Ceramics International xxx (xxxx) xxx

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Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Provenance of the cobalt pigment used for Jingdezhen minyao

blue-and-white porcelain in the early Qing dynasty
Ruiqi Zhang a, *, Peter Gethin b
a
College of Liberal Arts, Shanghai University, 99 Shangda Road, 200444, PR China
b
Department of Archaeology, Classics and Egyptology, University of Liverpool, L69 7WZ, UK

A R T I C L E I N F O A B S T R A C T

Keywords: The earliest cobalt application to porcelains can be traced back to the Tang dynasty (618–907). The production of
Blue-and-white porcelain the widely recognised blue-and-white porcelains in Jingdezhen did not mature until the late Yuan dynasty.
Jingdezhen According to historical texts, imported cobalt pigments were applied to blue-and-white porcelains in Jingdezhen
Cobalt pigment
kilns from the Yuan dynasty (1271–1368), and native Chinese cobalt pigments replaced imported sources in the
Minyao
Ming dynasty (1368–1644). As such, scholars have focused intensive studies on the sources of these blue pig­
ments used in the Yuan and Ming dynasties. In this study, fifteen fragments of blue-and-white porcelain exca­
vated from Jingdezhen minyao sites were selected to investigate the provenance of the cobalt pigment used in the
Reigns of Kangxi (1662–1722), Yongzheng (1723–1735) and Qianlong (1735–1795). The results suggests that
the cobalt rich materials correlate more closely to the Yunnan asbolites, rather than the widely-accepted Zhejiang
asbolites mentioned in the historical texts and publications.

1. Introduction
Archaeologically recovered evidence indicates that the oldest Chi­
nese blue-and-white porcelains were manufactured in Jingdezhen dur­
ing the Tang dynasty (618–907); yet, the production methodology did
not properly mature until the end of Yuan dynasty (1271–1368). Due to
the significant demand for blue-and-white porcelains from the Arab
regions, and the availability of imported cobalt pigments from Persia,
the Jingdezhen blue-and-white porcelains were produced on a notably
large scale. During the Ming and Qing dynasties (1368–1911) this pro­
duction was booming. However, after the Reign of Qianlong
(1735–1795), Jingdezhen ceramics experienced a decline in quantity,
quality and variety. This was mainly due to a shrinking market and the
widespread reproduction of blue-and-white wares in European and
Asian markets.
In the development of porcelain production technology, Jingdezhen
(Map 1) occupied a position of primacy, particularly in the early Qing
dynasty. This period encompassed the Reigns of Kangxi (1662–1722),
Yongzheng (1723–1735) and Qianlong (1735–1795); and was associ­
ated with an era of social and economic prosperity. The production of
Jingdezhen blue-and-white porcelains reached its peak during this
period, which has been described as the golden age of blue-and-white
porcelain.
Previous research conducted on Jingdezhen blue-and-white porce­
lains were primarily focused on artistic appreciation and typological
classification, which principally concentrated on collating historical
documents and archaeological categorisation. In terms of scientific ex­
amination, existing studies mainly focus on the blue-and-white porce­
lains manufactured in the Yuan and Ming dynasties, due to their
uncommonness and therefore higher economic value. The research
questions in these cases can be divided in to four categories; classifica­
tion [1,2], dating [3], change of “recipe” [4] and characterisation of blue
pigments [5–8]. The historical texts additionally assert that the appli­
cation of blue pigments in the Yuan and Ming dynasties underwent
technological changes. Therefore, studies on the origins of cobalt blue
pigments focus mainly on the Yuan and the Ming guanyao
blue-and-white porcelains [9–13]. However, the thriving circumstances
associated with blue-and-white porcelains has been ascribed to the
productions of minyao [14]. As such, studies conducted on minyao
blue-and-white porcelains are also significant and noteworthy, espe­
cially in the golden age of the early Qing dynasty.

* Corresponding author.
E-mail address: rqzhang7@shu.edu.cn (R. Zhang).

https://doi.org/10.1016/j.ceramint.2021.05.303
Received 24 May 2021; Accepted 30 May 2021
Available online 4 June 2021
0272-8842/© 2021 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Please cite this article as: Ruiqi Zhang, Peter Gethin, Ceramics International, https://doi.org/10.1016/j.ceramint.2021.05.303
R. Zhang and P. Gethin
2. Experiments
2.1. Samples and methodology
In this experiment, fifteen sherds of Jingdezhen minyao blue-and-
white porcelain made in the Kangxi (C⋅P⋅K), Yongzheng (C⋅P⋅Y), and
Qianlong (C⋅P.Q) periods were sampled, five for each period (Fig. 1).
The shards were sampled using a low speed micro cutting machine
equipped with a thin corundum blade. The cut samples were mounted in
epoxy resin blocks, ground flat and polished, then coated with carbon to
avoid charging in the electron beam of the scanning electron micro­
scope. The backscatter electron images of the cross-sections were
collected using a Hitachi TM3000 tabletop scanning electron micro­
scope. Quantitative analyses of the major and minor elements within the
blue pigment and glaze were conducted using a Bruker Quantax 70
energy dispersive spectroscopy system. The experimental conditions
under which the analyses were performed were: an accelerator voltage
of 15 kV, and a spectrum collection time of 5 min. The experiment was
carried out in the Environmental Laboratory in the University of Liver­
pool’s Central Teaching Laboratories.
3. Results
The results of major and minor simple oxide compositions (Na2O,
MgO, Al2O3, SiO2, K2O, CaO, MnO, Fe2O3, CoO) in cobalt pigment and
glaze are listed in Table 1 and Table 2 respectively.
4. Analytical results and review
In terms of mineralogy; manganese, iron, copper, arsenic, nickel, and
zinc, as well as other related elements, will typically correspond with
particular cobalt ore sources [15]. Due to the different origins of
Fig. 1. Blue-and-white porcelain excavated from Jingdezhen minyao sites. (For interpretation of the references to colour in this figure legend, the reader is referred to
the Web version of this article.)
2
Ceramics International xxx (xxxx) xxx
pigment ores, the types and quantities of paragenetic elements are also
changeable. Therefore, examining the variability in symbiotic elements
is presently the universal method for provenance study of blue pigment
[16].
There are numerous factors that can affect the absolute content of
elemental components, such as their concentrations within the pigment
mineral; thus there is no sense in comparing the absolute contents values
[17]. Iron and manganese are considered to be the two elements with
the most significant impact on blue colouration [10]. The traditional
method of determining the provenance of blue pigments used in Chinese
blue-and-white porcelains is to compare the ratios of both iron and
manganese with cobalt, namely MnO/CoO and Fe2O3/CoO, between
known cobalt asbolites and samples with unknown pigment source [12,
15,18]. The MnO/CoO and Fe2O3/CoO ratios could potentially be
characteristic of particular cobalt rich materials [8], thus the compar­
ative results can often approximately discern the provenance.
Imported cobalt pigments contained arsenic and exhibited low
manganese concentrations, such as sumaliqing 苏麻离青 [12]. Therefore,
it can be inferred that the cobalt rich materials used in the early Qing
dynasty were not imported. The majority of Chinese domestic cobalt
mines are located in Jiangxi ( Map 1, yellow), Zhejiang (Map 1, blue)
and Yunnan provinces (Map 1, red). The compositions of various cobalt
rich materials have been compiled from prior publication sources, these
have been listed in Table 3. Ratios of iron, manganese and cobalt for the
fifteen study samples are presented in Table 4. The MnO/CoO ratios for
the Kangxi, Yongzheng and Qianlong periods are in the range of
0.73–2.15, 2.26–5.67 and 0.80–2.37 respectively, whilst the Fe2O3/CoO
ratios for these three periods are 0.42–1.25, 1.09–1.86 and 0.48–1.83
respectively. Upon comparing the ratios displayed in Tables 3 and 4, the
result demonstrates that almost all of the study samples appear to
contain cobalt associated with materials from Yunnan, with a significant
proportion exhibiting composition ratios similar to the refined Yunnan
R. Zhang and P. Gethin Ceramics International xxx (xxxx) xxx

Table 1
Chemical composition in blue pigment of samples by EDS (wt%).
Na2O MgO Al2O3 SiO2 K2O CaO MnO Fe2O3 CoO

C⋅P⋅K1 1.23 0.48 28.67 51.57 1.12 12.12 2.16 0.83 1.82
C⋅P⋅K2 2.63 0.56 25.53 55.59 1.43 9.93 2.17 0.94 1.22
C⋅P⋅K3 1.48 0.63 28.78 51.04 1.23 12.50 1.47 0.89 2.00
C⋅P⋅K4 1.33 0.47 27.25 54.51 1.06 13.12 0.98 0.71 0.56
C⋅P⋅K5 1.37 0.44 27.71 50.05 1.35 11.67 4.45 0.88 2.07
C⋅P⋅Y1 1.99 0.43 19.50 62.30 1.73 9.25 3.19 1.05 0.56
C⋅P⋅Y2 1.48 0.37 20.14 61.43 1.97 11.80 1.61 0.69 0.50
C⋅P⋅Y3 1.21 0.50 17.59 63.19 2.06 9.51 3.68 1.37 0.89
C⋅P⋅Y4 1.08 0.34 15.96 67.31 2.39 8.54 2.83 1.00 0.55
C⋅P⋅Y5 1.61 0.39 22.53 58.65 1.75 11.17 2.02 0.98 0.89
C⋅P.Q1 1.39 0.53 32.17 48.98 1.18 12.92 0.86 0.92 1.06
C⋅P.Q2 1.61 0.43 26.22 53.10 1.00 11.78 3.20 1.07 1.59
C⋅P.Q3 1.23 0.69 28.92 51.78 1.07 13.81 0.76 0.98 0.77
C⋅P.Q4 1.24 0.41 29.75 49.15 1.30 12.84 2.05 1.05 2.19
C⋅P.Q5 2.28 0.41 23.29 60.52 2.48 9.27 0.80 0.62 0.34

Table 2
Chemical composition of glaze of samples by EDS (wt%).
Na2O MgO Al2O3 SiO2 K2O CaO MnO Fe2O3

C⋅P⋅K1 1.36 0.32 14.85 72.33 2.95 7.42 0.19 0.58

C⋅P⋅K2 2.62 0.40 15.69 68.33 2.66 9.44 < lod 0.86
C⋅P⋅K3 1.68 0.43 16.59 67.97 2.80 9.75 < lod 0.78
C⋅P⋅K4 1.25 0.34 13.74 72.32 2.90 8.76 < lod 0.69
C⋅P⋅K5 1.59 0.40 15.61 69.47 3.37 8.82 < lod 0.73
C⋅P⋅Y1 1.86 0.36 14.57 69.80 3.07 7.40 2.16 0.78
C⋅P⋅Y2 1.34 0.35 14.14 66.83 2.96 11.45 2.18 0.74
C⋅P⋅Y3 1.72 0.45 16.68 65.94 2.90 11.55 < lod 0.77
C⋅P⋅Y4 0.95 0.23 13.65 70.79 2.57 11.48 < lod 0.34
C⋅P⋅Y5 1.54 0.57 14.64 69.38 3.12 8.48 1.70 0.56
C⋅P.Q1 1.55 0.52 14.69 73.21 3.42 5.69 0.14 0.78
C⋅P.Q2 1.64 0.40 14.44 70.17 2.44 9.85 0.23 0.83
C⋅P.Q3 1.21 0.37 14.10 68.23 2.67 11.29 1.11 1.03
C⋅P.Q4 1.37 0.36 14.48 69.45 3.30 10.18 0.26 0.59
C⋅P.Q5 1.83 0.36 14.30 70.53 3.58 7.62 0.98 0.80

* < lod = below the limits of detection.

Table 3
Chemical compositions of different cobalt containing materials.
Cobalt sources SiO2 Al2O3 MgO CaO Fe2O3 MnO CoO MnO/CoO Fe2O3/CoO reference

Yunnan Zhuming raw ore 23.61 29.79 0.68 0.53 2.64 16.84 2.29 7.35 1.15 [26]
Yunnan Zhuming pigment (refined) 28.33 34.96 0.41 0.37 2.80 22.53 6.02 3.74 0.47 [26]
Yunnan asbolite (refined) 28.97 32.81 < lod 0.66 6.58 19.36 4.46 4.34 1.48 [26]
Yunnan Yiwei pigment 20.27 23.95 0.26 0.03 5.92 21.92 4.45 4.92 1.33 [25]
Yunnan Chongming pigment (calcined) 0.85 26.23 0.02 0.06 1.19 48.88 11.06 4.42 0.11 [25]
Jiangxi Ganzhou asbolite raw ore 37.91 18.68 0.48 0.33 4.65 20.03 1.26 15.90 3.69 [27]
Jiangxi Shanggao pigment 21.18 17.58 0.14 0.05 5.38 29.87 4.15 7.20 1.30 [27]
Zhejiang Jiangshan pigment 35.38 19.70 0.24 0.06 4.40 19.97 1.81 11.03 2.43 [25]
Zhejiang Jiangshan pigment (calcined) 5.87 26.73 0.09 0.03 1.51 47.96 6.79 7.06 0.22 [27]
Zhejiang asbolite raw ore 18.31 19.01 0.20 0.16 6.96 30.12 1.86 16.19 3.74 [26]

* < lod = below the limits of detection.

Zhuming pigment and a smaller fraction exhibiting composition ratios

Table 4 close to the refined Yunnan asbolite/Yunnan Yiwei pigment.
Ratios of iron, manganese and cobalt in blue pigment (%).
Nonetheless, Yunnan pigments were never cited in Chinese ancient
No. Kangxi Yongzheng Qianlong texts. The Nanyao Notes 南窑笔记 (published in the Qianlong period)
MnO/ Fe2O3/ MnO/ Fe2O3/ MnO/ Fe2O3/ quotes that “there are various sorts of pigments produced from Zhejiang,
CoO CoO CoO CoO CoO CoO Jiangxi, Guangdong (Map 1, orange) and Guangxi (Map 1, green)
1 1.19 0.46 5.67 1.86 0.81 0.87 provinces … Zhejiang ones are the best.” [“料有数种,产于浙江、江西、
2 1.78 0.77 3.20 1.37 2.02 0.67 两广 … …总以浙料为上”] [19]. Illustrations and Explanations of Ceramic
3 0.73 0.44 4.15 1.55 0.98 1.27 Production 陶冶图说 (composed in the Qianlong period) says that “the
4 1.74 1.25 5.10 1.80 0.94 0.48
blue pigments used {on blue-and-white porcelain} come from moun­
5 2.15 0.42 2.26 1.09 2.37 1.83
tains in Zhejiang Shaoxing and Jinhua … there are some that are pro­
duced from Jiangxi and Guangdong provinces, but they do not have
good fire-resistant properties, thus could only be used on coarse porce­
lain for markets” [”(青花) 料出浙江绍兴、金华二郡所属诸山 … …其江

3
R. Zhang and P. Gethin Ceramics International xxx (xxxx) xxx

西、广东诸山间有采者,色泽淡薄,不耐煆炼,止可画染市卖粗器”] [20]. materials (0.03–0.66 wt%). Therefore, elevated calcium levels observed
Generally speaking, Zhejiang pigments are the leading choice for the in the blue pigments can be used as an indicator of dilution by the glaze.
finest blue colour, whilst Jiangxi, Guangdong and Guangxi pigments are The dilution ratios can then be calculated using formula (1), with the
typically considered as inferior. Furthermore, there is a consensus results given in Table 5:
amongst previous researchers that the cobalt pigments used in the early ⃒ ⃒
⃒ Cp − Cg ⃒
Qing dynasty came largely from Zhejiang [21–23], although Yunnan d= (1)
sources were regarded as being exploited after the middle Qing dynasty Cp
[21,23].
In order to address this apparent difference more clearly and * d = dilution ratio, C = CaO concentration, Cp = CaO in pigment, Cg
adequately, the experimental results will be reviewed and tested using = CaO in glaze.
an alternative calculation method. In the preceding experimental work,
the most difficult procedure was to precisely analyse the chemical The dilution factors are then used, in combination with the ratios of
compositions of pigment inclusions, this is due to both the small size and MnO, Fe2O3 and CoO, to determine the dilution corrected ratios. These
irregular morphologies of the cobalt mineral particles (Fig. 2, A), which corrected ratios should better represent the characteristics of blue pig­
are frequently smaller than the analytical spot size of the electron mi­ ments, allowing for a more representative comparison. The calculation
croscope. The nature of the analytical method used to determine the methods are as shown in Eqs. (2) and (3), and the results are presented in
composition of the pigment inclusions means that there will inevitably Table 5.
be a contributing signal collected from the surrounding glaze matrix, ⃒ ⃒
which will be combined with the overall composition of the analysed Fe2 O3 ⃒⃒PFe2 O3 ∗(d + 1) − GFe2 O3 ⃒⃒
=⃒ (2)
inclusion. Chen et al. [25] and Tian et al. [22] take this situation, that CoO PCoO ∗(d + 1) − GCoO ⃒
pigment was diluted somewhat by the glaze matrix, into consideration; ⃒ ⃒
this provided the concept of dilution ratio correction using a MnO ⃒⃒PMnO ∗(d + 1) − GMnO ⃒⃒
=⃒ (3)
calculation-estimation method. CoO PCoO ∗(d + 1) − GCoO ⃒
To apply this method, firstly it is necessary to find the indicator of
dilution. By comparing the major and minor chemical constituents of the * G = glaze, P = pigment.
pigments in the study samples (Table 1) and various cobalt containing
materials (Table 3); it becomes apparent that calcium content of the When comparing the results presented in Table 5 with Chinese cobalt
pigments (8.54–13.12 wt%) is much higher than that of the cobalt rich rich materials in Table 3, the MnO/CoO ratios for the Kangxi,

Fig. 2. Cross-section of selected samples under SEM. The small size and irregular morphologies of the cobalt mineral particles (A) surrounded by anorthite (B) and
glaze are difficult to be tested directly. (a) C⋅P⋅K.3, (b) C,P⋅Y.1, (c) K⋅Y.Q.2.

4
R. Zhang and P. Gethin
Map 1. Location of Jingdezhen and mentioned provinces in this study. The map is marked based on Mino Y. and Wilson P.‘s book published in 1973 [24].
Yongzheng and Qianlong periods are in the range of 0.73–2.15,
0.82–5.10 and 0.02–1.90 respectively, and Fe2O3/CoO ratios are
0.10–0.43, 0.05–1.32 and 0.13–0.54 respectively, which are all
commensurate to that of Yunnan asbolites and more closely comparable
to the refined Yunnan Zhuming pigment. Therefore, the reviewed data
are still concordant with the initial findings and interpretation.
5. Discussion
The result of the first ratio comparison and further data review
indeed share the same conclusion; that it is highly probable that Yunnan
cobalt ores were used for blue-and-white porcelains made in Jingdezhen
in the early Qing dynasty, rather than the widely-accepted under­
standing of the cobalt material provenance from prior research.
In order to clarify this doubt, we should reconsider the historical
documentation. In fact, the aforementioned records are official
5
Ceramics International xxx (xxxx) xxx
documents that pertain to the porcelain production in Jingdezhen; to be
exact, to that of imperial porcelain. This is especially the case for the
document Illustrations and Explanations of Ceramic Production, whose
author, Tang Ying 唐英, was the Ceramic Officer 督陶官 serving the
Court. He duly recorded the production information of the imperial kiln.
In addition, for the imperial porcelains, all materials must be chosen
from the finest sources. Therefore, Zhejiang pigments would be their
first choice because of its superior properties.
From a geological viewpoint, most of the rock sources in the middle
of Zhejiang province are tertiary basalts, while most of those in the
north-eastern Yunnan are Permian basalt; as such, this implies a similar
petrological composition for the two regions [21]. Therefore, cobalt rich
minerals from both of these locations are likely to exhibit similar com­
positions, providing a comparable appearance and blue colouration. As
a consequence, Yunnan pigments could conceivably be used to as a
substitute for Zhejiang pigments in blue-and-white porcelains. This not
R. Zhang and P. Gethin Ceramics International xxx (xxxx) xxx

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