• Korean Journal of Materials Research
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• v.32 no.4
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• pp.230-236
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• 2022

The formation behavior of a passive state film on the surface of STS304 in electrolytic solution was analyzed to determine its metallic ion composition. The properties of passive state films vary depending on the Fe and Cr ions in the electrolytic solution. It was observed that the passive state film surface became flat and glossy as the concentration of Fe and Cr ions in the electrolytic solution increased. The corrosion resistance property of the passive state film was proportional to the amount of Fe and Cr in the electrolytic solution. An initial passive state film with high Fe concentration was formed on the surface of STS304 during early electrolytic polishing. Osmotic pressure of Fe ions occurs between the passive state film and electrolytic solution due to the Fe ion concentration gradient. The Fe in the passive state film is dissolved into the electrolyte, and Cr fills up the Fe ion vacancies. As a result, a good corrosion-resistant floating film was formed. The more Fe ions in the electrolytic solution, the faster the film is formed, and as a result, a flat passive state film containing a large amount of Cr can be formed.

• Corrosion Science and Technology
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• v.2 no.4
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• pp.171-177
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• 2003

The electronic properties of the passive film formed on Fe-20Cr ferritic stainless steel in pH 8.5 buffer solution containing 0.05 M EDTA (ethylene diammine tetraacetic acid) were examined by the photocurrent measurements and Mott-Schottky analysis for the film. XPS depth profile for the film demonstrated that Cr content in the outermost layer of the passive film was higher in the solution with EDTA than that in the solution without EDTA, due to selective dissolution of Fe by EDTA. In the solution with EDTA, the passive film showed characteristics of an amorphous or highly disordered n-type semiconductor. The band gap energies of the passive film are estimated to be ~ 3.0 eV, irrespective of film formation potential from 0 to 700 $mV_SCE$ and of presence of EDTA. However, the donor density of the passive film formed in the solution with EDTA is much higher than that formed in the solution without EDTA, due to an increase in oxygen vacancy resulted from the dissolution of Fe-oxide in the outermost layer of the passive film. These results support the proposed model that the passive film formed on Fe-20Cr in pH 8.5 buffer solution mainly consists of Cr-substituted $\gamma$-$Fe_2O_3$.

• Corrosion Science and Technology
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• v.2 no.5
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• pp.212-218
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• 2003

Electronic properties of passive films formed on Ti at film formation potentials $(E_f)V_{SCE}$ in pH 8.5 buffer solution and in an artificial seawater were examined through the photocurrent measurement and Mott-Schottky analysis. The passive films formed on Ti in pH 8.5 buffer solution exhibited a n-type semiconductor with a band gap energys $(E_g);E_g^{n=2}=3.4$ eV for nondirect electron transition, and $E_g^{n=0.5}=3.7$ eV for direct electron transition. These band gap values were almost same as those for the passive films formed in artificial seawater, indicating that chloride ion ($Cl^-$ in solution did not affect the electronic structure of the passive film on Ti. $E_g$ for passive films formed on Ti were found to be greater than those ($E_g^{n=0.5}=3.1$ eV, $E_g^{n=2}=3.4$) for a thermal oxide film formed on Ti in air at $400^{\circ}C$. The disorder energy of passive film, determined from the absorption tail of photocurrent spectrum, was much greater than that for the thermal oxide film farmed on Ti in air at $400^{\circ}C$. The greater $E_g$ and the higher disorder energy for the passive film compared with those for the thermal oxide fIlm suggest that the passive film on Ti exhibited more disorded structure than the thermal oxide film. The donor density (about $2.4{\times}10^{20}cm^{-3}$) for the passive film formed in artificial seawater was greater than that (about $20{\times}10^{20}cm^{-3}$) formed in pH 8.5 buffer solution, indicating that $Cl^-$ increased the donor density for the passive film on Ti.

• Corrosion Science and Technology
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• v.5 no.4
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• pp.141-148
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• 2006

The chemical composition and the semiconducting properties of the passive films formed on Alloy 690 in various film formation conditions were investigated by XPS, photocurrent measurement, and Mott-Schottky analysis. The XPS and photocurrent spectra showed that the passive films formed on Alloy 690 in pH 8.5 buffer solution at ambient temperature, in air at $400^{\circ}C$, and in PWR condition comprise $Cr_2O_3$, $Cr(OH)_3$, ${\gamma}-Fe_2O_3$, NiO, and $Ni(OH)_2$. The thermally grown oxide in air and the passive film formed at high potential (0.3 $V_{SCE}$) in pH 8.5 buffer solution were highly Cr-enriched, whereas the films formed in PWR condition and that formed at low potential (-0.3 $V_{SCE}$) in pH 8.5 buffer solution showed relatively high Ni content and low Cr content. The Mott-Schottky plots exhibited n-type semiconductivity, inferring that the semiconducting properties of the passive films formed on Alloy 690 in various film formation conditions are dominated by Cr-substituted ${\gamma}-Fe_2O_3$. The donor density, i.e., concentration of oxygen vacancy, was measured to be $1.2{\times}10^{21}{\sim}4.6{\times}10^{21}cm^{-3}$ and lowered with increase in the Cr content in the passive film.

• Corrosion Science and Technology
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• v.6 no.6
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• pp.311-315
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• 2007

The anodic polarization behavior of equiatomic TiNi shape memory alloy with pure titanium as a reference material was investigated by means of open circuit potential measurement and potentiodynamic polarization technique. And the structure of passive films on TiNi intermetallic compounds was also conducted using AES and ESCA. While the dissolved Ni(II) ion did not affect the dissolution rate and passivation of TiNi alloy, the dissolved Ti(III) ion was oxidated to Ti(IV) ion on passivated TiNi surface at passivation potential. It has also been found that the Ti(IV) ion increases the steady state potential, and passivates TiNi alloy at a limited concentration of Ti(IV) ion. The analysis by AES showed that passive film of TiNi alloy was composed of titanium oxide and nickel oxide, and the content of titanium was three times higher than that of nickel in outer side of passive film. According to the ESCA analysis, the passive film was composed of $TiO_2$ and NiO. It seems reasonable to suppose that NiO could act as unstabilizer to the oxide film and could be dissolved preferentially. Therefore, nickel oxide contained in the passive film may promote the dissolution of the film, and it could be explained the reason of higher pitting susceptibility of TiNi alloy than pure Ti.

• Corrosion Science and Technology
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• v.9 no.1
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• pp.20-28
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• 2010

According to the bipolar model, ion selectivity of some species in the passive film is important factor to control the passivation. An increase of cation selectivity of outer layer of the passive film can stabilize the film and improves the corrosion resistance. Therefore, the formation and roles of ionic species in the passive film should be elucidated. In this work, two types of solution (hydrochloric or sulfuric acid) were used to test high N and Mo-bearing stainless steels. The objective of this work was to investigate the formation of oxyanions in the passive film and the roles of oxyanions in passivation of stainless steel. Nitrogen exists as atomic nitrogen, nitric oxide, nitro-oxyanions (${NO_x}^-$), and N-H species, not nitride in the passive film. Because of its high mobility, the enriched atomic nitrogen can act as a reservoir. The formation of N-H species buffers the film pH and facilitates the formation of oxyanions in the film. ${NO_x}^-$ species improve the cation selectivity of the film, increasing the oxide content and film density. ${NO_x}^-$ acts similar to a strong inhibitor both in the passive film and at active sites. This facilitates the formation of chromium oxide. Also, ${NO_x}^-$ can make more molybdate and nitric oxide by reacting with Mo. The role of Mo addition on the passivation characteristics of stainless steel may differ with the test environment. Mo exists as metallic molybdenum, molybdenum oxide, and molybdate and the latter facilitates the oxide formation. When nitrogen and molybdenum coexist in stainless steel, corrosion resistance in chloride solutions is drastically increased. This synergistic effect of N and Mo in a chloride solution is mainly due to the formation of nitro-oxyanions and molybdate ion. Oxyanions can be formed by a 'solid state reaction' in the passive film, resulting in the formation of more molybdate and nitric oxide. These oxyanions improve the cation selectivity of the outer layer and form more oxide and increase the amount of chromium oxide and the ratio of $Cr_2O_3/Cr(OH)_3$ and make the film stable and dense.

• Corrosion Science and Technology
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• v.12 no.4
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• pp.163-170
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• 2013

In NaCl solutions acidified with $H_2SO_4$, Fe20Cr1.1N alloy showed enhanced pitting corrosion resistance than Fe20Cr alloy. An XPS analysis revealed that the passive film of Fe20Cr1.1N alloy contained higher cationfraction of Cr than that of Fe20Cr alloy, and nitrogen was incorporated into the film. In addition, it was found that the passive film of Fe20Cr1.1N alloy was thinner and had higher oxygen vacancy density than that of Fe20Cr alloy. Based on these observations, it was concluded that the chemical composition was the determining factor for the protectiveness of the passive film of Fe20Cr based alloy in dilute $H_2SO_4$ solution.

• Journal of the Korean Electrochemical Society
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• v.12 no.3
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• pp.258-262
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• 2009

The composition and semiconducting properties of the passive films formed on Ni- (15, 30)Cr-5Mo alloys in pH 8.5 buffer solution were examined. The depth concentration profile of passive films formed on Ni-(15, 30)Cr-5Mo in pH 8.5 buffer solution showed that Mo enhances the enrichment of Cr. The Mott-Schottky plot for the passive film on Ni-(15, 30)Cr- 5Mo closely resembled that for the film on Cr, whereas those for the less Cr-enriched film on Mo-free alloys showed similar behavior to that for the film on Ni. The acceptor density was reduced by increasing Cr content in Ni-(15, 30)Cr-(0, 5)Mo alloys, but addition of Mo considerably increased the acceptor density.

• Corrosion Science and Technology
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• v.2 no.1
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• pp.12-17
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• 2003

The effects of Cr content and film formation potential on electronic behaviors of the passive film on Fe-Cr alloys were investigated in borate buffer solution. Influence of pH on passive films of both Fe-Cr and Fe-Cr-Mo alloys was also investigated. Mott-Schottky and cyclic voltammetry techniques were used to elucidate electronic behaviors of passive films and their electrochemical characteristics. AES analysis of passive films was carried out. Results showed that doping density decreased as Cr content and film formation potentials increased. The addition of Mo to Fe-Cr alloy had little influence on donor densities in pH 9.2 solution but some effects on the decrease in donor densities in pH 1.6 acidic solution.

• Corrosion Science and Technology
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• v.7 no.1
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• pp.40-44
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• 2008

Passive metal forms an interfacial diffuse layer on the surface of passive film by its reaction with $H^+$ or $OH^-$ ions in solution depending on solution pH. There is a critical pH, called pH point of iso-selectivity ($pH_{pis}$) at which the nature of the diffuse layer is changed from the anion-permeable at pH<$pH_{pis}$ to the cation-permeable at pH>$pH_{pis}$. The $pH_{pis}$ for a passivated Fe was determined by examining the effects of pH on the thickness of passive film and on the dissolution reaction occurring on the passive film under a gavanostatic reduction in borate-phosphate buffer solutions at various pH of 7~11. The steady-state thickness of passive film formed on Fe showed the maximum at pH 8.5~9, and further the nature of film dissolution reaction was changed from a reaction producing $Fe^{3+}$ ion at $pH\leq8.5$ to that producing $FeO_2{^-}$ at $pH\geq9$, suggesting that the $pH_{pis}$ of Fe is about pH 8.5~9. In addition, the passive film formed at pH 8.5~9, $pH_{pis}$, was found to be the most protective with the lowest defect density as confirmed by the Mott-Schottky analysis. Pitting potential was decreased with increasing $Cl^-$ concentration at $pH\leq8.5$ due probably to the formation of anion permeable diffuse layer, but it was almost constant at $pH\geq9$ irrespective of $Cl^-$ concentration due primarily to the formation of cation permeable diffuse layer on the film, confirming again that $pH_{pis}$ of Fe is 8.5~9.