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The Mussel Adhesive Protein (Mefp-1): A GREEN Corrosion Inhibitor
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Surface and Corrosion Science.ORCID iD: 0000-0001-5180-9895
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 [en]
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: urn:nbn:se:kth:diva-123489ISBN: 978-91-7501-738-9 (print)OAI: oai:DiVA.org:kth-123489DiVA: diva2:626667
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
List of papers
1. Localized corrosion behaviour of reinforcement steel in simulated concrete pore solution
Open this publication in new window or tab >>Localized corrosion behaviour of reinforcement steel in simulated concrete pore solution
2009 (English)In: Corrosion Science, ISSN 0010-938X, E-ISSN 1879-0496, Vol. 51, no 9, 2130-2138 p.Article in journal (Refereed) Published
Abstract [en]

The correlation of localized corrosion behavior and microstructure of reinforcement steel in simulated concrete pore solutions was investigated. The SEM/EDS analysis showed that most of ferrite, minor amount of pearlite and some MnS inclusions existed on the steel surface. The SKPFM results indicated a higher corrosion tendency at the ferrite grain boundaries, pearlite grains and MnS inclusions. The EIS and electrochemical polarization measurements demonstrated the influence of pH and chloride concentration on the corrosion behavior. in situ optical observations and AFM images revealed a detail of the localized corrosion behavior, which was in good agreement with the results from the other measurements.

Keyword
Steel, AFM, Pitting corrosion
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-33120 (URN)10.1016/j.corsci.2009.05.044 (DOI)000269597000030 ()2-s2.0-68049114482 (Scopus ID)
Note

QC 20110428

Available from: 2011-04-28 Created: 2011-04-28 Last updated: 2017-12-11Bibliographically approved
2. Electrochemical and AFM studies of mussel adhesive protein (Mefp-1) as corrosion inhibitor for carbon steel
Open this publication in new window or tab >>Electrochemical and AFM studies of mussel adhesive protein (Mefp-1) as corrosion inhibitor for carbon steel
2011 (English)In: Electrochimica Acta, ISSN 0013-4686, E-ISSN 1873-3859, Vol. 56, no 3, 1636-1645 p.Article in journal (Refereed) Published
Abstract [en]

Adsorption of mussel adhesive protein (Mefp-1) derived from the marine mussel Mytilus edulis and its corrosion inhibition for carbon steel were studied by electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization measurements in NaCl solutions at 01 4.6. The results indicate that the Mefp-1 confers significant corrosion inhibition of carbon steel, and the chloride concentration of the solution has an influence on the inhibition efficiency. Within a short exposure time, the inhibition efficiency is higher in the solution with a higher chloride concentration, whereas, for longer exposure time, up to one week, higher inhibition efficiency was obtained in the solution with a lower chloride concentration. AFM imaging was used both ex situ and in situ to investigate Mefp-1 adsorption. The in situ AFM measurements enable the protein adsorption on carbon steel to be visualized in real time in the solution. The AFM images illustrate how the Mefp-1 layer is formed on carbon steel. Measurements using bovine serum albumin (BSA) were also performed for comparison. The results showed that BSA also confers significant corrosion inhibition of carbon steel even though the BSA film formation process is slightly different from that of Mefp-1.

Keyword
Mussel adhesive protein, Protein adsorption, Corrosion inhibition, Carbon steel, In situ AFM
National Category
Physical Chemistry
Identifiers
urn:nbn:se:kth:diva-33238 (URN)10.1016/j.electacta.2010.10.033 (DOI)000289225400087 ()2-s2.0-78650513128 (Scopus ID)
Note

QC 20110509

Available from: 2011-05-09 Created: 2011-05-02 Last updated: 2017-12-11Bibliographically approved
3. Electrochemical, atomic force microscopy and infrared reflection absorption spectroscopy studies of pre-formed mussel adhesive protein films on carbon steel for corrosion protection
Open this publication in new window or tab >>Electrochemical, atomic force microscopy and infrared reflection absorption spectroscopy studies of pre-formed mussel adhesive protein films on carbon steel for corrosion protection
2012 (English)In: Thin Solid Films, ISSN 0040-6090, E-ISSN 1879-2731, Vol. 520, no 24, 7136-7143 p.Article in journal (Refereed) Published
Abstract [en]

Electrochemical measurements, in situ and ex situ atomic force microscopy (AFM) experiments and infrared reflection absorption spectroscopy (IRAS) analysis were performed to investigate the formation and stability as well as corrosion protection properties of mussel adhesive protein (Mefp-1) films on carbon steel, and the influence of cross-linking by NaIO 4 oxidation. The in situ AFM measurements show flake-like adsorbed protein aggregates in the film formed at pH 9. The ex situ AFM images indicate multilayer-like films and that the film becomes more compact and stable in NaCl solution after the cross-linking. The IRAS results reveal the absorption bands of Mefp-1 on carbon steel before and after NaIO 4 induced oxidation of the pre-adsorbed protein. Within a short exposure time, a certain corrosion protection effect was noted for the pre-formed Mefp-1 film in 0.1 M NaCl solution. Cross-linking the pre-adsorbed film by NaIO 4 oxidation significantly enhanced the protection efficiency by up to 80%.

Keyword
Adsorption, Chemical analysis, Corrosion protection, Cross-linking, Films, In situ AFM, Mussel adhesive protein
National Category
Chemical Engineering
Identifiers
urn:nbn:se:kth:diva-103531 (URN)10.1016/j.tsf.2012.07.115 (DOI)000308691700017 ()2-s2.0-84866023690 (Scopus ID)
Funder
Mistra - The Swedish Foundation for Strategic Environmental Research
Note

QC 20121017

Available from: 2012-10-17 Created: 2012-10-15 Last updated: 2017-12-07Bibliographically approved
4. In situ investigations of Fe3+ induced complexation of adsorbed Mefp-1 protein film on iron substrate
Open this publication in new window or tab >>In situ investigations of Fe3+ induced complexation of adsorbed Mefp-1 protein film on iron substrate
Show others...
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
Keyword
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:nbn:se:kth:diva-124709 (URN)10.1016/j.jcis.2013.05.016 (DOI)000320737000009 ()2-s2.0-84878984889 (Scopus ID)
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
5. Thin Composite Films of Mussel Adhesive Proteins and Ceria Nanoparticles on Carbon Steel for Corrosion Protection
Open this publication in new window or tab >>Thin Composite Films of Mussel Adhesive Proteins and Ceria Nanoparticles on Carbon Steel for Corrosion Protection
Show others...
2012 (English)In: Journal of the Electrochemical Society, ISSN 0013-4651, E-ISSN 1945-7111, Vol. 159, no 8, C364-C371 p.Article in journal (Refereed) Published
Abstract [en]

Thin composite films of the mussel adhesive proteins (Mefp-1) and ceria nanoparticles were deposited on substrate surfaces by alternating immersions. The film formation was studied by quartz crystal microbalance with dissipation (QCM-D) monitoring. Both the changes in frequency and dissipation recorded by QCM-D demonstrate buildup of a composite film of Mefp-1 and nanoceria. Micro-and nanostructure and composition of the film on carbon steel were characterized by optical and atomic force microscopy (AFM), electron probe micro analyzer (EPMA) and confocal Raman microspectroscopy (CRM). Optical and EPMA observations of the film show micron-sized aggregates and AFM imaging of the compact and smooth areas reveal the nanostructure. EPMA elemental mapping indicates that the micron-sized aggregates are rich in ceria and Mefp-1, whereas CRM analysis shows the presence of Mefp-1-Fe complexes in the film. Corrosion protection of the composite film on carbon steel was investigated by electrochemical impedance spectroscopy and potentiodynamic polarization measurements in NaCl solution, and compared with Mefp-1 added in the solution as an inhibitor. The measurements show that the composite film provides a higher corrosion resistance compared with Mefp-1 added as inhibitor. The corrosion resistance increases with exposure time and approaches a high level.

National Category
Corrosion Engineering
Identifiers
urn:nbn:se:kth:diva-103397 (URN)10.1149/2.061208jes (DOI)000308559400047 ()2-s2.0-85016854440 (Scopus ID)
Funder
Vinnova
Note

QC 20121011

Available from: 2012-10-11 Created: 2012-10-11 Last updated: 2017-12-07Bibliographically approved
6. In situ confocal Raman micro-spectroscopy and electrochemical studies of mussel adhesive protein and ceria composite film on carbon steel in salt solutions
Open this publication in new window or tab >>In situ confocal Raman micro-spectroscopy and electrochemical studies of mussel adhesive protein and ceria composite film on carbon steel in salt solutions
Show others...
2013 (English)In: Electrochimica Acta, ISSN 0013-4686, E-ISSN 1873-3859, 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.

Keyword
Ceria nanoparticle, Corrosion inhibition, Electrochemical impedance spectroscopy, In situ confocal Raman micro-spectroscopy, Mefp-1
National Category
Corrosion Engineering
Identifiers
urn:nbn:se:kth:diva-128386 (URN)10.1016/j.electacta.2013.05.078 (DOI)000326661200035 ()2-s2.0-84880183495 (Scopus ID)
Funder
VinnovaSwedish Foundation for Strategic Research
Note

QC 20130911

Available from: 2013-09-11 Created: 2013-09-11 Last updated: 2017-12-06Bibliographically approved

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