Quantitative SIMS Analysis of Hydroxyl Ion Content in Thin Oxide Films

Abstract

This paper demonstrates that SIMS is a very sensitive method for determining the hydroxyl content of thin oxide films on metals and alloys, provided standards are used to calibrate the technique. Detection limits of ±0.1% hydroxyl have been achieved. Within this limit, no hydroxyl is present within passive films on iron and nickel, while passive films on Fe−25Cr contain only 0.6±0.1%normalhydroxyl within the inner chromium‐rich part of the film and 1.1±0.1%normalhydroxyl within the outer iron‐rich part of the film. Nonpassive films, such as the electropolish film on nickel and Fe−25Cr, and the film formed on nickel in F− containing solution, contain significant amounts of hydroxyl ions.

Composition and structure of iron oxidation surface layers produced in weak acidic solutions

“…Competition between these two parallel reactions (15) and (16) could explain the higher coverage by lepidocrocite at a solution concentration of 5 × 10 −4 mol/L iron than at 2 × 10 −3 mol/L. The observed changes in Fe 2+ ion concentration in solution support this explanation.…”

“…O'Grady and Bockris [15] described the surface layer as a polymeric gel-like film of hydrated oxide, after using in situ Mössbauer spectroscopy. Mitchell and Graham [16] using SIMS did not observe hydroxyl ions in the iron passive layer, suggesting merely the presence of iron oxides. The lack of a hydroxyl group in the form of OH or H 2 O was confirmed by Tjong and Yeager [17].…”

Hydrogen gas production during corrosion of copper by water

“…It has been observed for many years that hydroxide can be related to a poor protective ability of an oxide [14]. In view of this it is important and interesting that we should rather expect an initial CuOH formation than an initial hydrogen-free copper oxide formation [4].…”

“…Fig. 7 shows hydrogen-containing ions from the reaction product on Cu in Pd-and Pt-enclosed containers [14] short time exposure in the NaOH solution. In this figure, with the same analysis conditions, low counts in the exposure in the NaOH solution with air contact are observed.…”

Study of the Effect of Temperature on the Hardness, Grain Size, and Yield in Electrodeposition of Chromium on 1045 Steel

“…Zone (B) is where the release of hydrogen begins and stop when the formation of the cathodic film is complete. The third zone (C) is attributable to the reduction of the Cr 6+ to Cr 0 , as well to the release of hydrogen; where Cr 6+ and other species of chromium with less oxidation states are part of trichromate ion 4,[8][9][10][11] . The trichromate ion is necessary by protection the Cr +3 ions, preventing the formation of a stable aquo complex.…”