Non-invasive Techniques in the Scope of Cultural Heritage: Pigments, Binders and Degradation Products from Ancient, Modern and Contemporary Artworks

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

Deadline for manuscript submissions: closed (21 March 2023) | Viewed by 13670

Special Issue Editor

Department of Chemistry, University of Milan, 20133 Milan, Italy
Interests: analytical chemistry; Raman spectroscopy; infrared spectroscopy; SEM-EDX; chromatography; cultural heritage; archaeology; pigments; binders
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

For many years now, archaeological and historical studies have been concerned with the contribution of scientific research, particularly those aiming at the chemical-physical characterisation of materials.

The in-depth knowledge of the characteristics of the materials used in creating works of art is undoubtedly an added value in their study. Indeed, it turns out to be a suitable tool for understanding works of art themselves as well as their intrinsic value and the historical and social context in which they were made. Furthermore, scientific and technological advances of recent years have made it possible to create increasingly effective investigation tools and, furthermore, many of them are suitable to be used in situ, i.e., directly on the works of art, even in the places where they are stored.

This Special Issue aims to cover the latest applications of non-destructive and/or in-situ methods in the scope of cultural heritage, with a particular interest in spectral imaging techniques.

Dr. Vittoria Guglielmi
Guest Editor

Manuscript Submission Information

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Published Papers (8 papers)

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Research

15 pages, 9361 KiB  
Article
Material and Imaging Analysis Procedure for the Investigation of Paintings in the Archbishop’s Palace of Seville
Heritage 2023, 6(6), 4527-4541; https://doi.org/10.3390/heritage6060240 - 27 May 2023
Cited by 1 | Viewed by 1151
Abstract
The Archbishop’s Palace of Seville harbours an important art collection with mostly works by great Renaissance and Baroque artists. However, the authorship of some paintings is unknown, and, in a few cases, there is an interest in discovering the painter due to the [...] Read more.
The Archbishop’s Palace of Seville harbours an important art collection with mostly works by great Renaissance and Baroque artists. However, the authorship of some paintings is unknown, and, in a few cases, there is an interest in discovering the painter due to the quality of the artwork. As a first step for this purpose, a systematic analysis procedure has been established using non-destructive techniques, such as UV photography and IR reflectography, to locate interventions and underpaintings, as well as X-ray fluorescence to identify original pigments and those of later interventions. The study following this established protocol is presented with the example of two paintings by unknown authors. They were made in different centuries representing, consequently, different styles. UV images showed several retouches, while IR reflectography revealed under-drawing and composition corrections (pentimenti). Furthermore, XRF identified the pigments applied in the production of the different colours and tonalities, allowing to characterise the artist’s palette, whose pigments generally agree with the dates when the artworks were produced. This study resulted in valuable information on painting materials and techniques, which will be useful in the search for authorships, among others. Full article
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12 pages, 7274 KiB  
Article
Portable X-ray Fluorescence Analysis of Levantine and Schematic Art Pigments from the River Vero Shelters (Huesca, NE Spain)
Heritage 2023, 6(4), 3789-3800; https://doi.org/10.3390/heritage6040201 - 20 Apr 2023
Cited by 1 | Viewed by 1126
Abstract
The River Vero canyon (Huesca, Spain) contains an exceptional archaeological legacy with more than sixty rock shelters with cave paintings and forms part of the World Heritage ‘Rock Art of the Mediterranean Basin on the Iberian Peninsula’. This study presents the results of [...] Read more.
The River Vero canyon (Huesca, Spain) contains an exceptional archaeological legacy with more than sixty rock shelters with cave paintings and forms part of the World Heritage ‘Rock Art of the Mediterranean Basin on the Iberian Peninsula’. This study presents the results of the in situ and non-destructive multi-elemental composition analysis of the pigments used in eight of the main shelters through portable X-ray fluorescence spectroscopy (pXRF). Specifically, the cave paintings of the rock shelters of Chimiachas, Muriecho, and Arpán (Levantine Art); and Mallata, Barfaluy, Quizans, Lecina Superior, and Forau del Cocho (Schematic Art) were investigated. The red pigments, based on iron minerals, were the most abundant in all the River Vero rock shelters, with Fe contents in the 0.51–3.06% range. The iron contents of the paintings of Mallata B1 and I, Muriecho, and Forau del Cocho were higher than those of Arpán, Barfaluy, Lecina, and Chimiachas rock-shelters; and, in turn, these were higher than those of Quizans, pointing to noticeable differences in the degree of conservation. Black pigments, in the absence of manganese, were associated with bone char or carbon black. Through the phosphorus content, evidence is provided of the use of bone phosphates as a component of the paints, either as a filler or as a binder. Geological studies indicate that the detected gypsum is of external origin, probably associated with gypsum-rich atmospheric dust. The reported pXRF analysis of this large set of paintings may serve as a basis for future characterization studies involving other portable chemical analysis techniques. Full article
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35 pages, 9585 KiB  
Article
The Vindolanda Vessel: pXRF and Microphotography of an Enamel-Painted Roman Gladiator Glass
Heritage 2023, 6(4), 3638-3672; https://doi.org/10.3390/heritage6040194 - 12 Apr 2023
Viewed by 2838
Abstract
Roman glass is well studied and known to have been produced from a mineral soda source and calcareous sand with variation between elements relating to naturally occurring minerals in the sands. While the common characteristics of colourants and opacifiers used in opaque and [...] Read more.
Roman glass is well studied and known to have been produced from a mineral soda source and calcareous sand with variation between elements relating to naturally occurring minerals in the sands. While the common characteristics of colourants and opacifiers used in opaque and translucent glasses are well understood, the diverse elemental composition of colouring agents associated with the highly specialised, and largely unexplored, technique of enamel-painted glass has never been firmly established. There remains a significant gap in knowledge of pigments used for this technological innovation which is here addressed through the deployment of non-invasive portable X-ray Flourescence (pXRF) analysis and microphotography on a unique Roman enamel-painted gladiator glass from Vindolanda fort. This vanguard research has successfully established, for the first time, a palette of pigments associated with this specialist technique. It is now possible to unravel previously unknown information on complex manufacturing processes and significantly expand the repertoire of the pigments bound up in enamelling recipes used to depict the striking iconographic scenes on the Vindolanda vessel and, potentially, other Roman enamelled glassware. The detection of Cinnabar, Egyptian blue, Orpiment and other pigments are ground-breaking discoveries that will have a transformative impact on early glassmaking studies and push the boundaries of scholarship into new directions of analytical approaches in heritage materials science to complement recent success in this field with Raman spectroscopy and other techniques. The methodology is unprecedented and has been validated through the high quality of the resulting data which permits the extrapolation of elemental compositions of enamelling materials from those associated with the base vessel. This unique approach provides remarkable insights that will revolutionise our understanding of enamelling technologies using the Vindolanda vessel as the investigative platform for forgotten practice. Full article
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18 pages, 5742 KiB  
Article
Scientific Investigation of Contemporary Pastel Painting by Roberto Sebastian Matta: Characterization of Original Materials through Multispectral Imaging and Spectroscopic Techniques
Heritage 2023, 6(3), 2541-2558; https://doi.org/10.3390/heritage6030134 - 28 Feb 2023
Cited by 2 | Viewed by 1521
Abstract
The conservation of contemporary art often offers unique occasions to study complex multi-material artworks and understand their creative process and esteem degradation distress. The recent diagnostic campaign on the surrealist artwork Perché le vittime vincano (For the victims to win) (1974–75) [...] Read more.
The conservation of contemporary art often offers unique occasions to study complex multi-material artworks and understand their creative process and esteem degradation distress. The recent diagnostic campaign on the surrealist artwork Perché le vittime vincano (For the victims to win) (1974–75) by the artist Roberto Sebastian Matta allowed us to characterize the original painting materials (pastels on spolvero paper), never investigated and completely unknown, in order to support the imminent restoration. Due to the great dimensions of the artwork and its conservative issues, non-invasive multispectral imaging (HMI) analyses were done to investigate the whole painted surface, mapping and differentiating original materials and possible degradation patterns. Imaging data supported analytical characterization analyses run through elemental (portable X-ray fluorescence spectroscopy and scanning electron microscopy coupled with energy-dispersive spectroscopy) and molecular spectroscopy (Fourier transform infrared and portable µ-Raman spectroscopy) to identify the original artist’s materials and to support the restoration operations. The analysis revealed that the painting materials used by Matta are pastels characterized by modern pigments and dyes, such as Cu-phthalocyanines, chrome orange, titanium and zinc whites, compacted with kaolin without any organic binder or with a possible minuscule amount of gum. Full article
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12 pages, 9858 KiB  
Article
Complex Study of a Painted Gypsum XVIII Century Bas-Relief by Optoelectronic Methods to Develop a Combined Cleaning Technique
Heritage 2023, 6(2), 1891-1902; https://doi.org/10.3390/heritage6020101 - 11 Feb 2023
Cited by 1 | Viewed by 1242
Abstract
In this work, a painted gypsum bas-relief from the facades of the inner courtyard of the St. Petersburg Academy of Arts building was examined using UV and visible light photography and optical and electron scanning microscopy, which showed the heterogeneous layers of white [...] Read more.
In this work, a painted gypsum bas-relief from the facades of the inner courtyard of the St. Petersburg Academy of Arts building was examined using UV and visible light photography and optical and electron scanning microscopy, which showed the heterogeneous layers of white painting on the surface of the bas-relief that covered the historical ones. These undesirable layers should be removed during the restoration work, but it was found that the traditional method of removing surface layers of painting with the help of chemical solvents and mechanical cleaning does not solve the problem to the full extent. A cross-section of all the painting layers was prepared to investigate the stratigraphy of the paint layers. These studies were conducted using optical and electron scanning microscopy in order to determine the structure of the paint layers more properly and study the chemical composition of every layer. After this study, a complex cleaning technique was developed. This technique combines chemical and laser cleaning, making it possible to effectively remove the upper dense layers of paint without damaging the historical paint layers. Full article
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15 pages, 5878 KiB  
Article
Non-Invasive Study of Pigment Palette Used by Olga Boznańska Investigated with Analytical Imaging, XRF, and FTIR Spectroscopy
Heritage 2023, 6(2), 1429-1443; https://doi.org/10.3390/heritage6020078 - 31 Jan 2023
Cited by 2 | Viewed by 1572
Abstract
The scientific examination and comparative investigation of pigments are fundamental for further understanding and analysis of historic and artistic works, and particularly useful for conservators. In fine art authentication, investigations are strongly focused on the identification of the painting materials used by the [...] Read more.
The scientific examination and comparative investigation of pigments are fundamental for further understanding and analysis of historic and artistic works, and particularly useful for conservators. In fine art authentication, investigations are strongly focused on the identification of the painting materials used by the author. This study is focused on the use of non-invasive analytical techniques to increase the knowledge of the painting technique of Olga Boznańska. The aim of this study was to assess the technology, painting technique, and materials used by Olga Boznańska. The pallets, tubes with the paints, and several oil paintings were studied. For each painting, a series of images were recorded using various ranges of electromagnetic radiation, including near-infrared, visible light, ultraviolet, and X-rays. In order to characterize the pigments present in the paint layer, measurements of the elemental composition by X-ray fluorescence spectroscopy (XRF) were carried out. The ground layers and paints were measured with infrared spectroscopy (FTIR). This allowed us to identify the artist’s painting technique and determine how she executed her painting, how she applied the paints, and what pigments she used. Full article
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19 pages, 10970 KiB  
Article
Russian Icons, 17th–18th c. Non-Destructive, Non-Invasive Diagnostic Methodology for an Integrated Study of Micrographic Triptychs from the Benaki Museum Collection
Heritage 2023, 6(2), 1325-1343; https://doi.org/10.3390/heritage6020073 - 30 Jan 2023
Cited by 2 | Viewed by 1556
Abstract
The study aims to enhance our knowledge of the materials and techniques applied in the making of Russian, portable ecclesiastical paintings produced after the 16th century, and to evaluate a pilot, non-destructive, non-invasive, research methodology proposed for their examination. Based on research relating [...] Read more.
The study aims to enhance our knowledge of the materials and techniques applied in the making of Russian, portable ecclesiastical paintings produced after the 16th century, and to evaluate a pilot, non-destructive, non-invasive, research methodology proposed for their examination. Based on research relating to the historical background of their production and distribution in the South, the availability of materials and the applied techniques, a non-destructive, non-invasive methodology is exploited to examine three triptychs and two polyptych side panels belonging to the collection of the Benaki Museum. As their small size and excellent state of preservation prohibit sampling, a study scheme based on visual examination, the implementation of a series of spectral imaging techniques (VIS, IRRFC, SWIR, UVL, RTI, X ray) and a non-invasive micro XRF analysis is tested. Fiber and wood-type identification are carried out microscopically. The collected information relates to the making of the frames and the supports, the design, the use of metal foils and pigments, the order of application of paint layers and the rendering techniques. Due to the non-destructive, non-invasive character of the procedure, organic constituents are not thoroughly examined. Use of an expected palette was confirmed, but the modelling proved rather sophisticated. Among the most interesting finds were the use of distinct pigment mixtures for the underpaints of the flesh parts and certain deviations from the expected rendering techniques. The methodology proved very effective in terms of its output, the global approach of the construction technique, the user-friendly application, the low cost and time consumption factors. Full article
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23 pages, 8117 KiB  
Article
Microanalytical Investigation of Prehistoric Colorants from Uralian Rock Art (Ignatievskaya Cave and Idrisovskaya II and Zmiev Kamen’ Pictographs)
Heritage 2023, 6(1), 67-89; https://doi.org/10.3390/heritage6010004 - 21 Dec 2022
Viewed by 1722
Abstract
Uralian parietal and rock art (cave paintings and pictographs, or “pisanitsy”) represents a unique archaeological and cultural phenomenon, comprising 90 sites stretching for more than 800 km from north to south, which date from the Paleolithic era extending into the present Holocene epoch. [...] Read more.
Uralian parietal and rock art (cave paintings and pictographs, or “pisanitsy”) represents a unique archaeological and cultural phenomenon, comprising 90 sites stretching for more than 800 km from north to south, which date from the Paleolithic era extending into the present Holocene epoch. The identification of the nature of prehistoric colorants provides an insight into their provenance, manufacture and utilization, as well as contributing to the conservation and restoration of drawings. The studies of mineral, elemental and organic phase composition of the colorant micro-samples from the drawings of Ignatievskaya cave and Idrisovskaya II and Zmiev Kamen’ pictographs (Southern and Middle Urals, Russia) discussed in the present work were carried out using a special set of microspectroscopic methods (SEM-EDS and Raman spectroscopy) offering high spatial resolution. The fatty acid composition of the organic phase was analyzed by GC–MS. The technology of colorant manufacture could have included thorough grinding and mixing of unheated hematite with an organic binder made from animal fat and a clayey extender in order to achieve the desired hue and intensity of the color. It is possible that the colorant was applied in layers (Idrisovskaya II and Zmiev Kamen’ pictographs). The development of authigenic phosphate and sulfate (gypsum) mineralization, which is observed in all studied sites, as well as oxalate encrustation on the Idrisovskaya II pictograph, indicates the conditions and processes of secondary mineral formation. Full article
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