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CMD
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Cultural Heritage Materials Degradation and Its Prevention
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Cultural Heritage Materials Degradation and Its Prevention

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

Deadline for manuscript submissions: closed (31 March 2021) | Viewed by 23180

Special Issue Editors

Prof. Dr. Panayota Vassiliou

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Guest Editor
School of Chemical Engineering, National Technical University of Athens, 15780 Athens, Greece
Interests: specialized coatings for the protection of metals; electroless Nickel-oxides composite plating; atmospheric corrosion and protection; marine corrosion and protection; n-semiconducting protective coatings
Special Issues, Collections and Topics in MDPI journals
Prof. Dr. Emma Angelini

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Guest Editor
Department of Applied Science and Technology, Politecnico di Torino, Torino, Italy
Interests: corrosion of metals; protection of metals; cultural heritage safeguard; cultural heritage dissemination
Prof. Dr. Sabrina Grassini

E-Mail Website1 Website2
Guest Editor
Department of Applied Science and Technology, Politecnico di Torino, Torino, Italy
Interests: corrosion of metals; cultural heritage; coatings and thin films; environmental monitoring
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Studies of Cultural Heritage (CH) transcend numerous scientific fields, from Archaeology and History to Physics, Physical Chemistry, Materials Science, Electronics, Computer Science, and many more. Man’s urge to comprehend his past and safeguard it has led to perpetually augmenting research throughout the 20th century up to the present. Myriad studies among scientists have explored the degradation modes of artefacts to delineate their manufacturing methods and predict what will occur to them under exposure in the environment, and how they may be optimally preserved for future generations. This Special Issue focuses on these domains of interdisciplinary study, providing new challenges in the Cultural Heritage field. Specific topics of interest include:

  • Corrosion and degradation mechanisms of CH artefacts
  • Effects of the environment on CH surfaces
  • Non-destructive testing of CH materials
  • Manufacturing techniques in CH
  • Nanotechnology in service of CH
  • Ethical issues regarding conservation of CH

Prof. Dr. Panayota Vassiliou
Prof. Dr. Emma Angelini
Prof. Dr. Sabrina Grassini
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. Corrosion and Materials Degradation is an international peer-reviewed open access quarterly 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 1000 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

  • Cultural Heritage
  • corrosion
  • degradation
  • metals
  • stones
  • pigments
  • mortars
  • ceramics
  • environmental effects
  • nanotechnology

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Published Papers (6 papers)

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Research

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16 pages, 4614 KiB  
Article
Development of an Optimized NDT Methodology for the Investigation of Ancient Greek Copper-Based Artifacts
by Amani-Christiana Saint, Vasiliki Dritsa and Maria Koui
Corros. Mater. Degrad. 2021, 2(2), 325-340; https://doi.org/10.3390/cmd2020017 - 15 Jun 2021
Cited by 2 | Viewed by 3123
Abstract
A multi-analytical non-destructive testing (NDT) methodology was applied to copper-based artifacts originated from various archaeological sites of Greece. X-ray fluorescence (XRF), fiber optics diffuse reflectance spectroscopy (FORS) and scanning electron microscopy coupled with an energy dispersive X-ray detector (ESEM-EDX) were used for the [...] Read more.
A multi-analytical non-destructive testing (NDT) methodology was applied to copper-based artifacts originated from various archaeological sites of Greece. X-ray fluorescence (XRF), fiber optics diffuse reflectance spectroscopy (FORS) and scanning electron microscopy coupled with an energy dispersive X-ray detector (ESEM-EDX) were used for the characterization of the alloys and the corrosion products. The key elements of the artifacts belonging to the Early Bronze Age (2700–2300 BC) were copper and arsenic, while tin bronze was used for the fabrication of the Late Bronze Age (1600–1100 BC) artifacts. The effectiveness of XRF for the determination of the bulk composition was confirmed by comparative study with the previously applied atomic absorption spectroscopy (AAS) and inductively coupled plasma–atomic emission spectrometry (ICP-AES) destructive techniques. Significant differences between the artifacts were revealed through the spectral measurement of their surface corrosion products color by FORS. ESEM-EDX provided information on the microstructure, the elemental composition of the corrosion layers and bulk, as well as the distribution of the corrosion products on the surface. Conclusively, the combined NDT methodology could be regarded as a valuable and appropriate tool for the elemental composition of the bulk alloy, thus leading to the classification of their historical period and the corrosion products, contributing significantly to their conservation–restoration. Full article
(This article belongs to the Special Issue Cultural Heritage Materials Degradation and Its Prevention)
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19 pages, 4123 KiB  
Article
Microbial-Driven Stabilisation of Archaeological Iron Artefacts
by Sarah James and Edith Joseph
Corros. Mater. Degrad. 2021, 2(2), 274-292; https://doi.org/10.3390/cmd2020015 - 4 Jun 2021
Cited by 2 | Viewed by 3328
Abstract
The instability of iron artefacts is rooted in salt contamination during burial and damages associated with exposure to alternative oxygen levels and high relative humidity once excavated. While a combination of chemical and mechanical treatments is utilised to remove the harmful ions (chlorides, [...] Read more.
The instability of iron artefacts is rooted in salt contamination during burial and damages associated with exposure to alternative oxygen levels and high relative humidity once excavated. While a combination of chemical and mechanical treatments is utilised to remove the harmful ions (chlorides, sulphur species) and excess bulky corrosion products, these methods can be hazardous for conservation staff’s health, have limited success, or require extensive treatment times. Bio-based treatments provide a potentially greener alternative for removing damaging corrosion and creating biogenic mineral passivation layers, thus remediating concerns over costs, duration, and health and safety. Pseudomonas putida mt-2 (KT2440) is capable of utilising iron under certain conditions and for phosphating mild steel; however, applications have not been made in the cultural heritage sector. To address the potential of using bacteria for conservation purposes, Pseudomonas was assessed for both the bioremediation of salt contaminates and the production of a passivation layer suitable for iron artefacts, with specific conservation concerns in mind. Key factors for optimisation include the role of agitation, chloride content, and oxygen content on bacterial growth and biomineralisation. The initial results indicate a growth preference, not reliance, for NaCl and agitation with partial success of bioconversion of a mineral source. Full article
(This article belongs to the Special Issue Cultural Heritage Materials Degradation and Its Prevention)
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21 pages, 6120 KiB  
Article
The Influence of Archaeometallurgical Copper Alloy Castings Microstructure towards Corrosion Evolution in Various Corrosive Media
by Olga Papadopoulou and Panayota Vassiliou
Corros. Mater. Degrad. 2021, 2(2), 227-247; https://doi.org/10.3390/cmd2020013 - 19 May 2021
Cited by 12 | Viewed by 3552
Abstract
The local patterns at the interfaces of corrosion stratification, developed on two archaeometallurgical bronzes (a Cu-Sn-Pb and a Cu-Zn-Sn-Pb alloy), in the as-cast condition, were assessed by OM and SEM-EDS systematic elemental chemical analyses. Previously, the alloys—whose metallurgical features and electrochemical behaviour were [...] Read more.
The local patterns at the interfaces of corrosion stratification, developed on two archaeometallurgical bronzes (a Cu-Sn-Pb and a Cu-Zn-Sn-Pb alloy), in the as-cast condition, were assessed by OM and SEM-EDS systematic elemental chemical analyses. Previously, the alloys—whose metallurgical features and electrochemical behaviour were already well studied—have been subjected to laboratory corrosion experiments. The corrosion procedures involved electrochemical anodic polarization experiments in various chloride media: 0.1 mol/L NaCl, 0.6 mol/L NaCl and two other synthetic chloride-containing solutions, representing electrolytes present in marine urban atmosphere and in the soil of coastal sites. The characterization of the Cu-Sn-Pb alloy electrochemical patinas after anodic sweep (OCP+ 0.6 V) revealed that the metal in all electrolytes undergoes extensive chloride attack and selective dissolution of copper which initiates from the dendritic areas acting as anodic sites. The most abundant corrosion products identified by FTIR in all electrochemical patinas were Cu2(OH)3Cl), Cu2(OH)2CO3 and amorphous Cu and Sn oxides. The characterization of the Cu-Sn-Pb alloy electrochemical patina after slow anodic sweep (OCP+ 1.5 V) in 0.1 mol/L NaCl reveals selective oxidation of dendrites and higher decuprification rate in these areas. Corrosion products of Sn-rich interdendritic areas are dominated by oxygen species (oxides, hydroxides, hydroxyoxides) and Cu-rich dendrites by chlorides. In the case of Cu-Zn-Sn-Pb, Zn in dendritic areas is preferentially attacked. The alloy undergoes simultaneous dezincification and decuprification, with the former progressing faster, especially in dendritic areas. The two processes at the alloy/patina interface leave behind a metal surface where α-dendrites are enriched in Sn compared to the alloy matrix. The results of this study highlight the dynamic profile of corrosion layer build-up in bronze and brass. Moreover, the perception of the dealloying mechanisms progression on casting features, at mid-term corrosion stages, is extended. Full article
(This article belongs to the Special Issue Cultural Heritage Materials Degradation and Its Prevention)
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13 pages, 4717 KiB  
Article
In-Situ Evaluation of the Protectivity of Coatings Applied to Metal Cultural Artefacts Using Non-Destructive Electrochemical Measurements
by Douglas J. Mills, Katarzyna Schaefer and Tomasz Wityk
Corros. Mater. Degrad. 2021, 2(1), 120-132; https://doi.org/10.3390/cmd2010007 - 9 Mar 2021
Cited by 3 | Viewed by 2664
Abstract
Electrochemical Noise Measurement (ENM) and DC electrolytic resistance measurement (ERM) can be used to assess the level of protectiveness provided by an organic coating (paint or varnish) to the underlying metal. These techniques also have applicability to the thinner, transparent type of coatings [...] Read more.
Electrochemical Noise Measurement (ENM) and DC electrolytic resistance measurement (ERM) can be used to assess the level of protectiveness provided by an organic coating (paint or varnish) to the underlying metal. These techniques also have applicability to the thinner, transparent type of coatings used to protect archaeological artefacts. Two studies are presented here demonstrating how ERM and ENM techniques can be applied in artefact preservation. The similarity of the techniques, both of which are a measure of resistance, means results can be considered to be analogous. The first study investigated the use of ERM to determine the protection levels provided by typical coatings in order to develop a database of coating type and application for objects, for specific environments. The second study used ENM to evaluate coatings which had been applied to historic artefacts recovered from shipwrecks in the Baltic Sea and displayed inside the museum or kept in the museum store area. The studies showed the usefulness of both techniques for determining the level of protection of a coating and how a better performing coating can be specified if a pre-existing coating on an artefact has been found to be unsuitable. Full article
(This article belongs to the Special Issue Cultural Heritage Materials Degradation and Its Prevention)
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15 pages, 33302 KiB  
Article
Biodegradation and Microbial Contamination of Limestone Surfaces: An Experimental Study from Batalha Monastery, Portugal
by Yufan Ding, Catia Sofia Clemente Salvador, Ana Teresa Caldeira, Emma Angelini and Nick Schiavon
Corros. Mater. Degrad. 2021, 2(1), 31-45; https://doi.org/10.3390/cmd2010002 - 13 Jan 2021
Cited by 19 | Viewed by 4590
Abstract
An experimental study was conducted to assess the nature and extent of the biodeterioration of the limestone in the Batalha Monastery in Portugal. Stone fragments covered with microbial biofilms and lichenous crusts were investigated using Optical Microscopy (OM), Low Vacuum Scanning Electron Microscopy [...] Read more.
An experimental study was conducted to assess the nature and extent of the biodeterioration of the limestone in the Batalha Monastery in Portugal. Stone fragments covered with microbial biofilms and lichenous crusts were investigated using Optical Microscopy (OM), Low Vacuum Scanning Electron Microscopy with Energy Dispersive Spectroscopy (LV-SEM + EDS), and X-ray micro-Diffractometry (μ-XRD). Microbial samples were collected from the stone surface, cultured, and analyzed with NGS metagenomic DNA test to classify the bacterial communities associated with the formation of the biofilms. Particulate air pollutants collected on Pall GN-6 paper filters using a cascade impactor were characterized by SEM-EDS + NGS. The results showed that lichens play a major role in biodeterioration by promoting both physical and chemical attack on the limestone substrate via hyphae mechanical penetration along calcite inter-crystalline spaces, the dissolution/leaching of calcite minerals, and the precipitation of secondary minerals such as Ca-oxalates within the stone porosity framework. DNA analyses identified the bacterial communities within the biofilms and their relative abundances. Air quality monitoring results suggest that the microbial population colonizing the monastery limestone could at least partially be derived from the dry and wet deposition of airborne biological particles on the stone surfaces and that S, N, and P-rich air pollutants may have provided nutrients and energy for the bacteria communities, thus indirectly facilitating biofilm formation, the growth of a lichenous crusts, and limestone biodeterioration effects. Full article
(This article belongs to the Special Issue Cultural Heritage Materials Degradation and Its Prevention)
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Review

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13 pages, 4547 KiB  
Review
Curious Corrosion Compounds Caused by Contact: A Review of Glass-Induced Metal Corrosion on Museum Exhibits (GIMME)
by Gerhard Eggert and Andrea Fischer
Corros. Mater. Degrad. 2022, 3(3), 553-565; https://doi.org/10.3390/cmd3030030 - 16 Sep 2022
Cited by 6 | Viewed by 4535
Abstract
Many heritage objects consist of glass in contact with metals. By ion exchange with absorbed water, alkaline aqueous films are formed on the glass surface. They contain sodium and/or potassium, hydroxide, and carbonate (uptake of carbon dioxide) ions. These electrolytes induce corrosion while [...] Read more.
Many heritage objects consist of glass in contact with metals. By ion exchange with absorbed water, alkaline aqueous films are formed on the glass surface. They contain sodium and/or potassium, hydroxide, and carbonate (uptake of carbon dioxide) ions. These electrolytes induce corrosion while in contact with metal. Surprisingly, this phenomenon has only been realised by research in Stuttgart in the last two decades. About 350 affected objects were detected in the meantime in a number of heritage collections. Because of the special electrolytes, unusual corrosion products are often formed. The unknown structure and formula of three of them could be determined by modern X-ray powder diffraction data evaluation. One example is the basic potassium lead carbonate, KOH‧2PbCO3, detected on a pewter lid of a glass jug. The sodium analogon of already known structure was found in hollow glass balls mirrored on the inside with molten lead. Chalconatronite, Na2[Cu(CO3)2]‧3H2O, is known as a corrosion product of copper alloys in contact with soda solutions (here: from glass degradation). Exposed to acetic acid emissions (e.g., from wood), it transforms to a sodium copper acetate carbonate of hitherto undetermined structure. The ubiquitous pollutant formaldehyde reacts directly to formate in the alkaline medium provided by glass degradation. On copper alloys in contact with glass, formates are, therefore, frequent: Na4Cu4O(HCOO)8(OH)2‧4H2O in 50% of all cases and in 33% Cu2(HCOO)(OH)3. Zinc (from brass) forms Zn(HCOO)2‧2H2O and Zn4Cu3(Zn1−xCux)6(HCOO)8 (OH)18·6H2O. There are a number of other corrosion products, e.g., containing zinc and carboxylates awaiting further characterisation. Preventive conservation needs to slow down corrosion by dry storage (not lower than 35% rH). Pollutants need to be avoided by careful selection of materials for storage, display, and conservation. Full article
(This article belongs to the Special Issue Cultural Heritage Materials Degradation and Its Prevention)
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