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Nondestructive Analysis on Ancient Porcelain of Longquan Kiln in Zhejiang Province by WDXRF *

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Nondestructive Analysis on Ancient Porcelain of Longquan Kiln in Zhejiang Province by WDXRF * Chinese Physics C (HEP & NP) Vol. 32, Suppl./, Oct., 2008 Nondestructive analysis on ancient porcelain of Longquan Kiln in Zhejiang Province by WDXRF * FENG Song-Lin(¾t)1;1) FENG Xiang-Qian(¾c)1 ZHU Ji-Hao(ÁUÓ)1 XIE Guo-Xi(IU)1 YAN Ling-Tong(A(Ï)1 LI Li(ow)1 LI Gang(of)2 SHEN Qiong-Hua(! u)2 1 (Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China) 2 (Zhejiang Province Museum, Hangzhou 310007, China) Abstract Nuclear analytical technique is an efficient method in study of rarity cultural relic for its advantage of nondestructive analysis. Longquan celadon is one kind of the most important ancient porcelain in China. In order to determine the inner provenance property and age's characteristic of ancient Longquan porcelain, ten components in porcelain body and glaze were measured by the Wave Dispersive X-ray Fluorescence (WDXRF). Multivariates Statistical Analysis was used to analyze the experiment data. The results showed that the chemical compositions in porcelain body of three typical kilns were similar. The difference of components in porcelain glaze can be used to identify the provenance and age. Key words WDXRF, nondestructive analysis, ancient Longquan porcelain, provenance property, ages char- acteristic PACS 32.30.Rj, 82.80.Ej 1 Introduction ware. Longquan Kiln locates Longquan county of Zhe- X-ray Fluorescence (XRF)[1], Proton Induced X- jiang Province. It began to fire celadon porcelain ray Emission (PIXE)[2] and Synchrotron Radiation since Former Northern Song (960|1127 A.D.) and X-ray Fluorescence (SRXRF)[3] can be used to non- is famous for its distinctive glaze color in China and destructive analyze the elemental composition of sam- other countries. It reached at the height of power ples. This excellence could not be substituted by and splendour since Later Southern Song (1127| other analytic methods. These analytic techniques 1279 A.D.) to Ming Dynasty (1368|1644 A.D.). were widely applied in biology, material, geology, Longquan Kiln of Yuan Dynasty (1271|1368 A.D.) agriculture and archaeology[4] for its advantage of and Ming Dynasty was final illustrious period in nondestructive analysis. Wavelength dispersive X- celadon history of China. Longquan Kiln was con- ray Fluorescence (WDXRF) is clipping, handy and sisted of about thousand kilns sites which distributed economical multi elemental analytic method. The el- in the region of Longquan County. Dayao Kiln site emental concentration of Z >11 can be determined by which made from one hundred and twenty-six porce- this method. Especially, it is suite to original position lain kiln sites was the most history, art and scien- and nondestructive analyze the chemical composition tific importance one of Longquan Kiln. It began to in body and glaze of rarity ancient small porcelain fire celadon porcelain since Five Dynasty (907|960 Received 8 July 2008 * Supproted by Knowledge Innovative Program of Chinese Academy of Sciences (KJCX3.SYW.N12) and National Natural Science Foundation of China (50432010, 10675143) 1) E-mail: [email protected] 284 | 288 FENG Song-Lin et alµNondestructive analysis on ancient Suppl./ porcelain of Longquan Kiln in Zhejiang Province by WDXRF 285 A.D.) and closed at Qing Dynasty (1644|1911 A.D.). The incision section of the sample was polished for It was announced as the one of most important cul- nondestructive analysis of Wave Dispersive X-ray flu- tural relic site of nation and rigorously protected by orescence (WDXRF). The strip specimen was washed government. At present, the ancient porcelain of typ- in ultrasonic cleaner with tap water and deionized wa- ical Longquan Kiln site has not been systemically ter respectively, and then baked in 80℃for 8 hours. scientific studied. Therefore, we have no represen- In order to reduce the effect results from the in- tational and statistical analytic data to identify the homogeneous of elemental distribution in body and ancient Longquan ware which was handed down from glaze, these samples of porcelain body thickness were ancient times and excavated from city ruins and mau- less than 5 mm and surface was too bend to sat- soleums. The provenance and age's characteristic of isfy the measuring requirement. The X-ray spot of ancient Longquan porcelain produced in different kiln φ5 mm was used to measure the porcelain body due site and various history periods can be described by to the limitation of body thickness. The X-ray spot of using the experimental data of chemical composition φ10 mm was used to analyze the porcelain glaze. In in body and glaze. It would offer the scientific crite- this case, ten pieces samples of Dayao, eleven pieces rion for distinguishing provenance, age and fakemnet. specimen of Jincun and five samples of Xikou were se- Otherwise, it is very useful to study the manufacture lected to be analyzed by WDXRF in our experiment. technology, rise and fall of porcelain phylogeny. The WDXRF experiment was performed at the XRF-1800 in Tsinghua University, Beijing of China. 2 Samples and experimental The conditions of the experiment are: Voltage of X- ray tube is 40 kV, Current of X-ray tube is 70 mA. In this paper, 144 pieces sherds of celadon porce- Almost all the sample bodies were thicker than 5 mm lain produced in three typical Longquan kilns sites and their glaze surface was larger enough. The X-ray were offered by Zhejiang Province museum. Forty- beam can directly irradiate on the transverse section three pieces sherds of Longquan Dayao Kiln site were and glaze surface to determine the elemental compo- produced in the period from Southern Song to Yuan sition in the specimen. Ten elemental compositions of Dynasty. Forty-eight pieces sherds of Longquan Jin- SiO2, Al2O3, Fe2O3, TiO2, MnO, K2O, Na2O, CaO, cun Kiln site were fired in Later Northern Song. Cu and Zn were determined under these conditions. Fifty-three pieces sherds of Longquan Xikou Kiln The average values of each elemental composition in site were manufactured in the period from South- porcelain body and glaze are displayed in Table 1 and ern Song to Yuan Dynasty. A small strip of about Table 2. 10 mm×20 mm was cut down from porcelain sherd. Table 1. The average contents of chemical composition in body of three Longquan Kilns. Kiln site Ages Body color Glaze color SiO2(%) Al2O3(%) K2O(%) CaO(%) TiO2(%) Dayao Southern Song Hoariness Blue 67.41.6 28.21.1 3.090.44 0.0280.021 0.0680.010 to Yuan Dynasty Jincun Later Northern Grey Blue with 73.01.2 23.81.3 1.860.26 0.0240.009 0.1860.040 Song Dynasty light yellow Xikou Southern Song Grey Blue with 68.25.6 25.71.1 2.040.20 0.0330.023 0.1720.057 to Yuan Dynasty light brown Kiln site Ages Body color Glaze color MnO(%) Fe2O3(%) Na2O(%) Cu/ppm Zn/ppm Dayao Southern Song Hoariness Blue 0.0480.022 0.860.08 0.400.09 2.20.8 12.55.0 to Yuan Dynasty Jincun Later Northern Grey Blue with 0.0130.007 0.970.18 0.130.04 5.00.7 10.43.8 Song Dynasty light yellow Xikou Southern Song Grey Blue with 0.0230.013 1.030.05 0.180.08 2.10.8 14.32.6 to Yuan Dynasty light brown 286 Chinese Physics C (HEP & NP) Vol. 32 Table 2. The average contents of chemical composition in glaze of three Longquan Kilns. Kiln site Ages Body color Glaze color SiO2(%) Al2O3(%) K2O(%) CaO(%) TiO2(%) Dayao Southern Song Hoariness Blue 72.21.1 17.90.8 3.420.29 4.540.53 0.0490.009 to Yuan Dynasty Jincun Later Northern Grey Blue with 71.62.0 18.31.1 2.120.16 6.631.17 0.0920.064 Song Dynasty light yellow Xikou Southern Song Grey Blue with 73.82.0 17.61.2 3.140.43 4.000.49 0.0550.011 to Yuan Dynasty light brown Kiln site Ages Body color Glaze color MnO(%) Fe2O3(%) Na2O(%) Cu/ppm Zn/ppm Dayao Southern Song Hoariness Blue 0.320.13 0.870.09 0.700.16 5.31.2 14.75.1 to Yuan Dynasty Jincun Later Northern Grey Blue with 0.410.11 0.730.28 0.180.05 11.03.5 14.57.3 Song Dynasty light yellow Xikou Southern Song Grey Blue with 0.170.06 0.850.39 0.400.12 4.92.2 9.60.8 to Yuan Dynasty light brown As shown in table1, the average content of SiO2 of was relatively higher than other two kilns. The av- porcelain body in Jincun was (73.01.2)% which is erage contents of CaO and Fe2O3 in porcelain body the highest one of three typical Longquan Kiln. It was of Xikou Kiln produced in the period from Southern closed to each other for Dayao Kiln and Xikou Kiln. Song to Yuan Dynasty was relatively higher. The mean values of Al2O3 and K2O in body of Dayao were the highest ones. They reached (28.21.1)% 3 Results and Discussion and(3.090.44)% respectively. The lowest ones of these two chemical composition occurred in the porce- There were no evident differences of average con- lain body of Jincun Kiln. They were (23.8 1.3)% centration of SiO2 and Al2O3 in the porcelain glaze and(1.860.26)% respectively. The concentrations of of three Longquan Kilns as shown in Table 2. The CaO in porcelain body of three typical Longquan average contents of K2O and Fe2O3 in glaze of Dayao Kiln were nearly lower, but it was relatively slight and Xikou Kiln were similar, but it was higher than high for Jincun.
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