In-situ observation
The in situ microphotographs as shown in Fig.3, reveal multiple paint layers of the statues. The results indicated that the general sequences and combinations of layers are different for the three statues. As seen from Fig.3a,at least four paint layers were found at the statue of Tutang Buddha from top to the bottom which are: black (L1)-paper-red (L2)-paper-green (L3)-paper-dark green(L4).At the bottom of the kasaya (Fig.3(b)), the sequence of the paint layers presents as gold (L1)-paper-red (L2)-paper-red (L3)-white(L4). Also, the examination (Fig.3(c)) of the statue of Mahasthamaprapta bodhisattva demonstrated that the white pigment layer is overlapped by the green pigment layer.
The phenomenon of repainting seriously damaged statues was universal in ancient China. The ancient Chinese craftsmen usually applied mud and lime to cover the original paint layer, then repainted it. Later, mainly in the Ming and Qing Dynasties, the processes were varied slightly, the paint layer was covered with paper sequently repainted[16]. According to the in-situ observation, at least two layers of paper were found at the three statues with three or four layers of paper in some parts. Meanwhile, the inscriptions proved the results that the statues were restored repeatedly in A.D.1541 (the reign of the Jiajing Emperor in the Ming dynasty) and A.D.1739 (the reign of the Qianlong Emperor in the Qing dynasty).Multi-layers paintings were also investigated in the paintings [17]and wooden statues[18]. The result not only helps us to deepen the knowledge of the historical and cultural value but also supports the restorers to determine whether the over layers need to be removed.
Fig.3
Multiple paint layers of the statues:(a) at the lotus of the statue of Tutang Buddha; (b) at the bottom of the kasaya of the statue of Avalokitesvara bodhisattva;(c) at the bottom of the skirt of the statue of Mahasthamaprapta bodhisattva
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Analysis of the pigments
The major colours of the statues in Jingyin Temple contain gold, red, blue, green, white, black and so on. Table 2 shows an overview of the pigments that were identified by SEM-EDS and Micro-Raman spectroscopy (Fig 4-1, 4-2, 5-1, 5-2).
Compositional analysis of the gilded materials of the three statues were detected by SEM-EDS. The results suggested a high level of gold (Au). Gold was frequently used as a gilding material in decorating precious painted sculpture in ancient China. In Northern China, the clay statues were decorated with gold and colors in ancient times. The technique of gilding the entire statue was widely used in Ming and Qing dynasties [19], which was also discovered in the statue of Tutang Buddha.
Three red samples were analysed by SEM-EDS and Micro-Raman spectroscopy. The elements of Hg, S and Pb were found by SEM-EDS in the Sample JYS-2-3. Different results of the Micro-Raman spectroscopy were obtained at two detection points of red Sample JYS-2-3. At one of the points we have detected the strong Raman peaks at 252,286,342 cm-1 which correspond well to characteristic Raman bands of cinnabar (HgS)[20-22]. Moreover, the strong Raman peaks at 160,225,313,475,546cm-1 are assigned to minium (Pb3O4). The strong absorption at 546cm-1 is attributed to the stretching of the Pb-O bond[14,23,24].The result agrees with SEM-EDS analysis and conforms the red pigment is a mixture of cinnabar and minium. The same red pigment may also be used for the Sample JYS-2-3. Although the result of Micro-Raman spectroscopy indicated the existence of cinnabar, the elements of Hg and Pb are detected. The same analytical method is applicable to Sample JYS-1-3.
The blue pigment (JYS-2-4), which used in decorating the parts ofkasaya of the statue of Avalokitesvara bodhisattva, was identified as azurite (2CuCO3·Cu(OH)2). All peaks between 100 and 1600cm-1 (137,174,247, 400,543, 766, 836, 944, 1096,1348, 1425 and1581 cm −1) are diagnostic Raman peaks assigned to azurite[25]. The main element of the sample was Cu detected by SEM-EDS.It is well know that azurite was the most important blue pigment not only in European paintings throughout the Middle Ages and Renaissance[26] but also in Ancient China[27].
The skirt and streamer of the statue of Mahasthamaprapta bodhisattva were painted with green pigment and gold which forms the brilliant colors and exquisite patterns. The green pigment (JYS-3-1) was identified as atacamite (Cu2Cl (OH)3). SEM-EDS analysis reports relatively high level of Cu. Micro-Raman study of the sample exhibited peaks at 360, 514, 825, 915, 981cm-1, which are assigned to atacamite [28,29].
SEM-EDS analysis indicates the main element of the lime layer fragment is Ca. The Raman peaks at 152, 278, 1087cm-1 are assigned to Calcium carbonate (CaCO3)[30]. Calcium carbonate has been used to paint white for quite a long time and was reported to be used in of art and archaeological objects, such as the mural painting [31,32], architecture, et al. More interestingly, the main chemical constituent of the white pigments of JYS2-1 and JYS-2-4 is Pb. The Raman band registered at 1051cm-1 is attributed to lead white (2PbCO3 ·Pb(OH) 2)[33]. The result indicated that the statue of Avalokitesvara bodhisattva was decorated by the white pigment of lead white.
Unfortunately due to the poor conservation of the black pigments (JYS1-6, JYS3-3) or other reasons, the information of the black pigments were not obtained. Further analytical methods will be used to detect the black pigments in subsequent studies.
Table 2. The analysis results of major color pigments of the statues
Fig.4-1
SEM/EDS results of the samples:(a)JYS-1-1;(b) JYS-1-2;(c) JYS-1-3;(d) JYS-1-4;(e) JYS-2-1;(f) JYS-2-2.
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Fig.4-2
SEM/EDS results of the samples: (g) JYS-2-3;(h) JYS-2-4;(i) JYS-2-5;(j) JYS-3-1;(k) JYS-3-2;(l) JYS-3-3.
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Fig.5-1
Raman spectrum of samples: (a) JYS-1-2; (b) JYS-1-4;(c) JYS-2-1;(d) JYS-2-3-1.
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Fig.5-2
Raman spectrum of samples: (e) JYS-2-3-2;(f) JYS-2-4;(g) JYS-2-5;(h) JYS-3-1.
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Paper analysis
Herzberg stain is usually used to distinguish fiber sources, because different fibers of different plant sources are dyed in different colors by the iodide/iodine mixed with zinc chloride solution[34]. Fig.6 (a),(b),(c) show the three paper samples with reddish brown color. The thickness of the fibers are different, in the range of 12-60μm. There are numerous longitudinal stripes and transversal striations on the fiber walls. By comparing stained fibers with those most commonly used in Oriental papermaking, such as bast fibers (hemp, flex, ramie, paper mulberry, etc.), bamboos, and grass fibers (wheat and rice straws), we could deduce that the fiber sources of the three samples are ramie[35].It is well known that China is the origin of ramie. Documental evidences show Tsai-lun invented a new process of paper-making, and remie was used as one of the materials in Eastern Han Dynasty[15]. Remie paper has been used so far.
Fig.6
Morphology of paper fibers: (a) JYS-1-1; (b) JYS-2-4; (c) JYS-3-1.
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Analysis of the clay fragments
Only samples of fine clay layer were taken for testing because of technical restrictions on historical artifacts sampling. XRD patterns shown in Fig.7 suggested that quartz (SiO2)[36] and calcite (CaCO3 )[37] be the primary crystalline phases in the fine clay layers and the soil from the hillside close to Jingyin Temple. XRD analysis show the presence of albite (Na(AlSi3O8)) and gypsum(Ca(SO4)(H2O)2) as minor ones of both JYS2-6 and JYS3-5 which were the same dynasty. XRD analyses revealed albite (Na(AlSi3O8)) being the minor component with the JYS-1-5. The granulometric analysis of JYS-4,JYS-1-5,JYS-2-6,JYS-3-4 show that the particle sizes are mainly in the range of 0.0002–0.20mm. The component particles of the samples are predominantly between 0.075mm and 0.01mm, with the content of coarse powder particle over 50%. It is also found that the proportion of the fine powder particle is close to the proportion of the clay particles. Refer to the relevant studies, it is suggested that the craftsmen made clay statues by collecting the raw materials from local area[38,39]. The results analysis helped us to investigate the sources of the materials, which were important for working out the restoration scheme.
Table 3. Particle size distribution of the fine clay layer.