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197 Original Article DEGRADATION of VERMILION RED COLOR IN id4248453 pdfMachine by Broadgun Software - a great PDF writer! - a great PDF creator! - http://www.pdfmachine.com http://www.broadgun.com Egyptian Journal of Archaeological and Restoration Studies "EJARS" An international peer-reviewed journal published bi-annually Volume 9, Issue 2, December - 2019: pp: 197-206 www. ejars.sohag-univ.edu.eg Doi: 10.21608/ejars.2019.66990 Original article DEGRADATION OF VERMILION RED COLOR IN OIL AND MURAL PAINTINGS: A COMPARATIVE APPLIED STUDY Abo-Taleb, Th. & Orabi, E.( ) Conservation dept., Faculty of Archaeology, Aswan Univ., Aswan, Egypt E-mail: [email protected] Received 21/7/2019 Accepted 18/12/2019 Abstract The present study investigates and compares the vermilion red color change phenomenon in an oil painting executed on wood from the 18th century stored at the Archaeological Museum Store of Manial Palace Museum, Cairo and a mural painting executed using Tempera from the Greco-Roman Periodin a destroyed archeological house next to Medinet Madi Temple, (35kms far from Fayoum city). The vermillion red color may change to dark red, brown, or grayish-white due to the exposure to the environmental conditions and pollutants, the common role of both light and chlorine as the main factors of red discoloration, some impurities in color components, as well as the dissolved salts and organic media used in painting. The blackness of the color was detected after doing an analytical study to identify the damaged products of the vermillion red using different methods of analysis (i.e. microscopy, X-ray diffraction, Energy Dispersive X- rays and Infrared). The change to gray color in oil paintings due to the presence of the prokovite was associated with cinnabar. In the mural painting, it resulted from the conversion to black hypercinnabar, not to the resin. Keywords: Cinnabar, Meta cinnabar, Hypercinnabar, Vermillion, Effect of light, Chlorine, Humidity 1. Introduction The first use of red vermillion- known light, impurities, relative humidity, ino- as cinnabar- dates back to the New Stone rganic pollutants, chlorine, and faulty Age 3000 B.C. in funeral objects. Then, restoration using inappropriate materials it was used by ancient Greeks between and/or methods [3]. These factors often the third and fourth centuries BC. It has cooperate to make a change to the red color become scarcer since the mid-first century of the crystalline form by oxidation and AD [1]. Vermillion was used in classic its transformation into the black metac- mural paintings in Bombay, in the mural innabar of the crystalline form of cubic, paintings of the Gothic Church in the which changes the appearance of the art- Monastery of Pedralbes in 1326 AD in work. It is difficult to distinguish between Spain, and Love of the Mag oil painting HgS- -HgS by chemical analyzes by Robbins (1577-1640 AD) at the Royal á and â Museum of Fine Arts in Antwerp [2]. because they often identify sulfur and Vermillion red color deteriorates and cha- mercury only [4]. Thus, researchers con- nges slowly and irreversibly, affecting ducted various studies to find out the the cultural heritage in both museums basic process of decomposition. It was and archeological sites due to exposure to done using X-ray and electrochemical analysis. It has developed many hypo- causing color changes because chlorine is theses, e.g. chlorine can be a catalyst [5] a catalyst for the collection, analysis, for the degradation of color by light. display, and chemical oxidation inter- Therefore, á-HgS turns into mineral action, which turns Hg (II) S to Hg and mercury and sulfur [6]. The cause of S. After that, Cl interacts with Hg to the red color change can be effectively give HgCl2 and HgS for corderoite (á- explained in two separated stages. First, Hg3S2Cl2) formation (Hg3S2Cl2) that turns chlorine acts as a catalyst during the light- into calomel [12]. Exposure to light cont- induced conversion of mercury sulfide inues the changes of Hg2Cl2 to mercury HgS (photo-oxidation) to Hg (0) and S chloride (HgCl2) and mineral mercury (0) [7]. Then, mercury reacts with chlorine (Hg) [13]. The interaction mechanism to form different mercury chlorine com- continues in the light until the color deg- pounds. Light-sensitive á-Hg3S2Cl2 com- radation occurs completely. Damage dep- pounds can be converted to Hg2Cl2 after ends on the presence of air pollutants the loss of the crystalline network through [14]. After exposure to the light, chlorine oxidation and volatilization [8], leaving is a catalyst for chemical photo oxidant the underlying mercury [9]. Mineral mer- reaction [15], the á - Cinnabar changes to cury may cause Hg2Cl2 to become a mineral mercury and sulfur, then chlorine gray HgCl2 because of chlorine gas ClO, ion interacts with the mineral mercury which has been demonstrated through and the mercury chloride, and the ion microscopic studies of historical panels' chlorine interacts with cinnabar to give samples with a high concentration of chlo- sulfur (S) and corderoite (Hg3S2Cl2) that ride in areas adjunct to some degraded is converted to calomel. It is a light- areas [10]. It also explains the red color sensitive compound that turns into mer- resulting from increasing light, which cury chloride and mineral mercury. Dark causes automatic mercury deposition black also may occur because of the on the surface because the optical energy presence of other ions, such as pota- is converted to light energy. When the ssium, zinc [16], iron sulfide and selenium color absorbs light energy, electrons are [17], or other impurities in contact with excluded. They move from lower-energy HgS, which greatly affects the mineral orbits to higher orbits. By continuing nature and turns the color dark. X-ray this process, they gain their own colors diffraction was used to identify the dam- [11]. Light sensitivity electrons due to aged products on the red color surface, the red vermillion transformations can and UV spectroscopy was employed to cause color changes because photos- determine the color and its type. The ynthesis electrons have enough power interaction is performed according to the to reduce Hg2 to Hg. They may return following equations. to the basic state after losing energy, cl 1. á – HgS Hg (0) + S (0) -1 2. Hg (0) + 2Cl HgCl2 -1 3. á – 3HgS + 2Cl S (0) + Hg3S2Cl2 4. Hg S Cl Hg+2S+ Hg Cl 3 2 2 2 2 5. Hg2Cl2 Hg + HgCl2 This study aims to explain the avoid red color deterioration in the reasons for the most signifi-cant future and to choose appropriate treatment deterioration factors of color change to materials. 2. Materials and Methods 2.1. Study objects The study was carried out on two to Medinet Madi temple. Its decorative paintings. One of them is an oil painting units include geometric elements of tria- th dating back to the late 18 cen-tury ngles, as well as horizontal and vertical entitled "flower bouquet on oval wood" and lines. The house was built with bricks stored in the archaeological museum coated with mud plaster, whitewash made store of Manial Palace Museum that lies from lime, then a layer of red and orange on the main street with pollutants from colors. In the present case studies, red transportation. The other is a mural pai- changed to gray, black, and white areas in nting executed in the tempera technique oil painting, fig. (1-a). On the contrary, dating back to the Greco-Roman period it changed to gray and black in the in a destroyed archeological house next mural painting, fig. (1-b). Figure (1) Shows a. a bouquet of flowers with the red color that changed to gray and white, b. a Roman-era mural painting with a red color that changed to gray and black 2.2. Methods of investigation The study materials were examined mponent, and medium. UV/VIS spec- by oblique light, scanning electron mic- trophotometer analysis was utilized for roscopy and Olympus (DP 731) connected color determination and concentration to a computer unit with a camera (100x estimation. It could produce comparable magnification), X-ray diffraction, Energy spectra of the analyzed samples in the Dispersive X-rays, and infrared spectr- spectral range of 360-1000 nm. Then, oscopy (FTIR). Analyses were performed the colored materials could be identified. to identify the type of painting, ground co- 3. Results 3.1. Results of the visual inspection and stereo microscopic examination The visual inspection method is the some places, fig. (2-b). Stereo microsc- first stage of screening using some lenses ope examination of the oil painting showed that magnify up to 6x. The visual inspe- the color change of red to dark brown, ction of the oil painting showed some dark gray, and white with a slight bluish- color changes. Most of the surface had gray, as shown in fig. (3-a,b). In the case accumulations of dust clots and some of the mural painting, stereo microscope crystallized salts, as shown in fig. (2-a). The mural painting had some crystallized examination showed some changes in salts inside the cracks and a weak and the red color to a dark color closer to fragile surface. It was very easily black with gray spots in some areas and fragmented because of its weak mineral heterogeneous points of dark gray that composition and the breakdown of its distorted the archeological surface as component grains, and color changed in shown in (3-c,d). a b Figure (2) Shows a. the changed color from pink to dark red in the oil painting, b. the changed color from pink to dark red and from dark pink to dark gray in the mural painting a b c d Figure (3) Shows stereo microscopic examination a.
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