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Heritage
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Metals in Heritage Science
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Metals in Heritage Science

A special issue of Heritage (ISSN 2571-9408). This special issue belongs to the section "Materials and Heritage".

Deadline for manuscript submissions: closed (31 December 2022) | Viewed by 32184

Special Issue Editor

Dr. Chiara Soffritti

E-Mail Website
Guest Editor
Department of Engineering, University of Ferrara, Ferrara, Italy
Interests: archaeometallurgy; heritage science; metal alloys; chemical composition; microstructure; heat treatment; corrosion products; restoration solutions
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

The valorisation of our Cultural Heritage is deeply grounded on the study of the production, use and consumption of ancient metals. Especially, modern analytical techniques allow to achieve detailed information about the composition and microstructure of metal artefacts. This information is very useful for understanding the historic materials and manufacturing process. Moreover, the assessment of the state of conservation of metal objects allows to detect degradation mechanisms and establish suitable conservation strategies for the safeguard of the Cultural Heritage.

The aim of this Special Issue ‘Metals in Heritage Science’ is to collect full papers, communications and review articles highlighting recent achievements on the study of composition, technological process and deterioration phenomena of metal alloys, with a special focus on the development of new analytical techniques and instrumentation for investigating the history of metal technology. Submissions of works dealing with innovative conservation and restoration solutions are also encouraged. Papers reporting case studies of historical relevance will be evaluated.

I am pleased to invite you to submit original research articles for this Special Issue to be published in the open access journal Heritage. High-quality papers from researchers in the scientific community are welcome.

You may choose our Joint Special Issue in Metals.

Dr. Chiara Soffritti
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. Heritage is an international peer-reviewed open access monthly 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 1600 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

  • Metal alloys
  • Microstructure
  • Heat treatment
  • Corrosion phenomena
  • Portable/laboratory instrumentation
  • Spectroscopic analyses
  • Isotope-based studies
  • Restoration solutions
  • Case studies

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Further information on MDPI's Special Issue polices can be found here.

Published Papers (11 papers)

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Editorial

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4 pages, 154 KiB  
Editorial
Metals in Heritage Science
by Chiara Soffritti
Heritage 2024, 7(3), 1822-1825; https://doi.org/10.3390/heritage7030086 - 21 Mar 2024
Viewed by 1194
Abstract
The valorization of our Cultural Heritage is deeply grounded in the study of the production, use and consumption of ancient metals [...] Full article
(This article belongs to the Special Issue Metals in Heritage Science)

Research

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14 pages, 5739 KiB  
Article
Spectroscopic and Morphologic Investigation of Bronze Disease: Performance Evaluation of Portable Devices
by Daniela Porcu, Silvia Innocenti, Monica Galeotti, Jana Striova, Luigi Dei, Emiliano Carretti and Raffaella Fontana
Heritage 2022, 5(4), 3548-3561; https://doi.org/10.3390/heritage5040184 - 18 Nov 2022
Cited by 6 | Viewed by 2429
Abstract
Copper alloy artworks are particularly subjected to chloride attack, which may trigger bronze disease. Therefore, early identification of the phenomenon is crucial in order to stabilize the reactive copper chloride (CuCl) and remove the harmful corrosion products (atacamite and polymorphs). Confocal Raman Microspectroscopy [...] Read more.
Copper alloy artworks are particularly subjected to chloride attack, which may trigger bronze disease. Therefore, early identification of the phenomenon is crucial in order to stabilize the reactive copper chloride (CuCl) and remove the harmful corrosion products (atacamite and polymorphs). Confocal Raman Microspectroscopy (CRM) has proven to be effective for the detection of small amounts of atacamite, ascribable to the initial phases of corrosion. The handling of bronze artworks is often difficult or even impossible given their large size and weight, and sampling is not always allowed, making the use of portable instruments mandatory for on-site diagnostics. This paper proposes a method for the early detection of corrosion using non-invasive approaches. In this work, we present the results obtained from a set of artificially aged bronze samples with a suite of either laboratory (bench-top) or field (portable/transportable) instruments with the aim of highlighting their characteristics and performances in the diagnosis of bronze disease. Raman spectroscopy, Fiber Optics Reflectance Spectroscopy (FORS), Optical Coherence Tomography (OCT), and Scanning Electron Microscopy (SEM) were applied for chemical and morphological characterization of the samples. Full article
(This article belongs to the Special Issue Metals in Heritage Science)
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16 pages, 22610 KiB  
Article
Silver-Doped TiO2-PDMS Nanocomposite as a Possible Coating for the Preservation of Serena Stone: Searching for Optimal Application Conditions
by Marwa Ben Chobba, Maduka L. Weththimuni, Mouna Messaoud, Jamel Bouaziz, Rached Salhi, Filomena De Leo, Clara Urzì and Maurizio Licchelli
Heritage 2022, 5(4), 3411-3426; https://doi.org/10.3390/heritage5040175 - 11 Nov 2022
Cited by 6 | Viewed by 2063
Abstract
The main objective of this research is to determine the optimal application conditions of a newly synthesized multifunctional coating containing Ag-doped TiO2 nanoparticles when used as a possible protective agent for sandstone. Firstly, Ag-TiO2 nanoparticles with anatase structure, spherical shape and [...] Read more.
The main objective of this research is to determine the optimal application conditions of a newly synthesized multifunctional coating containing Ag-doped TiO2 nanoparticles when used as a possible protective agent for sandstone. Firstly, Ag-TiO2 nanoparticles with anatase structure, spherical shape and controllable sizes were prepared using the sol–gel method and characterized. The biocidal activity of Ag-doped TiO2 NPs was studied by comparing its performance to pure TiO2 NPs against two representative Gram-positive and Gram-negative bacterial strains, under both visible irradiation and in the dark; then, the antimicrobial efficiency of two different concentrations of Ag-TiO2 nanoparticles (0.1–1 mol%) was evaluated against two phototrophic strains commonly isolated from deteriorated surfaces. Results showed that the photoactivation and photokilling activity of TiO2 were highly improved by doping with Ag. Next, prepared nanopowders were dispersed in a binder with different powder/PDMS ratios: (0.1, 0.2, 0.5 and 1% w/v TiO2) and then applied in different amounts (2, 3 and 6 g/m2) on Serena stone specimens. Results revealed that the application of 2 g/m2 nanocomposite at powder/binder ratios equal to 1% w/v TiO2 provided a fine hydrophobic character for the stone material with acceptable chromatic variations. Full article
(This article belongs to the Special Issue Metals in Heritage Science)
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23 pages, 14899 KiB  
Article
Unveiling the Complexity of Japanese Metallic Threads
by Ludovico Geminiani, Francesco Paolo Campione, Cristina Corti, Sila Motella, Laura Rampazzi, Sandro Recchia and Moira Luraschi
Heritage 2021, 4(4), 4017-4039; https://doi.org/10.3390/heritage4040221 - 28 Oct 2021
Cited by 4 | Viewed by 3053
Abstract
In the framework of an extensive survey campaign on a collection of Japanese samurai armors, metallic threads from different parts of the traditional equipment were studied by several analytical techniques. The collection of armors belongs to Museo delle Culture (Lugano, Switzerland) and it [...] Read more.
In the framework of an extensive survey campaign on a collection of Japanese samurai armors, metallic threads from different parts of the traditional equipment were studied by several analytical techniques. The collection of armors belongs to Museo delle Culture (Lugano, Switzerland) and it is composed of ten elements, which date back from the 15th to 20th century. Metallic threads under study come from six of ten elements of the collection and represent a complex and unique multimaterial, which shows specific characteristics in Japanese tradition (kinran). The multianalytical approach based on ATR-FTIR (Attenuated Total Reflection-Fourier Transform Infrared) spectroscopy and SEM-EDX (Scanning Electron Microscopy, Energy Dispersive X-Ray) analysis, together with a careful observation with optical and digital microscopy, permitted to obtain a complete characterization of materials, which have shown a great variability in metal foils and in organic adhesives (urushi, animal glue, starch). Gold and silver turned out to be not so largely used as scholars thought, while aluminum showed a great diffusion. Within the collection of analyzed armors, the obtained results allowed us for the first time to get a complete comprehension of materials and techniques used by Japanese craftsmen, and to observe differences in the quality of the materials and in manufacture technology over the centuries. Full article
(This article belongs to the Special Issue Metals in Heritage Science)
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15 pages, 3579 KiB  
Article
Art Casting in Portuguese 19th Century Industrial Foundries: A Multi-Analytical Study of an Emblematic Copper-Based Alloy Monument
by Pablo General-Toro, Rui Bordalo, Patrícia Raquel Moreira, Eduarda Vieira, Antonio Brunetti, Roberta Iannaccone and Carlo Bottaini
Heritage 2021, 4(4), 3050-3064; https://doi.org/10.3390/heritage4040170 - 2 Oct 2021
Cited by 4 | Viewed by 3128
Abstract
The outdoor sculpture of the first Portuguese king, D. Afonso Henriques (c. 1109–1185 AD), placed in Guimarães (North Portugal), is one of the most emblematic national sculptures. Created in 1887 by António Soares dos Reis, it possesses a remarkable symbolic value in the [...] Read more.
The outdoor sculpture of the first Portuguese king, D. Afonso Henriques (c. 1109–1185 AD), placed in Guimarães (North Portugal), is one of the most emblematic national sculptures. Created in 1887 by António Soares dos Reis, it possesses a remarkable symbolic value in the presumed birthplace of the king. In addition to the artistic and heritage importance of the monument, it is one of the few sculptures cast by a Portuguese industrial foundry in the 19th century. This study obtained data on the sculpture’s elemental composition and corrosion products, gathering important historical and technical information. For this purpose, a multi-analytical approach consisting of X-ray fluorescence (XRF), X-ray diffraction (XRD), optical microscopy (OM) and scanning electron microscopy (SEM-EDS) was carried out to characterise the bulk metal and corrosion layers. The data revealed a ternary alloy of Cu, Sn and Zn, with Pb, Fe, As, Bi and Mn as minor elements. The alloy matches that of other sculptures cast in that period. In terms of corrosion, it is characterised by the presence of oxides. These results represent the first step for applying an appropriate conservation strategy for bronze sculptures with similar characteristics. Full article
(This article belongs to the Special Issue Metals in Heritage Science)
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25 pages, 4587 KiB  
Article
Ancient Ceramic Casting Molds from the Southern Russian Far East: Identification of Alloy Traces via Application of Nondestructive SEM-EDS and pXRF Methods
by Irina S. Zhushchikhovskaya and Igor Yu. Buravlev
Heritage 2021, 4(4), 2643-2667; https://doi.org/10.3390/heritage4040149 - 24 Sep 2021
Cited by 6 | Viewed by 2322
Abstract
The investigation presented in this paper is a unique assemblage of ceramic casting molds discovered at one of the sites from the Bohai period (698–926) in the territory of the southern Russian Far East. The main research aim is to recognize probable traces [...] Read more.
The investigation presented in this paper is a unique assemblage of ceramic casting molds discovered at one of the sites from the Bohai period (698–926) in the territory of the southern Russian Far East. The main research aim is to recognize probable traces of metal alloys cast in ceramic molds. Nondestructive pXRF and SEM-EDS methods were used as the research instruments for detecting the expected alloys’ chemical components. As a result, the elements Pb, Sn, Cu, and As were indicated at the surfaces of the molds’ cavities with evidence of carbonization caused by the casting process. Preliminarily, two groups of alloys were distinguished: lead-bearing alloys and lead-free alloys. Our new insights are in good accordance with the results of previous investigations on chemical compositions of bronzes from the Bohai period archaeological sites of the southern Russian Far East. In particular, data on the examination of ceramic molds confirm the conclusion that various kinds of copper alloys were known and used in the bronze casting craft of the Bohai period. Full article
(This article belongs to the Special Issue Metals in Heritage Science)
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13 pages, 2820 KiB  
Article
Oxygen Depletion Testing of Metals
by David Thickett
Heritage 2021, 4(3), 2377-2389; https://doi.org/10.3390/heritage4030134 - 13 Sep 2021
Cited by 9 | Viewed by 3132
Abstract
The altered nature of archaeological metals means they deteriorate at much lower relative humidity (RH) conditions than historical metals. The study of deterioration for such materials is hampered by their complexity, variability and difficulties in measuring deterioration. Placing an object in a sealed [...] Read more.
The altered nature of archaeological metals means they deteriorate at much lower relative humidity (RH) conditions than historical metals. The study of deterioration for such materials is hampered by their complexity, variability and difficulties in measuring deterioration. Placing an object in a sealed container, controlling the RH and pollutant gases and measuring any decrease in oxygen concentration is an accessible method to measure the deterioration rate. It has been used for research into suitable environmental conditions to manage the deterioration rates of such artefacts, including the differences in the response of artefacts from different excavation sites. Some objects need the careful control of RH to low values; this is expensive to maintain and poses risks to other artefacts displayed together. Many objects are actually stable up to quite high RH values, and oxygen depletion testing has been used to identify those that can be safely displayed with minimal environmental control. The accelerated corrosion ‘Oddy’ test is frequently used to sift out unsuitable display materials. T the visual assessment is widely recognized to be subjective. the test container has been modified and oxygen depletion appears to give good quantitative measurements of corrosion that correspond with both visual comparison and corrosion loss measurement with linear stripping voltametry or chemical stripping for copper, lead and steel but not for silver. Full article
(This article belongs to the Special Issue Metals in Heritage Science)
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8 pages, 4418 KiB  
Article
Monte Carlo Simulations of ED-XRF Spectra as an Authentication Tool for Nuragic Bronzes
by Carlo Nocco, Antonio Brunetti and Sergio Augusto Barcellos Lins
Heritage 2021, 4(3), 1912-1919; https://doi.org/10.3390/heritage4030108 - 19 Aug 2021
Cited by 3 | Viewed by 2397
Abstract
The high artistic and cultural relevance of particular objects, in this case from the Nuragic civilization, have stimulated the growth of a forgery industry, replicating small bronze boats (navicelle), statues (bronzetti), and other objects. It is often the case [...] Read more.
The high artistic and cultural relevance of particular objects, in this case from the Nuragic civilization, have stimulated the growth of a forgery industry, replicating small bronze boats (navicelle), statues (bronzetti), and other objects. It is often the case where the forgeries are of such quality that it becomes difficult to distinguish them from authentic artifacts without a proper chemical analysis. In this research, a Monte Carlo simulation algorithm for X-ray interactions with matter is used to obtain the chemical composition from the bulk of each object from a set of five. The method employed has the advantage of being completely nondestructive and relatively fast. The objects’ chemical composition and morphology were compared with the data available from authentic artifacts so their authenticity could be inferred. Four of the five objects are likely to be authentic, where two of them could be associated with a Sardinian origin. Full article
(This article belongs to the Special Issue Metals in Heritage Science)
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9 pages, 3142 KiB  
Article
Multispectral Analysis of Miniature Nuragic Bronze Flasks
by Carlo Nocco, Francesca Assunta Pisu, Daniele Chiriu, Anna Depalmas, Sergio Augusto Barcellos Lins and Antonio Brunetti
Heritage 2021, 4(3), 1716-1724; https://doi.org/10.3390/heritage4030095 - 11 Aug 2021
Cited by 1 | Viewed by 2432
Abstract
Miniaturized bronze flasks represent a small portion of a wide metallurgical production that flourished in Sardinia (Italy) between the Final Bronze Age (FBA) and the Early Iron Age (EIA). They replicate a well-known and symbolic type of object, the pilgrims’ flask, common in [...] Read more.
Miniaturized bronze flasks represent a small portion of a wide metallurgical production that flourished in Sardinia (Italy) between the Final Bronze Age (FBA) and the Early Iron Age (EIA). They replicate a well-known and symbolic type of object, the pilgrims’ flask, common in all Europe and Mediterranean basin, and have but few archaeological parallels. For these reasons, their characterization can be considered important from an archaeological perspective. Three flasks, preserved at the Antiquarium Arborense museum (Oristano), were analyzed by X-Ray Fluorescence Spectroscopy (XRF) and Raman spectroscopy, integrated by multispectral images. The samples, coming from illegal excavations, posed two problems: establishing their authenticity and investigating the alloy composition of such particular objects. All specimens presented a widespread degradation in the outer surface: XRF and Raman spectroscopy indicated the presence of copper oxides, calcium and copper carbonates deposits. The abscence of Zn, a clear marker of forgeries, was not detected by XRF. In two of the flasks, an unusual Sn content above 20%, was detected. For FBA and EIA, especially regarding southern Europe, Sn was extremely rare, and was possibly used with caution. Further results are presented herein. Full article
(This article belongs to the Special Issue Metals in Heritage Science)
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15 pages, 5576 KiB  
Article
Archaeometallurgical Analyses on Two Renaissance Swords from the “Luigi Marzoli” Museum in Brescia: Manufacturing and Provenance
by Carolina Mori, Giorgia Ghiara, Paolo De Montis, Paolo Piccardo, Giacomo D. Gatta and Stefano Pierpaolo Trasatti
Heritage 2021, 4(3), 1269-1283; https://doi.org/10.3390/heritage4030069 - 14 Jul 2021
Cited by 3 | Viewed by 3877
Abstract
Two Venetian types of swords coming from the “Luigi Marzoli” Arms Museum in Brescia were characterized in this study, to understand their manufacturing process and to gather information about their provenance. Both the blades and the hilts components are analyzed using a multi-methodological [...] Read more.
Two Venetian types of swords coming from the “Luigi Marzoli” Arms Museum in Brescia were characterized in this study, to understand their manufacturing process and to gather information about their provenance. Both the blades and the hilts components are analyzed using a multi-methodological approach, to describe possible differences in the metallurgical features that involved classical metallographic and spectroscopic techniques. Microstructural results indicate a complex process for the manufacturing of the blades, by hot-forging, confirmed by a sequence of different microstructures even on the same sample. Furthermore, an interesting and unusual manufacturing technique is used on one of the pommels, which consists of two hemispheres connected by copper joints. Hypothesis about the ironmaking and the provenience of raw materials are obtained by the features and composition of the inclusions. It is suggested that there is the use of both a direct and an indirect process on the swords. It is likely that the minerals used to obtain iron and copper of the swords come from the mines of the Brescia and Bergamo territories. All the hypotheses are consistent with the historical documents of the time that also give information on the diffusion of such swords in the Brescia area. Full article
(This article belongs to the Special Issue Metals in Heritage Science)
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Review

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33 pages, 42435 KiB  
Review
Long-Term Embrittlement of Ancient Copper and Silver Alloys
by Omid Oudbashi and Russell Wanhill
Heritage 2021, 4(3), 2287-2319; https://doi.org/10.3390/heritage4030130 - 10 Sep 2021
Cited by 16 | Viewed by 3873
Abstract
The manifestations of ancient metals’ embrittlement, cracking and fracture, are challenging problems for restorers and conservators, yet the scientific understanding of these problems is limited. In particular, the study and interpretation of fracture surfaces, fractography, is a minor or non-existent consideration for most [...] Read more.
The manifestations of ancient metals’ embrittlement, cracking and fracture, are challenging problems for restorers and conservators, yet the scientific understanding of these problems is limited. In particular, the study and interpretation of fracture surfaces, fractography, is a minor or non-existent consideration for most archaeometallurgical investigations. This paper presents a survey of fractographic analyses, in combination with the more widely used disciplines of microstructural studies, metallography, and chemical analyses for some Old-World copper alloy (bronzes) and high-silver alloy artifacts that have undergone long-term corrosion and embrittlement damage. We show that fractography, as an adjunct to metallography, can improve the interpretation of these types of damage and assist in selecting the best methods for restoration and conservation of the objects made from these alloys. Full article
(This article belongs to the Special Issue Metals in Heritage Science)
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