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Fundamental and Research Frontier of Atmospheric Corrosion

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A special issue of Materials (ISSN 1996-1944).

Deadline for manuscript submissions: closed (28 February 2017) | Viewed by 70176

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Special Issue Editor

Prof. Dr. Manuel Morcillo

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Guest Editor

National Centre for Metallurgical Research (CENIM-CSIC), Avda Gregorio del Amo 8, 28040 Madrid, Spain
Interests: atmospheric corrosion, anticorrosive protection by surface coatings

Special Issue Information

Dear Colleagues,

Atmospheric corrosion has been extensively researched over the last one hundred years, and, as a result the effects of meteorological variables and pollution on atmospheric corrosion, are now quite well known. Even so, our knowledge of this issue still holds many gaps, such as how to accurately estimate the total time of wetness of metallic surfaces, the effects of climate change and acid rain, and the corrosion mechanisms that act in chloride-rich and marine-industrial atmospheres; the latter being particularly important in less developed countries where factories are often located in coastal regions.
For engineers and political policy-makers it is fundamental to be able to predict atmospheric corrosion well into the future (25, 50, 100 years). Data mining and modelling tools can help to improve atmospheric corrosion forecasts and anti-corrosive designs, but despite great progress in the development of damage functions (dose-response) in wide-scale international cooperative research programmes there is still a way to go for such long term modelling of atmospheric corrosion processes. Nonetheless, in some highly developed countries efforts are now being made to design civil structures such as bridges and other load-bearing structures for 50–100 years of service without any maintenance.
Finally, mankind is concerned about the degradation , restoration and conservation of its historic heritage. The effects of atmospheric corrosion on old buildings and structures, statues and monuments, etc., have resulted in substantial degradation of artistic and historic objects.
For this Special Issue, we invite authors to publish research articles or comprehensive reviews on the topics referred to above.

Prof. Dr. Manuel Morcillo
Guest Editor

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Materials is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2600 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

climate, time of wetness, climate change
aerosols, particle induced corrosion
chloride-rich atmospheres, de-icing salts
impact of atmospheric corrosion on the environment (runoff)
prediction, modelling
degradation and conservation of cultural heritage
weathering steels, copper (alloys), etc.
surface coatings
worldwide atmospheric corrosion research
new analytical techniques

Published Papers (11 papers)

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Research

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12563 KiB

Open AccessArticle

ICP Materials Trends in Corrosion, Soiling and Air Pollution (1987–2014)

by Johan Tidblad, Kateřina Kreislová, Markus Faller, Daniel De la Fuente, Tim Yates, Aurélie Verney-Carron, Terje Grøntoft, Andrew Gordon and Ulrik Hans

Materials 2017, 10(8), 969; https://doi.org/10.3390/ma10080969 - 19 Aug 2017

Cited by 26 | Viewed by 6250

Abstract

Results from the international cooperative programme on effects on materials including historic and cultural monuments are presented from the period 1987–2014 and include pollution data (SO₂, NO₂, O₃, HNO₃ and PM₁₀), corrosion data (carbon steel, weathering steel, zinc, copper, aluminium and limestone) and data on the soiling of modern glass for nineteen industrial, urban and rural test sites in Europe. Both one-year and four-year corrosion data are presented. Corrosion and pollution have decreased significantly and a shift in the magnitude is generally observed around 1997: from a sharp decrease to a more modest decrease or to a constant level without any decrease. SO₂ levels, carbon steel and copper corrosion have decreased even after 1997, which is more pronounced in urban areas, while corrosion of the other materials shows no decrease after 1997, when looking at one-year values. When looking at four-year values, however, there is a significant decrease after 1997 for zinc, which is not evident when looking at the one-year values. This paper also presents results on corrosion kinetics by comparison of one- and four-year values. For carbon steel and copper, kinetics is relatively independent of sites while other materials, especially zinc, show substantial variation in kinetics for the first four years, which needs to be considered when producing new and possibly improved models for corrosion. Full article

(This article belongs to the Special Issue Fundamental and Research Frontier of Atmospheric Corrosion)

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6179 KiB

Open AccessFeature PaperArticle

New Insights in the Long-Term Atmospheric Corrosion Mechanisms of Low Alloy Steel Reinforcements of Cultural Heritage Buildings

by Marie Bouchar, Philippe Dillmann and Delphine Neff

Materials 2017, 10(6), 670; https://doi.org/10.3390/ma10060670 - 19 Jun 2017

Cited by 12 | Viewed by 4793

Abstract

Reinforcing clamps made of low alloy steel from the Metz cathedral and corroded outdoors during 500 years were studied by OM, FESEM/EDS, and micro-Raman spectroscopy. The corrosion product layer is constituted of a dual structure. The outer layer is mainly constituted of goethite and lepidocrocite embedding exogenous elements such as Ca and P. The inner layer is mainly constituted of ferrihydrite. The behaviour of the inner layer under conditions simulating the wetting stage of the RH wet/dry atmospheric corrosion cycle was observed by in situ micro-Raman spectroscopy. The disappearance of ferrihydrite near the metal/oxide interface strongly suggests a mechanism of reductive dissolution caused by the oxidation of the metallic substrate and was observed for the first time in situ on an archaeological system. Full article

(This article belongs to the Special Issue Fundamental and Research Frontier of Atmospheric Corrosion)

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2110 KiB

Open AccessArticle

Annual Atmospheric Corrosion of Carbon Steel Worldwide. An Integration of ISOCORRAG, ICP/UNECE and MICAT Databases

by Belén Chico, Daniel De la Fuente, Iván Díaz, Joaquín Simancas and Manuel Morcillo

Materials 2017, 10(6), 601; https://doi.org/10.3390/ma10060601 - 31 May 2017

Cited by 60 | Viewed by 5965

Abstract

In the 1980s, three ambitious international programmes on atmospheric corrosion (ISOCORRAG, ICP/UNECE and MICAT), involving the participation of a total of 38 countries on four continents, Europe, America, Asia and Oceania, were launched. Though each programme has its own particular characteristics, the similarity of the basic methodologies used makes it possible to integrate the databases obtained in each case. This paper addresses such an integration with the aim of establishing simple universal damage functions (DF) between first year carbon steel corrosion in the different atmospheres and available environmental variables, both meteorological (temperature (T), relative humidity (RH), precipitation (P), and time of wetness (TOW)) and pollution (SO₂ and NaCl). In the statistical processing of the data, it has been chosen to differentiate between marine atmospheres and those in which the chloride deposition rate is insignificant (<3 mg/m².d). In the DF established for non-marine atmospheres a great influence of the SO₂ content in the atmosphere was seen, as well as lesser effects by the meteorological parameters of RH and T. Both NaCl and SO₂ pollutants, in that order, are seen to be the most influential variables in marine atmospheres, along with a smaller impact of TOW. Full article

(This article belongs to the Special Issue Fundamental and Research Frontier of Atmospheric Corrosion)

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4061 KiB

Open AccessFeature PaperArticle

Prediction of First-Year Corrosion Losses of Carbon Steel and Zinc in Continental Regions

by Yulia M. Panchenko and Andrey I. Marshakov

Materials 2017, 10(4), 422; https://doi.org/10.3390/ma10040422 - 18 Apr 2017

Cited by 30 | Viewed by 4734

Abstract

Dose-response functions (DRFs) developed for the prediction of first-year corrosion losses of carbon steel and zinc (K₁) in continental regions are presented. The dependences of mass losses on SO₂ concentration, K = f([SO₂]), obtained from experimental data, as well as nonlinear dependences of mass losses on meteorological parameters, were taken into account in the development of the DRFs. The development of the DRFs was based on the experimental data from one year of testing under a number of international programs: ISO CORRAG, MICAT, two UN/ECE programs, the Russian program in the Far-Eastern region, and data published in papers. The paper describes predictions of K₁ values of these metals using four different models for continental test sites under UN/ECE, RF programs and within the MICAT project. The predictions of K₁ are compared with experimental K₁ values, and the models presented here are analyzed in terms of the coefficients used in the models. Full article

(This article belongs to the Special Issue Fundamental and Research Frontier of Atmospheric Corrosion)

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9360 KiB

Open AccessArticle

Corrosion Prediction with Parallel Finite Element Modeling for Coupled Hygro-Chemo Transport into Concrete under Chloride-Rich Environment

by Okpin Na, Xiao-Chuan Cai and Yunping Xi

Materials 2017, 10(4), 350; https://doi.org/10.3390/ma10040350 - 28 Mar 2017

Cited by 7 | Viewed by 4111

Abstract

The prediction of the chloride-induced corrosion is very important because of the durable life of concrete structure. To simulate more realistic durability performance of concrete structures, complex scientific methods and more accurate material models are needed. In order to predict the robust results of corrosion initiation time and to describe the thin layer from concrete surface to reinforcement, a large number of fine meshes are also used. The purpose of this study is to suggest more realistic physical model regarding coupled hygro-chemo transport and to implement the model with parallel finite element algorithm. Furthermore, microclimate model with environmental humidity and seasonal temperature is adopted. As a result, the prediction model of chloride diffusion under unsaturated condition was developed with parallel algorithms and was applied to the existing bridge to validate the model with multi-boundary condition. As the number of processors increased, the computational time decreased until the number of processors became optimized. Then, the computational time increased because the communication time between the processors increased. The framework of present model can be extended to simulate the multi-species de-icing salts ingress into non-saturated concrete structures in future work. Full article

(This article belongs to the Special Issue Fundamental and Research Frontier of Atmospheric Corrosion)

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4810 KiB

Open AccessFeature PaperArticle

Analysis of Historic Copper Patinas. Influence of Inclusions on Patina Uniformity

by Tingru Chang, Inger Odnevall Wallinder, Daniel De la Fuente, Belen Chico, Manuel Morcillo, Jean-Marie Welter and Christofer Leygraf

Materials 2017, 10(3), 298; https://doi.org/10.3390/ma10030298 - 16 Mar 2017

Cited by 16 | Viewed by 5112

Abstract

The morphology and elemental composition of cross sections of eight historic copper materials have been explored. The materials were taken from copper roofs installed in different middle and northern European environments from the 16th to the 19th century. All copper substrates contain inclusions of varying size, number and composition, reflecting different copper ores and production methods. The largest inclusions have a size of up to 40 μm, with most inclusions in the size ranging between 2 and 10 μm. The most common element in the inclusions is O, followed by Pb, Sb and As. Minor elements include Ni, Sn and Fe. All historic patinas exhibit quite fragmentized bilayer structures, with a thin inner layer of cuprite (Cu₂O) and a thicker outer one consisting mainly of brochantite (Cu₄SO₄(OH)₆). The extent of patina fragmentation seems to depend on the size of the inclusions, rather than on their number and elemental composition. The larger inclusions are electrochemically nobler than the surrounding copper matrix. This creates micro-galvanic effects resulting both in a profound influence on the homogeneity and morphology of historic copper patinas and in a significantly increased ratio of the thicknesses of the brochantite and cuprite layers. The results suggest that copper patinas formed during different centuries exhibit variations in uniformity and corrosion protection ability. Full article

(This article belongs to the Special Issue Fundamental and Research Frontier of Atmospheric Corrosion)

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11488 KiB

Open AccessArticle

Rust Formation Mechanism on Low Alloy Steels after Exposure Test in High Cl− and High SOx Environmen

by Toshiyasu Nishimura

Materials 2017, 10(2), 199; https://doi.org/10.3390/ma10020199 - 17 Feb 2017

Cited by 10 | Viewed by 4497

Abstract

Exposure tests were performed on low alloy steels in high Cl− and high SOx environment, and the structure of the rust were analyzed by TEM (Transmission Electron Microscopy) and Raman Spectroscopy. In the exposure test site, the concentrations of Cl− and SOx were found to be high, which caused the corrosion of the steels. The conventional weathering steel (SMA: 0.6% Cr-0.4% Cu-Fe) showed higher corrosion resistance as compared to the carbon steel (SM), and Ni bearing steel exhibited the highest one. Raman spectroscopy showed that the inner rust of Ni bearing steel was mainly composed of α-FeOOH and spinel oxides. On the other hand, SMA contained β- and γ-FeOOH in inner rust, which increased the corrosion. TEM showed that nano-scale complex iron oxides containing Ni or Cr were formed in the rust on the low alloy steels, which suppressed the corrosion of steels in high Cl− and high SOx environment. Full article

(This article belongs to the Special Issue Fundamental and Research Frontier of Atmospheric Corrosion)

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Review

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201 KiB

Open AccessFeature PaperReview

Recent Progress and Required Developments in Atmospheric Corrosion of Galvanised Steel and Zinc

by Ivan S. Cole

Materials 2017, 10(11), 1288; https://doi.org/10.3390/ma10111288 - 09 Nov 2017

Cited by 31 | Viewed by 3782

Abstract

This paper reviews the progress in atmospheric corrosion of zinc since 2009. It firstly summarises the state of the art in 2009, then outlines progress since 2009, and then looks at the significance of this progress and the areas the need more research. Within this framework, it looks at climate effects, oxide formation, oxide properties, pitting, laboratory duplication of atmospheric corrosion, and modelling. The major findings are that there have been major advances in the fields understanding of the structure of corrosion patina, in particular their layered structure and the presence of compact layers, local corrosion attacks have been found to be a significant process in atmospheric corrosion and experiments under droplets are leading to new understanding of the criticality of drop size in regulating atmospheric corrosion processes. Further research is indicating that zinc oxide within corrosion products may promote the oxygen reduction reaction (ORR) and that, in porous oxides, the ORR would control pore chemistry and may promote oxide densification. There is a strong need for more research to understand more deeply the formation and properties of these layered oxides as well as additional research to refine and quantify our emerging understanding of corrosion under droplets. Full article

(This article belongs to the Special Issue Fundamental and Research Frontier of Atmospheric Corrosion)

7600 KiB

Open AccessReview

Vibrational Spectroscopy in Studies of Atmospheric Corrosion

by Saman Hosseinpour and Magnus Johnson

Materials 2017, 10(4), 413; https://doi.org/10.3390/ma10040413 - 18 Apr 2017

Cited by 18 | Viewed by 6486

Abstract

Vibrational spectroscopy has been successfully used for decades in studies of the atmospheric corrosion processes, mainly to identify the nature of corrosion products but also to quantify their amounts. In this review article, a summary of the main achievements is presented with focus on how the techniques infrared spectroscopy, Raman spectroscopy, and vibrational sum frequency spectroscopy can be used in the field. Several different studies have been discussed where these instruments have been used to assess both the nature of corrosion products as well as the properties of corrosion inhibitors. Some of these techniques offer the valuable possibility to perform in-situ measurements in real time on ongoing corrosion processes, which allows the kinetics of formation of corrosion products to be studied, and also minimizes the risk of changing the surface properties which may occur during ex-situ experiments. Since corrosion processes often occur heterogeneously over a surface, it is of great importance to obtain a deeper knowledge about atmospheric corrosion phenomena on the nano scale, and this review also discusses novel vibrational microscopy techniques allowing spectra to be acquired with a spatial resolution of 20 nm. Full article

(This article belongs to the Special Issue Fundamental and Research Frontier of Atmospheric Corrosion)

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19219 KiB

Open AccessReview

Marine Atmospheric Corrosion of Carbon Steel: A Review

by Jenifer Alcántara, Daniel de la Fuente, Belén Chico, Joaquín Simancas, Iván Díaz and Manuel Morcillo

Materials 2017, 10(4), 406; https://doi.org/10.3390/ma10040406 - 13 Apr 2017

Cited by 211 | Viewed by 18454

Abstract

The atmospheric corrosion of carbon steel is an extensive topic that has been studied over the years by many researchers. However, until relatively recently, surprisingly little attention has been paid to the action of marine chlorides. Corrosion in coastal regions is a particularly relevant issue due the latter’s great importance to human society. About half of the world’s population lives in coastal regions and the industrialisation of developing countries tends to concentrate production plants close to the sea. Until the start of the 21st century, research on the basic mechanisms of rust formation in Cl⁻-rich atmospheres was limited to just a small number of studies. However, in recent years, scientific understanding of marine atmospheric corrosion has advanced greatly, and in the authors’ opinion a sufficient body of knowledge has been built up in published scientific papers to warrant an up-to-date review of the current state-of-the-art and to assess what issues still need to be addressed. That is the purpose of the present review. After a preliminary section devoted to basic concepts on atmospheric corrosion, the marine atmosphere, and experimentation on marine atmospheric corrosion, the paper addresses key aspects such as the most significant corrosion products, the characteristics of the rust layers formed, and the mechanisms of steel corrosion in marine atmospheres. Special attention is then paid to important matters such as coastal-industrial atmospheres and long-term behaviour of carbon steel exposed to marine atmospheres. The work ends with a section dedicated to issues pending, noting a series of questions in relation with which greater research efforts would seem to be necessary. Full article

(This article belongs to the Special Issue Fundamental and Research Frontier of Atmospheric Corrosion)

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2083 KiB

Open AccessReview

The Results of 45 Years of Atmospheric Corrosion Study in the Czech Republic

by Katerina Kreislova and Dagmar Knotkova

Materials 2017, 10(4), 394; https://doi.org/10.3390/ma10040394 - 07 Apr 2017

Cited by 29 | Viewed by 5162

Abstract

Atmospheric corrosion poses a significant problem with regard to destruction of various materials, especially metals. Observations made over the past decades suggest that the world’s climate is changing. Besides global warming, there are also changes in other parameters. For example, average annual precipitation increased by nearly 10% over the course of the 20th century. In Europe, the most significant change, from the atmospheric corrosion point of view, was an increase in SO₂ pollution in the 1970s through the 1980s and a subsequent decrease in this same industrial air pollution and an increase in other types of air pollution, which created a so-called multi-pollutant atmospheric environment. Exposed metals react to such changes immediately, even if corrosion attack started in high corrosive atmospheres. This paper presents a complex evaluation of the effect of air pollution and other environmental parameters and verification of dose/response equations for conditions in the Czech Republic. Full article

(This article belongs to the Special Issue Fundamental and Research Frontier of Atmospheric Corrosion)

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