing process. Specifically, local corrosion and stress corrosion cracking can develop under the following service conditions after passive films are damaged by surface scratching and contaminants. Thus, inspecting and characterising passive films are critical processes in ASS manufacturing.

Various inspection techniques can be applied to characterise passive films on ASS. For instance, quantitative approaches via physical methods, such as Auger electron spectroscopy and X-ray photoelectron spectroscopy (XPS),

can reveal the chemical structure of passive films, whose quality can then be evaluated based on the inspected information [47]. However, most physical methods require drastic experimental conditions, such as ultra-high vacuum conditions, and very expensive or unavailable equipment. Electrochemical tests can entirely reflect the electrochemical property of passive films on ASS. For example, electrochemical cathodic reduction and voltammetry offer quantitative and qualitative assessments of passive films [810]. Capacitance measurements were also successfully used to determine the semi-conductive behaviour of passive films [1113]. The intensively red-coloured ferroin, which consists of divalent iron and phenanthroline, has been used extensively for several years for the colourimetric determination of iron and as an oxidation-reduction indicator [14]. This fact suggests that chemical colouration reaction may become one of the potential approaches for the convenient inspection of passive films. However, ferroin is mostly applicable as an indicator in solution titration analysis. No research has been reported on the application of ferroin in the inspection of passive films. Conveniently characterising passive films on a large scale using the traditional titration method with ferroin as the indicator is difficult. When a phenanthroline solution creates contact with a scratched ASS, the colour at the scratched region changes into red because of the formation of ferroin. The redness degree is directly correlated with the damage degree of passive films. This phenomenon highlights a possibility to characterise film quality using the redness degree of the ferroin indicator. Two typical types of passive film usually grow during ASS manufacturing: the spontaneously formed films by air exposure and the artificial films formed by chemical passivation. This study aims to elucidate an inexpensive and rapid method, namely, chromaticity inspection, for discerning the quality of passive films. This method consists of two procedures. The first one is the colouration reaction of phenanthroline to produce the red-coloured ferroin indicator, and the second is the subsequent inspection of the redness degree of the formed ferroin indicator via colour measurement.

The measured result response to air exposure and chemical passivation was analysed by electrochemical test and XPS examination. The role of passive films during the colouration reaction was also discussed based on cyclic voltammetry and cathodic polarisation. 2. Experimental method A commercial AISI 304 ASS plate was used for the experiments. The chemical composition was 0.025 wt.% C, 17.95 wt.% Cr, 9.2 wt.% Ni, 1.06 wt.% Mn, 0.63 wt.% Si, 0.09 wt.% Mo, 0.02 wt.% P, 0.005 wt.% S and the rest is Fe. The 304 ASS plate was cut into pieces 3 mm in height and 10 mm in diameter. The samples were ground up to 1200 grit size using SiC paper. Passivation treatment was then conducted by air exposure and chemical passivation. The samples were exposed to air at a relative humidity of 46%9% for different periods from 0 h to 120 h. Fujimoto et al. [15] reported that this variation in relative humidity below 70% has no obvious influence on passive film growth. Chemical passivation was carried out by immersing the samples in 20 vol.% HNO3 solution at 45 C for 30 min.

2.1 Chromaticity inspection

The quality of the passive films was evaluated by chromaticity inspection, which consists of phenanthroline colouration reaction and colour measurement of the produced ferroin indicator. The phenanthroline solution, which was composed of 0.1 g/L C12H8N2H2O (1,10-phenanthroline monohydrate) as a complexing agent, 1.954 g/L to 0.109 g/L C6H8O7H2O (citric acid momohydrate) and 0.206 g/L to 2.735 g/L of C6H5O7Na3H2O (trisodium citrate dehydrate) as a buffer solution to provide the desired redness degree, was employed to interact with 304 ASS and produce the ferroin indicator. A piece of white test paper saturated with the phenanthroline solution was attached on the samples for colouration reaction. The phenanthroline solution showed good complexation ability with Fe ions. The ferrous form in ferroin has a deep red colour, whereas the passive film can inhibit the release of Fe ions and retard the complexation reaction. The quality of the passive films can be indirectly characterised by the redness degree of the ferroin indicator. After 3 min of colouration reaction, the ferroin indicator was evaluated by colour measurement.
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In the current study, a colour reader (Konica Minolta, CR-10) was used to measure the colour of the ferroin indicator in the CIE Lab space. A national standard colour card (Pantone formula guide, No. 1797U) was first measured as the reference. The redness difference between the test paper and the reference was measured, and the redness degree of the ferroin indicator was calculated based on the redness difference.

2.2 Electrochemical test

All electrochemical measurements were performed in 3.5 wt.% NaCl solution with a conventional three-electrode cell at room temperature. The test cell consisted of the samples as a working electrode, a platinum foil as a counter electrode and a saturated calomel electrode (SCE) as a reference electrode. In the text and figures, the potentials were reported vs. SCE. The exposed area of the samples that made contact with the NaCl solution was a circle with a diameter of 10 mm.

The potentiodynamic polarisation was scanned from -0.4 V to 1.5 V (SCE) at a scan rate of 1 mV/s. Capacitance measurement was performed in the cathodic direction at a frequency of 1000 Hz using an AC signal of 10 mV and a step rate of 25 mV.

Cyclic voltammetry and cathodic polarisation were examined to explore the interaction mechanism of the phenanthroline solution with the passive films. Cyclic voltammetry was scanned at a rate of 50 mV/s between 0.1 and -1.5 V (SCE). Cathodic polarisation was conducted at a potential range of -0.4 V to -1.4 V (SCE) for 600 s. After cathodic polarisation, some of the samples were rinsed quickly with deionised water. The other samples not rinsed were used for comparison. Surface residual water was absorbed by filter paper, and surface quality was inspected by the chromaticity method as mentioned above.

2.3 XPS examination

XPS measurement was carried out using an XPS spectrometer (Thermo ESCALAB 250Xi) without any sputtering technique. The X-ray source employed was a monochromator Al-K (1486.6 eV, 15 kV, 14.9 mA). The spectrometer was
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operated with a constant pass energy of 20 eV. 3. Results 3.1 Chromaticity measurement of passive films on 304 ASS Fig. 1 shows the colour characteristics of the optical photos during the colouration reaction of phenanthroline in the 304 ASS samples subjected to air exposure and chemical passivation in HNO3 solution. The grinding procedure before air exposure and chemical passivation results in many fine scratches. The chemical passivation shows no obvious effect on the surface [Fig. 1(a)]. The coated sheet after 3 s of colouration reaction is shown in Fig. 1(b). A weak red circle is observed in the sample exposed to air for 0 h, but circles with white background images are found in the samples exposed to air for 3 h and in the samples subjected to chemical passivation. After 180 s of colouration reaction, the red-coloured circles are revealed in the samples exposed to air for 0 and 3 h. The intensity of redness is higher in the samples exposed to air for 0 h than in those exposed to air for 3 h. However, the colour of the test paper is still white on the samples subjected to chemical passivation. The experimental result from Fig. 1 indicates that the colour induced by the colouration reaction may be sensitive to the passivation conditions. Moreover, the redness degree can be utilised to semi-quantitatively evaluate the quality of the passive films.

Colour measurement can provide an objective specification of the quality of a colour regardless of its luminance, i.e., as determined by its hue and its dominant wavelength. The quality of a colour for a target can be described by several colour coordinate systems. One of the most popular systems is the CIE Lab. The CIE Lab space is based on the concept that colours can be considered as a combination of lightness, red and green, yellow and blue. The three coordinates in the CIE Lab space represent the lightness of the colour (L = 0 refers to black, whereas L = 100 indicates diffuse white), wherein a indicates the position between red and green. Negative a values indicate green, positive values indicate red, and b is the position between yellow (b positive) and blue (b negative). In addition, the difference (value) between the target and the reference can be evaluated by subtracting the background value of the reference [16]. In the current study,

the redness difference (value) between the test paper and the national standard colour card was measured in the CIE Lab space. The redness degree of the ferroin indicator can be characterised by a* as follows:

a*=ai a0

(1)

where a0 and ai are the redness difference between the test paper and the reference before the attachment and after the reaction, respectively. The redness degree (a*) corresponding to the colouration reaction in the present work is shown in Fig. 2. Results of the preliminary experiments demonstrating the effective scope of the colouration reaction time are presented in Fig. 2(a). When the phenanthroline solution makes contact with 304 ASS, Fe ions are released from the substrate quickly and react with the test solution to produce red-coloured ferroin. Therefore, the measured a* value is rapidly increased within the initial reaction period of 60 s, as shown in Fig. 2(a). After 180 s of reaction, the complexation reaction is stabilised, and then the measured a* value is slightly increased. The a* values of the samples are in the following order: 0 h of air exposure > 0.2 h of air exposure > 12 h of air exposure > chemical passivation in HNO3 solution. This result suggests that the complexation reaction parameter for 180 s is suited to distinguish passive films under air exposure and chemical passivation. The results of a* variations for the 304 ASS samples are shown in Fig. 2(b) after 180 s of colouration reaction. Significant differences between the samples subjected to air exposure and chemical passivation are observed. The highest measured a* value corresponds to the sample exposed to air for 0 h. The inspected a* values decrease as the thin passive films grow during air exposure. The measured a* values in the samples exposed to air for more than 3 h are close to 2, indicating that more passive films have formed. Compared with the samples exposed to air, the samples subjected to chemical passivation in HNO3 solution have a* values close to 0. This finding suggests that the optimum film quality can be found in the samples subjected to chemical passivation in HNO3 solution. The chromaticity measurement response to cathodic polarisation of the samples after 48 h of air exposure and after
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chemical passivation, with and without rinsing after cathodic polarisation, is shown in Fig. 3. The a* values of the samples subjected to chemical passivation are close to 0 after polarisation at the potential region above -0.7 V (SCE). The measured a* values increase rapidly at potentials more negative than -0.7 V (SCE). However, a corresponding increase in the a* values are not observed after rinsing (Fig. 3). The a* value of the samples exposed to air is approximately 1.6 after polarisation at the potential range of -0.4 V (SCE) to -0.6 V (SCE) and then reaches approximately 17 at potentials below -1.2 V (SCE) without rinsing. The a* value after rinsing decreases to 12, as shown in Fig. 3. 3.2 Electrochemical behaviour of the passive films and its relationship with chromaticity measurement Cyclic voltammetry was carried out to realise the reduction reaction related to the chromaticity measurement during cathodic polarisation. Fig. 4 shows the cyclic voltammetry curves of the 304 ASS samples after 48 h of air exposure and after chemical passivation. The voltammogram of the 304 ASS samples exposed to air shows a reduction peak I at approximately -0.7 V (SCE) corresponding to the reduction and dissolution of Fe2O3 or FeOOH oxides during cathodic polarisation; an anodic peak II corresponding to the oxidation of Fe to Fe2+ and Fe3+ is also found [10, 17]. The current density of the samples subjected to chemical passivation is significantly weakened, and both peaks are nearly negligible. This result suggests that the reduction and preferential dissolution of Fe-rich oxides occur during cathodic polarisation at potentials below -0.7 V (SCE).

To understand the corrosion properties of 304 ASS, which is dependent on surface passive film, the electrochemical corrosion behaviour of 304 ASS in 3.5 wt.% NaCl solution was examined. Fig. 5 shows the potentiodynamic polarisation curves of the 304 ASS samples in 3.5 wt.% NaCl solution and highlights their calculated pitting potentials Epitting from the polarisation curves corresponding to chromaticity measurement. All samples exhibit passive behaviour in the test solution. The passive region of the samples subjected to chemical passivation is at the potential range of 0 V to 1.04 V (SCE). At this range, the passive film becomes stable. The pitting potential Epitting is approximately 1.04 V (SCE), above which the breakdown of the passive films likely occurs [Fig. 5(a)]. For the samples exposed to air, both the passive

region and Epitting increase with prolonged air exposure, whereas the passive current density decreases with prolonged air exposure. This result indicates that the corrosion resistance can be improved by air exposure. The current density at the extremely wide passive region after chemical passivation in HNO3 solution is the lowest, indicating the optimum corrosion resistance of the samples. Fig. 5(b) shows the relationship between the measured a* values from Fig. 2(b) and the calculated Epitting from the potentiodynamic polarisation curves in Fig. 5(a), which signifies the property of local corrosion resistance. The graphs in Fig. 5(b) show that a lower value of a* gives rise to a higher local corrosion resistance. This result may be expected because a lower value of a* and a higher value of Epitting are expected after the growth of the passive films during air exposure, as shown in Figs. 2(b) and 5(a), respectively. The lowest value of a* and the highest value of Epitting at 1024 mV (SCE) in the sample subjected to chemical passivation provide the optimum local corrosion resistance of the passive films at the a* value of 0. Mott-Schottky analysis was employed to examine the semiconductor properties of the passive film in 3.5 wt.% NaCl solution by measuring the capacitance developed in the films as a function of the applied electrode potential. According to Mott-Schottky theory, the doping densities of n-type and p-type semiconductors are given by [13, 18]
1 2 kT = ( E EFB ) 2 0eAN D C e 1 2 kT = ( E EFB ) C 2 0 eAN A e

n-type p-type

(2) (3)

where E is the applied potential (SCE), e is the electron charge, is the dielectric constant of the passive films, 0 is the vacuum permittivity, A is the surface area of the electrode interface, k is the Boltzman constant, T is the absolute temperature, EFB is the flat-band potential and ND and NA are the donor density for n-type semiconductor and acceptor density for p-type semiconductor, respectively. Fig. 6 shows the Mott-Schottky plots of the passive films in 3.5 wt.% NaCl after air exposure and chemical passivation in HNO3 solution. The capacitance of the samples without air exposure is much higher than that after air exposure and chemical passivation. Two linear regions are identified in the Mott-Schottky plot. One has a positive slope at the potential

region of -0.5 V to 0.2 V (SCE), showing the properties of n-type semiconductor. The other has a negative slope, showing the properties of p-type semiconductor. As shown in Fig. 6, the potential region ranges of -1.15 V to -0.89 V (SCE) and -1.35 V to -0.89 V (SCE) are observed in the samples subjected to air exposure and chemical passivation, respectively. Providing the relative dielectric constant in Eqs. (2) and (3) as 12 [12, 13], the donor and accepter densities can be calculated from the slopes of these linear regions, and the calculated value of ND and NA has an order of 1021 cm-3, which is comparable with the reported values [12, 13]. Compared with the samples exposed to air for 0 h, the samples exposed to air for 1 and 12 h show a decrease in the donor density ND but demonstrated nearly no obvious change in the acceptor density NA. After chemical passivation, however, both donor and acceptor densities are remarkably decreased (Table 1). The relationship between doping density and the measured a* value for the passive films is shown in Fig. 7. The donor density gradually increases with increasing a* value. The acceptor density rapidly increases at the region of a*< 3, but nearly no obvious increment is found when the value of a* is higher than 3. 3.3 XPS results

The XPS spectra obtained in the present study are shown in Fig. 8. The high-resolution spectra of Cr 2p3/2 are shown in Fig. 8(a). The spectra of Cr 2p3/2 for the passive films show a broad distinct peak that can be attributed to the presence of Cr3+ oxides [Cr3+(ox) 576 eV], Cr3+ hydroxides [Cr3+(hyd) 577.3 eV] and Cr6+ oxides [Cr6+(ox) 578.4 eV], with a small shoulder-related Cr metal [Cr(met) 574.1 eV]. The corresponding binding energies, which are in agreement with the literature [12, 19], and the fitting results are shown in Fig. 8(a). The Fe 2p3/2 ionisation shown in Fig. 8(b) reveals the presence of metallic Fe [Fe(met)706.8 eV], Fe2+ oxides [Fe2+(ox) 708.6 eV], Fe3+ oxides [Fe3+(ox) 710.6 eV] and hydroxides [Fe3+(hyd) 711.8 eV]. Fig. 8(c) shows the spectra of O1s fitted by components at binding energies of 530.1 and 531.8 eV, corresponding to oxygen in metallic oxides and to surface-adsorbed oxygen, respectively. Based on the XPS spectra, the relative concentration between the two types of atomic i and j in the analysed surface can be calculated

using the following equation [20]:

0.5 ni Ii j E k j = n j I j i E ki 0.5

(4)

where n is the amount of surface atomics, I is the intensity integrity of the spectra, is the photoionisation cross-section of the corresponding energy level of the related elements and Ek is the kinetics energy of photoelectron. In the present study, the values used for Cr 2p3/2, Fe 2p3/2 and O 1s are 7.69, 10.82 and 2.93, respectively [21]. Table 2 shows the relative concentration of Cr and Fe atoms calculated from the spectra of Cr 2p3/2 and Fe 2p3/2. The existence of distinct chromium and ferric oxide peaks in the samples exposed to air for 0 h suggests that the passive films can grow quickly in the atmosphere. The fact that the ratio of {[Crox]+[Crhyd]}/ {[Crox]+[Crhyd]+[Crmet]} shows no obvious changes during air exposure indicates the very slow growth of Cr-rich oxides in the passive films. The ratio of {[Feox]+ [Fehyd]}/{ [Feox]+ [Fehyd]+[Femet]} is increased from 0.78 to 0.88 after 12 h of air exposure, suggesting the growth of Fe-rich oxides in the passive films. Spontaneously, the ratio of {[Crox]+[Crhyd]}/{[Feox]+ [Fehyd]} is decreased from 0.5 to 0.4 after 12 h of air exposure. This result agrees well with the report of Fujimoto et al. [15], who stated that the ratio of [Cr]/{[Cr]+[Fe]} in passive films is approximately 30% after air exposure. However, the relative content of Cr in oxide and hydroxide layers after chemical passivation is significantly higher than that after air exposure. The concentration of {[Crox]+[Crhyd]} in the passive films is approximately two times that of {[Feox]+ [Fehyd]} after chemical passivation (Table 2). The XPS spectra of the passive films on 304 ASS after chemical passivation were also investigated by Vayer et al. [4] and Seo et al. [5]. Our experimental results are in good agreement with previously obtained results [4, 5]. 4. Discussion 4.1 Interaction mechanism between the test solution and passive films during chromaticity inspection The experimental results show that the quality of the passive films can be characterised by the measured value of chromaticity a*. The chromaticity measurement is dependent on the colouration reaction of phenanthroline with 304 ASS.
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The involved chemical reaction may be formulated as follows:

phen + Fe 2+ [Fe(phen)3 ]2+ (red coloured Ferroin)

(5)

The Fe2+ ions, namely ferrous, and the surface passive film involved in the colouration reaction are important to the inspection measurement. The bilayer structure of the passive films with outer Fe-rich oxides and inner Cr-rich oxides affects the release of ferrous cations involved in the colouration reaction. Fe-rich oxides do not react with phenanthroline solution because the measured a* value is close to 0 with the existence of outer Fe-rich oxides after chemical passivation [Figs. 2(b) and 8]. For the samples exposed to air, the content of outer Fe-rich oxides is increased and the measured a* value is decreased with prolonged exposure time. This finding illustrates that the growth of outer Fe-rich oxides can inhibit the colouration reaction. The reduction and preferential dissolution of Fe-rich oxides possibly affects the measurement. The cyclic voltammetry curves (Fig. 4) indicates that the preferential dissolution of outer Fe-rich oxides occurs during the cathodic polarisation in 3.5% NaCl solution at potentials below -0.7 V (SCE). An increase in a* value at the cathodic potentials below -0.7 V (SCE) (Fig. 3) indicates that the residual ferrous due to the preferential dissolution of outer Fe-rich oxides affects the colouration reaction. Moreover, the maximum a* value at the potentials below -1.2 V (SCE) is attributed to the complete dissolution of outer Fe-rich oxides. Although the residual ferrous that originated from the preferential dissolution possibly increases the value of a*, the rinsing process after polarisation can relieve the influence of the residual ferrous. Consequently, the colouration reaction is dependent on the ferrous in the presence of inner Cr-rich oxides. The value of
a* is decreased to 0 after the rinsing treatment (Fig. 3) of the samples subjected to chemical passivation. This result

indicates that the inner Cr-rich oxides can prevent the colouration reaction. Therefore, the ferrous involved in the colouration reaction possibly comes from the matrix beneath the passive films, and the growth of both outer Fe-rich oxides and inner Cr-rich oxides in the passive films can inhibit the colouration reaction. A comparison between Fig. 3 and Fig. 2(b) shows that the a* values before polarisation are higher than the

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corresponding values after polarisation at potentials above -0.6 V (SCE). At the potential range of -0.4 V (SCE) to -0.6 V (SCE), the measured a* value is approximately 1.6. This result is possibly attributed to the formation of surface oxide during polarisation. According to the cyclic voltammetry curves (Fig. 4), the oxidation peak of Fe is approximately -0.6 V (SCE). This finding may be attributed to the fact that the surface passive films continue to grow because of the oxidation reaction of Fe. The formation of Fe oxides is supposed to be responsible for the decrease in a* when the samples are polarised in 3.5% NaCl solution at potentials above -0.6 V (SCE).
4.2 Growth and structural integrity of the passive films during air exposure and chemical passivation

The structural integrity or the porosity of the passive films may play important roles during the colouration reaction because the parameter a* informs about ferrous entering from the steel matrix through the passive films. Based on the polarisation curves in Fig. 5, the enlargement of the passive range and the increase in Epitting reveal the protective property and stability of the passive films. At the initial period of air exposure, Epitting linearly increases with decreasing a* because of the growth of the passive films. No difference in a* is observed between the samples exposed to air for 36 and 240 h [Fig. 2(b)]. However, the Epitting of the two samples differs by more than 200 mV. This result highlights that the measured a* is more sensitive to the structural integrity of the passive films compared with film thickness and chemical structure because an intact and stable passive film can inhibit the dissolution of Fe from the matrix. The XPS spectra demonstrate that the outer Fe-rich oxides in the passive films grow during air exposure. The decrease in a* during air exposure proves that the structural integrity of the outer Fe-rich oxides is improved. The chromaticity measurement after cathodic reduction is associated with the integrity of the inner Cr-rich oxides when the surface residual ferrous is removed by the rinsing process. The XPS analysis revealed the small amount of inner Cr-rich oxides and the very slow growth of inner oxides in the passive films during air exposure (Fig. 8 and Table 2). The high value of a* after reduction below -0.7 V (SCE) and the following rinsing treatment (Fig. 3) indicates the localised distribution of inner Cr-rich oxides. For the samples subjected to chemical passivation, the measured a* value is close to

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0 [Figs. 2(b) and Fig. 3]. This result suggests the high integrity of both outer Fe-rich and inner Cr-rich oxides in the passive films. Vayer et al. [4] proposed that inner Cr-rich oxides are promoted by chemical passivation and uniformly distributed all over the passive layer. However, they revealed that oxidised iron is concentrated in the outer layer and that oxidised chromium is locally distributed in the inner layer of 304 ASS after air exposure. The difference in structural integrity of the passive films revealed by the chromaticity measurement is in accordance with previous studies [4]. The Mott-Schottky plots showed the p-type and n-type semi-conductivity behaviours in the passive films at different potential regions, as well as the various doping densities after air exposure and chemical passivation. Previous studies [12, 2224] reported that the capacitance response in the p-type and n-type regions are controlled by the inner Cr-rich oxides and outer Fe-rich oxides in passive films, respectively, thereby suggesting the dual semiconducting properties of the films. According to point defect theory [25, 26], doping density is an indicator of non-stoichiometric defects (vacancies or cation interstitials) in the space charge region of passive films. A decrease in doping density indicates a depletion in defects [2227]. Therefore, the evolution of porosity and point defects in the passive films during air exposure and chemical passivation can be revealed by the relationship between a* value and doping density. The fact that the donor density decreases with decreasing a* value during air exposure suggests that both porosity and point defects are decreased and hence more protective. The optimum structural integrity of the passive films can be expected from the minimum doping densities and value of a* after chemical passivation.
5. Conclusion

(1) Based on the chromaticity characterisation of passive films after air exposure and chemical passivation, the redness degree of ferroin produced from the colouration reaction decreases with increasing passive film quality. The value of a*, which represents the redness degree of colour measurement, decreases with prolonged air exposure, and the minimum value of a* is found in the samples subjected to chemical passivation. (2) According to cyclic voltammetry and cathodic polarisation, the colouration reaction during chromaticity

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measurement can be affected by the cathodic potentials. At the potential region above -0.6 V (SCE), the reaction is dependent on the released ferrous from the 304 ASS matrix under the inhibition of both outer Fe-rich oxides and inner Cr-rich oxides in the passive films. At the potential region below -0.7 V (SCE), the preferential dissolution of outer Fe-rich oxides can also affect the reaction, and inner Cr-rich oxides in the passive films are critical for the measurement. (3) Based on the electrochemical behaviour and XPS spectra, the corrosion resistance increases with decreasing a* value, and the donor density decreases because of the growth of outer Fe-rich oxides in the passive films during air exposure. The best corrosion resistance of the samples after chemical passivation and the rapid increase in acceptor density at the region of a*< 2 may be attributed to the high ratio of Cr/Fe in oxides and the high structural integrity of the passive films.

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Acknowledgements

This work is supported by National Basic Research Program of China (2009CB724305) and National Nature Science Foundation of China (51101024).

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oxides on AISI 304 stainless steel, Corros. Sci. 53 (2011) 2688-2699. [12] Z. Feng, X. Cheng, C. Dong, L. Xu, X. Li, Passivity of 316L stainless steel in borate buffer solution studied by Mott-Schottky nalysis, atomic absorption spectrometry and X-ray photoelectron spectroscopy, Corros. Sci. 52 (2010) 3646-3653. [13] H. Sun, X.Q. Wu, E.H. Han, Influences of temperature on the oxide film properties of 304 stainless steel in high temperature lithium borate buffer solution, Corros. Sci. 51(2009)2840-2847. [14] T.S. Lee, I.M. Kolthoff, D.L. Leussing, Reaction of Ferrous and Ferric Iron with 1,10-Phenanthroline. I. Dissociation Constants of Ferrous and Ferric Phenanthroline, J. Am. Chem. Soc., 70(1948) 2348-2352. [15] R. Jung, H. Tsuchiya, S. Fujimoto, XPS characterization of passive films formed on Type 304 stainless steel in humid atmosphere, Corros. Sci. 58 (2012) 62-68. [16] M. L. Gietl, H.W. Schmidt, R. Giesa, A. Terrenoire, R. Balkb, Semiquantitative method for the evaluation of grease barrier coatings, Prog. Org. Coat. 66 (2009) 107-112. [17] N.L. Bozec, C. Compere, M. LHer, A. Laouenan, D. Costa, P. Marcus, Influence of stainless steel surface treatment on the oxygen reduction reaction in seawater, Corros. Sci. 43(2001) 765-786. [18] I. Nici, D.D. Macdonald, The passivity of type 316L stainless steel in borate buffer solution, J. Nucl. Mater. 379(2008)54-58. [19] D. Mandrino, C. Donik, Chemical-state information obtained by AES and XPS from thin oxide layers on duplex stainless steel surfaces, Vacuum 86 (2011) 18-22. [20] Y. Boudevilie, F. Figueras, M. Forissier, J. Portefaix, J. C Vedrine, Correlations between X-ray photoelectron spectroscopy data and catalytic properties in selective oxidation on Sb Sn O catalysts, J. Catal., 58 (1979) 52-60. [21] Scofield J. H., Hartree-slater subshell photoionization cross-sections at 1254 and 1487 eV, J. Elec. Spec., 8 (1976) 129-137.

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[22] S. Ningshena, U. Kamachi Mudalia, V.K. Mittalb, H.S. Khatak, Semiconducting and passive film properties of nitrogen-containing type 316LN stainless steels, Corros. Sci. 49(2007) 481-496. [23] K. Azumi, T. Ohtsuka, N. Sato, Mott-Schottky plot of the passive film formed on iron in neutral borate and phosphate solutions, J. Electrochem. Soc. 134 (1987) 1352-1357. [24] L. Hamadou, A. Kadri, N. Benbrahim, J-P. Petit, Characterization of thin anodically grown oxide films on AISI 304L stainless steel, J. Electrochem. Soc. 154 (1987) G291-G297. [25] M. Kamrunnahar, J. Bao, D.D. Macdonald, Challenges in the theory of electron transfer at passive interfaces, Corros. Sci. 47(2005) 3111-3139. [26] A. Fattah-alhosseini, F. Soltani, F. Shirsalimi, B. Ezadi, N. Attarzadeh, The semiconducting properties of passive films formed on AISI 316L and AISI 321 stainless steel: A test of the point defect model (PDM), Corros. Sci. 53(2011) 3186-3192. [27] C.A. Della Rovere, J.H. Alano, R.Silva, P.A.P. Nascente, J.Otubo, S.E. Kuri, Characterization of passive films on shape memory stainless steels. Corros. Sci. 57(2012) 154-161.

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Figure captions

Fig.1 Optical photograph during colouration reaction of phenanthroline solution with 304 ASS samples after air exposure and chemical passivation in HNO3 solution: (a) before colouration reaction, (b) after colouration reaction for 3 s, (c) after colouration reaction for 180 s. Fig. 2 Colour measurement after colouration reaction of phenanthroline solution with 304 ASS samples after air exposure and chemical passivation in HNO3 solution: (a) value of a* measured at different colouration reaction time, (b) value of
a* after colouration reaction for 180 s.

Fig. 3 Chromaticity measurements under various cathodic reduction conditions for 304 ASS after air exposure for 48 hr (Sair-48 hr) and that after chemical passivation in HNO3 solution (Scp). Fig. 4 Cyclic voltammetry curves for 304 ASS in 3.5 % NaCl solution at a sweep rate of 50 mV/s after various passivation treatment: (a) after air exposure for 48 hr and the sequence of cycles at the selected area of peak I (top insert), (b) after chemical passivation in HNO3 solution. Fig. 5 (a) Potentiodynamic polarisation curves in 3.5 % NaCl solution for 304 ASS after air exposure and chemical passivation in HNO3 solution, (b) relationship between the value of a* in Fig. 2(b) and the Epitting calculated from Fig. 3(a). Fig. 6 Mott-Schottky plots of passive film in 3.5 wt. % NaCl solution for 304 ASS after air exposure and chemical passivation in HNO3 solution. Fig. 7 Relationship between values of measured a* and the calculated doping densities in Tab. 1 Fig. 8 XPS spectra Cr 2p3/2, Fe 2p3/2, and O 1s detected for passive films on 304 ASS after air exposure and chemical passivation in HNO3 solution: (a) Cr 2p3/2, (b) Fe 2p3/2, (c) O 1s.

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Tab. 1 Calculated doping densities in passive films on 304 ASS after air exposure and chemical passivation in HNO3 solution. Tab. 2 Relative atomic concentration calculated from XPS spectra for 304 ASS after air exposure and chemical passivation in HNO3 solution.

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Tab. 1

Air exposure Chemical passivation 0 hr ND (1021 cm-3) NA (1021 cm-3) 3.56 4.37 1 hr 2.68 4.51 12 hr 1.75 4.29 1.7 1.9

21

Tab. 2

Air exposure Relative atomic concentration 0 hr {[Crox]+[Crhyd]}/ {[Crox]+[Crhyd]+[Crmet]} 0.81 1 hr 0.83 12 hr 0.85

Chemical passivation 0.92

{[Feox]+ [Fehyd]}/{ [Feox]+ [Fehyd]+[Femet]}

0.78

0.77

0.88

0.71

{[Crox]+[Crhyd]}/ {[Feox]+ [Fehyd]}

0.5

0.6

0.4

1.86

[O2-]/ [OH-]

0.5

0.4

0.4

0.7

22

Fig. 1

23

Fig. 2

24

Fig. 3

25

Fig. 4

26

Fig. 5

27

Fig. 6

28

Fig. 7

29

Fig. 8

Fig. 8 (a)

30

Fig. 8(b)

31

Fig. 8(c)

32

 A passive film inspection composed of colouration reaction and colour measurement. This inspection is of good capability to evaluate the quality of passive films. The measured value consists well with electrochemical behaviour of passive films. The measurement is dependent on the barrier of passive film on colouration reaction. Reducing dissolution of Fe-rich oxides in passive film affects the measurement too.

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