A Photocurrent Spectroscopic Investigation of Passive Films on Ferritic Stainless Steels

Sunseri, C.; Piazza, S.; Paola, A. Di; Quarto, F. Di

doi:10.1149/1.2100213

Cited by 69 publications

(33 citation statements)

References 43 publications

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“…in a potential range in which chromium keeps its usual Cr +3 oxidation state. Actually, such an expectation has been confirmed in the literature by several investigators, 8,[49][50][51][52][53][54][55][56][57][58][59][60] who characterized passive films grown on ironchromium alloys or both ferritic and austenitic stainless steel (SS) by using PCS. We have to mention that in the case of SS other ex-situ analytical techniques (such as: XPS, EXAFS etc.)…”

Section: Critical Issues In the Fieldmentioning

confidence: 90%

“…This value is typically measured for passive films grown on pure iron, 69 but it was also measured in the case of films grown on ferritic SS exposed to a chloride containing solution at high potential. 50 Under these severe conditions, it is likely that localized corrosion processes occur producing an excess of Fe 3+ ions in solution with consequent precipitation on the SS surface of iron(III) oxide or oxy-hydroxide. According to the literature 70 several iron oxides and oxy-hydroxides polymorphs have such a bandgap value.…”

Section: Critical Issues In the Fieldmentioning

confidence: 99%

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Critical Review—Photocurrent Spectroscopy in Corrosion and Passivity Studies: A Critical Assessment of the Use of Band Gap Value to Estimate the Oxide Film Composition

Quarto

Zaffora

Franco

et al. 2017

J. Electrochem. Soc.

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A critical assessment of the Photocurrent Spectroscopy (PCS) Technique for the semi-quantitative characterization of passive film and corrosion layers composition is carried out. We take into account more than three decades of PCS usage as "in-situ" analytical technique and related results as well as the criticism of the underlying semi-empirical correlation relating the measured optical bandgap (E g ) to the passive film composition. The discrepancies between the experimental data, gathered by PCS measurements, and E g estimates originating from recently developed Density Functional Theory based modeling of solid state properties are stressed with particular emphasis on the case of anodic passive film grown on technologically important alloys (Fe-Cr and stainless steels). The extension of this correlation to mixed oxides and its use for relating the oxide composition to the bandgap values is critically reviewed by comparing the predicted E g of mixed oxides with the experimental values. Suggestions on how to account for different bandgap values of oxide polymorphs and how to correlate the E g values to the composition of mixed s,p-d-metal oxides are presented and discussed on the basis of experimental results reported in the literature. On the basis of this assessment, the ability of PCS in providing quantitative information on the composition of passive film and corrosion layer is generally confirmed. Fujimoto (fujimoto@mat.eng.osaka-u.ac.jp) and HeeJin Jang (heejin@chosun.ac.kr). . This paper is a Critical Review in Electrochemical and Solid State Science and Technology (CRES 3 T). This article was reviewed by ShinjiPhotocurrent Spectroscopy (PCS) is currently employed for the characterization of solid-state properties of semiconducting and insulating materials, since the knowledge of their bandgap is a prerequisite to any possible application in different fields such as solar energy conversion (photoelectrochemical and photovoltaic solar cells, photocatalysis) and microelectronics (high-k, high band-gap materials). 1,2In the last 20-30 years an increasing number of electrochemists working in the field of corrosion have been attracted by this technique owing to its versatility and ability to scrutinize "in-situ" corrosion layers and passive films having semiconducting or insulating behavior. In previous as well as in very recent works 3-7 we have shown that PCS is able to provide detailed information on characteristic energy levels of passive film/electrolyte junctions (flatband potential: U FB ; internal photoemission threshold: E th ; bandgap value: E g ). Such information is necessary for a deeper understanding of the possible mechanisms of charge transfer (electrons and ions) at the metal/corrosion layer/electrolyte interface. Further advantages stem from the fact that the PCS technique does not require particular surface finishing control, it can be used both on large areas as well as in microscopic regions of the electrode, and can reach high sensitivity by using a lock-in amplifier coupled to a mec...

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Section: Critical Issues In the Fieldmentioning

confidence: 90%

Section: Critical Issues In the Fieldmentioning

confidence: 99%

Critical Review—Photocurrent Spectroscopy in Corrosion and Passivity Studies: A Critical Assessment of the Use of Band Gap Value to Estimate the Oxide Film Composition

Quarto

Zaffora

Franco

et al. 2017

J. Electrochem. Soc.

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“…By the way, different photoelectrochemical data on such systems are reported in the literature and the interested reader can access to the published works. 104,[160][161][162][163][164][165][166][172][173][174][175][176][177][178][179][180][181][182][183] Owing to space limitations we will discuss shortly and qualitatively some selected PCS data pertaining to such systems, which can be compared in some extent to more recent quantitative analysis based on in situ and ex situ techniques (XANES, XPS, EQCM). [184][185][186][187] The formation of Cr(OH) 3 on passive Cr at low potentials (U E ≤ -0,6V(MSE)) and in a wide range of pH (0 < pH < 9) has been suggested on the basis of the measured optical band gap value (E g = 2.45 ± 0.1 eV, see Refs.…”

Section: (V) Pcs Analysis Of Passive Films and Corrosion Layers On Bamentioning

confidence: 99%

“…On the other hand E g values around 2.60 eV were measured, at higher electrode potentials (U E = 0.6V(SCE)), for passive films formed on analogous ferritic SS containing small amount (< 4% in weight) of Mo and Ni. 172 Due to the large range of E g values collected in the literature for passive films on Fe-Cr alloys, the loss of sensitivity of PCS for photon energies near the band gap of passive films does not seems a satisfactory explanation. The data on passive films composition obtained by in situ and ex situ analytical techniques reported in Refs.…”

mentioning

confidence: 99%

Physicochemical Characterization of Passive Films and Corrosion Layers by Differential Admittance and Photocurrent Spectroscopy

Quarto

Mantia

Santamaria

2009

Modern Aspects of Electrochemistry

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“…The passive films formed on stainless steels and Nibased alloys reveal a semiconductive behaviour [1][2][3][4][5][6] and therefore, the electronic properties should play an important role in the corrosion resistance. Under certain conditions, the electronic structure of these films can be more accurately described as a bi-layer composed of a ntype outer region containing iron oxide and hydroxide and a p-type inner region containing chromium oxide.…”

Section: Introductionmentioning

confidence: 99%

Semiconducting properties of oxide and passive films formed on AISI 304 stainless steel and Alloy 600

Ferreira¹,

Belo²,

Hakiki³

et al. 2002

J. Braz. Chem. Soc.

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Estudaram-se as propriedades semicondutoras de filmes passivos formados em aço inoxidável AISI 304 e em ligas de base Ni (Alloy 600) em soluções tampão de borato. Os filmes foram estudados por medidas de capacidade (Mott-Schottky ) e de fotocorrente. Estudaram-se também filmes formados em aço inoxidável AISI 304 por oxidação ao ar, à temperatura de 350ºC. Os resultados mostram que a estrutura electrónica dos filmes é comparável à de uma heterojunção do tipo p-n, onde as cargas de espaço desenvolvidas nas interfaces filme -metal e filme -electrólito devem ser consideradas. O estudo electroquímico está de acordo com os resultados analíticos que demonstram que os filmes de óxido são, em todos os casos, compostos por uma região interna rica em óxido de crómio e por uma região externa rica em óxido de ferro.The semiconducting properties of passive films formed on AISI 304 stainless steel and Alloy 600 in borate buffer solution were studied by capacitance (Mott-Schottky approach) and photocurrent measurements. Oxide films formed on 304 stainless steel in air at 350 ºC have also been studied. The results obtained show that, in all cases the electronic structure of the films is comparable to that of a pn heterojunction in which the space charges developed at the metal-film and film-electrolyte interfaces have also to be considered. This is in accordance with analytical results showing that the oxide films are in all cases composed of an inner region rich in chromium oxide and an outer region rich in iron oxide.

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A Photocurrent Spectroscopic Investigation of Passive Films on Ferritic Stainless Steels

Cited by 69 publications

References 43 publications

Critical Review—Photocurrent Spectroscopy in Corrosion and Passivity Studies: A Critical Assessment of the Use of Band Gap Value to Estimate the Oxide Film Composition

Critical Review—Photocurrent Spectroscopy in Corrosion and Passivity Studies: A Critical Assessment of the Use of Band Gap Value to Estimate the Oxide Film Composition

Physicochemical Characterization of Passive Films and Corrosion Layers by Differential Admittance and Photocurrent Spectroscopy

Semiconducting properties of oxide and passive films formed on AISI 304 stainless steel and Alloy 600

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