Marianna Pascucci

National Research Council

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Cristina Riccucci

Institute of Nanostructured Materials

Gabriella Di Carlo

Institute of Nanostructured Materials

G. M. Ingo

Institute of Nanostructured Materials

Elena Messina

National Research Council

Chiara Giuliani

National Agency for New Technologies, Energy and Sustainable Economic Development

Francesca Boccaccini

Sapienza University of Rome

G. Fierro

Sapienza University of Rome

Maria Paola Staccioli

Institute of Nanostructured Materials

Monica Albini

National Research Council

Marino Lavorgna

Institute of Polymers, Composites and Biomaterials

Cooperative Institutions

National Research Council

Institute of Nanostructured Materials

Sapienza University of Rome

Consorzio Roma Ricerche

University of Naples Federico II

Institute of Structure of Matter

National University of San Marcos

University of Florence

Institute of Polymers, Composites and Biomaterials

Istituto Nazionale di Fisica Nucleare

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Roman sophisticated surface modification methods to manufacture silver counterfeited coins

Applied Surface Science (2017)

G. M. Ingo Cristina Riccucci F. Faraldi Marianna Pascucci Elena Messina

Energy-dispersive X-ray spectroscopy

Surface Modification

10.1016/j.apsusc.2017.01.101

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Citations (17)

Artificial patina formation onto copper-based alloys: Chloride and sulphate induced corrosion processes

Applied Surface Science (2017)

Gabriella Di Carlo Chiara Giuliani Cristina Riccucci Marianna Pascucci Elena Messina

Naturally grown patinas are typically detected onto the surface of modern copper-based artefacts and strictly affect their surface reactivity and appearance. The production of representative patinas is a key issues in order to obtain model systems which can be used for the development and validation of appropriate conservation materials and methods. In this study, we have prepared different artificial representative patinas by using a quaternary Cu-Sn-Zn-Pb alloy with chemical composition and metallurgical features similar to those of valuable modern works of art. In order to produce degradation products usually observed onto their surface, chloride and sulphate species were used to induce corrosion processes. Different patinas were produced by changing the nature of corrosive species and the set-up for the accelerated degradation. The composition and structural properties of the patinas were investigated by attenuated total reflectance Fourier transform infrared spectroscopy, X-ray diffraction, optical microscopy and scanning electron microscopy combined with energy dispersive X-ray spectroscopy. The results allow to identify degradation products and to distinguish copper hydroxychloride polymorphs and copper hydroxysulphates with similar structure. Our findings show that patina composition can be tailored by modifying the degradation procedure and patinas representative of modern artefacts made of quaternary Cu-Sn-Zn-Pb alloy can be obtained.

Degradation

10.1016/j.apsusc.2017.01.080

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Citations (53)

Multi-Spectroscopic Approach for the Non-invasive Characterization of Paintings on Metal Surfaces

Frontiers in Chemistry (2020)

Monica Albini Stefano Ridolfi Chiara Giuliani Marianna Pascucci Maria Paola Staccioli

The aim of this study is to propose a non-invasive multi-spectroscopic approach for the characterization of oil painting artworks that use a copper plates as substrate in place of a canvas. Indeed, in the last decade, many studies have been conducted on artworks made of single materials (e.g., paintings, stones, metals). However, the characterization and conservation of composite artifacts has never be fully investigated even though many masterpieces were created using this particular technique. In this work, several spectroscopic techniques such as Infrared Spectroscopy (FTIR), Energy-Dispersive X-Ray Fluorescence spectroscopy (EDXRF), and high spatial resolution Field Emission Scanning Electron Microscopy coupled with Energy Dispersive X-ray Spectroscopy (EDS), and Optical Microscopy (OM) were performed. The obtained results allowed to fully characterize the micro-chemical and microstructural features of the painted surfaces and of the metal plate. Particularly effective was the use of MA-XRF, resulting in the chemical map of the painted surfaces. Furthermore, traces of the mechanical preparation of the plate were found under the painted layers. Finally, the interface area between the paint film and the metallic support was characterized at a micro scale. This was particularly important in order to identify the degradation products formed by the interaction between the fatty acids of the binder and copper-based substrates.

Characterization

Energy-dispersive X-ray spectroscopy

X-Ray Fluorescence

10.3389/fchem.2020.00289

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Citations (8)

Micro-structural and micro-chemical investigation of Samnite high-tin bronze cuirass discs: ancient metallurgy in central Italy

Microchemical Journal (2021)

Cristina Riccucci G. M. Ingo Marianna Pascucci Maria Paola Staccioli Maria Isabella Pierigè

Bronze

Energy-dispersive X-ray spectroscopy

Microanalysis

10.1016/j.microc.2021.107136

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Citations (2)

Surface studies of patinas and metallurgical features of uncommon high-tin bronze artefacts from the Italic necropolises of ancient Abruzzo (Central Italy)

Applied Surface Science (2018)

G. M. Ingo Cristina Riccucci Chiara Giuliani Amalia Faustoferri I. Pierigè

Bronze

10.1016/j.apsusc.2018.11.115

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Citations (27)

Toward a Green and Sustainable Silver Conservation: Development and Validation of Chitosan-Based Protective Coatings

International Journal of Molecular Sciences (2022)

Francesca Boccaccini Chiara Giuliani Marianna Pascucci Cristina Riccucci Elena Messina

When exposed to air, silver artifacts undergo an unpleasant darkening and shiny loss, commonly known as tarnishing. At the present, the development of protective coatings by using eco-friendly and biocompatible materials, able to ensure high transparency and to hinder the degradation of silver objects, remains a huge challenge. In this study, chitosan was used for the first time to realize sustainable coatings for silver protection. Both pure and benzotriazole-containing chitosan coatings were prepared and applied on sterling silver disks. A commercial product based on acrylic resin was used as a reference. The aesthetic features and protective properties of these coatings were evaluated by performing two different types of aging treatments. In particular, the assessment of the protective efficacy was carried out by reproducing both highly aggressive polluted environments and real-like museums' storage conditions. In the first case, chitosan-based coatings with benzotriazole performed better, whereas in storage conditions all the chitosan films showed comparable efficacy. Compositional, morphological and structural analyses were used to evaluate the protective properties of the coatings and to detect any physical or chemical modifications after the aging treatments. Our findings reveal that the two different testing methods provide complementary information. Moreover, chitosan coatings can achieve protective efficacy comparable with that of the commercial product but using non-toxic solvents and a renewable biopolymer. Chitosan coatings, designed for cultural heritage conservation, are thus promising for the protection of common sterling silver objects.

Benzotriazole

Biopolymer

Conservation

10.3390/ijms232214454

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Citations (12)

Combined use of FE-SEM+EDS, ToF-SIMS, XPS, XRD and OM for the study of ancient gilded artefacts

Applied Surface Science (2018)

G. M. Ingo Cristina Riccucci Marianna Pascucci Elena Messina Chiara Giuliani

10.1016/j.apsusc.2018.01.278

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Citations (25)

Novel, effective and safe coatings for the protection of copper-based artefacts

Francesca Boccaccini Aurelio Barbetta Elena Messina Marianna Pascucci Cristina Riccucci

Degradation processes in cultural heritage metal artefacts represents a critical issue since they can irreversibly compromise the conservation status of valuable works of art.The protective materials commonly used to hinder these processes are based on harmful or toxic corrosion inhibitors and solvents.Moreover, large amounts of organic solvents are typically used by conservators for their application and removal.In the last decades, the search for new materials that can simultaneously satisfy protective, aesthetic and safety requirements is receiving increasing attention.In this contest, we have focused our attention on the development of sustainable polymer coatings that can provide an active protection and that are easy to be applied and removed using water-based solvents.A green polymer from renewable sources, such as chitosan, was selected and functionalized with anticorrosive species.Validation tests were performed on model copper-based substrates with different composition and surface finish.The performances were compared with a commercial benchmark.

CONTEST

Compromise

10.21014/tc4-arc-2023.090

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Surface investigation of naturally corroded gilded copper-based objects

Applied Surface Science (2016)

G. M. Ingo Cristina Riccucci Marino Lavorgna Martina Salzano de Luna Marianna Pascucci

Noble metal

Galvanic cell

10.1016/j.apsusc.2016.06.082

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Citations (11)

Microchemical Investigation of Long-Term Buried Gilded and Silvered Artifacts From Ancient Peru

Frontiers in Materials (2020)

G. M. Ingo Monica Albini Ángel Bustamante Sandra del Pilar Zambrano Alva Arabel Fernández

A large number of metal artefacts with exceptional artistic value of the Moche culture have been found in the tombs of the Lords of Sipán (Lambayeque, Peru) and of the Lady of Cao (El Brujo, Peru) characterised by different burial conditions. Some of the objects, dated around 300-400 AD, are constituted by substrates of Cu- or Ag-based alloys coated by uniformly distributed thin films of precious metal (1 - 4 microns) that create also polymetallic bicoloured surfaces with "gold" and "silver" areas. In order to investigate the corrosion product structure and composition as well as to identify the techniques used to give the gold or silver appearance, an integrated analytical approach has been adopted. The selected complementary methodologies were scanning electron microscopy (SEM) coupled with energy dispersive spectroscopy (EDS), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and optical microscopy (OM). The findings reveal that the substrates are mainly composed by Cu-Ag-Au alloys that at the site of Sipán have been almost completely corroded during the burial. Furthermore, the results show that the main aggressive agent is Cl- coming from the soil and that the degradation phenomena were likely enhanced by the galvanic coupling between the precious metal layer and the less noble substrate. The degradation products have formed mainly layered structures containing chloroargyrite (AgCl), cuprite (Cu2O), nantokite (CuCl), and atacamite (CuCl23Cu(OH)2) polymorphs. These latter species warn that dangerous copper cyclic corrosion is occurring, a harmful phenomenon, commonly defined as "bronze disease", which must be be firmly mitigated. Finally, the findings reveal that the Moche metal workers used the depletion gilding to selectively modify the surface chemical composition of the artefacts to produce the Ag or Au thin films. According to this subtractive method, the surface of the Cu-Au-Ag alloys was enriched with a layer of precious metal by means of cycles of thermal treatments and removal of Cu or both Cu and Ag from the outermost region by using pickling solutions.

Cuprite

Noble metal

Precious metal

Energy-dispersive X-ray spectroscopy

Bronze

Malachite

Galvanic cell

10.3389/fmats.2020.00230

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Citations (9)