Nuclear Instruments and Methods in Physics Research B 240 (2005) 527–531

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Some new results of PIXE study on Chinese ancient porcelain

H.S. Cheng a,*, B. Zhang a, D. Zhu a, F.J. Yang a, X.M. Sun b, M.S. Guo b

a Institute of Modern Physics, Fudan University, Shanghai 200433, Chinab The Cultural Relics and Archaeology Research Institute of Henan Province, Zheng Zhou 450000, China

Available online 3 August 2005

Abstract

This paper reports some new results obtained by PIXE on Chinese ancient porcelain. The first results concern theprovenance of blue and white porcelain made during the Tang Dynasty (AD618–907), which are the earliest productsfound in China. The PIXE experimental results show that they were fired in Huangye Kiln, Gongyi, Henan Province.The chemical composition of the body, white glaze and of the cobalt pigment will be reported. This paper also reportsthe results for early Chinese blue and white porcelain made under the Yuan dynasty (AD1206–1368) in Jingdezhen,Jiangxi Province. Experimental results show that the chemical composition of the cobalt pigment used by officersand popular are similar. These materials were imported from another country. The local asbolite was used as cobaltpigment material since the early Ming Dynasty (AD1368–1644) in Jingdezhen at folk kiln, and it was used at officialkiln until the 16th century.� 2005 Elsevier B.V. All rights reserved.

PACS: 32.30.Rj; 82.80.Ej; 91.65.Nd

Keywords: PIXE; Ancient porcelain; Cobalt pigment

1. Introduction

The origin of Chinese blue and white porcelainand the sources of the cobalt pigment used in Chi-na already studied [1]. From 1975 to 1989, 15sherds of blue and white porcelain of the Tang

0168-583X/$ - see front matter � 2005 Elsevier B.V. All rights reservdoi:10.1016/j.nimb.2005.06.151

* Corresponding author. Tel.: +86 21 65643460; fax: +86 2165642787.

E-mail address: hscheng@fudan.edu.cn (H.S. Cheng).

Dynasty (AD618–907) were found in a buildingsite in Yangzhou, Jiangsu Province. In 1990, theruins of a Tang Dynasty City were scientificallyexcavated in Yangzhou. Fourteen sherds of blueand white porcelains were unearthed in the stra-tum corresponding to the Tang Culture. Thesesamples are the earliest products of blue andwhite porcelain found in China. In the Yangzhouregion there was no ancient kiln found. TheseTang blue and white porcelains must be from

ed.

528 H.S. Cheng et al. / Nucl. Instr. and Meth. in Phys. Res. B 240 (2005) 527–531

another place. In 2003, some sherds of blue andwhite porcelain were unearthed together withTang tricolour-glazed pottery, white-glazed porce-lain, brown-glazed porcelain and black-glazedporcelain from the ancient kiln site of Huangyein Gongyi, Henan Province. Huangye Kiln is wellknown for producing the famous Tang tricolour-glazed pottery, but very few people know that italso produced blue and white porcelain. It isinteresting that Tang blue and white porcelainfound in Yangzhou were made at the HuangyeKiln? The basic way to find the provenance ofthe blue and white porcelains is by comparingtheir chemical composition of their body, whiteglaze and cobalt pigment used. This paper will re-port the experimental results.

Table 1The chemical composition of Tang blue and white porcelain measure

Sample Al2O3 SiO2 P2O5 K2O

1# Huangye Body 30.4 62.6 0.00 2.48WG 13.1 69.3 0.22 3.23BG 12.2 68.6 0.10 3.16

2# Yangzhou Body 32.5 61.6 0.00 1.86WG 14.7 70.6 0.32 3.20BG 13.5 66.8 0.15 2.90

3# Yangzhou Body 32.6 60.6 0.37 2.24WG 13.2 66.2 0.51 4.92BG 12.7 65.6 0.51 5.47

4# Body 32.6 60.7 0.00 2.20WG 6.41 41.5 1.49 0.59BG 8.18 37.6 0.91 1.62

5# Body 28.8 63.0 0.00 2.44WG 3.60 46.6 1.34 0.29BG 4.20 39.0 1.61 0.31

6# Body 30.4 62.7 0.00 2.32WG 5.27 55.5 0.68 0.77BG 4.34 49.5 1.48 0.44

7# Body 29.4 63.6 0.00 2.24WG 3.92 54.8 0.85 0.34BG 4.99 50.1 0.77 0.84

8# Body 28.3 63.7 0.00 2.35WG 6.91 48.5 1.39 0.81BG 5.20 37.2 1.40 1.13

9# Body 30.0 62.6 0.00 2.15WG 3.25 44.2 0.66 0.37BG 4.21 35.9 1.11 0.02

Note: WG – white glaze; BG – blue glaze.

2. Experimental and results

The experiments were performed at theNEC9SDH-2 Pelletron tandem accelerator of Fu-dan University. In this study the external-beamPIXE method was used, the experimental proce-dure has been reported elsewhere [2,3]. Beforethe PIXE analysis the samples were cleaned withalcohol. A 3.0 MeV collimated proton beam ofdiameter 1 mm was used in this study.

2.1. The compositional relation of Tang blue and

white porcelain with Huangye Kiln

Table 1 lists the chemical compositions of body,the white glaze and the blue glaze. The samples

d by PIXE (wt%)

CaO TiO2 MnO Fe2O3 CoO PbO

0.30 1.19 0.01 0.8411.2 0.15 0.06 1.2411.2 0.15 0.08 1.36 1.56

0.32 1.09 0.01 1.098.39 0.14 0.07 1.17 0.0113.0 0.16 0.08 1.34 0.38

0.36 1.03 0.00 1.2513.1 0.16 0.14 1.2512.5 0.16 0.11 1.56 0.40

0.55 1.06 0.01 1.190.80 0.20 0.00 0.37 0.01 47.02.92 0.33 0.04 1.21 1.00 44.5

0.77 1.22 0.00 1.620.90 0.15 0.00 0.14 0.00 45.31.92 0.16 0.05 0.60 0.74 49.3

0.48 1.03 0.01 1.402.02 0.14 0.00 0.29 0.01 33.71.00 0.11 0.01 0.81 1.46 39.0

0.77 1.06 0.01 1.210.81 0.12 0.00 0.18 0.00 37.53.04 0.20 0.02 0.81 0.50 37.1

1.04 1.12 0.01 1.832.76 0.18 0.00 0.52 0.00 37.43.67 0.26 0.01 0.70 0.60 48.1

0.80 1.20 0.02 1.552.36 0.28 0.00 0.70 0.00 46.61.76 0.17 0.03 0.64 0.60 53.9

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listed in Table 1 can be divided into two groupsaccording to the chemical composition of theglaze. For the samples no. 4–9 the high concentra-tions of PbO (35–54 wt%) are found in the glaze,so they do not correspond to blue and whiteporcelain. but to lead-glazed pottery. Samplesno. 1–3 are blue and white porcelains, PbO is notfound in the glaze. Sample no. 1 is unearthed fromHuangye Kiln site and no. 2–3 were unearthedfrom Yangzhou. The chemical compositions ofbodies listed in Table 1 are very similar to eachother, showing that the same mineral sources wereused.The contents of Al2O3 and TiO2 in the body

range from 28.3 to 32.5 wt%, 1.03 to 1.22 wt%,respectively. This shows that these samples belongto northern porcelain body system made in north-ern kiln of China. For the porcelain productsmade in Southern China (for example, Jingdezhen)in the same period the contents of Al2O3 and TiO2are <20 and <1 wt%, respectively which means,lower than the data above.To get more information on products made at

Huangye Kiln we measured 20 sherds of white-

Fig. 1. A factorial analysis diagram from the composition of the TaKiln, Ding Kiln, Xing Kiln and Ru Kiln. (,) Huangye white porceHuangye tricolour-glazed pottery, (}) Tang blue and white porcelF1 = �0.291Al2O3 � 0.151SiO2 + 0.839K2O � 0.179CaO + 0.900TiO2F2 = �0.940Al2O3 + 0.933SiO2 � 0.151K2O � 0.142CaO + 0.148TiO2

glazed porcelain and 9 sherds of Tang tricolour-glazed pottery which are blue-glazed on. To studythe provenance of Tang blue and white porcelainthe multivariate statistical analysis method wasused. Fig. 1 shows a factorial analysis diagramfrom the composition of the bodies made at differ-ent kilns in the Tang period. These samples arefrom objects made at Huangye Kiln, Xing Kiln,Ding Kiln and Ru Kiln, respectively. Xing andDing kilns are located in the Hebei Province. Bothare famous for producing white-glazed porcelainunder the Tang. The chemical compositions ofXing and Ding samples are from [4,5]. The Ru kilnis famous for producing celadon and located at100 km away from Huangye Kiln.From Fig. 1 we can see that the samples from

the sites of Xing and Ding are scattered in the low-er part of the diagram, and departed from those ofHuangye. Tang blue and white samples (noted by1–3) stay in the area which is occupied by the Hua-ngye samples, though they are not in the central re-gion. This result supports the hypothesis that theTang blue and white samples were made at Hua-ngye Kiln.

ng porcelain bodies found in Yangzhou and made at Huangyelain, (d) Xing white porcelain, (�) Ding white porcelain, (n)ain, (j) Ru kiln celadon, (h) Huangye blue-glazed pottery.+ 0.768Fe2O3.+ 0.295Fe2O3.

530 H.S. Cheng et al. / Nucl. Instr. and Meth. in Phys. Res. B 240 (2005) 527–531

2.2. Cobalt blue pigment used for Tang blue and

white porcelain

Cobalt pigment was used for Tang blue andwhite porcelain. From the PIXE spectrum of theblue glaze the concentration of cobalt oxide, man-ganese oxide and ferric oxide in the pigment wereobtained. The cobalt oxide produces the blue glazewhich also effected by manganese oxide and ferricoxide. The measured results are listed in Table 2.The concentrations of trace element As, Ni andCu are also listed in this table. The ratios ofMnO/CoO, Fe2O3/CoO range from 0.002 to 0.06and from 0.09 to 0.9, respectively. The yellow,white and green pattern were often used for Tangtricolour-glazed pottery made at Huangye Kiln,but the blue, brown and black pattern also ap-peared on the products. The data for ratiosMnO/CoO and Fe2O3/CoO measured on 20 blue-glazed samples shows that only one kind of bluepigment material was used at Huangye Kiln. Suchkind of cobalt mineral has not been found in Chinaso far. This is the best blue pigment used for blueand white porcelain during successive dynasties.Most of the researchers believe that it was importedfrom another country through the Silk Road.

2.3. Cobalt blue pigment used for early blue and

white porcelain at Jingdezhen folk kilns

The earliest blue and white porcelain was madeunder the Tang (AD618–907) at Huangye Kiln,

Table 2Cobalt pigment used for blue and white porcelain in Tang, Yuan, M

Data Main chemicalcomposition

MnO/CoO Fe2O3/CoO

Tang (AD618–907) 0.002–0.06 0.09–0.9

Yuan (AD1206–1368) Folk kiln 0.005–0.19 2.17–16.20Official kiln 0.005–0.15 2.0–24.0

Ming (AD1368–1644) Folk kiln 5.28–11.8 0.37–3.74

Qing (AD1616–1911) Folk kiln 5.89–7.40 1.92–2.32Official kiln 5.08–7.0 0.35–1.0

Asbolite cobalt pigments 4.8–9.0 0.35–1.66

but the remains are very few. It implies that theyield was very low. Until the Yuan Dynasty(AD1206–1368) many blue and white porcelainwere produced in Jingdezhen and spreading inmany countries. There were two kinds of kiln inJingdezhen: one was the official kiln (Kuan), andanother was the folk kiln. The product quality ofofficial kiln is much better than that of folk, andthe raw material used might be different from eachother, for example the cobalt blue pigment used.In [2], we reported the experimental results forthe cobalt pigment used at Kuan. In this studywe report the experimental results of cobalt pig-ment used at folk kiln. Table 2 lists the resultsfor the blue pigment. The data for Yuan, Mingand Qing dynasty are measured on 20, 25 and 20samples, respectively.From Table 2 we can see that for the Yuan folk

blue and white porcelain the ratios MnO/CoO andFe2O3/CoO range from 0.005 to 0.19 and from2.17 to 16.20, respectively. These data are in agree-ment with that of Yuan official product. It meansthat the same kind of cobalt blue pigment materialwas used at official and folk kilns. Furthermore,such kind of cobalt pigment was marketable atJingdezhen under the Yuan dynasty, although itwas imported from other country [2]. Under theMing the ratios of MnO/CoO and Fe2O3/CoOrange from 5.29 to 11.81 and from 0.37 to 3.74,respectively. These data are in agreement with thatof asbolites produced in China. This result indi-cates that at the early Ming period the local cobalt

ing and Qing

Trace elements

As Ni Cu

�100 ppm 100–300 ppm –100 ppm

20–200 ppm <20 ppm <35 ppm20–200 ppm <30 ppm <30 ppm

<50 ppm 379–6569 ppm 85–305 ppm

<20 ppm 522–2522 ppm 74–352 ppmNot detected by PIXE 140–400 ppm 74–352 ppm

Not detected by PIXE 0.13–1.3% in thepigment materials

H.S. Cheng et al. / Nucl. Instr. and Meth. in Phys. Res. B 240 (2005) 527–531 531

pigment had been used for blue and white porce-lain at Jingdezhen folk kiln.

3. Summary

By comparing the chemical composition of bodyand cobalt pigment measured by PIXE, we believethat the Huangye Kiln, Henan Province, producedthe Tang blue and white porcelain. The cobalt pig-ment used for this blue and white porcelain was im-ported. It is the best cobalt pigment used for blueand white porcelain during successive dynasty.During the Yuan period another kind of im-

ported cobalt pigment was used for blue and whiteporcelain by official and folk kilns at Jingdezhen.In the early Ming period (AD1368–1391) the local

cobalt pigment (asbolite) started to be used atJingdezhen folk kilns.

References

[1] Y.C. Chen, F.K. Zhang, X.W. Zhang, et al., in: Proceedingsof the International Symposium, Shanghai, 1995, p. 204.

[2] H.S. Cheng, Z.Q. Zhang, H.N. Xia, J.C. Jiang, F.J. Yang,Nucl. Instr. and Meth. B 190 (2002) 488.

[3] H.S. Cheng, Z.Q. Zhang, B. Zhang, F.J. Yang, Nucl. Instr.and Meth. B 219–220 (2004) 16.

[4] J.Z. Li, Y.Y. Guo, Scientific and Technical Achievements inAncient Chinese Pottery and Porcelain, Shanghai Scientificand Technical Publishers, 1985, p. 175.

[5] Y.C. Chen, F.K. Zhang, Z.Z. Zhang, N.H. Bi, in: Pro-ceedings of the International Symposium, Shanghai,1989, Shanghai Scientific and Technical Publishers, 1989,p. 191.