安徽铜陵师姑墩遗址出土原始瓷的初步分析研究

通过对铜陵师姑墩遗址出土的29件原始瓷进行的检测分析表明,师姑墩原始瓷胎为高硅低铝型,部分器物胎体的Fe_2O_3和TiO_2含量较高;釉属高温钙釉,釉中Mn和P含量相对较高,其可能由草木灰引入,部分器物釉中含较高的Fe_2O_3,致使釉色较深。这一结果为皖南地区先秦时期原始瓷手工业发展研究提供了新的科学依据。     

Elemental Characterization by EDXRF of Imperial Longquan Celadon Porcelain Excavated from Fengdongyan Kiln,Dayao County

A mass of Longquan porcelain shards carved with ‘Guan’ or the dragon patterns were unearthed in the early Ming Dynasty layer of the Fengdongyan kiln site at Dayao County. These celadon shards were fired in the Hongwu and Yongle eras of the Ming Dynasty. In order to research the raw materials and firing technology of the imperial porcelain, 85 typical shards were analysed by energy‐dispersive X‐ray fluorescence (EDXRF). The results indicate that the contents of TiO₂ and Fe₂O₃ in the body vary in the Hongwu and Yongle eras. Compared with Longquan glazes in the Southern Song Dynasty, the average values of K₂O, Fe₂O₃ and TiO₂ are higher, but that of CaO is lower in early Ming imperial porcelain glazes. Principal components analysis (PCA) shows that different degrees of elutriation of the same raw materials are the main reason for this difference in the Hongwu and Yongle periods. However, the raw materials of imperial porcelain glazes show no obvious changes and have inherited the earlier tradition. The production and firing technology of imperial porcelain reached a higher level and had not declined in the Early Ming Dynasty.     

Chemical analysis of white porcelains from the Ding Kiln site, Hebei Province, China

The Ding kilns were some of the most famous early kilns of medieval China, producing huge quantities of white and cream-white porcelains of outstanding technical and aesthetic quality. Since 1949 they have been excavated three times, in 1965, in 1987, and in 2009 respectively. In this latest study 69 white porcelain sherds from assured contexts and from the 2009 excavations were analyzed using laser ablation techniques (ICP-AES). The samples date from Five Dynasties, Northern Song and Jin Dynasties respectively (early 10^th to early 13^th C CE). The results show that Ding wares of different times show different characteristics that can be demonstrated through chemical composition. During the early phase of production the Ding ware bodies consisted largely of high firing kaolinitic clays with predominantly calcareous materials as fluxes. After the early Northern Song Dynasty, some calcareous material was replaced by a more potassic material. The compositions of the glazes show a parallel evolution to the bodies. However, because the glazes are very low in titania it seems unlikely that the main clay ingredients of the bodies could have been used in the glaze recipes. For much of the kiln site’s history the glazes appear to have been made mainly from the same siliceous flux-rich materials that had been blended with the main body-clays used to make the Ding ware porcelains, plus some extra calcareous material. The P₂O₅ contents of the glazes suggest that wood ash may have been one source of CaO in the glaze recipes.     

AN INVESTIGATION INTO THE RELATIONSHIP BETWEEN THE RAW MATERIALS USED IN THE PRODUCTION OF CHINESE PORCELAIN AND STONEWARE BODIES AND THE RESULTING MICROSTRUCTURES*

The microstructures of porcelain and stoneware bodies from north and south China, spanning the period from the Tang to the Ming dynasty (7th–17th centuries ad ), were examined in polished sections in a scanning electron microscope (SEM) after etching the sections with hydrofluoric acid (HF). Mullite, present as fine, mainly elongated crystals, is the dominant crystalline phase observed. The bulk chemical compositions of the bodies are determined by energy‐dispersive spectrometry in the SEM, and the relative amounts of mullite and quartz present in the different ceramics are estimated from X‐ray diffraction measurements. Mullite formed from areas of kaolinitic clay, mica particles and feldspar particles is distinguished through a combination of the arrangement of the mullite crystals, and the associated SiO₂/Al₂O₃ wt% concentration ratios. It is shown that very different microstructures are observed in ceramic bodies produced using kaolinitic clay from north China (Ding porcelain and Jun stoneware), porcelain stone from south China (qingbai and underglaze blue porcelain and Longquan stoneware), and stoneware clays from south China (Yue and Guan stonewares). Therefore, SEM examination of HF‐etched, polished sections of the bodies of high‐refractory ceramics has considerable potential for investigating the raw materials used in their production.     

The Compositional study of ceramic samples from tombs dating to the Zhou Dynasty at Xiaoshan,Zhejiang Province (China)

Xiaoshan in Zhejiang Province was an important ceramic production area in ancient China. During recent years, local archaeologists have found a number of mound tombs dating to the Zhou Dynasty and the Spring and Autumn period. Many shards of stamped stoneware and proto‐porcelain have been unearthed from these tombs. In this paper, we report how we collected ceramic shards from tombs and samples from local ancient kilns as reference materials in order to clarify their relationship. We have used the energy‐dispersive X‐ray fluorescence technique to analyse the chemical composition of the ceramic samples. The results indicate that some of the tomb artefacts may be imported from other production areas. We infer that the other tomb samples were produced at local kilns, but due to production process–related compositional differences, there are small differences in chemical composition between different categories of samples.     

Compositional and Microstructural Study of KoryŎ Celadon and Whiteware Excavated from SŎRi Kiln in Kyŏnggi Province

An extensive study of the composition and microstructure of celadon and whiteware sherds excavated at Sori, one of the most important sites that were active during the founding stage of the stoneware and porcelain industry in Korea, was carried out. The analysed sherds were organized according to four different levels of the excavation and four different styles of haemurigup foot rim. Principal component analysis of the chemical compositions of the sherds revealed slight differences in their body and glaze compositions between the levels of excavation. Porcelain stone with high silica and low aluminium contents was generally used as the body material and wood ash as the chief flux in the glaze. Over the period of operation, the aluminium content in the bodies of the ceramics decreased and the P₂O₅ content in the glazes increased. Glazed bodies were fired in a single step, in contrast to the two‐step method used in later ceramic production. Firing conditions were adjusted to produce vitrification of the glazes, which meant that vitrification of the ceramic bodies occurred to varying extents, mostly determined by the relative contents of flux in the body and the glaze.     

The earliest high-fired glazed ceramics in China: the composition of the proto-porcelain from Zhejiang during the Shang and Zhou periods (c. 1700–221 BC)

Bodies and glazes of 54 proto-porcelain sherds and 18 non proto-porcelain samples from Shang and Zhou periods production sites in Deqing, Zhejiang province were analysed by EPMA-WDS. The results indicate that the bodies of all samples were made from local raw material – porcelain stone, with the proto-porcelain samples being made from clay of higher quality. Wood ashes, high in lime and low in potash, were intentionally applied to the proto-porcelain samples, resulting in the formation of lime-rich glazes whose compositions were determined by a temperature-controlled mechanism. In contrast, kiln fragments and furniture show a potash-rich fuel vapour glaze, which formed unintentionally during use of the kiln. The firing temperature for most of the proto-porcelain glazes is around the maturing temperature for typical more recent lime glazes, showing that the potters were already at such an early time able to attain sufficiently high temperature in their kilns.     

上林湖越窑青瓷胎釉化学组成的EDXRF分析

为系统了解历代上林湖地区越窑青瓷胎釉化学组成的特点,本研究采用能量色散X射线荧光光谱技术(EDXRF),对唐代、五代、北宋和南宋上林湖越窑青瓷作了分析。分析结果表明,越窑胎釉组成是低铝高硅的南方青瓷特征,有一定量的杂质,历代瓷釉均为高钙釉;从唐代到南宋,越窑青瓷胎的化学组成未发生明显的变化,但唐代青瓷、北宋透明釉青瓷、南宋乳浊釉青瓷釉的化学组成存在一些差异;南宋越窑部分青瓷的外观虽然发生了变化,但釉料仍延续了越窑独特的工艺配方,与北方青瓷和南方官窑青瓷等的釉料差异明显。分析同时表明:该技术的使用为解决薄釉的样品处理难题提供了一条途径。     

RAW MATERIALS FOR MAKING PORCELAIN AND THE CHARACTERISTICS OF PORCELAIN WARES IN NORTH AND SOUTH CHINA IN ANCIENT TIMES

This is a review of the raw materials used for producing ancient traditional porcelains in the famous kiln areas of north and south China. The relation between the use of porcelain stone and the invention of Chinese porcelain is described. The characteristics of porcelain stone and kaolin and their important role in the development of southern porcelains are discussed. As porcelain stone, which mainly consists of quartz and sericite, occurs widely in south China, the ancient southern porcelains were of a highly siliceous nature. From the beginning of the Yuan through to the Qing Dynasty more and more kaolin was added to the bodies to improve the quality of Jingdezhen porcelain. The glazes in south China were prepared from a mixture of porcelain stone and grass-plus-wood ash or glaze ash, here defined as the ash made by calcining limestone with plant material. The raw materials used in the north for making porcelain bodies were mainly various kinds of clay minerals. Feldspar, quartz and dolomite or calcite were used for northern porcelain glazes.     

A Comparative Study of the Early High‐Fired Ceramic Shards from Dongtiaoxi,Zhejiang (China)

There is a generally accepted view that there is an obvious distinction between proto‐porcelain and stamped stoneware. However, some early shards unearthed from the Dongtiaoxi region (northern Zhejiang) inspire people to rediscuss the relationship between them, because it is difficult to identify them as proto‐porcelain or stamped stoneware. In this work, we have collected samples from three of the earliest kiln sites (Piaoshan, Beijiashan and Nanshan) in the Dongtiaoxi region. We have analysed the chemical composition, firing temperature and phase composition of the samples. Comparing samples from the three kiln sites, we find that, from Piaoshan and Beijiashan to Nanshan, there has been progression in the manufacturing technology. The Shang proto‐porcelain and the stamped stoneware from Nanshan have similar raw materials, firing temperatures and body phase compositions—and they have obviously different decorative appearances, such as glazing or stamping. For ceramics from Piaoshan and Beijiashan, there is no clear distinction between glazed and unglazed samples. We believe that in the Dongtiaoxi region, the difference in the decoration between proto‐porcelain and stoneware became obvious up to the time of the Nanshan production but that, subsequently, two different paths for the development of high‐fired ceramics began to diverge.     

A TECHNOLOGICAL STUDY OF CHINESE PORCELAIN OF THE YUAN DYNASTY

Optical and scanning electron microscopy, electron microprobe analysis and X-ray diffraction are used to determine the composition and microstructure of the bodies and glazes of Chinese porcelain of the Yuan dynasty from Jingdezhen, as well as samples of porcelain-stone and glaze-stone from the same region. The original mineralogical compositions of the porcelain bodies and glazes are estimated. The results indicate that the yingqing porcelain bodies were made using a kaolinised porcelain-stone whereas the underglaze blue porcelain bodies were prepared by the addition of kaolin to a kaolinite-free porcelain-stone. In both cases, the glazes were made by mixing ‘glaze-ash’ (i.e. lime) with the porcelain stone used to make the bodies.     

The Glaze Technology of Hispano‐Moresque Ceramic Tiles: A Comparison Between Portuguese and Spanish Collections

For the first time, Hispano‐Moresque glazed tiles from Portuguese and Spanish collections were studied together and compared. This work is included in a wider study tackling the technology of Hispano‐Moresque tile production from several collections in the Iberian Peninsula. While showing many similarities, differences were identified between collections, regarding both chemical and morphological characteristics. The collection from the Mosteiro de Santa Clara‐a‐Velha (Coimbra) stands out from the other collections, with higher SnO₂ content (up to 14 wt%), the highest Fe₂O₃ contents in amber glazes and a Ca‐rich interface layer (mostly comprised of wollastonite, CaSiO₃). Samples from Palácio Nacional de Sintra (near Lisbon) and Seville‐attributed samples (from the Instituto Valencia de Don Juan) are chemically similar, except that most Sintra's samples display a K‐rich glaze/ceramic interface, whereas the ones from Seville exhibit both K‐rich and Ca‐rich inclusions. The samples attributed to Toledo show glazes with many inclusions, contrasting with the homogeneous glazes in most Hispano‐Moresque tiles. From these results, we identify differences that can be used as markers in future studies on Hispano‐Moresque tiles.     

黄瓦窑琉璃构件胎釉原料及烧制工艺研究

黄瓦窑位于我国辽宁省鞍山市海城地区,经专家考证它是专门为清代辽宁地区烧制皇家建筑琉璃构件的窑厂。本文利用X射线荧光渡谱法、X射线衍射法、热膨胀分析等方法研究了黄瓦窑琉璃的胎釉原料及烧制工艺情况。研究表明：黄瓦窑烧制的建筑琉璃为低温铅釉、二次烧成,胎体属于我国陶瓷史上比较少见的MgO—Al2O3-SiO2三元体系,胎体的热膨胀系数比釉层高2～3×10—6／℃。     

The bronze artifacts from the Yejiashan site and the political presence of the Zhou dynasty in the middle Yangtze Plain: an application of lead isotope analysis

Lead isotope ratios of 15 Chinese bronze artifacts from the Yejiashan site (Suizhou City, Hubei Province) were analyzed and compared with copper ores across China. This study attempts to provide a new perspective to discuss the role that Zeng State played among all the vassal states in the early Zhou dynasty (ca. 1046–977 BC). The political presence of the Zhou dynasty in the middle Yangtze Plain is another main content of this paper. The lead isotopic characteristics of Chinese bronze artifacts between different historical periods are also in the scope of the study. By comparison, the lead isotopic ratios of the tested bronzes and copper deposits in the north Jiangxi Province show numerous overlaps. It indicates that the tested bronzes might have a single ore source, and this source was in the south of the Zhou dynasty. Combined with history and archaeological records, it is highly likely that the middle Yangtze Plain might be a part of the Zhou dynasty since the very beginning. Moreover, Zeng State might have a great influence in the ancient middle Yangtze Plain, and the nobles of Zeng State might even have authority to supervise certain area extending to Jiujiang. As lead isotopes of the bronzes appear to show a clear relation to chronology, the change of lead isotope patterns across times may further serve to distinguish the bronzes of the Western Zhou dynasty from the late Shang ones.     

High‐temperature magmatic fluid exsolved from magma at the Duobuza porphyry copper–gold deposit,Northern Tibet

The Duobuza porphyry copper–gold deposit (proven Cu resources of 2.7 Mt, 0.94% Cu and 13 t gold, 0.21 g t^?1 Au) is located at the northern margin of the Bangong‐Nujiang suture zone separating the Qiangtang and Lhasa Terranes. The major ore‐bearing porphyry consists of granodiorite. The alteration zone extends from silicification and potassic alteration close to the porphyry stock to moderate argillic alteration and propylitization further out. Phyllic alteration is not well developed. Sericite‐quartz veins only occur locally. High‐temperature, high‐salinity fluid inclusions were observed in quartz phenocrysts and various quartz veins. These fluid inclusions are characterized by sylvite dissolution between 180 and 360°C and halite dissolution between 240 and 540°C, followed by homogenization through vapor disappearance between 620 and 960°C. Daughter minerals were identified by SEM as chalcopyrite, halite, sylvite, rutile, K–feldspar, and Fe–Mn‐chloride. They indicate that the fluid is rich in ore‐forming elements and of high oxidation state. The fluid belongs to a complex hydrothermal system containing H₂O – NaCl – KCl ± FeCl₂ ± CaCl₂ ± MnCl₂. With decreasing homogenization temperature, the fluid salinity tends to increase from 34 to 82 wt% NaCl equiv., possibly suggesting a pressure or Cl/H₂O increase in the original magma. No coexisting vapor‐rich fluid inclusions with similar homogenization temperatures were found, so the brines are interpreted to have formed by direct exsolution from magma rather than trough boiling off of a low‐salinity vapor. Estimated minimum pressure of 160 MPa imply approximately 7‐km depth. This indicates that the deposit represents an orthomagmatic end member of the porphyry copper deposit continuum. Two key factors are proposed for the fluid evolution responsible for the large size of the gold‐rich porphyry copper deposit of Duobuza: (i) ore‐forming fluids separated early from the magma, and (ii) the hydrothermal fluid system was of magmatic origin and highly oxidized.     

AN ANALYSIS OF THE GEM‐BLUE GLAZE OF YE WANG'S KOJI POTTERY*

Koji pottery is a glazed ceramic art used widely for figurines. In early Taiwan, it was employed in temple construction for decorative purposes. Ye Wang (1826–87) is the first historically documented Koji artist of Taiwan and also the most prominent Koji pottery artist, noted for his modelling and glazing skills. Unfortunately, his unique technique was lost following his death in 1887. In order to provide vital information for ongoing conservation work on Koji pottery, this study analysed the physical and chemical characteristics of Ye Wang's gem‐blue glaze, to discover the glaze formula. DSC combined with the two‐thirds rule revealed that the firing temperature of Ye Wang's works of art was most probably around 878–923°C. EPMA revealed that the gem‐blue glaze has high alkali levels, and belongs to the PbO–K₂O–B₂O₃–Na₂O–SiO₂ system, deriving its unique colour from copper, iron, manganese and cobalt. This study found high potassium levels in the gem‐blue glaze, which are generally a characteristic of traditional Chinese glazes. In addition, a unique discovery of boron, commonly used in famille rose, was also identified in the glaze. By comparing spectra of historical and reconstructed glazes and adjusting the proportion of chromophoric elements, this study found a glazing formula with colours close to those of Ye Wang's gem‐blue glaze.     

TECHNOLOGY AND COLOUR DEVELOPMENT OF HISPANO-MORESQUE LEAD-GLAZED POTTERY

Lead-glazed pottery from the medieval workshop of Les Olleries Majors (Paterna, Spain) has been studied by Mössbauer spectroscopy, X-ray diffraction, X-ray fluorescence and optical spectroscopy. Yellow, brown and honey-coloured glazes occur on pots glazed on only one surface. They have virtually identical compositions and transmittance spectra, their apparent differences in colour are due to the colours of the underlying pastes. Yellow glazes occur on cream-coloured calcareous bodies, honey-coloured glazes occur on less calcareous bodies with some development of hematite, while brown glazes occur on red siliceous cooking-pots. Green glazes are found on pots glazed on both surfaces; the glazes trapped CO₂ evolved by decomposing carbonates, resulting in an internal reducing environment. This caused the reduction of iron to the ferrous state which coloured the glaze green by diffusion.     

Chemical and strontium isotope analysis of Yaozhou celadon glaze

To produce useful information about the raw materials used in northern Chinese Yaozhou celadon glazes Chinese glazes (especially the source of the calcium‐bearing flux), Sr isotope analysis has been used for the first time. Yaozhou celadon is one of the most important representatives of northern Chinese greenware. The study has enhanced our understanding of the raw material sources used to make Yaozhou glazes dating from the Tang to Northern Song dynasties. It is highly likely that ‘Fuping stone’ mentioned in the historical record is not the main raw material used to make Yaozhou celadon glazes of the Tang to Northern Song dynasties. The results of ⁸⁷Sr/⁸⁶Sr analysis of the Yaozhou celadon glazes studied produce relatively consistent ⁸⁷Sr/⁸⁶Sr isotopic signatures, with a wide variation of relatively high Sr concentrations. This is firm evidence that a calcium‐bearing plant ash was the source of the calcium and of the flux in the Celedon glazes studied, and not, as some have suggested, limestone or ‘Liaojiang stone’. The study had illustrated that the present approach has great potential in providing a new way of reconstructing porcelain glaze technology.     

临水窑与介休窑白底彩绘工艺的对比研究

白底黑花装饰风格的瓷器,始终是陶瓷、科技界和陶瓷爱好者关注的热点。临水窑(磁州窑)与介休窑白底黑花风格的瓷器之间有着密切的联系,但是对于两窑产品的科技分析甚少,至于两者的对比研究更是无从谈起。因此,本工作利用岩相分析、SEM-EDS等方法分析了临水窑(磁州窑)、介休窑样品的瓷胎、化妆土及瓷釉的化学成分和显微结构。比较分析显示,两窑样品的瓷胎均为低硅高铝配方,且介休窑瓷胎中的Al2O3含量更高;两窑瓷胎粗糙,Fe2O3、TiO2含量较高,致使其呈浅黄色。瓷胎表面均施有化妆土,所不同的是,介休窑的瓷胎表面施有两层化妆土,其靠近釉的一层化妆土(h2),Fe2O3、TiO2含量极低,靠近胎的一层化妆土(h1),Fe2O3、TiO2含量较高;临水窑样品的瓷胎表面仅施一层化妆土,其Fe2O3、TiO2含量较低,但高于介休窑近釉层化妆土中的相应含量。介休窑瓷釉为典型的高钙釉,而临水窑则为典型的碱钙釉和钙碱釉。不难认识到,介休窑似在临水窑白底黑花及化妆土工艺的基础上,因地制宜,勇于创新,形成了成本低廉、技术先进的两层化妆土工艺,在当地原料较为粗糙的条件下,生产出质量较好的白底釉下彩绘瓷器。     

A STUDY ON LATE MEDIEVAL TRANSPARENT‐GLAZED POTTERY AND ARCHAIC MAJOLICA FROM ORVIETO (CENTRAL ITALY)*

Nineteen samples of medieval transparent‐glazed pottery and archaic majolica from Orvieto (central Italy) were studied. They were classified by archaeological criterion as follows: five transparent‐glazed fragments with green and brown decorations (first half of the 13th century), eight green transparent‐glazed fragments (13th century) and six tin‐glazed fragments with green and brown decorations (second half of the 13th century). SEM–EDX, XRD (the Rietveld method) and XRF were used to characterize the chemical and mineralogical compositions both of the bodies and the coatings. In all of the samples, the paste is Ca‐rich with CaO contents as high as 13–20 wt%. The mineralogical composition is compatible with a firing temperature of about 950°C, which is the typical temperature reached in a wood kiln. No difference was observed between the bodies of transparent‐ and tin‐glazed pottery. In the case of transparent glazes, the burial conditions lead to heavy weathering of the samples. However, on the basis of the analyses carried out in non‐weathered areas, the typical composition is PbO 55–65 wt%, SiO₂31–35 wt%. In tin glazes, the tin is scattered on the mass of the glaze as SnO₂crystals with a concentration of 7–14 wt%. Concerning the decorations, it is established that the green colour is due to the presence of copper, while manganese is responsible for the brown colour. These pigments, which represent the typical colours of ‘archaic majolica’, are spread through the glaze homogeneously, apart from one case in which there is clear evidence of manganese oxide crystals.