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Corrosion Studies on Metallic Cultural Heritage
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Corrosion Studies on Metallic Cultural Heritage

A special issue of Materials (ISSN 1996-1944). This special issue belongs to the section "Corrosion".

Deadline for manuscript submissions: closed (20 January 2024) | Viewed by 9946

Special Issue Editors

Dr. Blanca Ramirez Barat

E-Mail Website1 Website2
Guest Editor
Centro Nacional de Investigaciones Metalúrgicas (CENIM), Consejo Superior de Investigaciones Científicas (CSIC), Avda. Gregorio del Amo 8, 28040 Madrid, Spain
Interests: cultural heritage; heritage science; conservation science; metallic heritage; corrosion; electrochemistry; coatings
Dr. Cristina Chiavari

E-Mail Website
Guest Editor
Dipartimento di Beni Culturali, Alma Mater Studiorum Università di Bologna, Via degli Ariani, 1, 48121 Ravenna, Italy
Interests: chemistry of the environment and cultural heritage; metals in CH, decay and protection; metals in industry: corrosion and protection; archaeometallurgy

Special Issue Information

Dear Colleagues,

Since ancient times, metals have played a fundamental role in human history, their use being closely linked to the development of societies—technologically, economically, socially and culturally. The versatility of metals, attributed to their mechanical properties, durability, formability and appearance, has enabled humanity to produce weapons and tools, but also coins, jewelry, sculptures, etc. For this reason, metal heritage is an important part of our historical and cultural legacy that needs to be preserved and passed on to future generations.

Although metal objects can also suffer mechanical damage, the main conservation problem in metal cultural heritage is corrosion. In fact, corrosion is the main cause of the deterioration of all metallic materials, whether or not they are part of our heritage, constituting a problem of global dimension.

The degradation of metallic materials due to corrosion entails considerable economic losses; however, in the case of metallic cultural heritage, the losses go far beyond the economic dimension since they are generally unique and irreplaceable pieces. Given the magnitude of the problem, the fight against corrosion is a very broad and constantly developing field of study, which is approached from different strategies. In the specific context of metallic cultural heritage, the need to preserve both the tangible and intangible aspects of the objects imposes several constraints. This makes it necessary to develop research approaches focused on this particular type of material.

The aim of this Special Issue is to compile the advances and strategies on corrosion studies on cultural heritage, for a better understanding of its causes, mechanisms and consequences, as well as improvements for the diagnosis and protection of metallic heritage.

In this Special Issue, original research articles and reviews are welcome. Research areas may include (but are not limited to) the following:

  • Corrosion of metallic cultural heritage, including causes, mechanisms, and the analysis of corrosion products.
  • Natural and artificial patinas: History, formation, composition and role in the aesthetics and conservation of metallic cultural heritage.
  • Environmental corrosion of metallic cultural heritage: indoor and outdoor.
  • Corrosion protection: Coatings, inhibitors and other strategies to prevent the corrosion of metallic cultural heritage.
  • Diagnostic and characterization techniques to evaluate corrosion and protection of metallic cultural heritage.

We look forward to receiving your contributions.

Dr. Blanca Ramirez Barat
Dr. Cristina Chiavari
Guest Editors

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

  • conservation
  • cultural heritage
  • corrosion protection
  • metallic heritage
  • archaeological metals
  • protective coatings
  • corrosion inhibitors
  • patinas

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Published Papers (5 papers)

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Research

17 pages, 5807 KiB  
Article
Early Stages of Metal Corrosion in Coastal Archaeological Sites: Effects of Chemical Composition in Silver and Copper Alloys
by Francesca Boccaccini, Cristina Riccucci, Elena Messina, Marianna Pascucci, Ferdinando Bosi, Luca Aldega, Alessandro Ciccola, Paolo Postorino, Gabriele Favero, Gabriel Maria Ingo and Gabriella Di Carlo
Materials 2024, 17(2), 442; https://doi.org/10.3390/ma17020442 - 17 Jan 2024
Viewed by 1131
Abstract
In this study, metal disks with different chemical composition (two Ag-based alloys and three Cu-based alloys) were buried in the soil of coastal archaeological sites for a period of 15 years. The aim was to naturally induce the growth of corrosion patinas to [...] Read more.
In this study, metal disks with different chemical composition (two Ag-based alloys and three Cu-based alloys) were buried in the soil of coastal archaeological sites for a period of 15 years. The aim was to naturally induce the growth of corrosion patinas to obtain a deeper insight into the role of alloying elements in the formation of the patinas and into the degradation mechanisms occurring in the very early stages of burial. To reach the aim, the morphological, compositional and structural features of the patinas grown over 15 years were extensively characterized by optical microscopy, field emission scanning electron microscopy coupled with energy dispersive spectrometry, X-ray diffraction and micro-Raman spectroscopy. Results showed that the Cu amount in Ag-based alloys strongly affected the final appearance, as well as the composition and structure of the patinas. Corrosion mechanisms typical of archaeological finds, such as the selective dissolution of Cu, Pb and Zn and internal oxidation of Sn, occurred in the Cu-based alloys, even if areas enriched in Zn and Pb compounds were also detected and attributed to an early stage of degradation. In addition, some unusual and rare compounds were detected in the patinas developed on the Cu-based disks. Full article
(This article belongs to the Special Issue Corrosion Studies on Metallic Cultural Heritage)
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20 pages, 2121 KiB  
Article
Pollution and Heritage Metals—Effectiveness of Oddy Testing and Mitigation
by David Thickett and Tayba Batool
Materials 2023, 16(24), 7596; https://doi.org/10.3390/ma16247596 - 11 Dec 2023
Viewed by 1492
Abstract
Metals are particularly sensitive to some pollutant gases. Many museum showcases and store rooms present atmospheres that can corrode cultural heritage artefacts containing metals. Whilst numerous strategies have been reported to mitigate such situations, avoiding them is preferable. Several approaches to testing materials [...] Read more.
Metals are particularly sensitive to some pollutant gases. Many museum showcases and store rooms present atmospheres that can corrode cultural heritage artefacts containing metals. Whilst numerous strategies have been reported to mitigate such situations, avoiding them is preferable. Several approaches to testing materials used in construction, fitting out or dressing are used. The relative merits and drawbacks are discussed. Several parameters of the most widely used, accelerated corrosion ‘Oddy’ test are investigated. The influence of abrasive on subsequent corrosion of lead and copper coupons are assessed. Quantification methods for tested coupons are reviewed. The influence of test duration and temperature are assessed through comparison with real-life, long-term experience of material behaviour. Direct contact tests with touching the test material are investigated. Several materials present in artefacts are known to potentially cause corrosion when enclosed with metals in other artefacts. A number of situations are investigated with pollution and RH and some corrosion rate measurements. Ways to isolate artefacts or mitigate are explored and a decision support model is further developed. Full article
(This article belongs to the Special Issue Corrosion Studies on Metallic Cultural Heritage)
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14 pages, 3210 KiB  
Article
Corrosion Risk to Metal-Based Artefacts in a Scientific and Technical Museum: An Assessment of Environmental and Exhibition Conditions
by María Teresa Molina, Emilio Cano, Irene Llorente and Blanca Ramírez-Barat
Materials 2023, 16(12), 4239; https://doi.org/10.3390/ma16124239 - 8 Jun 2023
Cited by 2 | Viewed by 2182
Abstract
Materials such as wood, textiles, or plastics that are part of the exhibition system in museums are known to emit pollutants such as organic acids. Scientific and technical objects that include these materials in their composition can themselves be a potential source of [...] Read more.
Materials such as wood, textiles, or plastics that are part of the exhibition system in museums are known to emit pollutants such as organic acids. Scientific and technical objects that include these materials in their composition can themselves be a potential source of emissions, which, together with inappropriate humidity and temperature conditions, can lead to corrosion of the metallic parts. In this work, we have studied the corrosivity of different locations in two venues of the Spanish National Museum of Science and Technology (MUNCYT). Coupons of the most representative metals from the collection were placed in different showcases and rooms for 9 months. The corrosion of the coupons has been evaluated in terms of the rate of mass gain, colour changes and characterisation of the corrosion products. The results were correlated to the relative humidity and concentration of gaseous pollutants to determine which metals are most susceptible to corrosion. The results show that metal artefacts exposed in showcases have a higher risk of corrosion than those exposed directly in the room, and that some pollutants are emitted by the artefacts. The corrosivity of the museum environment is low for copper, brass, and aluminium in most locations; however, some placements present a higher aggressivity for steel and lead, due to the high humidity and the presence of organic acids. Full article
(This article belongs to the Special Issue Corrosion Studies on Metallic Cultural Heritage)
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17 pages, 8488 KiB  
Article
The San Carlo Colossus: An Insight into the Mild Galvanic Coupling between Wrought Iron and Copper
by Chiara Petiti, Carla Martini, Cristina Chiavari, Silvia Vettori, Jean Marie Welter, Paulina Guzmán García Lascurain and Sara Goidanich
Materials 2023, 16(5), 2072; https://doi.org/10.3390/ma16052072 - 3 Mar 2023
Cited by 1 | Viewed by 1992
Abstract
The San Carlo Colossus, known as San Carlone, is a monument constituted by an internal stone pillar support to which a wrought iron structure is attached. Embossed copper sheets are fixed to the iron structure to give the final shape to the [...] Read more.
The San Carlo Colossus, known as San Carlone, is a monument constituted by an internal stone pillar support to which a wrought iron structure is attached. Embossed copper sheets are fixed to the iron structure to give the final shape to the monument. After more than 300 years of outdoor exposure, this statue represents an opportunity for an in-depth investigation of long-term galvanic coupling between wrought iron and copper. Most iron elements of the San Carlone appeared in good conservation conditions with scarce evidence of galvanic corrosion. In some cases, the same iron bars presented some portions in good conservation conditions and other nearby portions with active corrosion. The aim of the present study was to investigate the possible factors correlated with such mild galvanic corrosion of wrought iron elements despite the widespread direct contact with copper for more than 300 years. Optical and electronic microscopy and compositional analyses were carried out on representative samples. Furthermore, polarisation resistance measurements were performed both on-site and in a laboratory. The results revealed that the iron bulk composition showed a ferritic microstructure with coarse grains. On the other hand, the surface corrosion products were mainly composed of goethite and lepidocrocite. Electrochemical analyses showed good corrosion resistance of both the bulk and surface of the wrought iron, and galvanic corrosion is not occurring probably due to the iron’s relatively noble corrosion potential. The few areas where iron corrosion was observed are apparently related to environmental factors, such as the presence of thick deposits and to the presence of hygroscopic deposits that create localized microclimatic conditions on the surface of the monument. Full article
(This article belongs to the Special Issue Corrosion Studies on Metallic Cultural Heritage)
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15 pages, 5452 KiB  
Article
Protection of Patinated Bronze with Long-Chain Phosphonic Acid/Organic Coating Combined System
by Dajana Mikić and Helena Otmačić Ćurković
Materials 2023, 16(4), 1660; https://doi.org/10.3390/ma16041660 - 16 Feb 2023
Cited by 4 | Viewed by 1644
Abstract
Bronze cultural heritage in urban areas is susceptible to decay due to the significant amount of pollutants present in the air. This causes the dissolution of bronze and the patina on its surface. The efficient protection of outdoor bronze cultural heritage is still [...] Read more.
Bronze cultural heritage in urban areas is susceptible to decay due to the significant amount of pollutants present in the air. This causes the dissolution of bronze and the patina on its surface. The efficient protection of outdoor bronze cultural heritage is still an unresolved problem. The aim of this work is to investigate 16-phosphonohexadecanoic acid as an environmentally friendly and non-toxic corrosion inhibitor for patinated bronze. The corrosion protection of sulphide-patinated bronze by phosphonic acid alone and in combination with acrylic coating Paraloid B-72 is examined. In order to achieve efficient corrosion protection, various parameters of the phosphonic acid application were studied. The efficiency of protection is examined by electrochemical impedance spectroscopy (EIS) during the immersion in simulated acid rain solution and after exposure to a corrosion chamber. It was found that the studied phosphonic acid provides corrosion protection to patinated bronze and significantly improves the protective properties of Paraloid B72. This was also confirmed by scanning electron microscopy (SEM) examination of the coating surface after exposure to a corrosive environment. Full article
(This article belongs to the Special Issue Corrosion Studies on Metallic Cultural Heritage)
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