Atomic Emission Spectroelectrochemistry: Real-Time Rate Measurements of Dissolution, Corrosion, and Passivation

Ogle, K.

doi:10.5006/3336

Cited by 76 publications

(51 citation statements)

References 93 publications

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“…To evaluate the current thermodynamic analysis with an experiment, the atomic emission spectroelectrochemistry (AESEC) [49][50][51][52] was introduced to measure the total quantity of dissolved alloy components in aqueous solution, which was shown to be consistent with the 3D-APT and XPS analysis 36,37,52,53 . AESEC measurements of dissolved alloy components were performed in 0.1 M (i.e., mol per liter or molarity) NaCl, pH = 4 solution at applied potentials from 0.00 to 0.34 V vs. SHE.…”

Section: Experimental Validationmentioning

confidence: 99%

Potential-pH diagrams considering complex oxide solution phases for understanding aqueous corrosion of multi-principal element alloys

et al. 2020

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The potential-pH diagram, a graphical representation of the thermodynamically predominant reaction products in aqueous corrosion, is originally proposed for the corrosion of pure metals. The original approach only leads to stoichiometric oxides and hydroxides as the oxidation products. However, numerous experiments show that non-stoichiometric oxide scales are prevalent in the aqueous corrosion of alloys. In the present study, a room temperature potential-pH diagram considering oxide solid solutions, as a generalization of the traditional potential-pH diagram with stoichiometric oxides, is constructed for an FCC single-phase multi-principal element alloy (MPEA) based on the CALculation of PHAse Diagram method. The predominant reaction products, the ions in aqueous solution, and the cation distribution in oxides are predicted. The oxide solid solution is stabilized by the mixing free energy (or mixing entropy) and the stabilizing effect becomes more significant as the temperature increases. Consequently, solid solution oxides are stable in large regions of the potential-pH diagram and the mixing free energy mostly affects the equilibrium composition of the stable oxides, while the shape of stable regions for oxides is mostly determined by the structure of the stable oxides. Agreements are found for Ni2+, Fe2+, and Mn2+ between the atomic emission spectroelectrochemistry measurements and thermodynamic calculations, while deviations exist for Cr3+ and Co2+ possibly due to surface complexation with species such as Cl− and the oxide dissolution. By incorporating the solution models of oxides, the current work presents a general and more accurate way to analyze the reaction products during aqueous corrosion of MPEAs.

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Section: Experimental Validationmentioning

confidence: 99%

Potential-pH diagrams considering complex oxide solution phases for understanding aqueous corrosion of multi-principal element alloys

et al. 2020

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“…To facilitate the comparison, each profile is presented in arbitrary units. The phase shift of j M and j e * vs. E (ϕ j M ) results from the residence time distribution of the flow cell 5 , which means that it is not frequency dependent but time dependent. The actual phase shift between E and j e (ϕ) was nearly zero in all cases as shown in Fig.…”

Section: Aesec-eismentioning

confidence: 99%

“…The AESEC technique has been described in detail elsewhere 5,40 . The working electrode was in contact with the flowing electrolyte in a specially designed flow cell 5,41 with conventional three-electrode system; a Hg/HgO in 0.1 M NaOH (−165 mV vs. SHE) as a reference electrode and a Pt foil as a counter electrode. The elements released from the working electrode were transported to an Ultima 2 C Horiba Jobin-Yvon inductively coupled plasma atomic emission spectrometer (ICP-AES).…”

Section: Atomic Emission Spectroelectrochemistrymentioning

confidence: 99%

“…It is often useful to present j e * that represents the measured j e after a numerical convolution with the residence time distribution in the flow cell (a lognormal distribution), thereby allowing a direct comparison between the instantaneous values of j e * and j M (ref. 5 ). Cathodic reactions and the formation of insoluble or slightly soluble species are not directly detected by ICP-AES.…”

Section: Data Analysis Of the Aesec Techniquementioning

confidence: 99%

“…Atomic emission spectroelectrochemistry (AESEC) provides a direct measurement of elemental dissolution rates 5 . One of the difficulties of this technique is that dissolution may be directly related to a faradaic process, weakly related as in the case of anodic dissolution by way of an oxide intermediate, or unrelated as when dissolution is due to a non-faradaic process.…”

Section: Introductionmentioning

confidence: 99%

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Refining anodic and cathodic dissolution mechanisms: combined AESEC-EIS applied to Al-Zn pure phase in alkaline solution

2020

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In this work, the use of atomic emission spectroelectrochemistry (AESEC) coupled to electrochemical impedance spectroscopy (EIS) is presented as a method of revealing dissolution mechanisms. To illustrate the method, the dissolution kinetics of Al cations from an Al-Zn pure phase (Zn-68 wt.% Al) was investigated in an alkaline solution. In the cathodic potential domain, a nearly direct formation of dissolved Al 3+ was observed, while in the anodic potential domain the Al dissolution occurred by migration across a ZnO/Zn(OH) 2 film. It was demonstrated that this methodology can be applied to a nonstationary system during a potentiostatic experiment for a lower Al content phase (Zn-22 wt.% Al). The nature of the charge transfer mechanisms depended on the applied potential and could be identified by comparing the direct current and alternating current faradaic yield using AESEC-EIS.

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Recent insights in corrosion science from atomic spectroelectrochemistry

Choudhary

Ogle

Gharbi

et al. 2021

Electrochemical Science Adv

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A fundamental understanding of corrosion mechanisms is the key to developing suitable corrosion protection approaches, and for the prediction of service life of metallic structures. However, conventional corrosion testing methods such as mass loss and electrochemical testing do not guarantee estimation of "true" corrosion rate and often mask the underlying mechanisms, due to either low sensitivity or a lack of element-resolved information. Relatively recent work in corrosion science has led to the development of a new class of corrosion testing approaches, namely atomic spectroelectrochemistry; whereby direct insight of dissolution and corrosion mechanisms can be obtained during electrochemical testing. Atomic spectroelectrochemistry provides real-time and element resolved dissolution rate of material via coupling electrochemical flow cell with inductively coupled plasma -atomic spectroscopy. This concise review discusses the basic working principle of atomic spectroelectrochemistry and its recent applications in corrosion science to understand the true underlying corrosion mechanisms of a range of metallic materials.

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Atomic Emission Spectroelectrochemistry: Real-Time Rate Measurements of Dissolution, Corrosion, and Passivation

Cited by 76 publications

References 93 publications

Potential-pH diagrams considering complex oxide solution phases for understanding aqueous corrosion of multi-principal element alloys

Potential-pH diagrams considering complex oxide solution phases for understanding aqueous corrosion of multi-principal element alloys

Refining anodic and cathodic dissolution mechanisms: combined AESEC-EIS applied to Al-Zn pure phase in alkaline solution

Recent insights in corrosion science from atomic spectroelectrochemistry

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