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Some new results of PIXE study on Chinese ancient porcelain
Nuclear Instruments and Methods in Physics Research B 240 (2005) 527–531 www.elsevier.com/locate/nimb
Some new results of PIXE study on Chinese ancient porcelain H.S. Cheng b
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, China 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 the provenance of blue and white porcelain made during the Tang Dynasty (AD618–907), which are the earliest products found 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 reports the 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 officers and popular are similar. These materials were imported from another country. The local asbolite was used as cobalt pigment material since the early Ming Dynasty (AD1368–1644) in Jingdezhen at folk kiln, and it was used at official kiln until the 16th century. Ó 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 porcelain and the sources of the cobalt pigment used in China already studied [1]. From 1975 to 1989, 15 sherds of blue and white porcelain of the Tang *
Corresponding author. Tel.: +86 21 65643460; fax: +86 21 65642787. E-mail address: [email protected] (H.S. Cheng).
Dynasty (AD618–907) were found in a building site in Yangzhou, Jiangsu Province. In 1990, the ruins of a Tang Dynasty City were scientifically excavated in Yangzhou. Fourteen sherds of blue and white porcelains were unearthed in the stratum corresponding to the Tang Culture. These samples are the earliest products of blue and white porcelain found in China. In the Yangzhou region there was no ancient kiln found. These Tang blue and white porcelains must be from
0168-583X/$ - see front matter Ó 2005 Elsevier B.V. All rights reserved. doi:10.1016/j.nimb.2005.06.151
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 and white porcelain were unearthed together with Tang tricolour-glazed pottery, white-glazed porcelain, brown-glazed porcelain and black-glazed porcelain from the ancient kiln site of Huangye in Gongyi, Henan Province. Huangye Kiln is well known for producing the famous Tang tricolourglazed pottery, but very few people know that it also produced blue and white porcelain. It is interesting that Tang blue and white porcelain found in Yangzhou were made at the Huangye Kiln? The basic way to find the provenance of the blue and white porcelains is by comparing their chemical composition of their body, white glaze and cobalt pigment used. This paper will report the experimental results.
2. Experimental and results The experiments were performed at the NEC9SDH-2 Pelletron tandem accelerator of Fudan University. In this study the external-beam PIXE method was used, the experimental procedure has been reported elsewhere [2,3]. Before the PIXE analysis the samples were cleaned with alcohol. A 3.0 MeV collimated proton beam of diameter 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
Table 1 The chemical composition of Tang blue and white porcelain measured by PIXE (wt%) Sample
Al2O3
SiO2
P2O5
K2O
CaO
TiO2
MnO
Fe2O3
CoO
Body WG BG
30.4 13.1 12.2
62.6 69.3 68.6
0.00 0.22 0.10
2.48 3.23 3.16
0.30 11.2 11.2
1.19 0.15 0.15
0.01 0.06 0.08
0.84 1.24 1.36
1.56
Body WG BG
32.5 14.7 13.5
61.6 70.6 66.8
0.00 0.32 0.15
1.86 3.20 2.90
0.32 8.39 13.0
1.09 0.14 0.16
0.01 0.07 0.08
1.09 1.17 1.34
0.01 0.38
3# Yangzhou
Body WG BG
32.6 13.2 12.7
60.6 66.2 65.6
0.37 0.51 0.51
2.24 4.92 5.47
0.36 13.1 12.5
1.03 0.16 0.16
0.00 0.14 0.11
1.25 1.25 1.56
0.40
4#
Body WG BG
32.6 6.41 8.18
60.7 41.5 37.6
0.00 1.49 0.91
2.20 0.59 1.62
0.55 0.80 2.92
1.06 0.20 0.33
0.01 0.00 0.04
1.19 0.37 1.21
0.01 1.00
47.0 44.5
Body WG BG
28.8 3.60 4.20
63.0 46.6 39.0
0.00 1.34 1.61
2.44 0.29 0.31
0.77 0.90 1.92
1.22 0.15 0.16
0.00 0.00 0.05
1.62 0.14 0.60
0.00 0.74
45.3 49.3
Body WG BG
30.4 5.27 4.34
62.7 55.5 49.5
0.00 0.68 1.48
2.32 0.77 0.44
0.48 2.02 1.00
1.03 0.14 0.11
0.01 0.00 0.01
1.40 0.29 0.81
0.01 1.46
33.7 39.0
Body WG BG
29.4 3.92 4.99
63.6 54.8 50.1
0.00 0.85 0.77
2.24 0.34 0.84
0.77 0.81 3.04
1.06 0.12 0.20
0.01 0.00 0.02
1.21 0.18 0.81
0.00 0.50
37.5 37.1
Body WG BG
28.3 6.91 5.20
63.7 48.5 37.2
0.00 1.39 1.40
2.35 0.81 1.13
1.04 2.76 3.67
1.12 0.18 0.26
0.01 0.00 0.01
1.83 0.52 0.70
0.00 0.60
37.4 48.1
Body WG BG
30.0 3.25 4.21
62.6 44.2 35.9
0.00 0.66 1.11
2.15 0.37 0.02
0.80 2.36 1.76
1.20 0.28 0.17
0.02 0.00 0.03
1.55 0.70 0.64
0.00 0.60
46.6 53.9
1# Huangye
2# Yangzhou
5#
6#
7#
8#
9#
Note: WG – white glaze; BG – blue glaze.
PbO
H.S. Cheng et al. / Nucl. Instr. and Meth. in Phys. Res. B 240 (2005) 527–531
listed in Table 1 can be divided into two groups according to the chemical composition of the glaze. For the samples no. 4–9 the high concentrations of PbO (35–54 wt%) are found in the glaze, so they do not correspond to blue and white porcelain. but to lead-glazed pottery. Samples no. 1–3 are blue and white porcelains, PbO is not found in the glaze. Sample no. 1 is unearthed from Huangye Kiln site and no. 2–3 were unearthed from Yangzhou. The chemical compositions of bodies listed in Table 1 are very similar to each other, showing that the same mineral sources were used. 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 belong to northern porcelain body system made in northern kiln of China. For the porcelain products made in Southern China (for example, Jingdezhen) in the same period the contents of Al2O3 and TiO2 are <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-
529
glazed porcelain and 9 sherds of Tang tricolourglazed pottery which are blue-glazed on. To study the provenance of Tang blue and white porcelain the multivariate statistical analysis method was used. Fig. 1 shows a factorial analysis diagram from the composition of the bodies made at different kilns in the Tang period. These samples are from objects made at Huangye Kiln, Xing Kiln, Ding Kiln and Ru Kiln, respectively. Xing and Ding kilns are located in the Hebei Province. Both are famous for producing white-glazed porcelain under the Tang. The chemical compositions of Xing and Ding samples are from [4,5]. The Ru kiln is famous for producing celadon and located at 100 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 lower part of the diagram, and departed from those of Huangye. Tang blue and white samples (noted by 1–3) stay in the area which is occupied by the Huangye samples, though they are not in the central region. This result supports the hypothesis that the Tang blue and white samples were made at Huangye Kiln.
Fig. 1. A factorial analysis diagram from the composition of the Tang porcelain bodies found in Yangzhou and made at Huangye Kiln, Ding Kiln, Xing Kiln and Ru Kiln. (,) Huangye white porcelain, (d) Xing white porcelain, () Ding white porcelain, (n) Huangye tricolour-glazed pottery, (}) Tang blue and white porcelain, (j) Ru kiln celadon, (h) Huangye blue-glazed pottery. F1 = 0.291Al2O3 0.151SiO2 + 0.839K2O 0.179CaO + 0.900TiO2 + 0.768Fe2O3. F2 = 0.940Al2O3 + 0.933SiO2 0.151K2O 0.142CaO + 0.148TiO2 + 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 and white porcelain. From the PIXE spectrum of the blue glaze the concentration of cobalt oxide, manganese oxide and ferric oxide in the pigment were obtained. The cobalt oxide produces the blue glaze which also effected by manganese oxide and ferric oxide. The measured results are listed in Table 2. The concentrations of trace element As, Ni and Cu are also listed in this table. The ratios of MnO/CoO, Fe2O3/CoO range from 0.002 to 0.06 and from 0.09 to 0.9, respectively. The yellow, white and green pattern were often used for Tang tricolour-glazed pottery made at Huangye Kiln, but the blue, brown and black pattern also appeared on the products. The data for ratios MnO/CoO and Fe2O3/CoO measured on 20 blueglazed samples shows that only one kind of blue pigment material was used at Huangye Kiln. Such kind of cobalt mineral has not been found in China so far. This is the best blue pigment used for blue and white porcelain during successive dynasties. Most of the researchers believe that it was imported from 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 made under the Tang (AD618–907) at Huangye Kiln,
but the remains are very few. It implies that the yield was very low. Until the Yuan Dynasty (AD1206–1368) many blue and white porcelain were produced in Jingdezhen and spreading in many countries. There were two kinds of kiln in Jingdezhen: one was the official kiln (Kuan), and another was the folk kiln. The product quality of official kiln is much better than that of folk, and the raw material used might be different from each other, for example the cobalt blue pigment used. In [2], we reported the experimental results for the cobalt pigment used at Kuan. In this study we report the experimental results of cobalt pigment used at folk kiln. Table 2 lists the results for the blue pigment. The data for Yuan, Ming and Qing dynasty are measured on 20, 25 and 20 samples, respectively. From Table 2 we can see that for the Yuan folk blue and white porcelain the ratios MnO/CoO and Fe2O3/CoO range from 0.005 to 0.19 and from 2.17 to 16.20, respectively. These data are in agreement with that of Yuan official product. It means that the same kind of cobalt blue pigment material was used at official and folk kilns. Furthermore, such kind of cobalt pigment was marketable at Jingdezhen under the Yuan dynasty, although it was imported from other country [2]. Under the Ming the ratios of MnO/CoO and Fe2O3/CoO range from 5.29 to 11.81 and from 0.37 to 3.74, respectively. These data are in agreement with that of asbolites produced in China. This result indicates that at the early Ming period the local cobalt
Table 2 Cobalt pigment used for blue and white porcelain in Tang, Yuan, Ming and Qing Data
Main chemical composition
Trace elements
MnO/CoO
Fe2O3/CoO
As
Ni
Cu
Tang (AD618–907)
0.002–0.06
0.09–0.9
100 ppm
100–300 ppm
–100 ppm
Yuan (AD1206–1368)
Folk kiln Official kiln
0.005–0.19 0.005–0.15
2.17–16.20 2.0–24.0
20–200 ppm 20–200 ppm
<20 ppm <30 ppm
<35 ppm <30 ppm
Ming (AD1368–1644)
Folk kiln
5.28–11.8
0.37–3.74
<50 ppm
379–6569 ppm
85–305 ppm
Qing (AD1616–1911)
Folk kiln Official kiln
5.89–7.40 5.08–7.0
1.92–2.32 0.35–1.0
<20 ppm Not detected by PIXE
522–2522 ppm 140–400 ppm
74–352 ppm 74–352 ppm
4.8–9.0
0.35–1.66
Not detected by PIXE
0.13–1.3% in the pigment materials
Asbolite cobalt pigments
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 porcelain at Jingdezhen folk kiln.
cobalt pigment (asbolite) started to be used at Jingdezhen folk kilns.
3. Summary
References
By comparing the chemical composition of body and cobalt pigment measured by PIXE, we believe that the Huangye Kiln, Henan Province, produced the Tang blue and white porcelain. The cobalt pigment used for this blue and white porcelain was imported. It is the best cobalt pigment used for blue and white porcelain during successive dynasty. During the Yuan period another kind of imported cobalt pigment was used for blue and white porcelain by official and folk kilns at Jingdezhen. In the early Ming period (AD1368–1391) the local
[1] Y.C. Chen, F.K. Zhang, X.W. Zhang, et al., in: Proceedings of 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 in Ancient Chinese Pottery and Porcelain, Shanghai Scientific and Technical Publishers, 1985, p. 175. [5] Y.C. Chen, F.K. Zhang, Z.Z. Zhang, N.H. Bi, in: Proceedings of the International Symposium, Shanghai, 1989, Shanghai Scientific and Technical Publishers, 1989, p. 191.
Some new results of PIXE study on Chinese ancient porcelain H.S. Cheng b
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, China 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 the provenance of blue and white porcelain made during the Tang Dynasty (AD618–907), which are the earliest products found 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 reports the 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 officers and popular are similar. These materials were imported from another country. The local asbolite was used as cobalt pigment material since the early Ming Dynasty (AD1368–1644) in Jingdezhen at folk kiln, and it was used at official kiln until the 16th century. Ó 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 porcelain and the sources of the cobalt pigment used in China already studied [1]. From 1975 to 1989, 15 sherds of blue and white porcelain of the Tang *
Corresponding author. Tel.: +86 21 65643460; fax: +86 21 65642787. E-mail address: [email protected] (H.S. Cheng).
Dynasty (AD618–907) were found in a building site in Yangzhou, Jiangsu Province. In 1990, the ruins of a Tang Dynasty City were scientifically excavated in Yangzhou. Fourteen sherds of blue and white porcelains were unearthed in the stratum corresponding to the Tang Culture. These samples are the earliest products of blue and white porcelain found in China. In the Yangzhou region there was no ancient kiln found. These Tang blue and white porcelains must be from
0168-583X/$ - see front matter Ó 2005 Elsevier B.V. All rights reserved. doi:10.1016/j.nimb.2005.06.151
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 and white porcelain were unearthed together with Tang tricolour-glazed pottery, white-glazed porcelain, brown-glazed porcelain and black-glazed porcelain from the ancient kiln site of Huangye in Gongyi, Henan Province. Huangye Kiln is well known for producing the famous Tang tricolourglazed pottery, but very few people know that it also produced blue and white porcelain. It is interesting that Tang blue and white porcelain found in Yangzhou were made at the Huangye Kiln? The basic way to find the provenance of the blue and white porcelains is by comparing their chemical composition of their body, white glaze and cobalt pigment used. This paper will report the experimental results.
2. Experimental and results The experiments were performed at the NEC9SDH-2 Pelletron tandem accelerator of Fudan University. In this study the external-beam PIXE method was used, the experimental procedure has been reported elsewhere [2,3]. Before the PIXE analysis the samples were cleaned with alcohol. A 3.0 MeV collimated proton beam of diameter 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
Table 1 The chemical composition of Tang blue and white porcelain measured by PIXE (wt%) Sample
Al2O3
SiO2
P2O5
K2O
CaO
TiO2
MnO
Fe2O3
CoO
Body WG BG
30.4 13.1 12.2
62.6 69.3 68.6
0.00 0.22 0.10
2.48 3.23 3.16
0.30 11.2 11.2
1.19 0.15 0.15
0.01 0.06 0.08
0.84 1.24 1.36
1.56
Body WG BG
32.5 14.7 13.5
61.6 70.6 66.8
0.00 0.32 0.15
1.86 3.20 2.90
0.32 8.39 13.0
1.09 0.14 0.16
0.01 0.07 0.08
1.09 1.17 1.34
0.01 0.38
3# Yangzhou
Body WG BG
32.6 13.2 12.7
60.6 66.2 65.6
0.37 0.51 0.51
2.24 4.92 5.47
0.36 13.1 12.5
1.03 0.16 0.16
0.00 0.14 0.11
1.25 1.25 1.56
0.40
4#
Body WG BG
32.6 6.41 8.18
60.7 41.5 37.6
0.00 1.49 0.91
2.20 0.59 1.62
0.55 0.80 2.92
1.06 0.20 0.33
0.01 0.00 0.04
1.19 0.37 1.21
0.01 1.00
47.0 44.5
Body WG BG
28.8 3.60 4.20
63.0 46.6 39.0
0.00 1.34 1.61
2.44 0.29 0.31
0.77 0.90 1.92
1.22 0.15 0.16
0.00 0.00 0.05
1.62 0.14 0.60
0.00 0.74
45.3 49.3
Body WG BG
30.4 5.27 4.34
62.7 55.5 49.5
0.00 0.68 1.48
2.32 0.77 0.44
0.48 2.02 1.00
1.03 0.14 0.11
0.01 0.00 0.01
1.40 0.29 0.81
0.01 1.46
33.7 39.0
Body WG BG
29.4 3.92 4.99
63.6 54.8 50.1
0.00 0.85 0.77
2.24 0.34 0.84
0.77 0.81 3.04
1.06 0.12 0.20
0.01 0.00 0.02
1.21 0.18 0.81
0.00 0.50
37.5 37.1
Body WG BG
28.3 6.91 5.20
63.7 48.5 37.2
0.00 1.39 1.40
2.35 0.81 1.13
1.04 2.76 3.67
1.12 0.18 0.26
0.01 0.00 0.01
1.83 0.52 0.70
0.00 0.60
37.4 48.1
Body WG BG
30.0 3.25 4.21
62.6 44.2 35.9
0.00 0.66 1.11
2.15 0.37 0.02
0.80 2.36 1.76
1.20 0.28 0.17
0.02 0.00 0.03
1.55 0.70 0.64
0.00 0.60
46.6 53.9
1# Huangye
2# Yangzhou
5#
6#
7#
8#
9#
Note: WG – white glaze; BG – blue glaze.
PbO
H.S. Cheng et al. / Nucl. Instr. and Meth. in Phys. Res. B 240 (2005) 527–531
listed in Table 1 can be divided into two groups according to the chemical composition of the glaze. For the samples no. 4–9 the high concentrations of PbO (35–54 wt%) are found in the glaze, so they do not correspond to blue and white porcelain. but to lead-glazed pottery. Samples no. 1–3 are blue and white porcelains, PbO is not found in the glaze. Sample no. 1 is unearthed from Huangye Kiln site and no. 2–3 were unearthed from Yangzhou. The chemical compositions of bodies listed in Table 1 are very similar to each other, showing that the same mineral sources were used. 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 belong to northern porcelain body system made in northern kiln of China. For the porcelain products made in Southern China (for example, Jingdezhen) in the same period the contents of Al2O3 and TiO2 are <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-
529
glazed porcelain and 9 sherds of Tang tricolourglazed pottery which are blue-glazed on. To study the provenance of Tang blue and white porcelain the multivariate statistical analysis method was used. Fig. 1 shows a factorial analysis diagram from the composition of the bodies made at different kilns in the Tang period. These samples are from objects made at Huangye Kiln, Xing Kiln, Ding Kiln and Ru Kiln, respectively. Xing and Ding kilns are located in the Hebei Province. Both are famous for producing white-glazed porcelain under the Tang. The chemical compositions of Xing and Ding samples are from [4,5]. The Ru kiln is famous for producing celadon and located at 100 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 lower part of the diagram, and departed from those of Huangye. Tang blue and white samples (noted by 1–3) stay in the area which is occupied by the Huangye samples, though they are not in the central region. This result supports the hypothesis that the Tang blue and white samples were made at Huangye Kiln.
Fig. 1. A factorial analysis diagram from the composition of the Tang porcelain bodies found in Yangzhou and made at Huangye Kiln, Ding Kiln, Xing Kiln and Ru Kiln. (,) Huangye white porcelain, (d) Xing white porcelain, () Ding white porcelain, (n) Huangye tricolour-glazed pottery, (}) Tang blue and white porcelain, (j) Ru kiln celadon, (h) Huangye blue-glazed pottery. F1 = 0.291Al2O3 0.151SiO2 + 0.839K2O 0.179CaO + 0.900TiO2 + 0.768Fe2O3. F2 = 0.940Al2O3 + 0.933SiO2 0.151K2O 0.142CaO + 0.148TiO2 + 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 and white porcelain. From the PIXE spectrum of the blue glaze the concentration of cobalt oxide, manganese oxide and ferric oxide in the pigment were obtained. The cobalt oxide produces the blue glaze which also effected by manganese oxide and ferric oxide. The measured results are listed in Table 2. The concentrations of trace element As, Ni and Cu are also listed in this table. The ratios of MnO/CoO, Fe2O3/CoO range from 0.002 to 0.06 and from 0.09 to 0.9, respectively. The yellow, white and green pattern were often used for Tang tricolour-glazed pottery made at Huangye Kiln, but the blue, brown and black pattern also appeared on the products. The data for ratios MnO/CoO and Fe2O3/CoO measured on 20 blueglazed samples shows that only one kind of blue pigment material was used at Huangye Kiln. Such kind of cobalt mineral has not been found in China so far. This is the best blue pigment used for blue and white porcelain during successive dynasties. Most of the researchers believe that it was imported from 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 made under the Tang (AD618–907) at Huangye Kiln,
but the remains are very few. It implies that the yield was very low. Until the Yuan Dynasty (AD1206–1368) many blue and white porcelain were produced in Jingdezhen and spreading in many countries. There were two kinds of kiln in Jingdezhen: one was the official kiln (Kuan), and another was the folk kiln. The product quality of official kiln is much better than that of folk, and the raw material used might be different from each other, for example the cobalt blue pigment used. In [2], we reported the experimental results for the cobalt pigment used at Kuan. In this study we report the experimental results of cobalt pigment used at folk kiln. Table 2 lists the results for the blue pigment. The data for Yuan, Ming and Qing dynasty are measured on 20, 25 and 20 samples, respectively. From Table 2 we can see that for the Yuan folk blue and white porcelain the ratios MnO/CoO and Fe2O3/CoO range from 0.005 to 0.19 and from 2.17 to 16.20, respectively. These data are in agreement with that of Yuan official product. It means that the same kind of cobalt blue pigment material was used at official and folk kilns. Furthermore, such kind of cobalt pigment was marketable at Jingdezhen under the Yuan dynasty, although it was imported from other country [2]. Under the Ming the ratios of MnO/CoO and Fe2O3/CoO range from 5.29 to 11.81 and from 0.37 to 3.74, respectively. These data are in agreement with that of asbolites produced in China. This result indicates that at the early Ming period the local cobalt
Table 2 Cobalt pigment used for blue and white porcelain in Tang, Yuan, Ming and Qing Data
Main chemical composition
Trace elements
MnO/CoO
Fe2O3/CoO
As
Ni
Cu
Tang (AD618–907)
0.002–0.06
0.09–0.9
100 ppm
100–300 ppm
–100 ppm
Yuan (AD1206–1368)
Folk kiln Official kiln
0.005–0.19 0.005–0.15
2.17–16.20 2.0–24.0
20–200 ppm 20–200 ppm
<20 ppm <30 ppm
<35 ppm <30 ppm
Ming (AD1368–1644)
Folk kiln
5.28–11.8
0.37–3.74
<50 ppm
379–6569 ppm
85–305 ppm
Qing (AD1616–1911)
Folk kiln Official kiln
5.89–7.40 5.08–7.0
1.92–2.32 0.35–1.0
<20 ppm Not detected by PIXE
522–2522 ppm 140–400 ppm
74–352 ppm 74–352 ppm
4.8–9.0
0.35–1.66
Not detected by PIXE
0.13–1.3% in the pigment materials
Asbolite cobalt pigments
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 porcelain at Jingdezhen folk kiln.
cobalt pigment (asbolite) started to be used at Jingdezhen folk kilns.
3. Summary
References
By comparing the chemical composition of body and cobalt pigment measured by PIXE, we believe that the Huangye Kiln, Henan Province, produced the Tang blue and white porcelain. The cobalt pigment used for this blue and white porcelain was imported. It is the best cobalt pigment used for blue and white porcelain during successive dynasty. During the Yuan period another kind of imported cobalt pigment was used for blue and white porcelain by official and folk kilns at Jingdezhen. In the early Ming period (AD1368–1391) the local
[1] Y.C. Chen, F.K. Zhang, X.W. Zhang, et al., in: Proceedings of 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 in Ancient Chinese Pottery and Porcelain, Shanghai Scientific and Technical Publishers, 1985, p. 175. [5] Y.C. Chen, F.K. Zhang, Z.Z. Zhang, N.H. Bi, in: Proceedings of the International Symposium, Shanghai, 1989, Shanghai Scientific and Technical Publishers, 1989, p. 191.