1. Introduction
The Taiping Heavenly Kingdom Palace, located in Yixing City, Jiangsu Province, was declared as a provincial unit of protection of cultural relics by the Central People’s Government in March 1982. The Yixing Taiping Royal Palace was originally the residence of a scholar of the surname Shi during the Jiaqing period of the Qing Dynasty. In 1860, when the Taiping army captured Yixing, the old residence of Shi surname was used to convert it into a royal residence of Yang Fuqing, the king of the Taiping Dynasty. Twelve murals were saved in the royal residence of the Taiping Heavenly Kingdom. Each mural reflects some of the social events of the time. With regard to the Taiping murals, Yu Jianhua stated in his book History of Chinese Mural Painting that “(by) the end of the Qing dynasty, the decline of Chinese painting had reached its peak”.
The Yixing Taiping murals and color paintings are also of great scientific value. The differences and similarities between Qing dynasty folk color painting and official style color painting, from the craft practices to the materials used, are key topics of research. The present analytical study provides a deeper understanding of Qing dynasty color paintings. Color painting in ancient architecture involved three main components: the wood body support material, mortar layer, and pigments [1,2,3]. Mineral pigments were the most popular for use in paint in the past due to their availability, wide variety of colors, and physical and chemical properties. In color painting in ancient architecture, the red mineral pigments included vermilion (HgS), lead red (Pb3O4), and hematite (Fe2O3). Yellow pigments, such as realgar (As4S4), orpiment (As2S3), yellow ochre (FeO·OH/Fe2O3·XH2O), massicot (β-PbO), lead antimony yellow (Pb(SbO3)2), pyrite (FeS2), sulfur (S), malachite (CuCO3·Cu(OH)2), botallackite (Cu2(OH)3Cl), and emerald green (Cu(C2H3O2)2·3Cu(AsO2)2), were commonly used to produce green pigments. Blue pigments included ultramarine blue (Na6Al4Si6S4O20), covellite (CuS), and Chinese blue (BaCuSi4O10). White pigments included chalk (CaCO3) and lead white (2PbCO3·Pb(OH)2). Black pigments included iron black (Fe3O4), graphite (C), and lead dioxide (PbO2) [4,5].
Several studies have been conducted on the pigment composition and production process of frescoes, with testing methods comparable to those used for architectural paintings. To date, various methods have been used to analyze and identify pigments used in artefacts, including visible light microscopy, polarized light microscopy, scanning electron microscopy, X-ray diffraction (XRD) [6,7,8], energy dispersive X-ray detector (EDX) [9,10], X-ray fluorescence (XRF) [11], and micro-Raman spectroscopy (m-RS) [12,13,14,15,16]. For example, m-RS was used to identify pigments in the wall paintings of the Arshai caves [12] and the wall painting of Santa María de Lemoniz [17].
The mortar was composed of brick dust (albite gismondine), drying oil (tung oil), flour, limewater, and blood [1,18,19]. Artists in antiquity used a variety of natural organic materials, such as oils, lipids, proteins, polysaccharides, waxes, resins, and varnishes. The most common natural organic material used in polychromatic artworks in East-Asian and Western countries was drying oil, which served as a binding medium [20,21,22]. In addition, Western artists predominantly used linseed oil, poppy oil, or walnut oil, whereas East-Asian artists predominantly used tung oil [23]. The desiccation of drying oils is accompanied by chemical ageing reactions, which typically include photooxidation, the cleavage or decomposition reactions of cross-linked materials, and the hydrolysis of triacylglycerol bonds [24]. Drying oil films are chemically rich and their chemical composition changes over time. Studies have used gas chromatography–mass spectrometry (GC/MS) [24,25,26,27], capillary electrophoresis (CE) [28], nuclear magnetic resonance (NMR) [29], infrared spectroscopy (IR) [30,31], Raman spectroscopy (RS) [22,32,33], and micro-fluorimetry [34] to analyze drying oils. However, these methods are typically accompanied by complex pre-cracking reactions [35] or are unable to yield results on specific oil substances. Nonetheless, these methods can effectively distinguish drying oil from other binding media [32,33,34]. Researchers generally use Py–GC/MS to analyze the materials in mortar [36]. Compared with the aforementioned methods, Py–GC/MS is more efficient at identifying different types of binder mixtures [5,35,37,38].
To explore the materials used, samples were analyzed for structural thickness and pigment particles by using polarized light microscopy. A multi-analysis of the pigments was conducted by using energy dispersive X-ray fluorescence (ED-XRF) spectrometer and m-RS. XRD was used to analyze the inorganic filler materials in the mortar. Py–GC/MS was used to identify the binding materials in the mortar.
2. Materials and Experiment
2.1. Pigment Sample Information
The samples of red-1, white, black, and red-2 pigments from the Taiping Heavenly Kingdom Palace (YiXing, China) were taken from the east pillar of the Great Hall of the Palace, The pigment samples were taken from the damaged places (Table 1).
2.2. Cross-Section Preparation
A small number of samples, including red, white, black, and red-2 pigments, were embedded with resin, cooled, and solidified at room temperature. After cutting the samples with cutter bar to get the flakes, we ground the surface with mesh sandpaper beginning with 4000 grit and ending with 12,000 grit until it was smooth. Finally, the cross-section of the pigments was observed by using an optical microscope (Olympus BX53M, Shinjuku, Japan).
2.3. Analysis of Pigment
ED-XRF: The primary application of the Tokyo, Japan-based Energy Dispersive X-ray Spectroscopy EDX-7000 is for the elemental detection of pigments. ED-XRF has a high-performance silicon drift detector and X-ray tube (Rh target) installed. All tests were conducted at 25 kV; under air test conditions; at a range of 11 Na to 92 U; over 300 s; and with collimators of sizes 1, 3, 5, and 10 mm.
m-RS: The Renishaw InVia Reflex spectroscope (in Via Reflex, Renishaw Co., Wotton-under-Edge, UK) is equipped with Leica microscopes, an argon ion laser, a charge-coupled detector, and a 50× objective, with 400 lines/mm, a spot size of 2 mm, a scan range of 100–4000 cm−1 and an exposure time of 30 s, an accumulation of 1–3, and a laser power of 1–2 mW. Red and black pigments were analyzed with the 532-nm laser, white pigments were analyzed with the 785-nm laser.
POM: Polarized light microscopy (PLM, Olympus BX53M, Shinjuku, Japan) was used to visualize cross sections. The scraped pigment particles were soaked in ethanol and then dripped onto the glass slide. After ethanol evaporation, a cover glass was placed over the pigment particles, and resin was melted through the cover glass. Finally, PLM was used to examine the crystal characteristics of pigment particles (PLM; Olympus BX53M; Shinjuku, Tokyo, Japan). The PLM has an achromatic polarized light module acquisition lens to visualize cross sections. Horizontal and perpendicular polarized light was used to investigate the crystal properties of the pigment particles.
2.4. Analysis of the Mortar Layer Material
After grinding the red pigment into powder, we used the XDR assay to analyze the sample. The inorganic filler composition in the ointment was measured using XRD (Rigaku D/max-Rc, Tokyo, Japan) with Cu Kα radiation at a wavelength of 1.54059 A, a 2θ range of 10° to 80°; a tube voltage and tube current of 45 kV and 200 mA, respectively; and a discrete scan step of 0.01°.
Approximately 50 μg of the remaining sample was taken into a thermal laser with 3 μL of 20% tetramethylammonium hydroxide for pretreatment. The sample was placed in an autosampler and pyrolyzed at 600 °C after resting for 30 min. After the pyrolysis, the product was identified by using GC-MS. Py–GC/MS comprises two pieces of equipment, the first was used for pyrolysis (EGA/PY-3030D, Frontier Labs, Koriyama, Japan) at a thermal cracking temperature, thermal cracking time, syringe temperature, and interface temperature of the syringe and chromatograph at 600 °C, 10 s, 250 °C, and 320 °C, respectively. The other was used for GC/MS (QP2010Ultra, Shimadzu, Kyoto, Japan) and features a SLB-5MS chromatography column (5% diphenyl–95% dimethylsiloxane). The initial temperature of the oven containing the column was set to 50 °C and then held for 5 min. The temperature was then increased at a rate of 3 °C/min to a final temperature of 292 °C that was held for 3 min. The pre-column pressure, the flow rate, and the separation ratio were adjusted to 15.4 kPa, 0.6 mL/min, and 1:100, respectively. In addition, the ionization voltage, scan rate, and mass-to-charge ratio (M/Z) of the mass spectrometer were set to 70 eV, 0.5 s, and 50 to 750, respectively.
3. Results and Discussion
3.1. Cross-Section
The samples black, red-1, red-2, and white and base layers were selected for cross-sectional analysis. According to the cross sections in Table 2, the red-1 sample had three main layers: layer ‘a’ is a painting layer, layer ‘b’ is a base color, and layer ‘c’ is a ground layer with the thickness of approximately 55, 46, and 302 μm, respectively. The structure of the sample red-2 was comparable to that of the red-1. The thickness of the red-2 sample’s layers a, b, and c were approximately 35, 74, and 173 μm, respectively. The black sample mainly contained black pigment with the thickness of 67 μm and ground layer with the thickness of >1000 μm. In addition to white pigment and ground layer, the white sample contained two layers of the base color (b1 and b2), with the layers’ thickness of 25, 7, 57, and 302 μm, respectively. The red-1 and red-2 samples had the same cross-sectional composition and had three layers (pigment layer, base layer, and ground layer), which was common in painting in ancient Chinese architecture, with the black pigment being painted directly onto the ground layer but with the white pigment having two base layers with a possibility of subsequent repainting. Additional studies are needed to investigate the black and white pigments.
3.2. Pigment
3.2.1. Red-1 Pigment
The Raman spectra of the red pigment revealed distinct peaks at 253, 284, and 342 cm−1 (Figure 1a), was assigned to vermilion (HgS) [12,17,39,40,41,42,43,44]. The ED-XRF analysis revealed that the red pigment had main elements, such as Hg, S, Ca, Fe, Si, Pb, Hg, and S, which were the components of vermilion. The pigment particles of the red sample in Figure 2a are shown as long strips or fractured rocks, and those in Figure 2b are shown as fiery red and pale yellow under vertically polarized light. Consistent with the polarized character of the vermilion, vermilion red, an important and common red pigment, was used extensively in many ancient Chinese architectural paintings, frescoes, silk paintings, and paintings on silk and paper, and appeared in its own form as vermilion painting [45,46,47,48].
3.2.2. Black Pigment
Black pigment samples were analyzed by ED-XRF (Table 3). The ED-XRF analysis revealed a red pigment with main elements of Ca, Fe, S, K, and Si, with a high content of Fe (22.52%). Therefore, we propose that the black paint is iron black. The ED-XRF did not give provide definitive data on the components. We propose that the black pigment is carbon black. Figure 1b is the Raman spectrum of black pigment with two wide crests at approximately 1380 and 1590 cm−1, which were each attributed to the v(C–C) and v(C=C) D-band and G-band [41,42,43,49,50,51].
The black sample pigment particles were small, agglomerated, and irregular (Figure 2c) with full extinction under perpendicular polarized light (Figure 2d). This is comparable to the polarized character of the graphite. The high content of Fe might be caused by the partial shedding of pigment particles in the color painting sample and the detected the mortar layer material.
3.2.3. White Pigment
The ED-XRF results in Table 3 indicate white pigments with high amounts of lead elements. We speculate that the white pigment is a lead-based mineral pigment. The Raman spectrum of white pigment had two peaks at 417 and 1052 cm−1, indicating the presence of lead white (2PbCO3·Pb(OH)2) [12,41,43,52,53,54,55]. These peaks approximately at 165, 417 and 1052 cm−1 could be attributed to the band vibration of the Pb–O. The white sample pigment particles were flat crystals with black well-defined edges in Figure 2e that disappeared under perpendicular polarized light in Figure 2f. This was comparable to that of the polarized character of the lead white.
3.2.4. Red-2 Pigment
Figure 1 shows the Raman spectrum of the red-2 pigment peaks at 120 cm−1, which is consistent with those of previous studies, where the Raman spectrum of lead red (Pb3O4) peaked at 120 and 548 cm−1 [12,41,43,52,53,56]. The red-2 sample pigment particles were red-2-red in color, without good crystal edges, with a rough surface (Figure 2g), and with anomalous blue-green extinction under perpendicular polarized light in Figure 2h. At the same time, a small number of pigment particles showed the characteristics of cinnabar under vertical polarized light. The red-2 pigment is lead red (Pb3O4) with a bit of vermilion, which is consistent with the polarized feature of lead red and with the results of m-RS and ED-XRF elemental analysis. In order to adjust the color, the doping application of several pigments is a common painting process.
3.3. Analysis of the Mortar Layer Material
In the Ming and Qing dynasties, mortar was generally composed of brick ash, limewater, fiber, blood, and tung oil [19]. Because the cross-section analysis showed that the plastic did not contain hemp fibers, we ground the mortar part of the sample into a powder for XRD imaging.
The XRD spectra of the gypsum showed in the Figure 3 that many peaks were at 2θ values of 21°, 26°, 36°, 39°, 41°, 42°, 45°, 50°, 55°, 60°, and 68°, which was attributed to the mineral gismondine (CaAl2Si2O8-4H2O) based on JCPDS 20-0452 [57,58]. The peak at 28° was the same as the typical peak for dolomite. The diffraction peak at 30° differed from that of the calcite phase (CaCO3) according to JCPDS 43-0697 caused by limewater. This may be ascribed to the reaction between limewater and carbon dioxide in air [59]. The carbonization of cross-linked tung oil caused the diffraction peaks at 22°, 24°, 31°, and 35°, which could be assigned to graphitized coke. The formation of crystalline was different from that of the mineral elements in the biomass, which were formed during the pyrolysis process. During the formation of biochar by charring, a large amount of crystalline cellulose, amorphous carbon, and carbonates were formed [60,61].
Figure 4 illustrates the total ion chromatogram of the samples by using Py–GC/MS, with the pyrolysis byproducts shown in Table 4. Table 4 shows the results of the heated products containing mainly oxidation products of unsaturated fatty acids [62], including glycerol (peak 1), methyl 6-heptenoic acid (peak 2), octanoic acid (peak 3), heptanedioic acid (peak 6), 1-tetradecene (peak 5), 9-oxonononanoic acid (peak 6), octanedioic acid (peak 7), and azelaic acid (peak 8). Palmitic acid (peaks 9/10/11), bicyclo [3.1.1] hept-2-ene-2-ethanol,6,6-dimethyl-acetate (peak 12) and methyl arachidate (peak 13) are saturated fatty acids in the oil. The high content of azelaic acid (peak 8), an α-eleostearic acid, was formed by the autoxidation process of tung oil after boiling [36,62,63]. In addition, 9,10-dihydroxyoctadecanoic acid was not noted to be among the pyrolysis products. We speculate that 9,10-dihydroxyoctadecanoic acid was only present in poppy oil, wax oil, and hemp seed oil [64] but not tung oil. In conclusion, the mortar contained drying oil (tung oil) and, possibly, flour.
4. Conclusions
This study examined the pigments and the mortar layer material used in the painting of the royal residence of the Taiping Heavenly Kingdom. The analysis of cross sections of the painted samples showed that the red-1 and red-2 samples had a three-layer structure (the ground layer, base color layer, and pigment layer). The black sample primarily contained a black pigment and a ground layer. The white sample had four layers with an additional base color layer compared with those of the other three pigment samples. Additional studies are needed to investigate the causes of that phenomenon. We used ED-XRF, PLM, and m-RS spectroscopy to analyze the pigments of the Taiping royal palace color paintings. The results were as follows: the red pigments were vermilion, the black pigments were graphite, the white pigments were lead white, and the red-2 pigments were lead red and vermilion. The Py–GC/MS analysis indicated the possible presence of tung oil in the mortar. The XRD demonstrated the limewater and brick dust in the mortar. These results could be used as a reference for subsequent conservation and restoration of artwork. On the basis of these findings, samples can be made to simulate and validate the restoration process of colored paintings, which is crucial for the conservation of murals.
Y.L. (Yuhu Li); Data curation, G.T., P.F., K.H. and J.L.; Formal analysis, G.T. and Z.J.; Funding acquisition, Z.J.; Investigation, Y.L. (Yanli Li) and Y.W.; Methodology, Y.L. (Yuhu Li); Project administration, Y.L. (Yuhu Li); Writing—original draft, G.T. and Z.J.; Writing—review & editing, Z.J. All authors have read and agreed to the published version of the manuscript.
Not applicable.
Not applicable.
The datasets analyzed during the current study are available from the corresponding author on reasonable request.
The authors declare that they have no conflict of interest.
ED-XRF: energy dispersive X-ray spectroscopy; PLM: polarized light microscopy; XRD: X-ray diffraction; Py-GC/MS: pyrolysis-gas chromatography/mass spectrometry. m-RS: micro-Raman spectroscopy.
Publisher’s Note: MDPI stays neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Enlarge this image.Figure 1. Raman spectra of (a) the red-1 pigment (vermilion; HgS); (b) the black pigment (carbon black; C); (c) the white pigment (lead-white; 2PbCO3·Pb(OH)2); (d) the red-2 pigment (lead red; Pb3O4).
Enlarge this image.Figure 2. Pictures of horizontal polarized light (a,c,e,g) and perpendicular polarized light (b,d,f,h). PLM image of red pigment (M1), black pigment (M2), white pigment (M3) and red-2 pigment (M4).
The Taiping Heavenly Kingdom Palace sampling location.
| Sampling Location | Sample Positon | Micrographies of |
Color |
|---|---|---|---|
| [Image omitted. Please see PDF.] | [Image omitted. Please see PDF.] | [Image omitted. Please see PDF.] | Red-1 |
| [Image omitted. Please see PDF.] | [Image omitted. Please see PDF.] | White | |
| [Image omitted. Please see PDF.] | [Image omitted. Please see PDF.] | Red-2 | |
| [Image omitted. Please see PDF.] | [Image omitted. Please see PDF.] | Black |
Cross-section of a sample acquired by using ultra-depth three-dimensional microscopy.
| Sample | Cross-Section Micrograph | Composition | Thickness | Total Number of Layers |
|---|---|---|---|---|
| Red-1 | [Image omitted. Please see PDF.] | a-red pigment |
55 μm |
3 |
| Red-2 | [Image omitted. Please see PDF.] | a-red-2 pigment |
35 μm |
3 |
| Black | [Image omitted. Please see PDF.] | a-black pigment |
67 μm |
2 |
| White | [Image omitted. Please see PDF.] | a-white pigment |
25 μm |
4 |
Information on sample and elemental composition of the sample.
| Sample | Analysis |
Main Elements (wt%) | Composition of Pigments |
|---|---|---|---|
| Red-1 Pigment | ED-XRF, m-RS and PLM | Hg(40.27), S(30.64), Ca(12.79), |
HgS |
| Black Pigment | ED-XRF, m-RS and PLM | Ca(39.30), Fe(22.52), S(19.89), |
Iron black (Fe3O4) or C(graphite) |
| White Pigment | ED-XRF, m-RS and PLM | Pb(78.77), Ca(9.72), Si(5.99), |
2PbCO3·Pb(OH)2 |
| Red-2 Pigment | ED-XRF, m-RS and PLM | Pb(76.64), Hg(9.22), Si(7.89), |
Pb3O4 and HgS |
Composition of compound of mortar samples.
| Peak |
Retention Time |
Pear Area (%) | Compound |
|---|---|---|---|
| 1 | 7.339 | 1.7 | Glycerol |
| 2 | 10.55 | 0.91 | Methyl 6-heptenoic acid |
| 3 | 12.512 | 0.64 | Octanoic acid |
| 4 | 15.217 | 0.87 | Heptane dioic acid |
| 5 | 15.633 | 0.37 | 1-Tetradecene |
| 6 | 16.096 | 1.58 | 9-Oxo-nonanoic acid |
| 7 | 16.176 | 3.21 | Octane dioic acid |
| 8 | 17.049 | 18.37 | Dimethyl azelate (azelaic acid) |
| 9 | 19.875 | 19.95 | Palmitic acid |
| 10 | 21.039 | 7.75 | Palmitic acid |
| 11 | 21.183 | 17.11 | Stearic acid |
| 12 | 21.379 | 1.43 | Bicyclo [3.1.1] hept-2-ene-2-ethanol,6,6-dimethyl-acetate |
| 13 | 22.381 | 1.48 | Methyl arachidate |
References
1. Wang, L.Q.; Yang, L.; Zhou, W.H.; He, Q.J. Study on the analytical methods of component materials and making techniques of painting and colored drawing in ancient architectures. Relics Mus.; 2009; 6, pp. 451-454.
2. Wang, L.Q.; Yang, L.; Zhou, W.H.; Yan, J.; Guo, R. Analysis of the techniques and materials of the coloured paintings in the renshou hall in the summer palace. Anal. Methods; 2015; 7, pp. 5334-5337. [DOI: https://dx.doi.org/10.1039/C5AY00934K]
3. Mazzeo, R.; Cam, D.; Chiavari, G.; Fabbri, D.; Ling, H.; Prati, S. Analytical study of traditional decorative materials and techniques used in ming dynasty wooden architecture: The case of the drum tower in xi’an, pr of china. J. Cult. Herit.; 2004; 5, pp. 273-283. [DOI: https://dx.doi.org/10.1016/j.culher.2004.06.001]
4. Burgio, L.; Clark, R.J.; Firth, S. Raman spectroscopy as a means for the identification of plattnerite (pbo2), of lead pigments and of their degradation products. Analyst; 2001; 126, pp. 222-227. [DOI: https://dx.doi.org/10.1039/b008302j] [PubMed: https://www.ncbi.nlm.nih.gov/pubmed/11235107]
5. Hao, X.Y.; Wu, H.; Zhao, Y.; Tong, T.; Li, X.Y.; Yang, C.; Tang, Y.; Shen, X.Y.; Tong, H. Analysis on the composition/structure and lacquering techniques of the coffin of emperor qianlong excavated from the eastern imperial tombs. Sci. Rep.; 2017; 7, 11. [DOI: https://dx.doi.org/10.1038/s41598-017-08933-8]
6. Del Rio, M.S.; Martinetto, P.; Somogyi, A.; Reyes-Valerio, C.; Dooryhee, E.; Peltier, N.; Alianelli, L.; Moignard, B.; Pichon, L.; Calligaro, T. et al. Microanalysis study of archaeological mural samples containing maya blue pigment. Spectrochim. Acta Part B At. Spectrosc.; 2004; 59, pp. 1619-1625. [DOI: https://dx.doi.org/10.1016/j.sab.2004.07.027]
7. Hradil, D.; Hradilova, J.; Bezdicka, P.; Serendan, C. Late gothic/early renaissance gilding technology and the traditional poliment material “armenian bole”: Truly red clay, or rather bauxite?. Appl. Clay Sci.; 2017; 135, pp. 271-281. [DOI: https://dx.doi.org/10.1016/j.clay.2016.10.004]
8. Mazzocchin, G.A.; Agnoli, F.; Mazzocchin, S.; Colpo, I. Analysis of pigments from roman wall paintings found in vicenza. Talanta; 2003; 61, pp. 565-572. [DOI: https://dx.doi.org/10.1016/S0039-9140(03)00323-0]
9. Samanian, K. Identification of green pigment used in persian wall paintings (ad 1501–1736) using plm, ft-ir, sem/edx and gc-ms techniques. Archaeometry; 2015; 57, pp. 740-758. [DOI: https://dx.doi.org/10.1111/arcm.12102]
10. Kugler, V.; Bean, S.; Spring, M. Quantitative edx analysis of smalt pigment in sixteenth and eighteenth century paintings. Microsc. Microanal.; 2013; 19, pp. 1428-1429. [DOI: https://dx.doi.org/10.1017/S1431927613009136]
11. Freitas, R.P.; Felix, V.S.; Pereira, M.O.; Santos, R.S.; Oliveira, A.L.; Goncalves, E.A.S.; Ferreira, D.S.; Pimenta, A.R.; Pereira, L.O.; Anjos, M.J. Micro-xrf analysis of a brazilian polychrome sculpture. Microchem. J.; 2019; 149, 6. [DOI: https://dx.doi.org/10.1016/j.microc.2019.104020]
12. Bell, I.M.; Clark, R.J.; Gibbs, P.J. Raman spectroscopic library of natural and synthetic pigments (pre-approximately 1850 ad). Spectrochim. Acta. Part A Mol. Biomol. Spectrosc.; 1997; 53A, pp. 2159-2179. [DOI: https://dx.doi.org/10.1016/S1386-1425(97)00140-6]
13. Franquelo, M.L.; Duran, A.; Herrera, L.K.; de Haro, M.C.J.; Perez-Rodriguez, J.L. Comparison between micro-raman and micro-ftir spectroscopy techniques for the characterization of pigments from southern spain cultural heritage. J. Mol. Struct.; 2009; 924, pp. 404-412. [DOI: https://dx.doi.org/10.1016/j.molstruc.2008.11.041]
14. Lang, P.L.; Keefer, C.D.; Juenemann, J.C.; Tran, K.V.; Peters, S.M.; Huth, N.M.; Joyaux, A.G. The infrared microspectroscopic and energy dispersive x-ray analysis of paints removed from a painted, medieval sculpture of saint wolfgang. Microchem. J.; 2003; 74, pp. 33-46. [DOI: https://dx.doi.org/10.1016/S0026-265X(02)00101-7]
15. Perez-Alonso, M.; Castro, K.; Madariaga, J.M. Investigation of degradation mechanisms by portable raman spectroscopy and thermodynamic speciation: The wall painting of santa maria de lemoniz (basque country, north of spain). Anal. Chim. Acta; 2006; 571, pp. 121-128. [DOI: https://dx.doi.org/10.1016/j.aca.2006.04.049]
16. Svarcova, S.; Cermakova, Z.; Hradilova, J.; Bezdicka, P.; Hradil, D. Non-destructive micro-analytical differentiation of copper pigments in paint layers of works of art using laboratory-based techniques. Spectrochim. Acta Part A Mol. Biomol. Spectrosc.; 2014; 132, pp. 514-525. [DOI: https://dx.doi.org/10.1016/j.saa.2014.05.022]
17. Stanzani, E.; Bersani, D.; Lottici, P.P.; Colomban, P. Analysis of artist’s palette on a 16th century wood panel painting by portable and laboratory raman instruments. Vib. Spectrosc.; 2016; 85, pp. 62-70. [DOI: https://dx.doi.org/10.1016/j.vibspec.2016.03.027]
18. Ma, T.; Bai, B.B.; Yang, Q. Studies on the traditional techniques anf the conservation method of polychrome paintings on wooden structures of chinese traditioal buildings. Relics Mus.; 2009; 6, pp. 412-421.
19. Rao, H.Y.; Li, B.; Yang, Y.M.; Ma, Q.L.; Wang, C.S. Proteomic identification of organic additives in the mortars of ancient chinese wooden buildings. Anal. Methods; 2015; 7, pp. 143-149. [DOI: https://dx.doi.org/10.1039/C4AY01766H]
20. Kurouski, D.; Zaleski, S.; Casadio, F.; Van Duyne, R.P.; Shah, N.C. Tip-enhanced raman spectroscopy (ters) for in situ identification of indigo and iron gall ink on paper. J. Am. Chem. Soc.; 2014; 136, pp. 8677-8684. [DOI: https://dx.doi.org/10.1021/ja5027612]
21. Nigra, B.T.; Faull, K.F.; Barnard, H. Analytical chemistry in archaeological research. Anal. Chem.; 2015; 87, pp. 3-18. [DOI: https://dx.doi.org/10.1021/ac5029616] [PubMed: https://www.ncbi.nlm.nih.gov/pubmed/25354216]
22. Oakley, L.H.; Dinehart, S.A.; Svoboda, S.A.; Wustholz, K.L. Identification of organic materials in historic oil paintings using correlated extractionless surface-enhanced raman scattering and fluorescence microscopy. Anal. Chem.; 2011; 83, pp. 3986-3989. [DOI: https://dx.doi.org/10.1021/ac200698q] [PubMed: https://www.ncbi.nlm.nih.gov/pubmed/21524143]
23. Mills, J.S.; White, R. The Organic Chemistry of Museum Objects; 2nd ed. Butterworth Heinemann Ltd.: Oxford, UK, 1994; (Reprinted 2003)
24. Van den Berg, J.D.J.; van den Berg, K.J.; Boon, J.J. Determination of the degree of hydrolysis of oil paint samples using a two-step derivatisation method and on-column gc/ms. Prog. Org. Coat.; 2001; 41, pp. 143-155. [DOI: https://dx.doi.org/10.1016/S0300-9440(01)00140-0]
25. Echard, J.P.; Benoit, C.; Peris-Vicente, J.; Malecki, V.; Gimeno-Adelantado, J.V.; Vaiedelich, S. Gas chromatography/mass spectrometry characterization of historical varnishes of ancient italian lutes and violin. Anal. Chim. Acta; 2007; 584, pp. 172-180. [DOI: https://dx.doi.org/10.1016/j.aca.2006.10.048] [PubMed: https://www.ncbi.nlm.nih.gov/pubmed/17386601]
26. Gimeno-Adelantado, J.V.; Mateo-Castro, R.; Domenech-Carbo, M.T.; Bosch-Reig, F.; Domenech-Carbo, A.; Casas-Catalan, M.J.; Osete-Cortina, L. Identification of lipid binders in paintings by gas chromatography-influence of the pigments. J. Chromatogr. A; 2001; 922, pp. 385-390. [DOI: https://dx.doi.org/10.1016/S0021-9673(01)00914-1]
27. Kouloumpi, E.; Vandenabeele, P.; Lawson, G.; Pavlidis, V.; Moens, L. Analysis of post-byzantine icons from the church of the assumption in cephalonia, ionian islands, greece: A multi-method approach. Anal. Chim. Acta; 2007; 598, pp. 169-179. [DOI: https://dx.doi.org/10.1016/j.aca.2007.07.034]
28. Surowiec, I.; Kaml, I.; Kenndler, E. Analysis of drying oils used as binding media for objects of art by capillary electrophoresis with indirect uv and conductivity detection. J. Chromatogr. A; 2004; 1024, pp. 245-254. [DOI: https://dx.doi.org/10.1016/j.chroma.2003.10.065]
29. Cipriani, G.; Salvini, A.; Dei, L.; Macherelli, A.; Cecchi, F.S.; Giannelli, C. Recent advances in swollen-state nmr spectroscopy for the study of drying oils. J. Cult. Herit.; 2009; 10, pp. 388-395. [DOI: https://dx.doi.org/10.1016/j.culher.2008.11.004]
30. Stenberg, C.; Svensson, M.; Johansson, M. Study of the drying of linseed oils with different fatty acid patterns using rtir-spectroscopy and chemiluminescence (cl). Ind. Crops Prod.; 2005; 21, pp. 263-272. [DOI: https://dx.doi.org/10.1016/j.indcrop.2004.04.002]
31. Wang, Y.; Wang, Q.; Artz, W.E.; Padua, G.W. Fourier transform infrared spectra of drying oils treated by irradiation. J. Agric. Food Chem.; 2008; 56, pp. 3043-3048. [DOI: https://dx.doi.org/10.1021/jf073545m]
32. Vandenabeele, P.; Ortega-Aviles, M.; Castilleros, D.T.; Moens, L. Raman spectroscopic analysis of mexican natural artists’ materials. Spectrochim. Acta Part A Mol. Biomol. Spectrosc.; 2007; 68, pp. 1085-1088. [DOI: https://dx.doi.org/10.1016/j.saa.2007.01.031] [PubMed: https://www.ncbi.nlm.nih.gov/pubmed/17347030]
33. Vandenabeele, P.; Wehling, B.; Moens, L.; Edwards, H.; De Reu, M.; Van Hooydonk, G. Analysis with micro-raman spectroscopy of natural organic binding media and varnishes used in art. Anal. Chim. Acta; 2000; 407, pp. 261-274. [DOI: https://dx.doi.org/10.1016/S0003-2670(99)00827-2]
34. Matteini, P.; Camaiti, M.; Agati, G.; Baldo, M.A.; Muto, S.; Matteini, M. Discrimination of painting binders subjected to photo-ageing by using microspectrofluorometry coupled with deconvolution analysis. J. Cult. Herit.; 2009; 10, pp. 198-205. [DOI: https://dx.doi.org/10.1016/j.culher.2008.04.011]
35. Chiantore, O.; Riedo, C.; Scalarone, D. Gas chromatography-mass spectrometric analysis of products from on-line pyrolysis/silylation of plant gums used as binding media. Int. J. Mass Spectrom.; 2009; 284, pp. 35-41. [DOI: https://dx.doi.org/10.1016/j.ijms.2008.07.031]
36. Song, Y.; Gao, F.; Nevin, A.; Guo, J.W.; Zhou, X.; Wei, S.Y.; Li, Q.Q. A technical study of the materials and manufacturing process used in the gallery wall paintings from the jokhang temple, tibet. Herit. Sci.; 2018; 6, 13. [DOI: https://dx.doi.org/10.1186/s40494-018-0182-5]
37. De la Cruz-Canizares, J.; Domenech-Carbo, M.T.; Gimeno-Adelantado, J.V.; Mateo-Castro, R.; Bosch-Reig, F. Study of burseraceae resins used in binding media and varnishes from artworks by gas chromatography-mass spectrometry and pyrolysis-gas chromatography-mass spectrometry. J. Chromatogr. A; 2005; 1093, pp. 177-194. [DOI: https://dx.doi.org/10.1016/j.chroma.2005.07.058]
38. Niimura, N. Determination of the type of lacquer on east asian lacquer ware. Int. J. Mass Spectrom.; 2009; 284, pp. 93-97. [DOI: https://dx.doi.org/10.1016/j.ijms.2009.03.004]
39. Mazzocchin, G.A.; Agnoli, F.; Salvadori, M. Analysis of roman age wall paintings found in pordenone, trieste and montegrotto. Talanta; 2004; 64, pp. 732-741. [DOI: https://dx.doi.org/10.1016/j.talanta.2004.03.055]
40. Nusimovici, M.A.; Meskaoui, A. Raman Scattering by α-HgS (Cinnabar). Phys. Status Solidi B; 1973; 58, pp. 121-125. [DOI: https://dx.doi.org/10.1002/pssb.2220580112]
41. Dimitrios, L.; Ioannis, K.; Olga, K. Spectroscopic investigation leading to the documentation of three post-byzantine wall paintings. Appl. Spectrosc. Soc. Appl. Spectrosc.; 2017; 71, pp. 129-140.
42. Fostiridou, A.; Karapanagiotis, I.; Vivdenko, S.; Lampakis, D.; Mantzouris, D.; Achilara, L.; Manoudis, P. Identification of pigments in hellenistic and roman funeral figurines. Archaeometry; 2016; 58, pp. 453-464. [DOI: https://dx.doi.org/10.1111/arcm.12177]
43. Karapanagiotis, I.; Lampakis, D.; Konstanta, A.; Farmakalidis, H. Identification of colourants in icons of the cretan school of iconography using raman spectroscopy and liquid chromatography. J. Archaeol. Ence; 2013; 40, pp. 1471-1478. [DOI: https://dx.doi.org/10.1016/j.jas.2012.11.004]
44. Bouchard, M.; Smith, D.C. Catalogue of 45 reference raman spectra of minerals concerning research in art history or archaeology, especially on corroded metals and coloured glass. Spectrochim. Acta Part A Mol. Biomol. Spectrosc.; 2003; 9, pp. 2247-2266. [DOI: https://dx.doi.org/10.1016/S1386-1425(03)00069-6]
45. Ha, T.; Lee, H.; Sim, K.I.; Kim, J.; Jo, Y.C.; Kim, J.H.; Baek, N.Y.; Kang, D.I.; Lee, H.H. Optimal methodologies for terahertz time-domain spectroscopic analysis of traditional pigments in powder form. J. Korean Phys. Soc.; 2017; 70, pp. 866-871. [DOI: https://dx.doi.org/10.3938/jkps.70.866]
46. Li, N.S.; Yang, Y.M.; He, N.; Mao, Z.W. Spectral analysis of ceramic-painting pigments from taosi site. Spectrosc. Spectr. Anal.; 2008; 28, pp. 946-948.
47. Shi, J.L.; Li, T. Technical investigation of 15th and 19th century chinese paper currencies: Fiber use and pigment identification. J. Raman Spectrosc.; 2013; 44, pp. 892-898. [DOI: https://dx.doi.org/10.1002/jrs.4297]
48. Yan, X.; Liu, Y.; Liu, C.; Jing, B. A technological analysis of fish pattern painted pottery from the neolithic site of banpo. Bull. Chin. Ceram. Soc.; 2014; 33, pp. 1389-1393.
49. Zhu, T.Q.; Chen, J.; Hui, R.; Gong, L.; Zhang, W.H.; Zhang, Y.C. Spectroscopic characterization of the architectural painting from the cizhong catholic church of yunnan province, china. Anal. Lett.; 2013; 46, pp. 2253-2264. [DOI: https://dx.doi.org/10.1080/00032719.2013.796559]
50. Nakamizo, M.; Kammereck, R.; Walker, P.L. Laser raman studies on carbons. Carbon; 1973; 12, pp. 259-267. [DOI: https://dx.doi.org/10.1016/0008-6223(74)90068-2]
51. Tuinstra, F.; Koenig, J.L. Raman spectrum of graphite. J. Chem. Phys.; 1970; 53, pp. 1126-1130. [DOI: https://dx.doi.org/10.1063/1.1674108]
52. Martens, W.N.; Rintoul, L.; Kloprogge, J.T.; Frost, R.L. Single crystal raman spectroscopy of cerussite. Am. Mineral.; 2004; 89, pp. 352-358. [DOI: https://dx.doi.org/10.2138/am-2004-2-314]
53. Klisinska-Kopacz, A. Non-destructive characterization of 17th century painted silk banner by the combined use of raman and xrf portable systems. J. Raman Spectrosc.; 2015; 46, pp. 317-321. [DOI: https://dx.doi.org/10.1002/jrs.4634]
54. Arjonilla, P.; Dominguez-Vidal, A.; Correa-Gomez, E.; Domene-Ruiz, M.J.; Ayora-Canada, M.J. Raman and fourier transform infrared microspectroscopies reveal medieval hispano-muslim wood painting techniques and provide new insights into red lead production technology. J. Raman Spectrosc.; 2019; 50, pp. 1537-1545. [DOI: https://dx.doi.org/10.1002/jrs.5660]
55. Petrova, O.; Pankin, D.; Povolotckaia, A.; Borisov, E.; Krivul’ko, T.; Kurganov, N.; Kurochkin, A. Pigment palette study of the xix century plafond painting by raman spectroscopy. J. Cult. Herit.; 2019; 37, pp. 233-237. [DOI: https://dx.doi.org/10.1016/j.culher.2018.11.010]
56. Vigouroux, J.P.; Husson, E.; Calvarin, G.; Dao, N.Q. Etude par spectroscopié vibrationnelle des oxydes Pb3O4, SnPb2O4 et SnPb(Pb2O4)2. Spectrochim. Acta Part A Mol. Spectrosc.; 1982; 38, pp. 393-398. [DOI: https://dx.doi.org/10.1016/0584-8539(82)80013-5]
57. Guo, X.L.; Shi, H.S.; Dick, W.A. Compressive strength and microstructural characteristics of class c fly ash geopolymer. Cem. Concr. Compos.; 2010; 32, pp. 142-147. [DOI: https://dx.doi.org/10.1016/j.cemconcomp.2009.11.003]
58. Li, J.; Song, Y.; Yu, J.; Chen, P.; Xu, R. Transformations of a layer and a chain aluminophosphates to the zeotype ∣al–p–m–o∣–gis (m = co2+, mn2+, mg2+). Microporous Mesoporous Mater.; 2007; 98, pp. 47-54. [DOI: https://dx.doi.org/10.1016/j.micromeso.2006.04.004]
59. Pesenti, H.; Leoni, M.; Scardi, P. Xrd line profile analysis of calcite powders produced by high energy milling. Z. Fur Krist.; 2008; 27, pp. 143-150.
60. Zheng, Q.F.; Wang, Z.M.; Chen, B.G.; Liu, G.F.; Zhao, J. Analysis of xrd spectral structure and carbonization of the biochar preparation. Spectrosc. Spectr. Anal.; 2016; 36, pp. 3355-3359.
61. Qingfu, Z.; Zhimin, W.; Baoguo, C.; Guifeng, L.; Ji, Z. Analysis of xrd spectral structure and carbonization of the biochar preparation. Spectrosc. Spectr. Anal.; 2016; 36, 5.
62. Tamburini, D.; Sardi, D.; Spepi, A.; Duce, C.; Tine, M.R.; Colombini, M.P.; Bonaduce, I. An investigation into the curing of urushi and tung oil films by thermoanalytical and mass spectrometric techniques. Polym. Degrad. Stab.; 2016; 134, pp. 251-264. [DOI: https://dx.doi.org/10.1016/j.polymdegradstab.2016.10.015]
63. Qin, P.F.; Yi, D.Q.; Meng, Q.; Sun, A.J.; Sun, J.Q.; Zhang, Z.J.; Hao, J.W. Study and restoration of the yi ma wu hui layer of the ancient coating on the putuo zongcheng temple. Int. J. Archit. Herit.; 2021; 15, pp. 1707-1721.
64. Wang, N.; He, L.; Zhao, X.; Simon, S. Comparative analysis of eastern and western drying-oil binding media used in polychromic artworks by pyrolysis-gas chromatography/mass spectrometry under the influence of pigments. Microchem. J.; 2015; 123, pp. 201-210. [DOI: https://dx.doi.org/10.1016/j.microc.2015.06.007]
© 2022 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/). Notwithstanding the ProQuest Terms and Conditions, you may use this content in accordance with the terms of the License.