Corrosion and Protection of Steels in Marine Environments: State-of-the-Art and Emerging Research Trends

A special issue of Corrosion and Materials Degradation (ISSN 2624-5558).

Deadline for manuscript submissions: closed (30 September 2021) | Viewed by 52408

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Guest Editor
Laboratory of Engineering Sciences for the Environment (LaSIE), Université de La Rochelle, La Rochelle, France
Interests: corrosion of steels in natural environments; biocorrosion; corrosion in the marine environment; cathodic protection

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Co-Guest Editor
School of Engineering (Civil Engineering), University of Newcastle, Callaghan, Australia
Interests: structural engineering; structural materials science; infrastructure engineering and asset management
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Special Issue Information

Dear Colleagues,

We would like to invite you to submit your work to this Special Issue on “Corrosion and Protection of Steels in Marine Environments: State-of-the-Art and Emerging Research Trends”. Marine corrosion is a very ancient topic, as humankind has, since antiquity, struggled with the corrosiveness of seawater to exploit the countless and essential natural resources of the sea. It is also a wide topic because it combines chemical, biological and mechanical factors. Among the numerous materials used for marine applications, iron-based alloys (i.e., steels) are essential in various industrial domains such as (of course) naval (ships, submarines, etc.), energy (pipelines, offshore platforms, renewable energy devices, etc.), or buildings (seaport structures, bridges, steel reinforcement in concrete, etc.). Marine corrosion is still an issue to this day because the recent and necessary development of marine renewable energy devices has motivated innovative research. Currently, complete mastery of corrosion issues is a key aspect in the profitability of produced energy. Simultaneously, requirements for environmentally friendly anticorrosion methods and processes are clearly expressed. Numerous and fundamental recent advances in marine corrosion and protection of steels, including carbon steel, low alloy steel and stainless steel, can then be noted. This Special Issue is necessary to acknowledge the recent and sudden increase in the understanding of steel corrosion processes in marine environments and the associated optimization of anticorrosion methods. Last, but not least, a large part of our cultural heritage lies at the bottom of seas and oceans, and it will definitely be lost if scientific research does not include current and historical concerns as well.

In particular, the topics of interest include, but are not limited to, the following:

- steel corrosion mechanisms in marine environments;

- biocorrosion of steels in marine environments;

- development of new alloys, stainless steels and low alloy steels;

- coatings and surface treatments for marine applications;

- cathodic protection and associated phenomena (e.g., calcareous deposition);

- methods and corrosion tests in marine environments, in situ vs laboratory experiments; and

- ancient iron artefacts, corrosion mechanisms, protection and restoration.

Prof. Dr. Philippe Refait
Dr. Igor Chaves
Guest Editors

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Published Papers (10 papers)

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Research

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15 pages, 3507 KiB  
Article
Cathodic Protection of Complex Carbon Steel Structures in Seawater
by Philippe Refait, Anne-Marie Grolleau, Marc Jeannin and René Sabot
Corros. Mater. Degrad. 2022, 3(3), 439-453; https://doi.org/10.3390/cmd3030026 - 12 Aug 2022
Cited by 3 | Viewed by 3113
Abstract
Cathodic protection efficiency of complex carbon steel structures in confined seawater environment was studied using a specific experimental device. Schematically, this device consisted of a Plexiglas matrix, crossed by a channel 50 cm long, 5 mm deep, 1.5 to 5 cm wide, which [...] Read more.
Cathodic protection efficiency of complex carbon steel structures in confined seawater environment was studied using a specific experimental device. Schematically, this device consisted of a Plexiglas matrix, crossed by a channel 50 cm long, 5 mm deep, 1.5 to 5 cm wide, which moreover included four bends at 90°. Seawater flowed continuously inside the channel over 12 steel coupons embedded in the Plexiglas matrix. Cathodic protection was applied at a constant potential of −1060 mV vs. Ag/AgCl-seawater with respect to a reference electrode located outside the channel, at the seawater flow entry. The potential of four selected coupons was monitored over time via a microelectrode set close to each coupon. It varied significantly with the distance separating the coupons from the channel entry. At the end of the 3.5-month experiment, a polarization curve was acquired. The residual corrosion rate under cathodic protection was estimated via the extrapolation of the anodic Tafel line. It varied from <1 µm yr−1 to 16 µm yr−1, depending on the potential reached by the coupon (between −900 and −1040 mV vs. Ag/AgCl-seawater) at the end of the experiment and on the properties of the calcareous deposit formed on the steel surface. Full article
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15 pages, 7708 KiB  
Article
Corrosion Fatigue Behavior of Twin Wire Arc Sprayed and Machine Hammer Peened ZnAl4 Coatings on S355 J2C + C Substrate
by Michael P. Milz, Andreas Wirtz, Mohamed Abdulgader, Anke Kalenborn, Dirk Biermann, Wolfgang Tillmann and Frank Walther
Corros. Mater. Degrad. 2022, 3(1), 127-141; https://doi.org/10.3390/cmd3010007 - 2 Mar 2022
Cited by 5 | Viewed by 3774
Abstract
Offshore installations, e.g., offshore wind turbines and pipelines, are exposed to various mechanical loads due to wind or waves and corrosive loads such as seawater or mist. ZnAl-based thermal sprayed coatings, often in conjunction with organic coatings, provide sufficient corrosion protection and are [...] Read more.
Offshore installations, e.g., offshore wind turbines and pipelines, are exposed to various mechanical loads due to wind or waves and corrosive loads such as seawater or mist. ZnAl-based thermal sprayed coatings, often in conjunction with organic coatings, provide sufficient corrosion protection and are well established for applications in marine environments. In this study, machine hammer peening (MHP) is applied after twin wire arc spraying to improve corrosion fatigue behavior through increased hardness, reduced porosity, and roughness compared to as-sprayed coatings. Mn-alloyed structural steel S355 J2 + C with and without ZnAl4 coating as well as with MHP post-treated ZnAl4 coating were cyclically loaded in 3.5% NaCl solution. MHP leads to a uniform coating thickness with lower porosity and roughness. ZnAl4 coating and MHP post-treatment improved corrosion fatigue behavior in the high cycle fatigue regime with an increase of the stress amplitude, applied to reach a number of cycles 1.2 × 106, up to 115% compared to sandblasted specimens. Corrosive attack of the substrate steel was successfully avoided by using the coating systems. Stress- and microstructure-dependent corrosion fatigue damage mechanisms were evaluated by mechanical and electrochemical measurement techniques. Full article
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22 pages, 8674 KiB  
Article
Localized Corrosion of Mooring Chain Steel in Seawater
by Xiaolong Zhang, Nanni Noël-Hermes, Gabriele Ferrari and Martijn Hoogeland
Corros. Mater. Degrad. 2022, 3(1), 53-74; https://doi.org/10.3390/cmd3010004 - 16 Feb 2022
Cited by 11 | Viewed by 4470
Abstract
Corrosion of mooring chains is regarded as one of main threats to the offshore mooring systems. Localized corrosion is even more dangerous than uniform corrosion because it may not show significant mass loss but it can cause stress concentration and initiate cracks under [...] Read more.
Corrosion of mooring chains is regarded as one of main threats to the offshore mooring systems. Localized corrosion is even more dangerous than uniform corrosion because it may not show significant mass loss but it can cause stress concentration and initiate cracks under force, leading to accelerated degradation of mooring chains. Localized corrosion of steel in seawater is influenced by many factors such as the local heterogeneities of the steel, and the local electrochemical and microbiological environments. It is difficult to predict and the mechanism is not fully understood. The aim of this work was to study the mechanism of localized corrosion on mooring chain steel in seawater which is helpful in the search for corresponding monitoring tools and mitigation methods. The corrosion behavior of chain steel grade R4 was studied in artificial seawater and artificial seawater containing microorganisms collected from a practice field. The corrosion behavior of the steel was studied using different techniques such as potentiodynamic polarization, linear polarization resistance measurements and electrochemical impedance spectroscopy. The microstructures such as inclusions and compositions of the chain steel were studied using SEM: Scanning Electron Microscope and EDS: Energy Dispersive Spectroscopy. The microbial cells were observed using epi-fluorescence microscopy. The corrosion morphology and pit geometry were investigated using photo-microscopy. The localized corrosion rate has been found to be much higher than the uniform corrosion rate of the steel in the seawater in the presence of bacteria. In the case of localized corrosion, applying uniform corrosion measurement techniques and formulas is not considered representative. The representative areas have to be introduced to match physical results with the measurements. Inclusions, such as MnS and TiVCr found in the steel have a critical influence on localized corrosion. The corrosion mechanism of the steel in seawater is discussed. Full article
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16 pages, 3279 KiB  
Article
Influence of Organic Matter/Bacteria on the Formation and Transformation of Sulfate Green Rust
by Julien Duboscq, Julia Vincent, Marc Jeannin, René Sabot, Isabelle Lanneluc, Sophie Sablé and Philippe Refait
Corros. Mater. Degrad. 2022, 3(1), 1-16; https://doi.org/10.3390/cmd3010001 - 30 Dec 2021
Cited by 5 | Viewed by 2675
Abstract
The corrosion processes of carbon steel immersed in natural seawater are influenced by microorganisms due to important biological activity. An analysis of the corrosion product layers formed on carbon steel coupons in natural or artificial seawater revealed that sulfate green rust GR(SO4 [...] Read more.
The corrosion processes of carbon steel immersed in natural seawater are influenced by microorganisms due to important biological activity. An analysis of the corrosion product layers formed on carbon steel coupons in natural or artificial seawater revealed that sulfate green rust GR(SO42−) was favored in natural environments. In this paper, the role of organic matter/bacteria on the formation and transformation of this compound are addressed. GR(SO42−) was precipitated from Fe(II) and Fe(III) salts in the presence of various marine bacterial species not involved in the redox cycle of Fe or S. Abiotic experiments were performed for comparison, first without any organic species and then with sodium acetate added as a small organic ion. The obtained aqueous suspensions were aged at room temperature for 1 week. The number of bacteria (CFU/mL) was followed over time and the solid phases were characterized by XRD. Whatever the fate of the bacteria (no activity, or activity and growth), the formation of GR(SO42−) was favored and its transformation to magnetite completely inhibited. This effect is attributed to the adsorption of organic molecules on the lateral sides of the GR(SO42−) crystals. A similar effect, though less important, was observed with acetate. Full article
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22 pages, 6442 KiB  
Article
Aggressiveness of Different Ageing Conditions for Three Thick Marine Epoxy Systems
by Alexis Renaud, Victor Pommier, Jérémy Garnier, Simon Frappart, Laure Florimond, Marion Koch, Anne-Marie Grolleau, Céline Puente-Lelièvre and Touzain Sebastien
Corros. Mater. Degrad. 2021, 2(4), 721-742; https://doi.org/10.3390/cmd2040039 - 3 Dec 2021
Cited by 4 | Viewed by 3183
Abstract
Three different coated steel systems were aged in natural or artificial seawater, in neutral salt spray (NSS), and using alternate immersion tests in order to evaluate the aggressiveness of the different ageing conditions. Commercial epoxy coatings were applied onto steel (S355NL), hot-galvanized steel [...] Read more.
Three different coated steel systems were aged in natural or artificial seawater, in neutral salt spray (NSS), and using alternate immersion tests in order to evaluate the aggressiveness of the different ageing conditions. Commercial epoxy coatings were applied onto steel (S355NL), hot-galvanized steel (HDG), and Zn-Al15 thermal spraying coated steel. The defect-free systems were immersed in artificial seawater at 35 °C for 1085 days and in natural seawater for 1200 days and were characterized by electrochemical impedance spectroscopy (EIS). Panels with artificial defects were immersed for 180 days in artificial seawater and, regarding adhesion, were evaluated according to ISO 16276-2. In parallel, the three coated systems were submitted to cyclic neutral salt spray (NSS) for 1440 h: defect-free panels were regularly evaluated by EIS, while the degree or corrosion was measured onto panels with artificial defect. After NSS, defect-free panels were immersed in artificial seawater at 35 °C for further EIS investigations. Finally, alternate immersion tests were performed for 860 days for the three defect-free coated systems and for 84 days for panels with a defect. The results showed that, for defect-free panels, immersions in natural or artificial seawater and NSS did not allowed us to distinguish the three different systems that show excellent anticorrosion properties. However, during the alternate immersion test, the organic coating system applied onto HDG presented blisters, showing a greater sensitivity to this test than the two other systems. For panels with a defect, NSS allowed to age the coatings more rapidly than monotone conditions, and the coating system applied onto steel presented the highest degree of corrosion. Meanwhile, the coating systems applied onto HDG and the thermal spray metallic coating showed similar behavior. During the alternate immersion test, the three coated systems with a defect showed clearly different behaviors, therefore it was possible to rank the three systems. Finally, it appeared that the alternate immersion test was the most aggressive condition. It was then proposed that a realistic thermal cycling and an artificial defect are needed when performing ageing tests of thick marine organic coating systems in order to properly rank/evaluate the different systems. Full article
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17 pages, 3713 KiB  
Article
Effect of Multispecies Microbial Consortia on Microbially Influenced Corrosion of Carbon Steel
by Hoang C. Phan, Linda L. Blackall and Scott A. Wade
Corros. Mater. Degrad. 2021, 2(2), 133-149; https://doi.org/10.3390/cmd2020008 - 25 Mar 2021
Cited by 12 | Viewed by 3912
Abstract
Microbially influenced corrosion (MIC) is responsible for significant damage to major marine infrastructure worldwide. While the microbes responsible for MIC typically exist in the environment in a synergistic combination of different species, the vast majority of laboratory-based MIC experiments are performed with single [...] Read more.
Microbially influenced corrosion (MIC) is responsible for significant damage to major marine infrastructure worldwide. While the microbes responsible for MIC typically exist in the environment in a synergistic combination of different species, the vast majority of laboratory-based MIC experiments are performed with single microbial pure cultures. In this work, marine grade steel was exposed to a single sulfate reducing bacterium (SRB, Desulfovibrio desulfuricans) and various combinations of bacteria (both pure cultures and mixed communities), and the steel corrosion studied. Differences in the microbial biofilm composition and succession, steel weight loss and pitting attack were observed for the various test configurations studied. The sulfate reduction phenotype was successfully shown in half-strength marine broth for both single and mixed communities. The highest corrosion according to steel weight loss and pitting, was recorded in the tests with D. desulfuricans alone when incubated in a nominally aerobic environment. The multispecies microbial consortia yielded lower general corrosion rates compared to D. desulfuricans or for the uninoculated control. Full article
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20 pages, 35928 KiB  
Article
Experience-Based Physico-Chemical Models for Long-Term Reinforcement Corrosion
by Robert E. Melchers
Corros. Mater. Degrad. 2021, 2(1), 100-119; https://doi.org/10.3390/cmd2010006 - 3 Mar 2021
Cited by 10 | Viewed by 3347
Abstract
The long-term corrosion progression of steel reinforcement is important for estimating the life of reinforced concrete infrastructure. Reviews of field experience and results from recent controlled long-term experiments show that the development of reinforcement corrosion is much more complex than the classical empirical [...] Read more.
The long-term corrosion progression of steel reinforcement is important for estimating the life of reinforced concrete infrastructure. Reviews of field experience and results from recent controlled long-term experiments show that the development of reinforcement corrosion is much more complex than the classical empirical Tuutti model. A new, comprehensive model is proposed, referencing observations and inferences from many field and laboratory observations and built on the bi-modal model for the corrosion of steel. It includes the critical roles of air-voids in the concrete at the concrete-steel interface and the effect of long-term alkali leaching as accelerated by the presence of chlorides. Both are affected by compaction and concrete permeability. The role of chlorides in the early stages is confined to pitting within air-voids. These are critical for allowing initiation to occur, while their size influences the severity of early corrosion. Empirical data show that for seawater with an average water temperature in the range of 10–20 °C, the corresponding rate of long-term corrosion ra is in the range of 0.012–0.015 mm/y. Full article
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15 pages, 3569 KiB  
Article
Influence of Mg2+ Ions on the Formation of Green Rust Compounds in Simulated Marine Environments
by Philippe Refait, Julien Duboscq, Kahina Aggoun, René Sabot and Marc Jeannin
Corros. Mater. Degrad. 2021, 2(1), 46-60; https://doi.org/10.3390/cmd2010003 - 31 Jan 2021
Cited by 6 | Viewed by 3000
Abstract
Green rust compounds (GR), i.e., Fe(II-III) layered double hydroxides, are important transient compounds resulting from the corrosion of steel in seawater. The sulfated variety, GR(SO42−), was reported as one of the main components of the corrosion product layer, while the [...] Read more.
Green rust compounds (GR), i.e., Fe(II-III) layered double hydroxides, are important transient compounds resulting from the corrosion of steel in seawater. The sulfated variety, GR(SO42−), was reported as one of the main components of the corrosion product layer, while the chloride variety, GR(Cl), was more rarely observed. The carbonate variety, GR(CO32−), is favored by an increase in pH and forms preferentially in the cathodic areas of the metal surface. Since Mg(II) is abundant in seawater, it may have a strong influence on the formation of GR compounds, in particular as it can be incorporated in the hydroxide sheets of the GR crystal structure. In the present work, the influence of Mg2+ on the precipitation reaction of GR(SO42−) was investigated. For that purpose, Mg2+ was substituted, partially or entirely, for Fe2+. The GR was then prepared by mixing a solution of FeCl3·6H2O, Na2SO4·10H2O, NaCl, FeCl2·4H2O and/or MgCl2·4H2O with a solution of NaOH. The precipitation of the GR was followed or not by a 1-week aging period. The obtained precipitate was characterized by X-ray diffraction. It was observed that Mg(II) favored the formation of chloride green rust GR(Cl) and magnetite Fe3O4 at the detriment of GR(SO42−). The proportion of GR(Cl) and Fe3O4 increased with the Mg(II):Fe(II) substitution ratio. Without Fe(II), the precipitation reaction led to iowaite, i.e., the Mg(II)-Fe(III) compound structurally similar to GR(Cl). It is forwarded that the presence of Mg2+ cations in the hydroxide sheets of the GR crystal structure is detrimental for the stability of the crystal structure of GR(SO42−) and favors the formation of other mixed valence Fe(II,III) compounds. Full article
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Review

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27 pages, 1108 KiB  
Review
Corrosion Performance of Electrodeposited Zinc and Zinc-Alloy Coatings in Marine Environment
by Kranthi Kumar Maniam and Shiladitya Paul
Corros. Mater. Degrad. 2021, 2(2), 163-189; https://doi.org/10.3390/cmd2020010 - 21 Apr 2021
Cited by 40 | Viewed by 9764
Abstract
Electrodeposited zinc and zinc-alloy coatings have been extensively used in a wide variety of applications such as transport, automotive, marine, and aerospace owing to their good corrosion resistance and the potential to be economically competitive. As a consequence, these coatings have become the [...] Read more.
Electrodeposited zinc and zinc-alloy coatings have been extensively used in a wide variety of applications such as transport, automotive, marine, and aerospace owing to their good corrosion resistance and the potential to be economically competitive. As a consequence, these coatings have become the industry choice for many applications to protect carbon and low alloy steels against degradation upon their exposure in different corrosive environments such as industrial, marine, coastal, etc. Significant works on the electrodeposition of Zn, Zn-alloys and their composites from conventional chloride, sulfate, aqueous and non-aqueous electrolyte media have been progressed over the past decade. This paper provides a review covering the corrosion performance of the electrodeposited Zn, Zn-alloy and composite with different coating properties that have been developed over the past decade employing low-toxic aqueous and halide-free non-aqueous electrolyte media. The influence of additives, nano-particle addition to the electrolyte media on the morphology, texture in relation to the corrosion performance of coatings with additional functionalities are reviewed in detail. In addition, the review covers the recent developments along with cost considerations and the future scope of Zn and Zn-alloy coatings. Full article
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21 pages, 3689 KiB  
Review
Corrosion of Carbon Steel in Marine Environments: Role of the Corrosion Product Layer
by Philippe Refait, Anne-Marie Grolleau, Marc Jeannin, Celine Rémazeilles and René Sabot
Corros. Mater. Degrad. 2020, 1(1), 198-218; https://doi.org/10.3390/cmd1010010 - 3 Jun 2020
Cited by 98 | Viewed by 11789
Abstract
This article presents a synthesis of recent studies focused on the corrosion product layers forming on carbon steel in natural seawater and the link between the composition of these layers and the corrosion mechanisms. Additional new experimental results are also presented to enlighten [...] Read more.
This article presents a synthesis of recent studies focused on the corrosion product layers forming on carbon steel in natural seawater and the link between the composition of these layers and the corrosion mechanisms. Additional new experimental results are also presented to enlighten some important points. First, the composition and stratification of the layers produced by uniform corrosion are described. A focus is made on the mechanism of formation of the sulfate green rust because this compound is the first solid phase to precipitate from the dissolved species produced by the corrosion of the steel surface. Secondly, localized corrosion processes are discussed. In any case, they involve galvanic couplings between anodic and cathodic zones of the metal surface and are often associated with heterogeneous corrosion product layers. The variations of the composition of these layers with the anodic/cathodic character of the underlying metal surface, and in particular the changes in magnetite content, are thoroughly described and analyzed to enlighten the self-sustaining ability of the process. Finally, corrosion product layers formed on permanently immersed steel surfaces were exposed to air. Their drying and oxidation induced the formation of akaganeite, a common product of marine atmospheric corrosion that was, however, not detected on the steel surface after the permanent immersion period. Full article
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