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Abstract
An ≈4 nm FeCrNi film, deposited on a Ru/B4C multilayer (ML), is used to study cathodic hydrogen charging in electrolyte. A thin film on a ML allows obtaining precise quantitative information on surface metal composition and oxidation state using the X‐ray standing wave technique combined with near‐edge X‐ray absorption spectroscopy. The metal composition is found being close to the composition of stainless steel (SS) 304, and, as for bulk steel, the outer 2 nm passive layer, consisting of oxidized iron and chromium, is depleted of nickel. Overall, it is found that the film represented a useful replica of the surface of bulk steel. Following exposure to 0.1 m KCl electrolyte at −0.6 V versus Ag/AgCl, 11.3 (±3)% swelling of the film by hydrogen absorption is observed. The estimated absorbed amount is exceeding reported bulk absorption under similar conditions by more than an order of magnitude. Strong hydrogen absorption appears to be enabled by the 2D character of the thin film, i.e., a significantly lower associated strain energy compared with bulk absorption. The strong surface swelling is suggested to be related to the lowering of the pitting corrosion resistance of SS surfaces reported following hydrogen exposure.
Highlights
An %4 nm FeCrNi film, deposited on a Ru/B4C multilayer (ML), is used to study cathodic hydrogen charging in electrolyte
The findings presented here shed new light on reports that hydrogen loading decreases the resistance of stainless steel (SS) to pitting corrosion,[3,16,27,28,29,30] leading to embrittlement.[4,5,6]
An %4 nm-thick FeCrNi film with a metal composition close to SS 304 was used to study structural changes induced by electrolytic hydrogen charging at cathodic potential
Summary
An XSW is created during Bragg reflection. Its planes move inward by 1.85 nm, i.e., by half the d-spacing of the ML[20,31,32] (Figure 1a) when crossing the range of reflection. Qffiffiffiffiffiffiffiffiffiffiffiffi YðEγÞ 1⁄4 IðEγÞ=I0 1⁄4 1 þ RðEγÞ þ 2 RðEγÞFc cos1⁄2vðEγÞ À 2πPc In this case, YðEγÞ is the normalized X-ray fluorescence yield of Cr, Fe, or Ni, recorded when traversing the Bragg reflection. Traversing the rocking curve, the XSW maxima move inward by half the wavefield spacing dML from P 1⁄4 0.5 via 0.25 to P 1⁄4 0/1 and the mimima move from P 1⁄4 0/1 via 0.75 to P 1⁄4 0.5. Www.pss-b.com distribution around this mean position[20,31] (see Supporting Information for more details) Both parameters are defined on a scale from 0 to 1, with Fc 1⁄4 1 representing a delta-functionlike sharp distribution and Fc 1⁄4 0 describing a uniform distribution over the whole range of the wavefield spacing dML. Distances beyond dML cannot be determined without using additional information
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