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In situ investigations of Fe3+ induced complexation of adsorbed Mefp-1 protein film on iron substrate
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Surface and Corrosion Science.ORCID iD: 0000-0001-5180-9895
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
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2013 (English)In: Journal of Colloid and Interface Science, ISSN 0021-9797, E-ISSN 1095-7103, Vol. 404, 62-71 p.Article in journal (Refereed) Published
Abstract [en]

A range of in situ analytical techniques and theoretical calculations were applied to gain insights into the formation and properties of the Mefp-I film on iron substrate, as well as the protein complexation with Fe3+ ions. Adsorption kinetics of Mefp-1 and the complexation were investigated using QCM-D. The results 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 toward solution. Exposure to a diluted FeCl3 solution results in enhanced complexation within the adsorbed protein film, leading to water removal and film compaction. In situ Peak Force Tapping AFM was employed for determining morphology and nano-mechanical properties of the surface layer. The results, in agreement with the QCM-D observations, demonstrate that addition of Fe-3 induces a transition from an extended and soft protein layer to a denser and stiffer one. Further, in situ ATR-FTIR and Confocal Raman Micro-spectroscopy (CRM) techniques were utilized to monitor compositional/structural changes in the surface layer due to addition of Fe3+ ions. The spectroscopic analyses assisted by DFT calculations provide evidence for formation of tri-Fe3+/catechol complexes in the surface film, which is enhanced by Fe3+ addition.

Place, publisher, year, edition, pages
Academic Press, 2013. Vol. 404, 62-71 p.
Keyword [en]
Mefp-1, Complexation, QCM-D, In situ ATR-FTIR, In situ AFM, In situ confocal Raman micro-spectroscopy, DFT calculation
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:kth:diva-124709DOI: 10.1016/j.jcis.2013.05.016ISI: 000320737000009Scopus ID: 2-s2.0-84878984889OAI: oai:DiVA.org:kth-124709DiVA: diva2:638218
Funder
Swedish Research CouncilSwedish Foundation for Strategic Research
Note

QC 20130729

Available from: 2013-07-29 Created: 2013-07-29 Last updated: 2017-12-06Bibliographically 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.
Series
Trita-CHE-Report, ISSN 1654-1081 ; 2013:21
Keyword
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
Identifiers
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)
Opponent
Supervisors
Note

QC 20130610

Available from: 2013-06-10 Created: 2013-06-10 Last updated: 2013-09-11Bibliographically approved
2. Nanocomposite films for corrosion protection
Open this publication in new window or tab >>Nanocomposite films for corrosion protection
2013 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis describes technical and scientific aspects of new types of composite films/coatings for corrosion protection of carbon steel, composite films with nanometer thickness consisting of mussel adhesive protein (Mefp1) and ceria nanoparticles, and polymeric composite coatings with micrometre thickness consisting of conducting polymer and ceria nanoparticles in a UV‐curing polyester acrylate (PEA) resin.

The influence of microstructure on corrosion behaviour was studied for a Fe‐Cr‐V‐N alloy containing micro‐sized nitrides with different chemical composition spread in martensitic alloy matrix. The Volta potential mapping suggested higher relative nobility for the nitride particles than the alloy matrix, and the nitrides with higher amounts of nitrogen and vanadium exhibited higher nobility. Potentiodynamic polarization measurements in a 0.1 M NaCl solution at neutral pH and ambient temperature showed passivity breakdown with initiation of localized corrosion which started in the boundary region surrounding the nitride particles, especially the ones enriched in Cr and Mo.

Mefp1/ceria nanocomposite films were formed on silica and metal substrates by layer‐by‐layer immersion deposition. The film formation process was studied in situ using a Quartz Crystal Microbalance with Dissipation (QCM‐D). The film grows linearly with increasing number of immersions. Increasing Mefp1 concentration or using Mefp1 with larger size leads to more Mefp1 being deposited. Peak Force Quantitative Nanomechanical Mapping (Peak Force QNM) of the composite films in air indicated that the elastic modulus of the film increased when the film deposited had a higher Mefp1 concentration. It was also noted that the nature of the outermost layer can affect bulk morphology and surface mechanical properties of the film.

The QCM‐D study of Mefp1 on an iron substrate showed that Mefp1 adsorbs at a high rate and changes its conformation with increasing adsorption time. The QCM‐D and in situ Peak Force QNM measurements showed that the addition of Fe3+ ions causes a transition in the single Mefp1 layer from an extended and soft layer to a denser and stiffer layer. In situ ATR‐FTIR and Confocal Raman Microscopy (CRM) analyses revealed complex formation between Fe3+ and catechol groups in Mefp1. Moreover, optical microscopy, SEM and AFM characterization of the Mefp1/ceria composite film formed on carbon steel showed micron‐size aggregates rich in Mefp1 and ceria, and a nanostructure of well dispersed ceria particles in the film. The CRM analysis confirmed the presence of Mefp1/Fe complexes in the film. Electrochemical impedance microscopy and potentiodynamic polarization measurements showed that the Mefp1/ceria composite film can provide corrosion protection for carbon steel, and that the protection efficiency increases with exposure time.

Composite coatings of 10 μm thickness composed of a UV‐curing PEA resin and a small amount of conductive polymer and ceria nanoparticles were coated on carbon steel. The conductive polymer (PAni) was synthesized with phosphoric acid (PA) as the dopant by chemical oxidative polymerization. The ATR‐FTIR and SEM analyses confirmed that the added particles were well dispersed in the coatings. Electrochemical measurements during long exposure in 0.1 M NaCl solution, including open circuit potential (OCP) and EIS, were performed to investigate the protective performance of the coatings. The results showed that adding ceria nanoparticles can improve the barrier properties of the coating, and adding PAni‐PA can lead to active protection of the coating. Adding PAni‐PA and ceria nanoparticles simultaneously in the coating can improve the protection and stability of the composite coating, providing excellent corrosion protection for carbon steel.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2013. xi, 63 p.
Series
TRITA-CHE-Report, ISSN 1654-1081 ; 2013:37
Keyword
corrosion protection, nanocomposite, coating, tool alloy, layer‐by‐layer, polarization, passivity, nanomechanical, topography, Mefp‐ 1, ceria nanoparticle, PAni, UV‐cure, AFM, Peak Force QNM, EIS, SEM, CRM, QCM‐D, ATR‐FTIR
National Category
Corrosion Engineering
Identifiers
urn:nbn:se:kth:diva-132240 (URN)978-91-7501-850-8 (ISBN)
Public defence
2013-11-01, Kollegiesalen, Brinellvägen 8, KTH, Stockholm, 10:00 (English)
Opponent
Supervisors
Note

QC 20131024

Available from: 2013-10-25 Created: 2013-10-24 Last updated: 2017-03-02Bibliographically approved

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