Chemical state quantification of iron and chromium oxides using XPS: the effect of the background subtraction method

Aronniemi, Mikko; Sainio, Jani; Lahtinen, Jouko

doi:10.1016/j.susc.2005.01.019

Cited by 275 publications

(159 citation statements)

References 31 publications

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“…. These values are of the order reported in the literature [5,25,27,28,30]. Spinorbit splitting between the Cr 2p 3/2 and Cr 2p 1/2 peaks are 9.4 eV, 9.5 eV, 9.6 eV and 9.0 eV for Cr 0 , Cr 3+ (CrN), Cr 3+ (Cr 2 O 3 ) and Cr shake-up satellite peaks, respectively.…”

Section: Methodssupporting

confidence: 72%

New insight on early oxidation stages of austenitic stainless steel from in situ XPS analysis on single-crystalline Fe–18Cr–13Ni

Wiame

Maurice

et al. 2018

Corrosion Science

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In situ X-ray photoelectron spectroscopy real-time measurements and angular-dependent high resolution core level analysis were used for the first time to investigate the Cr enrichment and oxide growth mechanisms on a model 304 austenitic stainless steel surface in the very initial stages of oxidation leading to pre-passivation. The oxidation kinetics was followed for increasing oxygen exposure and temperature, revealing an early nucleation regime (for exposure < 10 L) leading to the formation of a strongly Cr-enriched Cr 3+ /Fe 3+ mixed layer followed by an oxide growth regime where preferential iron oxidation takes over and mitigate the initial chromium enrichment.

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Section: Methodssupporting

confidence: 72%

New insight on early oxidation stages of austenitic stainless steel from in situ XPS analysis on single-crystalline Fe–18Cr–13Ni

Wiame

Maurice

et al. 2018

Corrosion Science

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“…25 Values for Fe 2p binding energy in both α-Fe 2 O 3 and α-FeO(OH) range from 710.4 to 711.5 eV, presumably due to the effect of the background subtraction methods and the choice of the line-shapes used for spectra analysis, as well as the effects stated above. 26,27 Both spectra (Fig. 9) display the presence of relatively broad shake-up satellite peaks, which represent a well known characteristic of oxide spectra, occurring at the high binding energy side of both of the Fe 2p peaks, indicating again the presence of Fe 3+ species in these samples.…”

Section: Synthesis Of Nanowires and Nanosheetsmentioning

confidence: 81%

Laser-induced self-assembly of iron oxide nanostructures with controllable dimensionality

Henley

Mollah

Giusca

et al. 2009

Journal of Applied Physics

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The nanosecond pulsed laser ablation of a fine iron powder submerged under different liquid media (water, methanol, ethanol and isopropanol) is used to rapidly produce a variety of iron oxide nanostructures from nanoparticles to nanowires and nanosheets. The dimensionality of the nanostructres is shown to be a consequence of two controllable mechanisms. The rapid oxidation, collisional quenching and coalescence of the ablation products is suggested as the dominant mechanism for the formation of 0D nanostructures such as hematite (α-Fe 2 O 3 ) nanoparticles in water, or iron oxyhydroxide nanoparticles under alcohols. By employing different laser wavelengths (248 and 532nm) it is demonstrated that the growth of extended iron oxyhydroxide nanostructures (1D nanowires and 2D nanosheets) under methanol is possible and is a consequence of a second self-assembly mechanism driven by interaction between the UV laser pulses and the ablation products.Low dimensional iron oxide nanostructures, such as nanoparticles and nanowires are of particular industrial and academic interest, not least because of their magnetic properties. Hematite (α-Fe 2 O 3 ) 1D nanostructures also have applications in lithium ion battery electrodes, gas sensors, field-effect transistors, and field emission cathodes. 1-3 Hematite nanowires have been synthesized by many different techniques including surface oxidation, thermal oxidation and electrochemical deposition. [4][5][6][7] These are generally complex processes taking considerable time (1.5-120 h), needing different gas flows and high temperatures (400-800 • C). Also, these processes typically produce nanowires that are attached to a metallic substrate, and thus subsequent collection for device integration can be challenging. Therefore, a solution based synthesis method to collect nanowires for * Electronic mail: s.henley@surrey.ac.uk † Present address: Department of Physics, Aligarh Muslim University, Aligarh-202002, India.1 rapid processing would be of considerable interest. Table 1 shows a comparison of time scales and process temperatures used in selected recent publications detailing iron oxide nanowire synthesis.Rapidly after the invention of the ruby laser in the 1960s, the capability of pulsed lasers to ablate material from the surface of solids was identified. Applications for pulsed laser ablation 8 (PLA) in materials processing and thin film deposition followed swiftly. Traditionally PLA and the subsequent material deposition is performed in vacuum or in dilute gaseous environments. The collisions of energetic ablated atoms with gas molecules in low-pressure gaseous environment, and any subsequent chemical reactions, has been identified a route for synthesizing multicomponent films with controllable stoichiometry. When the ambient gas pressure is increased, such that ablated species are expected to suffer multiple collisions within the reaction chamber, 9,10 the medium can be considered as weakly confining. In such confining environments nanoclusters of the target material ca...

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“…The interpretation of the Cr2p spectrum is difficult because the binding energies of Cr(VI) and oxyfluoride of Cr(III) are very close. 12,[40][41][42][43][44][45][46] A low signal intensity at a binding energy of 579.8 eV can be observed so the presence of hexavalent chromium in the craters cannot be ruled out. It is possible to calculate the maximum quantity of Cr(VI) present at different depths of the layer (in each crater), and therefore calculate the maximum quantity of Cr(VI), which could be present in the TCP layer after PACS post-treatment.…”

Section: 33mentioning

confidence: 99%

Role of Post-Treatment in Improved Corrosion Behavior of Trivalent Chromium Protection (TCP) Coating Deposited on Aluminum Alloy 2024-T3

Ely

Światowska

Seyeux

et al. 2017

J. Electrochem. Soc.

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The effects of post-treatment applied on Trivalent Chromium Protection (TCP) coatings deposited on aluminum alloy 2024-T3 was studied by electrochemical and surface analytical techniques: X-ray Photoelectron Spectroscopy (XPS) and Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS). The aim of the post-treatment was to improve the corrosion resistance of the TCP coating. To understand the influence of the post-treatment, using a bath containing H 2 O 2 and a lanthanum salt as an inhibitor, our approach was to study the effect of these two components separately. It was found that the improved corrosion protection provided by the post-treated TCP was related to a synergetic effect of the two components. XPS and ToF-SIMS analyses showed that (i) the thickness of the TCP coating is not modified by the post-treatment, (ii) lanthanum is present on the surface and in the bulk of the TCP and (iii) is found in very small amount only on the extreme surface. The total concentration of Cr(VI) (oxide/hydroxide) was estimated to be below 0.1 wt% in the post-treated TCP layer. It was concluded that lanthanum plays a significant role in improving the coating density and homogeneity and has a beneficial effect on the TCP coating cracking as observed by Scanning Electron Aluminum alloys are used for aerospace applications for their low weight and good mechanical properties.1-3 To improve the corrosion properties of aluminum alloys and to provide good paint adhesion, the first layer of coating applied on the aluminum alloy surface used to be a chromate conversion coating (CCC).4-6 However, hexavalent chromium used in the CCC coatings is highly toxic, 4,7 its use is very much restricted in Europe 8 and the United States 9 and will be forbidden by 2024 by the European Community with respect to the Registration, Evaluation, Authorization and Restriction of Chemicals (REACh).8 Therefore, new conversion coatings have been developed, and one of the most promising solutions is the Trivalent Chromium Protection coating called also as the Trivalent Chrome Process (TCP).10-14 TCP conversion coatings are formed by immersion in a solution containing Zr 4+ , Cr 3+ and F − ions, at a pH between 3.8 and 4.0. As it has already been widely discussed, the coating formation mechanism occurs by multiple chemical steps. 10,11,13,[15][16][17] The initial step involves dissolution of the aluminum oxide layer by fluorides. The removal of the oxide layer exposes the metal surface where cathodic reactions take place. Oxygen reduction reaction, and possibly hydrogen discharge, which counterbalance aluminum oxidation, consume protons and causes a pH increase at the interface between the metallic substrate and the solution, as measured by Li et al. 15 The high pH favors the precipitation of ions present in the solution, forming a hydrated layer of zirconium and chromium oxide. The thickness of the TCP layer is usually of the order of 100 nm, depending on the nature of the aluminum alloy, the concentration of the solution and the immersion time.11,12,18 ...

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Chemical state quantification of iron and chromium oxides using XPS: the effect of the background subtraction method

Cited by 275 publications

References 31 publications

New insight on early oxidation stages of austenitic stainless steel from in situ XPS analysis on single-crystalline Fe–18Cr–13Ni

New insight on early oxidation stages of austenitic stainless steel from in situ XPS analysis on single-crystalline Fe–18Cr–13Ni

Laser-induced self-assembly of iron oxide nanostructures with controllable dimensionality

Role of Post-Treatment in Improved Corrosion Behavior of Trivalent Chromium Protection (TCP) Coating Deposited on Aluminum Alloy 2024-T3

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