• 한국전기화학회:학술대회논문집
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• 한국전기화학회 2005년도 춘계총회 및 학술발표회
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• pp.42-42
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• 2005

• Corrosion Science and Technology
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• 제5권4호
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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.

• Journal of Electrochemical Science and Technology
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• 제7권1호
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• pp.58-67
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• 2016

The corrosion behavior of duplex stainless steel AISI 2205 was investigated in ethylene glycol-water mixture in the presence of 50 W/V % LiBr at different concentrations and different temperatures. Cyclic polarization, impedance measurements and Mott-Schottky analysis were used to study the corrosion behavior the semi conductive properties of the passive films. The results showed that with increasing in the ethylene glycol concentration to 10 V/V%, the corrosion rate of the steel alloy substrate increased. In higher concentrations of ethylene glycol, corrosion current of steel decreased. The results of scanning electron microscopy of electrode surface confirmed the electrochemical tests. Electrochemical experiment showed that duplex steel was stable for pitting corrosion in this environment. The increase in the ethylene glycol concentration led to increasing the susceptibility to pitting corrosion. The corrosion current increased as the temperature rise and also pitting potentials and repassivation potentials shifted towards the less positive values as the temperature increased. According to Mott-Schottky analysis, passive films of stainless steel at the different temperatures showed both n-type and p-type semiconductor behavior in different potential.

• Corrosion Science and Technology
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• 제2권1호
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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.

• 전기화학회지
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• 제12권3호
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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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• 제2권5호
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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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• 제7권1호
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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.

• Corrosion Science and Technology
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• 제2권4호
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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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• 제12권4호
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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.

• 한국세라믹학회지
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• 제55권3호
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• pp.244-260
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• 2018

Issues in the electrical characterization of semiconducting photoanodes in a photoelectrochemical (PEC) cell, such as the cell geometry dependence, scan rate dependence in DC measurements, and the frequency dependence in AC measurements, are addressed, using the example of a $TiO_2$ photoanode. Contrary to conventional constant phase element (CPE) modeling, the capacitive behavior associated with Mott-Schottky (MS) response was successfully modeled by a Havriliak-Negami (HN) capacitance function-which allowed the determination of frequency-independent Schottky capacitance parameters to be explained by a trapping mechanism. Additional polarization can be successfully described by the parallel connection of a Bisquert transmission line (TL) model for the diffusion-recombination process in the nanostructured $TiO_2$ electrode. Instead of shunt CPEs generally employed for the non-ideal TL feature, TL models with ideal shunt capacitors can describe the experimental data in the presence of an infinite-length Warburg element as internal interfacial impedance - a characteristic suggested to be a generic feature of many electrochemical cells. Fully parametrized impedance spectra finally allow in-depth physicochemical interpretations.