Organic Materials in the Wall Paintings

A special issue of Applied Sciences (ISSN 2076-3417). This special issue belongs to the section "Materials Science and Engineering".

Deadline for manuscript submissions: closed (20 August 2022) | Viewed by 21017

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university of parma;department of Chemistry, Life Sciences and Environmental Sustainability,
Interests: chemical of cultural heritage, painting materials, pigments, binding media, cleaning of painting works of art; Innovative Methods of Cleaning Polychrome Works of Art, ancient paper characterization, ancient paper cleaning
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With the exception of some countries, especially eastern countries, which include among their murals those made on wooden walls, generally murals are only painted on walls of a mineral nature, both natural (such as cave paintings painted on walls of caves) and more often artificial walls, stone, or bricks. In most cases, the walls are further prepared with plasters as a sort of preparatory layer, the composition of which varies from simple clay (in the most primitive types) to 'calce and sand,' which constitute the most recurrent case study. The thickness of the plasters can vary from very thin to a few centimeters and the plasters can be both single and multiple, overlapping.

As for the techniques, it was obviously started by simple procedures. In order to obtain stable pictorial drafting, it was still necessary to have pigments and binders. As evidenced by the analytical studies carried out on ancient murals in different cultures (Egyptian, Maya, etc.), painting with plant tempera was among the first to be realized. It is obtained by 'softening' pigments, usually of mineral nature, into binders of a polysaccaride nature (plant gums mostly). From painting to plant tempera, the art moved to that of protein tempera. Protein binders consist of animal glue, egg and casein (skim milk). Glue, however, as a soluble binder or otherwise sensitive to water, has always been used minimally. Much more stable and commonly used are the other two: egg and milk. Local traditions, probably linked to the first experiences, have made one or the other the preference; for example, egg tempera was preferred in Italy, while in northern Europe, the casein, with some exceptions, was preferred. The egg is mainly the 'red' or the mixture of 'white' and 'red', The 'white' alone was instead employed as a fixative 'drink' for the restoration of frescoes in times past. Some artists (especially at the end of the fifteenth century) have also made use of greasy tempers, or egg tempers added to drying oils.

Dr. Antonella Casoli
Guest Editor

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Keywords

  • Wall paintings
  • plant gums
  • egg
  • animal glue
  • milk

Published Papers (9 papers)

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Research

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23 pages, 199201 KiB  
Article
Investigation of Gold Gilding Materials and Techniques Applied in the Murals of Kizil Grottoes, Xinjiang, China
by Jie Yang, Zhibo Zhou, Tianji Lu and Ling Shen
Appl. Sci. 2022, 12(21), 11202; https://0-doi-org.brum.beds.ac.uk/10.3390/app122111202 - 04 Nov 2022
Cited by 3 | Viewed by 1303
Abstract
The present work reports the identification of inorganic and organic materials applied in gildings of Kizil Grottoes mural paintings, located in the western part of China. A total of 10 gold gilding samples were collected from caves dated in the fourth–seventh century AD. [...] Read more.
The present work reports the identification of inorganic and organic materials applied in gildings of Kizil Grottoes mural paintings, located in the western part of China. A total of 10 gold gilding samples were collected from caves dated in the fourth–seventh century AD. In this research, optical microscopy, scanning electron microscopy (SEM) with energy-dispersive X-ray spectroscopy (EDX), UV fluorescence microscopy, and pyrolysis gas chromatography–mass spectrometry (Py-GC/MS) analyses were carried out to clarify the mordant materials and the coating materials on the foils. This research reports some new finds of the gilding technique in Kizil grottoes, such as oil and lac resin being used as mordant to provide a binding medium for gold gilding, gold powder probably being used as pigment, and some organic dyes being well preserved under gold foil. These interesting findings not only provide scientific evidence for us to understand the materials and techniques of gold gildings on Kizil Grottoes murals, but also illustrate material trade and technique exchanges along the Silk Road in the past. Full article
(This article belongs to the Special Issue Organic Materials in the Wall Paintings)
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25 pages, 4107 KiB  
Article
Organic Materials Used for Giant Buddhas and Wall Paintings in Bamiyan, Afghanistan
by Yoko Taniguchi, Kazuki Kawahara, Miho Takashima, Marine Cotte, Joy Mazurek, Yuki Kumazawa, Yuki Taga and Takashi Nakazawa
Appl. Sci. 2022, 12(19), 9476; https://doi.org/10.3390/app12199476 - 21 Sep 2022
Cited by 2 | Viewed by 3666
Abstract
Since 2004, scientific research on the damaged Giant Buddha statues and Buddhist paintings in Bamiyan, Afghanistan, has been conducted at various laboratories and large-scale facilities using mass-spectrometry techniques (GC-MS, LC-MS, LC-MS/MS, nano-LC/ESI-MS/MS), ELISA, and synchrotron-based micro-analyses) in parallel to conservation intervention. Studies on [...] Read more.
Since 2004, scientific research on the damaged Giant Buddha statues and Buddhist paintings in Bamiyan, Afghanistan, has been conducted at various laboratories and large-scale facilities using mass-spectrometry techniques (GC-MS, LC-MS, LC-MS/MS, nano-LC/ESI-MS/MS), ELISA, and synchrotron-based micro-analyses) in parallel to conservation intervention. Studies on samples from these cultural heritage objects have shown that each is composed of a polychromatic multilayered structure with sizing layers, ground layers, painted layers, and glaze. The carefully produced complex multilayered structures were examined using optical microscopy (visible and UV light) as well as synchrotron-based infrared microscopy, both of which revealed various organic and inorganic components in each layer. High sensitivity bulk MS and ELISA methods were used to further identify details regarding organic materials, such as fatty acids and collagens, and these results suggest different vegetable oils and animal species of glues. For example, cow milk casein and cow skin glue were identified in the Eastern Giant Buddha, suggesting that casein was used as a sizing agent and the cow skin glue as a binder for painting. The wall paintings from Cave N(a) (mid-7th century AD) were found to have horse glue used as sizing and drying oil (poppyseed/walnuts/perilla oils) as a binding media. The paintings’ complex structures and their organic and inorganic materials were fully understood using both imaging and bulk methods, and thus, these methods help to reconstruct historical wall painting techniques in full. Full article
(This article belongs to the Special Issue Organic Materials in the Wall Paintings)
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20 pages, 11636 KiB  
Article
The Susceptibility to Biodegradation of Some Consolidants Used in the Restoration of Mural Paintings
by Ioana Gomoiu, Roxana Cojoc, Robert Ruginescu, Simona Neagu, Mădălin Enache, Maria Dumbrăvician, Ioana Olteanu, Roxana Rădvan and Luminița Ghervase
Appl. Sci. 2022, 12(14), 7229; https://0-doi-org.brum.beds.ac.uk/10.3390/app12147229 - 18 Jul 2022
Cited by 4 | Viewed by 1419
Abstract
This study evaluated both the possible fungal metabolites involved in the degradation of the commercial consolidant known as Paraloid® B72 and the national artisanal consolidant named transparent dispersion of casein and the deteriorative potential of melanised fungi. Fungi were found to have [...] Read more.
This study evaluated both the possible fungal metabolites involved in the degradation of the commercial consolidant known as Paraloid® B72 and the national artisanal consolidant named transparent dispersion of casein and the deteriorative potential of melanised fungi. Fungi were found to have the capacity to produce organic acids, proteases and esterases when they grow on consolidants, which can be used as nutrients. Mycelia produced by melanised fungi affected the appearance, as well as the integrity, of consolidants applied on painted experimental models and fragments of frescoes. In treatment trials with biocides (Biotin R®, Biotin T® and Preventol® RI 80), the morphology of the consolidants, as well as the vitality of the fungi, were assessed 30 days after the inoculation with melanic fungi. Direct observation, optical microscopy, colourimetry and microbiological analysis highlighted the degradation of the consolidants by fungi and their acquired resistance after biocidal treatments. Biotin R® applied by brushing on the surface of the consolidants proved to be the most effective treatment, followed by Biotin T®. Considering the overall results for both Paraloid® B72 and transparent dispersion of casein, use of Biotin R® applied by brushing is recommended for preventive conservation. Full article
(This article belongs to the Special Issue Organic Materials in the Wall Paintings)
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9 pages, 603 KiB  
Article
Properties of Emulsion Paint with Modified Natural Rubber Latex/Polyvinyl Acetate Blend Binder
by Bahruddin Ibrahim, Zuchra Helwani, Ivan Fadhillah, Arya Wiranata and Joni Miharyono
Appl. Sci. 2022, 12(1), 296; https://0-doi-org.brum.beds.ac.uk/10.3390/app12010296 - 29 Dec 2021
Cited by 3 | Viewed by 3288
Abstract
The direct use of natural rubber latex (NRL) as a binder for emulsion paints did not produce emulsion paints with good opacity, washability resistance, and regulated touch drying time, even when mixed with polyvinyl acetate (PVAc). This study aimed to study the properties [...] Read more.
The direct use of natural rubber latex (NRL) as a binder for emulsion paints did not produce emulsion paints with good opacity, washability resistance, and regulated touch drying time, even when mixed with polyvinyl acetate (PVAc). This study aimed to study the properties of opacity (hiding power), washability resistance, and set drying touch time of emulsion paint with a binder added from a mixture of modified natural rubber latex (NRL) and PVAc. NRL modifications included UV photodepolymerization with TiO2 catalyst and grafting copolymerization of methyl methacrylate and styrene (NRL-g-(MMA-co-St)). NRL was mixed with PVAC at ratios of 0/100; 15/85; 25/75; 35/65; 50/50; 100/0% w/w before being used as a binder for emulsion paint. Emulsion paint samples had different binder contents, namely 2, 4, 6, and 8% w/w. Tests on paint samples included opacity using a UV-Vis spectrophotometer (EASYSPEC safas Monaco), washability using the Digital BGD 526 Wet Abrasion Scrub Tester, and drying time set using the ASTM STP500 procedure. The results showed that the opacity (hiding power), washability resistance, and set drying touch time met the emulsion paint standards for all binder levels, except the 100% w/w modified NRL composition. The higher level of NRL in the binder causes these properties to decrease and become unstable. The best opacity (hidden power), washing resistance, and drying touch time were obtained on modified NRL with a concentration of 15% w/w. The binder content in the paint was around 4% w/w, with an opacity of about 1.78% abs, washing resistance of 12 times, and the set drying touch time to 80 min. Full article
(This article belongs to the Special Issue Organic Materials in the Wall Paintings)
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19 pages, 4791 KiB  
Article
Organic Matter and Pigments in the Wall Paintings of Me-Taw-Ya Temple in Bagan Valley, Myanmar
by Maria Letizia Amadori, Valeria Mengacci, Manuela Vagnini, Antonella Casoli, Parviz Holakooei, Negar Eftekhari, Kyi Lin, Yoshifumi Maekawa and Giulia Germinario
Appl. Sci. 2021, 11(23), 11441; https://0-doi-org.brum.beds.ac.uk/10.3390/app112311441 - 02 Dec 2021
Cited by 6 | Viewed by 2171
Abstract
Pagán is an ancient city located in Myanmar that is renowned for the remains of about 4000 pagodas, stupas, temples and monasteries dating from the 11th to 13th centuries. Due to a magnitude 6.8 earthquake in 2016, more than 300 ancient buildings were [...] Read more.
Pagán is an ancient city located in Myanmar that is renowned for the remains of about 4000 pagodas, stupas, temples and monasteries dating from the 11th to 13th centuries. Due to a magnitude 6.8 earthquake in 2016, more than 300 ancient buildings were seriously damaged. As a part of the post-earthquake emergency program, a diagnostic pilot project was carried out on Me-taw-ya temple wall paintings to acquire further information on the materials and on their state of conservation. This article presents our attempts at characterising the painting materials at Me-taw-ya temple using non-invasive portable energy dispersive X-ray fluorescence (ED-XRF), portable Raman spectroscopy and micro-invasive attenuated total reflectance—Fourier transform infrared spectroscopy (ATR-FTIR), micro-Raman spectroscopy (µ-Raman), gas chromatography-mass spectrometry (GC-MS), polarized light microscopy (PLM) and environmental scanning electron microscope—X-ray energy dispersive system (ESEM-EDS) investigations with the aim of identifying the composition of organic binders and pigments. The presence of a proteinaceous glue mixed with the lime-based plaster was ascertained and identified by GC-MS. In addition, this technique confirmed the occurrence of plant-derived gums as binders pointing to the a secco technique. Fe-based compounds, vermillion, carbon black and As-compounds were identified to have been incorporated in the palette of the murals. Full article
(This article belongs to the Special Issue Organic Materials in the Wall Paintings)
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18 pages, 17901 KiB  
Article
The Characterization of the Materials Used by Gino Severini in his 20th C Wall Paintings at Semsales in Switzerland
by Patrizia Moretti, Stefan Zumbühl, Ottaviano Caruso, Nicola Gammaldi, Paola Iazurlo and Francesca Piqué
Appl. Sci. 2021, 11(19), 9161; https://0-doi-org.brum.beds.ac.uk/10.3390/app11199161 - 01 Oct 2021
Cited by 6 | Viewed by 1905
Abstract
The modern decoration of the Saint Nicolas de Myre Church at Semsales (1924–1926), is the first by renowned Italian artist Gino Severini in Switzerland. Following archival research and visual examination, the materials and the techniques used by Severini for the wall paintings of [...] Read more.
The modern decoration of the Saint Nicolas de Myre Church at Semsales (1924–1926), is the first by renowned Italian artist Gino Severini in Switzerland. Following archival research and visual examination, the materials and the techniques used by Severini for the wall paintings of this church were examined through a multi-technique analytical approach that included both non-invasive and invasive investigations. Archival research revealed lists of some of the materials purchased for the church and notes of the artists. In situ investigations included imaging methods and point analyses (X-ray fluorescence and reflection FT-IR spectroscopy). Based on non-invasive results, a limited number of representative samples were collected for laboratory invasive analyses (SEM-EDS, FTIR-FPA imaging, μ-Raman and GC-MS) to characterize the stratigraphy and the composition of the paintings. Results were coherent with artist’s notes and revealed protein-based binders, i.e. animal glue and casein, exclusively on the Trinity mural (in the apse) confirming the use of a secco technique. All the other wall paintings analyzed at Semsales are painted without the use of organic binders. These findings, integrated with archival researches and the visual examination by conservators, provided significant insights into the materials and techniques used by Gino Severini in his first Swiss murals. Full article
(This article belongs to the Special Issue Organic Materials in the Wall Paintings)
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13 pages, 1483 KiB  
Article
Graffiti Characterization Prior to Intervention in the Punta Begoña Galleries (Getxo, North of Spain): Raman and XRF Spectroscopy in the Service of Restoration
by Idoia Etxebarria, Nagore Prieto-Taboada, Estibaliz Lama, Gorka Arana, María Dolores Rodríguez-Laso and Juan Manuel Madariaga
Appl. Sci. 2021, 11(18), 8640; https://0-doi-org.brum.beds.ac.uk/10.3390/app11188640 - 17 Sep 2021
Cited by 1 | Viewed by 1564
Abstract
The Historical and Cultural Heritage of Punta Begoña Galleries in Getxo (Bizkaia, North of Spain) are currently in restoration after being abandoned for years. For that reason, many graffiti, which directly affect the wall paintings, appear on most of their walls. Moreover, several [...] Read more.
The Historical and Cultural Heritage of Punta Begoña Galleries in Getxo (Bizkaia, North of Spain) are currently in restoration after being abandoned for years. For that reason, many graffiti, which directly affect the wall paintings, appear on most of their walls. Moreover, several graffiti overlap each other, which makes their removal more difficult. For all these reasons, the chemical characterization of these pigments is a priority to optimize the cleaning and consolidation treatments of wall paintings. That being the case, an analysis based on Raman spectroscopy and X-ray fluorescence was carried out to obtain information to help conservators remove the graffiti without damaging the mural paintings and the support. Nevertheless, the first step, using X-ray fluorescence and Raman spectroscopy, involved the need for a database to compare the results and identify the compounds. Thus, different commercial inks were elementally and molecularly characterized to complete the existing databases. After this, an analysis of the inks was carried out that noted the presence of several organic pigments, such as phthalocyanines. Inorganic pigments such as titanium oxide were identified as well. After the analysis, the selection of the best removal process could be carried out to provide the most effective treatment, avoiding the “trial-and-error” classical practice. Full article
(This article belongs to the Special Issue Organic Materials in the Wall Paintings)
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16 pages, 8704 KiB  
Article
Multi-Technique Characterization of Pictorial Organic Binders on XV Century Polychrome Sculptures by Combining Micro- and Non-Invasive Sampling Approaches
by Elena C. L. Rigante, Cosima D. Calvano, Rosaria A. Picca, Simona Armenise, Tommaso R. I. Cataldi and Luigia Sabbatini
Appl. Sci. 2021, 11(17), 8017; https://0-doi-org.brum.beds.ac.uk/10.3390/app11178017 - 30 Aug 2021
Cited by 2 | Viewed by 1718
Abstract
A stony sculptural composition of the Nativity Scene is preserved in Altamura’s Cathedral (Apulia, Italy). This commonly called Apulian “presepe”, attributed to an unknown stonemason, is composed of polychrome carbonate white stone sculptures. While earlier stratigraphic tests have unveiled a complex [...] Read more.
A stony sculptural composition of the Nativity Scene is preserved in Altamura’s Cathedral (Apulia, Italy). This commonly called Apulian “presepe”, attributed to an unknown stonemason, is composed of polychrome carbonate white stone sculptures. While earlier stratigraphic tests have unveiled a complex superimposition of painting layers—meaning that several editions of the sculptures succeeded from the 16th to 20th century—a chemical investigation intended to identify the organic binding media used in painting layers was undertaken. Drawing on current literature, two strategies were exploited: a non-invasive in situ digestion analysis and an approach based on micro-removal of painting film followed by the Bligh and Dyer extraction protocol. Both peptide and lipid mixtures were analyzed by matrix-assisted laser desorption/ionization-mass spectrometry (MALDI-MS) and reversed-phase liquid chromatography coupled to mass spectrometry by electrospray ionization (RPLC-ESI-MS). Attenuated total reflectance Fourier-transform infrared spectroscopy (ATR-FTIR) examinations were also performed on micro-samples of painting films before lipids and proteins extraction. While human keratins were found to be common contaminants of the artwork’s surfaces, traces of animal collagen, siccative oils, and egg white proteins were evidenced in different sampling zones of the sculptures, thus suggesting the use of non-homogeneous painting techniques in the colored layers. Full article
(This article belongs to the Special Issue Organic Materials in the Wall Paintings)
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Review

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18 pages, 839 KiB  
Review
Research on the Organic Binders in Archaeological Wall Paintings
by Antonella Casoli
Appl. Sci. 2021, 11(19), 9179; https://0-doi-org.brum.beds.ac.uk/10.3390/app11199179 - 02 Oct 2021
Cited by 13 | Viewed by 2879
Abstract
Wall painting realized using organic binders is the oldest form of parietal painting and precedes the birth of the affresco by about 20,000 years. This paper reports the results obtained from the main studies in the field of archaeological wall paintings. The attention [...] Read more.
Wall painting realized using organic binders is the oldest form of parietal painting and precedes the birth of the affresco by about 20,000 years. This paper reports the results obtained from the main studies in the field of archaeological wall paintings. The attention was paid to the study of organic binders used for the application of the color, as well as on the instrumental techniques chosen to obtain such information. Different techniques can be used for the study of organic material in archeological paintings: non-destructive techniques, which can be applied directly in situ without sampling, and laboratory micro-invasive techniques for a more in-depth characterization. Among these, the chromatographic techniques represent a potential tool to acquire as much information as possible about chemical composition of binders. Full article
(This article belongs to the Special Issue Organic Materials in the Wall Paintings)
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