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In situ confocal Raman micro-spectroscopy and electrochemical studies of mussel adhesive protein and ceria composite film on carbon steel in salt solutions
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Surface and Corrosion Science.
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Applied Physical Chemistry.ORCID iD: 0000-0003-2673-075X
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Surface and Corrosion Science.
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2013 (English)In: Electrochimica Acta, ISSN 0013-4686, E-ISSN 0019-4686, Vol. 107, 276-291 p.Article in journal (Refereed) Published
Abstract [en]

Thin films composed of Mefp-1 and ceria nanoparticles have shown an increasing corrosion inhibition effect with time for carbon steel in acidic aqueous solutions containing phosphate, which motivates a detailed study of the inhibition mechanism by in situ confocal Raman micro-spectroscopy (CRM) and electrochemical impedance spectroscopy (EIS) measurements. The presence of both CeO2 and ferric oxides in the thin composite film was demonstrated by X-ray photoelectron spectroscopy analysis. The Raman spectra assisted by DFT calculations suggest that Mefp-1 forms tri-Fe3+/Mefp-1 complexes and binds to ceria nanoparticles in the composite film. The in situ CRM measurement allow us to follow the development of corrosion products. The measurements show a mixture of Fe oxides/oxyhydroxides, and also indicate that ferrous oxides may be further oxidized by the composite film. Moreover, phosphate ions react with the Fe ions released from the surface to form iron-phosphate deposits, which become incorporated into the corrosion product layer and the composite film. The EIS measurements suggest a layered surface structure formed by the initial Mefp-1/ceria composite layer and the corrosion products/iron-phosphate deposits. These measurements also demonstrate the greatly increased inhibition effect of the composite film in the presence of the phosphate ions. The consistent CRM and EIS results suggest that the iron-phosphate deposits heal defects in the composite film and corrosion product layer, which results in a significantly improved corrosion inhibition of the Mefp-1/ceria composite film during initial and long term exposure.

Place, publisher, year, edition, pages
2013. Vol. 107, 276-291 p.
Keyword [en]
Ceria nanoparticle, Corrosion inhibition, Electrochemical impedance spectroscopy, In situ confocal Raman micro-spectroscopy, Mefp-1
National Category
Corrosion Engineering
URN: urn:nbn:se:kth:diva-128386DOI: 10.1016/j.electacta.2013.05.078ISI: 000326661200035ScopusID: 2-s2.0-84880183495OAI: diva2:647431
VinnovaSwedish Foundation for Strategic Research

QC 20130911

Available from: 2013-09-11 Created: 2013-09-11 Last updated: 2013-12-10Bibliographically approved
In thesis
1. The Mussel Adhesive Protein (Mefp-1): A GREEN Corrosion Inhibitor
Open this publication in new window or tab >>The Mussel Adhesive Protein (Mefp-1): A GREEN Corrosion Inhibitor
2013 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Corrosion of metallic materials is a natural process, and our study shows that even in an alkaline environment severe corrosion may occur on a carbon steel surface. While corrosion cannot be stopped it can be retarded. Many of the traditional anti-corrosion approaches such as the chromate process are effective but hazardous to the environment and human health.

Mefp-1, a protein derived from blue mussel byssus, is well known for its extraordinary adhesion and film forming properties. Moreover, it has been reported that Mefp-1 confers a certain corrosion protection for stainless steel. All these facts indicate that this protein may be developed into corrosion inhibitors with ‘green’, ‘effective’ and ‘smart’ properties.

In this study, a range of surface-sensitive techniques have been used to investigate adsorption kinetics, film forming and film compaction mechanisms of Mefp-1. In situ atomic force microscopy (AFM) enables the protein adsorption on substrates to be visualized, whereas the ex situ AFM facilitates the characterization of micro- and nano-structures of the protein films. In situ Peak Force AFM can be used to determine nano-mechanical properties of the surface layers. The quartz crystal microbalance with dissipation monitoring (QCM-D) was used to reveal the build-up of the Mefp-1 film on substrates and measure the viscoelastic properties of the adsorbed film. Analytical techniques and theoretical calculations were applied to gain insights into the formation and compaction processes such as oxidation and complexation of pre-formed Mefp-1 films. The electron probe micro analyzer (EPMA) and X-ray photoelectron spectroscopy (XPS) were utilized to obtain the chemical composition of the surface layer. Electrochemical impedance spectroscopy (EIS) measurements were performed to evaluate the corrosion inhibition efficiency of different forms of Mefp-1 on carbon steel substrates.

The results demonstrate that Mefp-1 adsorbs on carbon steel surfaces across a broad pH interval, and it forms a continuous film covering the substrate providing a certain extent of corrosion protection. At a higher pH, the adsorption is faster and the formed film is more compact. At neutral pH, results on the iron substrate suggest an initially fast adsorption, with the molecules oriented preferentially parallel to the surface, followed by a structural change within the film leading to molecules extending towards solution. Both oxidation and complexation of the Mefp-1 can lead to the compaction of the protein films. Addition of Fe3+ induces a transition from an extended and soft protein layer to a denser and stiffer one by enhancing the formation of tri-Fe3+/catechol complexes in the surface film, leading to water removal and film compaction. Exposure to a NaIO4 solution results in the cross-linking of Mefp-1, which also results in a significant compaction of the pre-formed protein film. Mefp-1 is an effective corrosion inhibitor for carbon steel when added to an acidic solution, and the inhibition efficiency increases with time. As a film-forming corrosion inhibitor, the pre-formed Mefp-1 film provides a certain level of corrosion protection for short term applications, and the protection efficiency can be significantly enhanced by the film compaction processes.

For the long term applications, a thin film composed of Mefp-1 and ceria nanoparticles was developed. The deposited Mefp-1/ceria composite film contains micro-sized aggregates of Mefp-1/Fe3+ complexes and CeO2 particles. The Mefp-1/ceria film may promote the further oxidation of ferrous oxides, and the corrosion resistance increases with time. Moreover, phosphate ions react with Fe ions released from the surface and form deposits preferentially at the surface defect sites. The deposits incorporate into the Mefp-1/ceria composite film and heal the surface defects, which result in a significantly improved corrosion inhibition effect for the Mefp-1/ceria composite film in both initial and prolonged exposure situations

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2013. x, 62 p.
Trita-CHE-Report, ISSN 1654-1081 ; 2013:21
carbon steel, mussel adhesive protein, Mefp-1, inhibitor, adsorption, film forming, complexation, cross-linking, ceria nanoparticle, composite film, EIS, AFM, QCM-D, ATR-FTIR, Confocal Raman Micro-spectroscopy, DFT calculation
National Category
Chemical Sciences
urn:nbn:se:kth:diva-123489 (URN)978-91-7501-738-9 (ISBN)
Public defence
2013-06-13, F3, Lindstedtsvägen 26, KTH, Stockholm, 10:00 (English)

QC 20130610

Available from: 2013-06-10 Created: 2013-06-10 Last updated: 2013-09-11Bibliographically approved

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