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23 pages, 9906 KiB

Open AccessArticle

Characterization and Degradation Analysis of Pigments in Paintings by Martiros Sarian: Attenuated Total Reflection Fourier Transform Infrared Spectroscopic Imaging and X-ray Fluorescence Approach

by Guan-Lin Liu and Sergei G. Kazarian

Heritage 2023, 6(10), 6777-6799; https://doi.org/10.3390/heritage6100354 - 17 Oct 2023

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Abstract

This paper presents a preliminary scientific investigation of pigments used by Martiros Sarian, a prominent Armenian artist known for his vibrant and evocative paintings. The study focuses on five of Sarian’s paintings from different periods of his career, namely, Morning in Stavrino, [...] Read more.

This paper presents a preliminary scientific investigation of pigments used by Martiros Sarian, a prominent Armenian artist known for his vibrant and evocative paintings. The study focuses on five of Sarian’s paintings from different periods of his career, namely, Morning in Stavrino, Arabian Dancer, Caravan, Yerevan Zangu River, and Kirovakan, dated between 1909 and 1948. Non-destructive techniques, including micro-attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopic imaging and X-ray fluorescence (XRF), were employed to characterize the pigments in the samples extracted from these paintings. The results reveal the presence of various pigments, including ultramarine blue, cobalt blue, cobalt cerulean blue, viridian, emerald green, cobalt green, celadonite green, cadmium yellow, chrome yellow, Venetian red, yellow ochre, red ochre, lead white, zinc white, and calcium carbonate. Additionally, metal carboxylates and oxalates, degradation products associated with the paint layers, were observed and discussed. The findings contribute to a better understanding of Sarian’s artistic technique and provide valuable insights for the conservation and restoration of his artworks. Full article

(This article belongs to the Special Issue Photon-Based Techniques for the Examination of Cultural Heritage Artifacts)

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15 pages, 5527 KiB

Open AccessArticle

Understanding Frédéric Flachéron’s Paper Negative Process through Experimentation and Specular Reflection FTIR Analysis

by Elena Bulat, Laura Panadero, Erin L. Murphy and Arthur A. McClelland

Heritage 2023, 6(9), 6097-6111; https://doi.org/10.3390/heritage6090320 - 26 Aug 2023

Viewed by 1063

Abstract

Cultural heritage objects present a special set of challenges for chemical analysis. Often micro-sampling or even contacting the object is deemed an unacceptable risk to the object. This study examined if specular reflection FTIR, a non-sampling and non-contact analytical technique, can provide insight [...] Read more.

Cultural heritage objects present a special set of challenges for chemical analysis. Often micro-sampling or even contacting the object is deemed an unacceptable risk to the object. This study examined if specular reflection FTIR, a non-sampling and non-contact analytical technique, can provide insight into chemical composition of the layered coatings on Frédéric Flachéron’s paper negatives (1848–1852) in the Harrison D. Horblit Collection of Early Photography, in Houghton Library, at Harvard University. Specular reflection FTIR data confirmed the identification of beeswax and sandarac as the transparentizing media on Flachéron’s paper negatives, as previously published by Lee Ann Daffner. However, specular reflection FTIR analysis also indicated that some negatives had additional localized coatings of orange shellac in specific areas of the images. To understand why Flachéron retouched his negatives with orange shellac, modern experimental replications of the paper negative process were performed. Through modern experimentation with the paper negative technique, it was found that Flachéron’s coatings of shellac served as an integral part of his image-altering technique. The color of the orange shellac subtly alters contrast and density, but it does not mask an area the way an opaque watercolor or highly pigmented paint might. The fine adjustments to the negatives with orange shellac were an attempt to perfect the contrast in the print, and better render depth and detail. These discoveries add to a growing body of recent research that points to the historic and art historic importance of negatives and coatings in photography. The specificity with which specular reflection FTIR was able to nondestructively identify the chemical composition of the local coating, and specifically target the analysis on the areas in which it appeared, allowed for an understanding of Flachéron’s use of local coatings as a retouching method rather than a protective coating. Full article

(This article belongs to the Special Issue Photon-Based Techniques for the Examination of Cultural Heritage Artifacts)

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11 pages, 5085 KiB

Open AccessArticle

Integrated Imaging and Spectroscopic Analysis of Painted Fresco Surfaces Using Terahertz Time-Domain Technique

by Alessia Artesani, Francesco Abate, Raffaella Lamuraglia, Maria Antonietta Baldo, Federica Menegazzo and Arianna Traviglia

Heritage 2023, 6(7), 5202-5212; https://doi.org/10.3390/heritage6070276 - 10 Jul 2023

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Abstract

Terahertz time-domain (THz-TD) imaging plays an increasingly significant role in the study of solid-state materials by enabling the simultaneous extraction of spectroscopic composition and surface topography in the far-infrared region (3–300 cm⁻¹). However, when applied to works of art in reflection [...] Read more.

Terahertz time-domain (THz-TD) imaging plays an increasingly significant role in the study of solid-state materials by enabling the simultaneous extraction of spectroscopic composition and surface topography in the far-infrared region (3–300 cm⁻¹). However, when applied to works of art in reflection configuration, significant challenges arise, including weak signal intensity, multiple signal losses, and surface distortion. This study proposes a practical solution to overcome these limitations and conducts an integrated imaging and spectroscopic analysis on painted fresco surfaces, allowing for the retrieval of surface thicknesses, material distribution, and pigment spectroscopic signals. The study addresses the issue of surface geometrical distortion, which hampers the accurate determination of the THz phase signal. By tackling this challenge, this work successfully determines the absorption coefficient for each point on the surface and retrieves spectroscopic signatures. Additionally, the temporal deconvolution technique is employed to separate different layers of the sample and differentiate between outer and inner surface topography. The objective of this study is to demonstrate the advantages and limitations of THz-TD imaging in determining surface thicknesses, material distribution, and pigment spectroscopic signals. The results obtained highlight the potential of THz-TD imaging in investigating painted works of art, offering new possibilities for routine analysis in the field of cultural heritage preservation. Full article

(This article belongs to the Special Issue Photon-Based Techniques for the Examination of Cultural Heritage Artifacts)

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14 pages, 3387 KiB

Open AccessArticle

Methodologies for the Characterization and Identification of Natural Atacamite as a Pigment in Andean Colonial Painting

by Andrea De Haro, Milagros Córdova, Carlos Rua Landa, Cristián Huck-Iriart, Gabriela Siracusano, Marta S. Maier and Eugenia Tomasini

Heritage 2023, 6(7), 5116-5129; https://doi.org/10.3390/heritage6070272 - 03 Jul 2023

Viewed by 1202

Abstract

Painting materials used in Spanish American Colonial art comprised pigments and binders from European origin as well as those that were already known in pre-Hispanic times. In recent years, we have identified for the first time the mineral atacamite, a basic copper chloride [...] Read more.

Painting materials used in Spanish American Colonial art comprised pigments and binders from European origin as well as those that were already known in pre-Hispanic times. In recent years, we have identified for the first time the mineral atacamite, a basic copper chloride (Cu₂Cl(OH)₃), in Andean Colonial art pieces (Viceroyalty of Peru, 16th–18th centuries). This work proposes a methodology based on a multitechnical approach to identify and establish the origin (natural or synthetic) of the atacamite pigment in Andean cultural heritage objects. Optical microscopy (OM), scanning electron microscopy with energy-dispersive spectroscopy (SEM-EDS), portable X-ray fluorescence spectroscopy (pXRF), attenuated total reflection infrared spectroscopy (FTIR-ATR), micro-Raman spectroscopy, and wide-angle X-ray scattering (WAXS) were applied to analyse green pigments from the altarpiece of the Church of Ancoraimes, atacamite mineral samples from Chile, and atacamite obtained as a secondary product from traditional recipes used to produce verdigris, a copper acetate. Viride salsum by Teófilo Presbítero (SXII) and the Spanish translation by Andrés de Laguna (1566) of “De Materia Médica” from Dioscorides are both texts that include recipes involving the use of metallic copper as a starting material. These studies will contribute to the history of Spanish American Colonial art and to the knowledge on technological capacities and skills in the Andean region during this period. Full article

(This article belongs to the Special Issue Photon-Based Techniques for the Examination of Cultural Heritage Artifacts)

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15 pages, 7828 KiB

Open AccessArticle

In Situ Study of the Painting “Hiroshima I” (1958) by Werner Tübke (1929–2004)

by Aleksandra A. Smolianskaia, Ivan I. Andreev, Sergey V. Sirro, Vladimir A. Aseev, Elena Y. Tereschenko and Olga A. Smolyanskaya

Heritage 2023, 6(6), 4802-4816; https://doi.org/10.3390/heritage6060255 - 16 Jun 2023

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Abstract

This article presents the results of technical studies of the oil painting by the artist of German origin Werner Tübke “Hiroshima I” (1958). The creative heritage of this author has not been studied enough and represents scattered data on the technology of painting [...] Read more.

This article presents the results of technical studies of the oil painting by the artist of German origin Werner Tübke “Hiroshima I” (1958). The creative heritage of this author has not been studied enough and represents scattered data on the technology of painting and artistic techniques. The aim of this work was to determine the art materials and painting technology described in his diaries, using the example of his only painting represented in Russia: “Hiroshima I”. For this purpose, an in situ approach was implemented using some simple museum instrumentations—UV-induced visible luminescence, infrared reflectography (IRR), radiography, portable X-ray fluorescence (XRF), Fourier transform Infrared spectroscopy (FT-IR), and polarizing microscopy using microprobes. As a result, the pigment composition of the painting layers could be determined, the painting technology refined, and a previously unknown hidden portrait of Werner Tübke’s father revealed. Full article

(This article belongs to the Special Issue Photon-Based Techniques for the Examination of Cultural Heritage Artifacts)

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13 pages, 10517 KiB

Open AccessArticle

Nondestructive Evaluation of Lined Paintings by THz Pulsed Time-Domain Imaging

by Kaori Fukunaga

Heritage 2023, 6(4), 3448-3460; https://doi.org/10.3390/heritage6040183 - 30 Mar 2023

Cited by 2 | Viewed by 1198

Abstract

For the past 20 years, THz pulsed time-domain imaging has been used to study the internal structure of various paintings. The main advantage of this technique is that it can nondestructively provide depth profiles, as well as conditions of preparation and support layers, [...] Read more.

For the past 20 years, THz pulsed time-domain imaging has been used to study the internal structure of various paintings. The main advantage of this technique is that it can nondestructively provide depth profiles, as well as conditions of preparation and support layers, which are important in conservation planning. We have applied THz pulsed time-domain imaging to artworks with linings, which are additional layers of fabric or paper adhered to the back of an original painted work on canvas or paper to reinforce it, usually for conservation purposes. If the lining material or the interface between the lining and the original canvas or paper deteriorates over time, there is a risk of further problems. Therefore, THz pulsed time-domain imaging is expected to be suitable for examining lined paintings. In this paper, the investigation of artworks with lining layers using the THz pulsed time-domain imaging technique is presented, in addition to previous studies of Japanese panel screens and modern oil-canvas paintings with wax-resin linings, as well as a detached fresco painting mounted on a canvas by the “strappo” technique. Full article

(This article belongs to the Special Issue Photon-Based Techniques for the Examination of Cultural Heritage Artifacts)

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17 pages, 6182 KiB

Open AccessArticle

Contribution to Controlled Method of Varnish Removal from Easel Paintings by ns Pulsed Nd:YAG Laser

by Maxime Lopez, Xueshi Bai, Nicolas Wilkie-Chancellier and Vincent Detalle

Heritage 2023, 6(3), 3307-3323; https://doi.org/10.3390/heritage6030175 - 22 Mar 2023

Cited by 1 | Viewed by 1372

Abstract

Varnish removal from easel paintings is a restoration procedure that is regularly undertaken by cultural heritage conservators. In very few cases, traditional methods (chemical and mechanical) do not allow them to reach the goal of a perfectly controlled and selective cleaning. UV laser [...] Read more.

Varnish removal from easel paintings is a restoration procedure that is regularly undertaken by cultural heritage conservators. In very few cases, traditional methods (chemical and mechanical) do not allow them to reach the goal of a perfectly controlled and selective cleaning. UV laser ablation has been considered since the 1990s to overcome these limitations, but its application to real cases is far from common practice. This study proposes a calibrated procedure based on ablation by an ns UV Nd:YAG laser at 266 nm combined with optical coherence tomography for micrometric laser varnish removal from inhomogeneous and highly photosensitive pictorial layers. The use of this wavelength for varnish removal, not adapted according to the literature, is discussed again after the beam shaping leading to a homogeneous and controlled intensity distribution. The innocuity is controlled by laser-induced luminescence, and some solutions for the transparency loss of the residual varnish following ablation are proposed. Full article

(This article belongs to the Special Issue Photon-Based Techniques for the Examination of Cultural Heritage Artifacts)

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14 pages, 3073 KiB

Open AccessArticle

Inside the Scriptorium: Non-Invasive In Situ Identification of Dyes in Illuminated Manuscripts by Microspectrofluorimetry and Multivariate Analysis: The Crescenzago Choir Books (End 15th Century) as a Case Study

by Margherita Longoni, Noemi Hopes, Federico Rossi, Miriam Rita Tessera, Marco Petoletti and Silvia Bruni

Heritage 2023, 6(2), 2006-2019; https://doi.org/10.3390/heritage6020108 - 15 Feb 2023

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Abstract

In the present work, a method is proposed that combines spectrofluorimetry with multivariate analysis (cluster and principal components) to non-invasively investigate natural dyes used, mainly in the form of lakes, in illuminations. First, a consistent number of mock-up samples of red and purple [...] Read more.

In the present work, a method is proposed that combines spectrofluorimetry with multivariate analysis (cluster and principal components) to non-invasively investigate natural dyes used, mainly in the form of lakes, in illuminations. First, a consistent number of mock-up samples of red and purple lakes (from brazilwood, madder, kermes, cochineal, lac dye, folium and orcein) were prepared following the recipes reported in ancient treatises, then the experimental conditions for their non-invasive investigation were optimized by benchtop instrumentation and transferred to a portable microprobe suitable for in situ analyses. For all the coloring materials examined, it was thus possible to obtain a satisfactory grouping of samples containing the same dye. The analytical protocol was finally extended to the characterization of dyes in the Crescenzago choir books, illuminated manuscripts dating back to the end of the 15th century. Full article

(This article belongs to the Special Issue Photon-Based Techniques for the Examination of Cultural Heritage Artifacts)

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10 pages, 3405 KiB

Open AccessArticle

Time-Gated Pulsed Raman Spectroscopy with NS Laser for Cultural Heritage

by Xueshi Bai and Vincent Detalle

Heritage 2023, 6(2), 1531-1540; https://doi.org/10.3390/heritage6020082 - 01 Feb 2023

Cited by 1 | Viewed by 1867

Abstract

Raman spectroscopy, a non-destructive reference technique, is used in heritage science to directly identify materials like pigments, minerals, or binding media. However, depending on the material, the laser source can induce a strong fluorescence signal that may mask the Raman signal during spectral [...] Read more.

Raman spectroscopy, a non-destructive reference technique, is used in heritage science to directly identify materials like pigments, minerals, or binding media. However, depending on the material, the laser source can induce a strong fluorescence signal that may mask the Raman signal during spectral detection. This photo-induced effect can prevent the detection of a Raman peak. A pulsed Raman spectroscopy, using a time-gated detection and pulsed laser, is proven capable of rejecting the fluorescence background and working with the environmental light, which makes Raman spectroscopy more adapted for in situ applications. In this paper, we investigated how an ns pulsed laser can be an excitation source of Raman spectroscopy by focusing on different parameters of laser excitation and collection. With proper implementation, this pulsed Raman technique can be used for cultural heritage with an ns pulsed laser for the first time. Full article

(This article belongs to the Special Issue Photon-Based Techniques for the Examination of Cultural Heritage Artifacts)

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13 pages, 8325 KiB

Open AccessArticle

Preliminary X-ray Fluorescence Analysis of Metallic Samples from the Chovdar Necropolis in Azerbaijan

by Bakhtiyar Jalilov, Safar Ashurov, Muzaffar Huseynov, Lola Huseynova, Nicola Laneri, Stefano Valentini, Bruno Cocciaro, Stefano Legnaioli, Giulia Lorenzetti, Beatrice Campanella, Simona Raneri, Francesco Poggialini and Vincenzo Palleschi

Heritage 2023, 6(1), 199-211; https://doi.org/10.3390/heritage6010010 - 25 Dec 2022

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Abstract

Several samples coming from the recently discovered (February 2019) Late Bronze Age/Early Iron Age Chovdar necropolis in Azerbaijan were analysed using the X-ray fluorescence (XRF) technique. The analysis allowed a preliminary classification of the samples in eight groups based on their composition, obtained [...] Read more.

Several samples coming from the recently discovered (February 2019) Late Bronze Age/Early Iron Age Chovdar necropolis in Azerbaijan were analysed using the X-ray fluorescence (XRF) technique. The analysis allowed a preliminary classification of the samples in eight groups based on their composition, obtained from the XRF spectra using the fundamental parameter method. A more detailed classification was then obtained using the graph clustering method. Full article

(This article belongs to the Special Issue Photon-Based Techniques for the Examination of Cultural Heritage Artifacts)

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22 pages, 4455 KiB

Open AccessArticle

Interferometric Quantification of the Impact of Relative Humidity Variations on Cultural Heritage

by Vivi Tornari

Heritage 2023, 6(1), 177-198; https://doi.org/10.3390/heritage6010009 - 23 Dec 2022

Cited by 2 | Viewed by 1570

Abstract

It has been shown that Relative Humidity (RH) provokes dimensional displacement detectable directly from surfaces using holographic interferometry. RH variations constitute a physical environmental load that drives organic materials to a constant equilibrium cycle. This paper is a small synopsis of the interferometric [...] Read more.

It has been shown that Relative Humidity (RH) provokes dimensional displacement detectable directly from surfaces using holographic interferometry. RH variations constitute a physical environmental load that drives organic materials to a constant equilibrium cycle. This paper is a small synopsis of the interferometric research direction and a data acquisition on the detection of the dimensional impact of relative humidity on cultural heritage objects. Since RH cycling is unavoidable, the interferometric data change depends on the object structure and RH cycle characteristics. Based on the fact that each artwork is by construction unique, and on the observation that the effects of an RH cycle on the structural condition of any artwork are also unique but the preventive conservation strategies require generalised approaches and not on a case-by-case study, being introduced is a novel, universal, preventive deterioration methodology: “deformation threshold value” (DTV). DTV is assignable to each distinct object in order to control routinely its structural condition and prevent damage. DTV is not assigned hypothetically based on any assumed/expected reactions but from a monitored calibration of the artwork in its environment. Each artwork in its hosted environment has its unique reaction. The reaction, though, is not steady but changes as the artwork changes. DTV can be acquired routinely and valued accordingly to seasonal RH change. Monitoring the seasonal RH and seasonal dimensional reaction has been shown to correspond to a standard DTV pattern whose deviations violate the expected seasonal reaction. Through the interferometric monitoring of surface, the distinct DTV acts as a safeguard for the artwork. In this synopsis, some results of the generation of DTVs are shown. Our future plan is for the DTV numbers to serve as data inputs for preventive models to formulate a distinct risk index representative of each artwork condition and to be used as remote risk warning to prevent its deterioration. Based on the DTV concept, methods and instruments for sequential data acquisition aim to present experimental data outputs as DTVs that identify transient shape changes prior to visible damage have been developed. In this research, the starting point was the interferometric quantification of the displacement of well-characterized fresh samples. The fresh samples are known in terms of density, cut, thickness, moisture content, structural condition and are submitted to RH simulation cycles. Shown here are three exemplary cases: usual, abrupt and smooth. The interferometric monitoring following the cycles of RH is a long-term duration of several weeks; measurements are performed directly from the surface, and relative displacement (RD) from temporal measurements of interference fringes provide the required output data to calculate the rate of displacement (RoD) of the surface. Measuring the impact of RH directly from the artwork surface allows the detection of the temporal diversity of structural reactions to the same RH cycle for distinct artworks. The monitoring system uses interferometric precision provided by digital holographic speckle-pattern interferometry (DHSPI) placed on a specially designed climate chamber DHSPI monitoring workstation. Full article

(This article belongs to the Special Issue Photon-Based Techniques for the Examination of Cultural Heritage Artifacts)

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11 pages, 3650 KiB

Open AccessArticle

Necessity and Use of a Multilayer Test Object Based on an Anonymous 19th Century Copy of a Painting by Ivan Konstantinovich Aivazovsky (1817–1900)

by Ivan I. Andreev, Sergey V. Sirro, Anastasiya A. Lykina, Aleksandra A. Smolyanskaya, Alexander V. Minin, Olga V. Kravtsenyuk, Michel Menu and Olga A. Smolyanskaya

Heritage 2022, 5(4), 2955-2965; https://doi.org/10.3390/heritage5040153 - 04 Oct 2022

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Abstract

The emergence of new research methods in the field of heritage science always raises a large number of questions related to their applicability, reproducibility of results on similar objects, complementarity with other methods, and development of new research methods. To solve such problems, [...] Read more.

The emergence of new research methods in the field of heritage science always raises a large number of questions related to their applicability, reproducibility of results on similar objects, complementarity with other methods, and development of new research methods. To solve such problems, it is necessary to have a test object with the required structure. A multilayer test object based on a fragment of a copy of a 19th century painting by I.K. Aivazovsky was created and described. Analytical studies of the colourful layers were carried out on a Fourier-transform infrared (FT-IR) spectrometer with an attenuated total reflectance (ATR) attachment in single-reflection mode with a diamond crystal. As part of the use of one research method, differences between painting layers of the 19th and 20th centuries were revealed. Results are presented in the IR graphs. The aim of the work was to identify the characteristics of the pictorial layers inherent in the copy of the painting by I.K. Aivazovsky. This will improve the methodology of technological expertise of the I.K. Aivazovsky’s artworks. Full article

(This article belongs to the Special Issue Photon-Based Techniques for the Examination of Cultural Heritage Artifacts)

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11 pages, 4277 KiB

Open AccessTechnical Note

Raman Spectroscopic Analysis of a Mid-19th Century Reredos by Sir George Gilbert Scott

by Christopher Brooke, Howell Edwards, Peter Vandenabeele, Sylvia Lycke and Michelle Pepper

Heritage 2023, 6(7), 5082-5092; https://doi.org/10.3390/heritage6070269 - 30 Jun 2023

Viewed by 792

Abstract

A painted stone reredos in the Priory Church of St Cuthbert, Worksop, Nottinghamshire, UK, was analysed before recent conservation to determine the pigment scheme employed. The screen was created by the eminent British architect Sir George Gilbert Scott in the middle decade of [...] Read more.

A painted stone reredos in the Priory Church of St Cuthbert, Worksop, Nottinghamshire, UK, was analysed before recent conservation to determine the pigment scheme employed. The screen was created by the eminent British architect Sir George Gilbert Scott in the middle decade of the 19th Century. The results help inform the wider range of palettes employed by British architects and craftspeople working in the 19th and early 20th centuries which have previously been little studied. The pigments generally were high-quality vermilion (red), chrome yellow (yellow), and ultramarine (blue), and several alternatives were also evident such as red lead and haematite for red, bone black, and carbon black for black. Lightening and darkening agents were incorporated as lead white, barytes, and carbon, and pigment mixtures were used to achieve the colours dark blue-red, and green. Full article

(This article belongs to the Special Issue Photon-Based Techniques for the Examination of Cultural Heritage Artifacts)

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