Accepted Manuscript Title: Revealing the coloration mechanism in the earliest Chinese celadon glaze Authors: Yu Li, Bin Zhang, Huansheng Cheng, Jianming Zheng PII: DOI: Reference:
S0955-2219(18)30622-8 https://doi.org/10.1016/j.jeurceramsoc.2018.10.007 JECS 12125
To appear in:
Journal of the European Ceramic Society
Received date: Revised date: Accepted date:
11-7-2018 7-10-2018 9-10-2018
Please cite this article as: Li Y, Zhang B, Cheng H, Zheng J, Revealing the coloration mechanism in the earliest Chinese celadon glaze, Journal of the European Ceramic Society (2018), https://doi.org/10.1016/j.jeurceramsoc.2018.10.007 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
Revealing the coloration mechanism in the earliest Chinese celadon glaze
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Yu Li1,2, Bin Zhang1,2,*, Huansheng Cheng1,2, Jianming Zheng3
Author Affiliations: 1
Institute of Modern Physics, Fudan University, Shanghai, 200433, P. R. China.
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Key Laboratory of Nuclear Physics and Ion-beam Application (MOE), Fudan
Zhejiang Provincial Institute of Cultural Relics and Archaeology, Hangzhou, Zhejiang,
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University, Shanghai, 200433, P. R. China.
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310014, P. R. China.
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Bin Zhang
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*Corresponding Author:
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Institute of Modern Physics, Fudan University, Shanghai, 200433, P. R. China. Tel: (+86) 1376 442 9116
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E-mail:
[email protected].
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Abstract: The quality of ancient Chinese celadon is essentially affected by its glaze color. For a long time, due to the structural complexity of the amorphous glaze, the exact microstructure of the iron-based colorant in the celadon glaze, especially the local
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structure, is not well determined, therefore the coloration mechanism of the glaze remains unclear. This study exploits a unique opportunity to investigate the glazes of the earliest
Chinese celadon recently excavated from Jinshan, an unprecedented Yue kiln site, by X-
ray absorption fine structure (XAFS) spectroscopy. For the first time, we found that Fe in the celadon glaze is solely present in a trivalent state with distorted octahedral geometry
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[Fe3+O6]. Combined with ab initio calculations, we reveal that different Fe-O bonds in
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distorted octahedra can bring about different ligand field splitting energies of Fe-3d levels,
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which leads to differential absorption of visible light and consequently the varying colors
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of celadon glaze.
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Introduction Chinese ceramics as an art form have a long and splendid history, with its beginnings dating back as far as the Upper Paleolithic period. It is reported that the earliest pottery
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vessels found in China, dating from approximately 20,000 BP, were discovered at Xianrendong Cave in Jiangxi province.[1] After a long period of development,
technological breakthroughs, such as the use of porcelain stone and kaolin, the building
of high temperature kilns[2], and the invention of high-fired glazes[3], eventually led to
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the emergence of porcelain.[4]
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Celadon, essentially a high-fired glazed felspathic siliceous stoneware verging on
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porcelain, is considered one of the most influential south China ceramic types.[5] It is widely accepted that the celadon in real sense emerged in Zhejiang province during the
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Eastern Han dynasty (25–220 AD).[4] Among all types of Chinese celadon, Yue ware is
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the earliest and predominant one.[6] Yue kiln sites were widely distributed in Yuyao and Shangyu areas of Zhejiang province in China. Over the past several decades, two kiln
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sites, Shanglinhu (Shanglin Lake) and Xiaoxiantan, have been identified as two major
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sources of Yue wares.[4,5,7] Of the two, Xiaoxiantan kiln site, excavated in 1970s, had been acknowledged as the earliest celadon-producing site ever discovered in China.
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Unfortunately, remains of kilns at the Xiaoxiantan site were seriously damaged by natural processes and human activities for over a thousand years. Moreover, studies on celadon samples unearthed from these kiln sites had been handicapped by technical conditions at that time.
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In 2013, a local villager accidentally discovered a Yue kiln site at the southern foot of Jinshan (Forbidden Mountain) in Shangyu prefecture, Zhejiang province (Fig. 1a). Archaeologists carried out the excavation of the site from May to October 2014.[8]
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Consequently, various functional areas such as kilns, workshops and waste accumulation zones had been basically identified (Fig. 1c). The most striking finding was the presence of three complete Dragon kilns. One (Y1) of them dated to Eastern Han dynasty, while the other two (Y2 and Y3) occurred during the Three Kingdoms period (220–280 AD)
and Western Jin dynasty (265–316 AD), respectively. Meanwhile, over ten thousand fine-
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quality Yue wares (intact objects and sherds) with various shapes and elaborate
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ornaments have been unearthed (Fig. 1b). Afterwards, Jinshan kiln site was
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archaeologically proven to be one of the earliest Yue kiln sites, and remarkably the first
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known one with well-preserved kilns of different ages, which was unprecedented in the early history of Yue ware. For these reasons, Jinshan kiln site has been awarded as one of
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the Top 10 New Archaeological Discoveries of China in 2014.[9,10]
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The quality of Yue wares, to a great extent, depends on the color of the glaze. An elegant
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bluish grey-green was considered as the supreme color by the imperial court. It is commonly accepted that iron is the main colorant in celadon glaze, and the form of iron
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present plays an important role in the color variation of celadon glaze.[11] One popular explanation is that iron in celadon glaze exists in the form of the oxides such as FeO, Fe2O3 or Fe3O4. The main color effect is achieved by the chemical reaction from Fe2O3 to FeO during firing, which manifests as colors ranging from pale yellow to bluish green.[12–15] However, this might not be the case in this study. In order to produce the
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desired colors, celadons have to be fired in a reducing atmosphere and at a high temperature of about 1200 ℃. Under such conditions, the surface of the glaze generally melts into a glass-like amorphous structure with short-range orders. In view of the
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complexity of the amorphous state, the exact structure of iron in the celadon glaze, especially the local structure, is not well determined. Attempts had been made to
investigate the effect of iron on the coloration of some well-developed porcelain, e.g. Jian ware[16], Ru ware[17], Honglvcai (red and green porcelain)[18] and Qinghua (blue and white porcelain)[19,20]. However, the exact structure of iron in early celadon glaze has
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not been studied as much in the published literature. Therefore, the coloration mechanism
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of the early celadon remains unclear.
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In this paper, variation in the glaze color of different samples leads to a study of the
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coloration mechanism of Jinshan celadon. For the first time, the careful analysis of
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Jinshan glazes by Fe K-edge X-ray absorption fine structure (XAFS) spectra have made it possible to unambiguously quantify the local structural environment of iron in the
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glaze, and therefore to determine how changes in the iron local environment affect the
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colors of early celadon glazes. The analysis of XAFS and ab initio calculations using ligand field theory have revealed that varying splitting energy contributes to differential
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absorption in the visible light spectrum, producing the coloration of glaze.
Material and methods Materials: No permits were required for the described study, which complied with all relevant regulations. As shown in detail in Supplementary Table 1, the samples selected 5
for this study consist of 21 sherds from two different time periods (Eastern Han: n=11; Three Kingdoms–Western Jin: n=10) excavated from Jinshan kiln site. All the samples were sorted out during the excavation by Zhejiang Provincial Institute of Cultural Relics
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and Archaeology.
XAFS: The X-ray absorption fine structure (XAFS) data at the Fe K-edge of the samples were recorded at room temperature in transmission mode using ion chambers or in the fluorescent mode with silicon drift fluorescence detector at BL14W1 beamline of the
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Shanghai Synchrotron Radiation Facility (SSRF), China. The station was operated with a
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Si(111) double crystal monochromator. During the measurement, the synchrotron was
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operated at energy of 3.5 GeV and a current between 150-210 mA. The photon energy
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was calibrated with the first inflection point of Fe K-edge in Fe metal foil. Pellets pressed
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from powders of reagent-grade oxides Fe2O3 and Fe3O4 were used as standards and
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measured under identical conditions. Experimental XAFS spectra were fitted in R-space using an IFEFFIT package; FEFF8 was used for calculation of phase shift from crystal
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structures of corresponding oxides and silicates.[21,22]
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Ab initio calculations: Projected density of states (PDOS) calculations were performed using Quantum ESPRESSO program package[23], which is based on density functional
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theory (DFT), plane waves, and pseudopotentials for the description of core electrons, within the generalized gradient approximation (GGA) of the Perdew-Burke-Ernzerhof (PBE). We adopted the linearized augmented planewave (LAPW) method with tested basis sets for the electronic structure, and ultrasoft pseudopotentials Fe.pbe-nd-
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rrkjus.UPF and O.pbe-rrkjus.UPF from http://www.quantum-espresso.org. The theoretical calculation requires a periodic crystal structure with periodic boundary conditions at the unit cell boundaries. To do that, a modified [Fe3+O6] octahedron, which
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was constructed with the real Fe-O bond lengths acquired by EXAFS results, displaces a central octahedron in regular Al2O3 unit cell. A 2x2x1 supercell structure containing 120 atoms was modelled in order to take into account the response from local and mid-range environment around the central Fe atom (Supplementary Fig. 5). The plane-wave cutoff energy in the self-consistent field (SCF) calculations was set to 30 Ry, with the
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convergence threshold in the total unit-cell energy no worse than 1.0 × 10−6 Ry/atom.
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Details of all the other methods used in this study are presented in the supplementary
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Results and Discussion
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materials.
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Firstly, this research allows us to group the samples into two categories in terms of color with the unaided eye (Supplementary Table 1): all the samples of Eastern Han (n=11) and
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half of the samples of the Three Kingdoms-Western Jin period (n=5) are bluish-green,
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while the other half (n=5) are yellowish-green. Typical samples are shown in Fig. 2a.
The above directly perceived distinction has been confirmed by findings of chromatic characterizations and reflectance spectra of Jinshan glazes. Fig. 2b shows that in CIELAB color space, the b* values (red/magenta and green) of bluish-green samples 7
never reach +17, whereas the numbers are greater for yellowish-green samples, which means the glazes in the latter group are indeed yellower. Furthermore, the a* values (yellow and blue) of bluish-green samples range from -2 to +1, while the values for
group are slightly greener than those of the latter one.
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yellowish-green samples are between +1 and +4, indicating that the glazes in the former
Likewise, the results drawn from reflectance spectra are consistent with the above
findings, as shown in Fig. 2c. For glazes of Eastern Han, the dominant wavelength is
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around 660 nm. It shifts slightly to approximately 680 nm for those samples with similar
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color of the Three Kingdoms-Western Jin period. However, the yellowish-green glazes
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are characterized by a peak wavelength of greater than 800 nm, falling into the near
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infrared (NIR) region.
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Scanning Electron Microscopy (SEM) images demonstrate the existence of some crystals
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of different crystallinities in the glaze. Optical coherence tomography (OCT) and optical microscopy (OM) have also been used to characterize the microstructure of celadon glaze
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(Supplementary Fig. 1-2). A typical bubble surrounded by plenty of crystal granules is illustrated in the glaze of JS-7 (Fig. 3a). Judging from the scale of image, the sizes of the
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crystals range from about 0.5 to 2.5 μm. In comparison, two bubbles with fewer crystal granules in the glaze of JS-12 show another situation where the crystallinity is relatively lower (Fig. 3b). The sizes of the crystals are smaller accordingly.
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Raman spectra have been collected to ascertain the respective crystalline and glassy nature of the glaze. Two kinds of crystals are identified. For bigger crystal granules (Fig. 3c, f), a strong 463 cm-1 peak dominates the spectrum, along with two small peaks at 355
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and 395 cm-1, which refers to α-quartz (SiO2). Peaks at 355 and 463 cm-1 are assigned to oxygen vibration in Si–O–Si symmetrical stretching-bending modes (A1), while the 395 cm-1 peak is correlated to vibrational mode for E(TO) symmetry.[24,25] As to crystals in the glaze bubble, two peaks at 480 (or 476) and 506 cm-1 are observed (Fig. 3d, f),
indicating the presence of anorthite (CaAl2Si2O8). These vibrations can be respectively
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associated with the movement of oxygen atoms along a line bisecting the T–O–T bond
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angle creating a symmetric stretch.[26] This is the first time that anorthite crystals have
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been observed in the glaze of such an early celadon type. Intensive light scattering caused
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by plenty of submicron crystal droplets or needles plays an important role in the coloration of much later opaque green glazes and crystalline glazes in ancient China.
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[27,28] The naturally occurring anorthite crystals might provide the inspiration for
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ancient potters to control the optical properties of the glaze by artificially adding
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anorthite to the glaze recipe.
Other factors that may affect the glaze color are scrutinized. Fe contents in the glaze of
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all samples measured by proton-induced X-ray emission (PIXE) keep stable at a 2 wt% level (Supplementary Table 2-3). Besides, the firing temperatures of different samples remained basically the same (Supplementary Table 4 and Supplementary Fig. 3).
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Normalized X-ray absorption near edge structure (XANES) spectra of Fe K-edge in Jinshan glazes are shown in Fig. 4b. For the sake of comparison, spectra of Fe2O3 and Fe3O4 are also presented. It is known that Fe K-XANES pre-edge peaks of the glazes can
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be used to reveal the oxidation state and electronic structure of Fe.[29] The pre-edge peak of 7111 eV (free Fe ions) shifted to higher energy of around 7114.4 eV for all three samples, suggesting a dominant trivalent state for Fe ions. This indicates that Fe in
Jinshan glazes is in a more oxidized environment.[30] No evidence of a characteristic
peak at 7112 eV, which correlates to divalent Fe ions, is present. The results qualitatively
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demonstrate that Fe is solely present in a trivalent state in these samples and that no
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reduction reactions of Fe3+ to Fe2+ took place during firing. Notably, the spectra for JS-12
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and JS-13 seem to be quite similar. X-ray photoelectron spectroscopy (XPS)
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measurements have been performed to compliment the XANES results. Just like XAFS, XPS peaks can be interpreted to reveal the electronic state of irons. The peak position for
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Fe3+ 2p3/2 in Fe2O3 is 710.9 eV, while the value for Fe2+ 2p3/2 in FeO is 709.4 eV.[31] As
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shown in Supplementary Fig. 4, Fe 2p3/2 peaks are greater than 711 eV For all three
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samples (JS-1, 12 & 13), suggesting a dominant trivalent state for Fe ions. To have a deep insight into the differences in the edge feature, the first derivatives of normalized Fe
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K-edge XANES spectra are calculated (Fig. 4c) as well. Therefore, a number of variations in the original spectra are emphatically illustrated. Spectrum of Fe K-edge in
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the JS-1 glaze is slightly different from those of JS-12 and JS-13, with subtle differences related to edge and edge-crest features. It is noteworthy that peaks of all three spectra do not perfectly match up with those of the Fe2O3 spectrum, especially in the range of 7122–
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7127 eV, suggesting that the average coordination of Fe in Jinshan glazes is not exactly the same as Fe2O3, but a rather similar structure.
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The Fe K-edge XANES spectra reveal the following transitions to bound states: 1s-3d (pre-edge), 1s-4s (shoulder), and 1s-4p (edge crest). The electronic transition between 1s and 4p bands of Fe ions is a dipole transition. Therefore, the two XANES edge crests in the conduction band, evident in the first-derivative spectra as shown in Fig. 4c,
correspond to Fe-4pπ and 4pρ band of doublet, respectively. According to quantum
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theory, however, the transition from 1s (ℓ=0) to 3d (ℓ=2) is forbidden, since the dipole
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selection rule (Laporte rule) Δℓ=1 is not met.[32] ℓ denotes the azimuthal quantum
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number.
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The electron configuration of Fe is [Ar] 3d6 4s2. For Fe3+ ions, there are 5 electrons in the
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outermost occupied orbital, making its electron configuration 3d5. The 3d orbital can hold
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a maximum of 10 electrons. According to Hund's rules, an atom with outermost subshell half-filled or less is stable. The pre-edge peaks in XANES spectra suggest an electronic
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exchange interaction, namely an electronic hybridization, between the half-filled Fe-3d orbitals and the fully occupied outer 2p orbitals (O-2p) of the surrounding oxygen
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ions.[33] As a result, new 3d5L hybridized bands with p-like character are formed, where L denotes the O-2p bands. It is possible that electron transfer happens between 1s and 3d5L hybridized bands.[34,35]
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To further investigate the Fe local structure, Fourier transformed (FT) X-ray absorption fine structure (EXAFS) spectra of Fe K-edge in Jinshan glazes are shown in Fig. 4d. Fitting of EXAFS spectra is carried out for all three measured samples. The damped
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oscillating amplitude of XAFS spectra suggests that Fe ions are in an amorphous state, having orders over short distances (a few atoms) but not over longer distances.
At first, we assume that the short-range orders of Fe ions are in a crystal state of α-Fe2O3 or a similar structure. However, the theoretical calculation based on α-Fe2O3 structure
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proved not ideal, which supports the conclusion drawn from XANES results. The best
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fitting results (given in Supplementary Table 5), usually done by a non-linear least
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squares method with several refined parameters, arise from Fe substitution for Al in
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Al2O3. For comparison, fittings modelling standard [Fe3+O6] octahedra in Fe2O3 and
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Supplementary Fig. 6.
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[Fe3+O4] tetrahedra made of Fe substitution for Si in SiO2 are presented as well in
In Supplementary Table 5, the radial distance between central Fe atoms and coordinating
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O atoms of JS-12, which is yellowish-green, is clearly shorter than those of the bluishgreen samples (JS-1 and JS-13). For bluish-green samples, the nearest oxygens (CN=3)
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are positioned at a distance of 1.92 Å (JS-1) and 1.91 Å (JS-13), while the distances between central Fe atoms and the second nearest oxygens (CN=3) are 2.04 Å (JS-1) and 2.03 Å (JS-13) respectively. Both samples, although from different time periods, share a similar size in short-range structure of Fe substitution for Al in Al2O3. It is worth noting that for yellowish-green JS-12, the corresponding distances are 1.89 Å and 2.01 Å, 12
apparently smaller compared with the two samples above. Therefore, the average lengths of Fe-O bonds are 1.98 Å (JS-1), 1.97 Å (JS-13) and 1.95 Å (JS-12), respectively.
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We note that in regular α-Fe2O3 structure, the shortest Fe-O bond length is 1.94 Å, while the longer one is 2.12 Å. This means that the modified [Fe3+O6] octahedra in Jinshan
glazes are largely distorted to the original one in α-Fe2O3 structure.[36] It is obvious that
bluish-green celadon glazes from different time periods share similar Fe-O bond lengths,
while the yellowish-green celadon glazes are characterized by a shorter Fe-O bond length.
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It indicates that the modified [Fe3+O6] octahedron of JS-12 is more distorted than those of
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JS-1 and JS-13 with regards to the crystallographic symmetry, which increases the
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electronic overlapping between the Fe-3d and O-2p orbitals. The difference may play a
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vital part in the coloration of celadon glazes.
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According to the ligand field theory, the 3d electronic levels have equal energy for free
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Fe atoms. The d-electron would have equivalent probability of being in any one of the five degenerate orbitals. However, when the central Fe ion is surrounded by several O
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ions in the glaze, namely the ligands, the interaction of the electrons in the Fe-3d and O2p orbitals will cause a small splitting of the energy levels. In a regular octahedral ligand
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field, the five d-orbitals split into lower triplet t2g levels including dxy, dxz and dyz orbitals, and upper doublet eg levels, including 𝑑𝑥 2 −𝑦 2 and 𝑑𝑧 2 orbitals (Fig. 5a).[37] Since the splitting in energy levels (ΔO for octahedral field) generally ranges from 1 to 3 eV, the absorption of photons by electronic transitions between split 3d levels leads to visible coloration. 13
The electronic structures revealed by ab initio calculations provide insightful analysis of ligand field splitting. Using acquired results by EXAFS, modified [Fe3+O6] octahedra
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have been constructed with actual Fe-O bond lengths of three Jinshan samples (JS-1, 12 and 13). Projected density of states (PDOS) of Fe ions are determined using Quantum ESPRESSO program package. The resulting PDOS is presented in Fig. 5b. The peak positions allow for a rough determination of the ligand field splitting assuming d-d
interactions for different Fe-3d states. It is clear that the energy of separation (ΔO ) of JS-
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12 (1.83 eV) is significantly larger than those of JS-1 and 13 (1.70 eV and 1.75 eV
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respectively).
The differences indicate stronger Fe-O interactions in JS-12, as also suggested by the
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different Fe-O bond lengths in these three samples. Alterations in bond distance and bond
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strength between the coloring ions (Fe) and the surrounding ligands (O) bring about various ligand field splitting energies and therefore contribute to differential absorption
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in the visible. This is perceived as the mechanism for color variation[38]. The color we
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see for celadon glazes is a result of absorption of complementary colors. When the visible light is incident on the glaze, a characteristic portion of the spectrum is absorbed when
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passing through it, and the rest is reflected at the interface between the glaze and the body. The reflected light will be perceived by our eyes as the complementary color to the absorbed light. Since the photon energy needed to excite the electron from a lower dorbital into higher d-orbitals (d-d transition) is inversely proportional to the wavelength of the incident light, a larger splitting energy (ΔO ) corresponds to a smaller absorption 14
wavelength. This results in a longer coloration wavelength. Therefore, the glaze appears to be the complementary color of the absorption. The lower splitting energy (ΔO ), caused by a longer Fe-O bond length, leads to bluish-green color, while a higher splitting energy
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resulting from a shorter Fe-O bond length, breeds a yellower appearance (Fig. 5c).
Conclusion
In summary, for the first time, we have discovered that Fe in early celadon glaze is solely
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present in a trivalent state with distorted octahedral geometry [Fe3+O6]. In combination
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with ab initio calculations, we first reveal that the different Fe-O bonds in distorted
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octahedra can cause various ligand field splitting energies of Fe-3d level, leading to
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differential absorption of visible light and in turn producing a variation in the color of
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celadon glaze.
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Data availability: Data used in this study are publicly deposited in the Institute of Modern Physics, Fudan University and are freely available upon request.
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Acknowledgments: This work was sponsored by the Compass Special Plan from the
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State Administration of Cultural Heritage of China. The authors acknowledge with thanks the staff of accelerator maintenance team of Fudan University, for their strong support.
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We are much obliged to beamline BL14W1 (Shanghai Synchrotron Radiation Facility) for providing the beam time. Special thanks go to Zhejiang Provincial Institute of Cultural Relics and Archaeology, for kindly providing such rare samples in this study.
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Author contributions: Conceived and designed the experiments: BZ. Performed the experiments: YL BZ. Analyzed the data: YL BZ. Contributed reagents/materials/analysis
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tools: HC JZ. Wrote the paper: YL.
Competing interests: The authors declare no conflict of financial interests.
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Fig. 1. Location of Jinshan kiln site. a The geographical location of Jinshan kiln site in Shangyu, Zhejiang province. The red square indicates the area in which the Jinshan kiln site is located. The base map created using the Blue Marble Next Generation with Topography and Bathymetry, July (http://visibleearth.nasa.gov/view.php?id=73751).
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Miniature map data © OpenStreetMap contributors, CC BY-SA (https://creativecommons.org/licenses/by-sa/3.0/). b Yue wares with various shapes and elaborate ornaments have been unearthed. c The layout of Jinshan kiln site. Photograph
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courtesy of Jianming Zheng.
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Fig. 2. Optical properties of the excavated Jinshan celadon samples. a Typical bluish-
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green and yellowish-green samples. b Chromatic characterizations of Jinshan celadon
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glazes. c Reflectance spectra of Jinshan celadon glazes.
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SC RI PT U N A M D TE EP CC A Fig. 3. SEM images and Raman spectra of Jinshan celadon glazes. a SEM image of JS-7. b SEM image of JS-12. c-e The measured points of JS-11, JS-21 and JS-4, respectively. f Raman spectra of the three samples. 25
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Fig. 4. XAFS results and fitting. a Schematics of XAFS experimental setup. b Fe K-edge XANES spectra of Jinshan celadon glazes. c First derivatives of Fe K-edge XANES
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spectra of Jinshan celadon glazes. d Fourier transforms of k3 -weighted EXAFS (black
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square dotted lines) and fits (red circle dotted lines). Not corrected for phase shift.
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SC RI PT U N A M D TE EP CC A Fig. 5. Fe-3d level splits and projected density of states of Fe in EXAFS-measured [Fe3+O6] octahedron. a Schematic representation of [Fe3+O6] octahedron and the Fe-3d
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level splits in the octahedral (Oh), site symmetries. b projected density of states of Fe in EXAFS-measured [Fe3+O6] octahedron of 3 measured Jinshan samples. c The
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relationships among Fe-O bond length, splitting energy (ΔO ), and color of the glaze.
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