Chemistry in Ancient Times: The Development of Blue and Purple Pigments

Berke, Heinz

doi:10.1002/1521-3773(20020715)41:14<2483::aid-anie2483>3.0.co;2-u

Cited by 66 publications

(57 citation statements)

References 9 publications

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“…But even if there existed a connection between China and Egypt, it doesn't explain why the Chinese decided to substitute Ba for Ca (Kerr and Wood, 2004) and face the challenges related to the consequent elevation of the synthesis temperature. Egyptian Blue forms at w800 Ce900 C (Berke, 2002;Riederer, 1997), whereas Chinese Purple starts to form between 900e1100 C and Chinese Blue at temperatures in excess of 1100 C (Berke and Wiedemann, 2000;Berke, 2002). An additional problem with the Egyptian-Chinese connection theory is that, to our knowledge, no Ca-bearing Egyptian Blue has been found in China.…”

Section: Introductionmentioning

confidence: 93%

“…BaCuSi 2 O 6 is a mineral that has never been found in nature, which implies that the makers of the warriors must have been able to synthesize it. The process to synthesize BaCuSi 2 O 6 is now known to be highly complex (Berke and Wiedemann, 2000;Berke, 2002) and how the early Chinese chemists managed to synthesize barium copper silicates in an almost pure form, even preceding the invention of paper and the compass, is a mystery. Interestingly, these same materials are now being studied to gain insights into the mechanisms of high temperature superconductivity (Jaime et al, 2004;Sebastian et al, 2006).…”

Section: Introductionmentioning

confidence: 99%

“…In a detailed study, Berke (Berke and Wiedemann, 2000;Berke, 2002) showed that the manufacture of Chinese Purple was a very complicated process and that barium (BaSO 4 or BaCO 3 ), copper and lead compounds as well as quartz were used in the preparation. He pointed out that lead oxide played a very important role as a catalyst in transforming barite (BaSO 4 ) into barium oxide (BaO).…”

Section: Introductionmentioning

confidence: 99%

“…Berke discussed the striking similarities of the Chinese Purple and Chinese Blue (BaCuSi 4 O 10 ) with the Egyptian Blue pigment (CaCuSi 4 O 10 ) (Riederer, 1997). He conjectured a connection between the manufacture of the two pigments in the form of technology transfer from the makers of Egyptian Blue to the makers of Chinese Purple, and proposed that the Chinese Purple was in fact derived from the Egyptian Blue (Berke and Wiedemann, 2000;Berke, 2002). This would have been the earliest technology transfer between these two ancient civilizations.…”

Section: Introductionmentioning

confidence: 99%

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Influence of Taoism on the invention of the purple pigment used on the Qin terracotta warriors

Liu

Mehta

Tamura

et al. 2007

Journal of Archaeological Science

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Introduction:In March 1974, Chinese farmers made a remarkable archaeological find: during the sinking of wells for farmland irrigation construction near Xi'an (Shaanxi province, China) they discovered an army consisting of more than 8000 life-size terracotta figures of warriors and horses dating from the First Emperor of the Qin dynasty, Shi Huang Di (reigned ca 221 BC -ca 210 BC). The figures, facing east and ready for battle, were individually modelled with their own personal characteristics, and were accompanied by their weapons, real chariots, and objects of jade and bone. How, more than 2000 years ago, the ancient Chinese constructed these large and heavy statues and what technologies they used to finish such a large project are questions which are still only partially answered by modern archaeologists.The discovery that BaCuSi 2 O 6 (FitzHugh and Zycherman 1983, FitzHugh and Zycherman 1992), also known as "Chinese Purple", was the main constituent of the purple pigment used in the paint covering the warriors constitutes an enigma in itself.This pigment was also used later in the Han dynasty in pottery (hence its other common name of "Han Purple") and for trading. BaCuSi 2 O 6 is a mineral that has never been found in nature, which implies that the makers of the warriors must have been able to synthesize it. The process to synthesize BaCuSi 2 O 6 is now known to be highly complex ). An additional problem with the Egyptian-Chinese connection theory is that, to our knowledge, no Ca-bearing Egyptian Blue has been found in China. 4 In order to address these questions, we re-examined the chemistry and the morphology of purple pigments found on one of the Qin Terracotta warriors ( fig. 1). By combining our findings of the technology used in the synthesis of Chinese Purple with existing archaeological evidence, we conclude that Taoist alchemists invented this pigment as well as the related pigment Chinese Blue independently from any Egyptian influence. Experimental Methods:Our investigation was based on a two pronged approach. We used a small fraction of our specimen, ground it into fine powder and used synchrotron radiation high-resolution powder x-ray diffraction (XRD) analysis to identify the crystallographic phases present. Then based on this inventory, we used spatially resolved x-ray and electron micro-beam techniques, such as micro X-ray diffraction (µXRD), micro X-ray fluorescence (µXRF) and Scanning Electron Microscopy (SEM) based Energy Dispersive X-ray (EDX) microanalysis, to study the chemistry of individual pigment clumps and map the distribution of these and other minority phases in the pigment.These chemical and phase maps gave us an insight into how the pigment was synthesized.Synchrotron radiation is 8-12 orders of magnitude more brilliant than the high performance rotating anode x-ray tubes (Eisenberger 1986). The X-ray beams at current third generation synchrotron radiation sources can be focused to a one micrometer size spot and still maintain high photon fluxes (>10 10 ph/s/µm 2 ) to ob...

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Section: Introductionmentioning

confidence: 93%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Influence of Taoism on the invention of the purple pigment used on the Qin terracotta warriors

Liu

Mehta

Tamura

et al. 2007

Journal of Archaeological Science

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“…BaCuSi2O6 is known as Han purple, a pigment already used by Chinese artists centuries ago 1,2,3 . Interestingly, studies have shown that it is a quasi-two dimensional spin dimer system.…”

Section: Introductionmentioning

confidence: 99%

Crystal Growth with Oxygen Partial Pressure of the BaCuSi₂O₆ and Ba_1–xSr_xCuSi₂O₆ Spin Dimer Compounds

Well

Puphal

Wehinger

et al. 2016

Crystal Growth & Design

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BaCuSi2O6 is a quasi-two dimensional spin dimer system and a model material for studying Bose-Einstein condensation (BEC) of magnons in high magnetic fields. The new Ba1-xSrxCuSi2O6 mixed system, which can be grown with x ≤ 0.3, and BaCuSi2O6, both grown by using a crystal growth method with enhanced oxygen partial pressure, have the same tetragonal structure (I41/acd) at room temperature. The mixed system shows no structural phase transition, so that the tetragonal structure is stable down to low temperatures. The oxygen partial pressure acts as control parameter for the growth process. A detailed understanding of the crystal structure depending on the oxygen content will enable the study of the spin dynamics of field-induced order states in this model magnetic compound of high current interest with only one type of dimer layers, which shows the same distance between the Cu atoms, in the structure.

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Die Restaurierung des größten archäologischen Fundes – ein chemisches Problem: die Erhaltung der Farbfassungen der chinesischen Terrakotta‐Armee in Lintong

Langhals¹,

Bathelt²

2003

Angewandte Chemie

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Nach 2200 Jahren Lagerung im feuchten Erdreich verlieren die ursprünglich bunten, lebensecht bemalten Figuren der Terrakotta‐Armee des ersten chinesischen Kaisers Qin Shihuangdi bald nach der Ausgrabung irreversibel ihre Farbfassungen. Der Grund ist, dass sich die in zwei Schichten aufgetragene Lackgrundierung im Laufe der Lagerung so verändert hat, dass sie reißt, sich vom Untergrund löst, zusammenrollt und abfällt, wenn die relative Luftfeuchtigkeit unter 84 % sinkt; mit dem Abfallen der Lackgrundierung geht auch die über ihr liegende Pigmentschicht verloren. Daher wurde intensiv nach einer Möglichkeit zur Festigung dieser Grundierung gesucht. Sie gelang durch die durch Elektronenbestrahlung ausgelöste Polymerisation einer genau abgestimmten Kombination von Monomeren.

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Chemistry in Ancient Times: The Development of Blue and Purple Pigments

Cited by 66 publications

References 9 publications

Influence of Taoism on the invention of the purple pigment used on the Qin terracotta warriors

Influence of Taoism on the invention of the purple pigment used on the Qin terracotta warriors

Crystal Growth with Oxygen Partial Pressure of the BaCuSi₂O₆ and Ba_1–xSr_xCuSi₂O₆ Spin Dimer Compounds

Die Restaurierung des größten archäologischen Fundes – ein chemisches Problem: die Erhaltung der Farbfassungen der chinesischen Terrakotta‐Armee in Lintong

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Chemistry in Ancient Times: The Development of Blue and Purple Pigments

Cited by 66 publications

References 9 publications

Influence of Taoism on the invention of the purple pigment used on the Qin terracotta warriors

Influence of Taoism on the invention of the purple pigment used on the Qin terracotta warriors

Crystal Growth with Oxygen Partial Pressure of the BaCuSi2O6 and Ba1–xSrxCuSi2O6 Spin Dimer Compounds

Die Restaurierung des größten archäologischen Fundes – ein chemisches Problem: die Erhaltung der Farbfassungen der chinesischen Terrakotta‐Armee in Lintong

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Crystal Growth with Oxygen Partial Pressure of the BaCuSi₂O₆ and Ba_1–xSr_xCuSi₂O₆ Spin Dimer Compounds