余杭石马(土斗)东晋窑址发掘简报

德清窑是分布于浙江东苕溪中上游流域、自东汉至唐代、兼烧青釉器和黑釉器的瓷窑群的总称。位于杭州市余杭区良渚镇的石马(土斗)窑址属德清窑系列,产品包括青釉与黑釉两种,其中以青釉占大多数,黑釉比例较低。本文为自20世纪50年代德清窑概念提出以来的首篇考古发掘报告。     

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.     

清代红釉(彩)瓷的呈色元素分析

清代是我国古陶瓷生产最辉煌的时期,烧造的瓷器品种繁多,各类颜色釉的制作水平达到了历史高峰。清代的红釉(彩)名称更是多达几十种,如“矾红”、“抹红”、“珊瑚红”、“红彩”、“钧红”、“均红”、“鲜红”、“郎窑红”、“牛血红”、“霁红”、“宝石红”、“豇豆红”、“釉里红”、“胭脂红”、“胭脂水”、“粉红”等。为弄清各种称谓红釉(彩)的主要呈色元素及其影响作用,本工作采用无损的X射线能谱分析(EDXRF)技术对清代瓷器的红釉(彩)进行系统测试,获得了各种红釉(彩)呈色元素定性及半定量数据。分析结果表明,清代红釉彩可以依据呈色元素划分为四类,即低温铁红彩(Fe)、高温铜红釉(Cu)、低温金红彩(Au)和朱砂红彩(HgS),并且各元素含量的改变会影响红釉(彩)呈色。     

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.     

明清期间景德镇祭红釉的化学组成对比研究及其科技意义

为了进一步讨论明清两代祭红釉的发展沿革,用探针型能量色散X荧光光谱技术测定了10片明永乐祭红釉和胎的化学组成,并结合已发表的相关数据,进行了对明清期间祭红釉和胎的对比研究。结果表明,明代（永乐-宣德—万历）的祭红釉相比于清代（康熙—雍正-乾隆）的R2O＋RO（wt％）平均值约低20％,RO／R2O（mol/mol）平均值约低45％,RO2／R2O2,（mol/mol）平均值约高34％。明代永乐和宣德的祭红釉胎式分布RO：（m01）值均大于5．8,而清代样品均小于5．4。明清两代祭红釉化学组成的突然变化（shift）,可能暗示明代的制釉工艺在清代已经失传,而在清代则白行发展起来。     

Vietnamese (15th Century) Blue‐And‐White,Tam Thai and Lustre Porcelains/Stonewares: Glaze Composition and Decoration Techniques*

EDS, X‐ray fluorescence, Raman spectroscopy, thermal expansion–shrinkage measurement and scanning electron microscopy were applied to determine the elemental components, structural phases and glazing temperatures of the transparent glazes, blue underglaze and overglaze tam thai (including gold‐like lustre) decorations from the 15th‐century Vietnamese porcelains/stonewares found at the Chu Ðâu–My Xa kiln site and in the Cù Lao Chàm (Hôi An) cargo. The ancient technology for colouring the glazes is discussed. The various blue tones in the underglazed décor result from cobalt‐containing manganese ore, with the intentional addition of iron oxide. The overglaze copper‐green and the gold‐like lustre were obtained by dispersing copper in lead‐based glass. The red colour was made using hematite dispersed in lead‐rich flux.     

The production and technology of glazed ceramics from the middle ages,found in the saepinum territory (Italy): a multimethodic approach*

A collection of ceramics from the Middle Ages found in Altilia and Terravecchia (the Saepinum area, Campobasso, Italy) were characterized by using different mineralogical analyses to investigate their provenance and production techniques. The body ceramic was investigated using Rietveld phase analysis of X‐ray powder diffraction patterns, X‐ray fluorescence spectrometry and scanning electron microscopy. The chemical compositions of the coatings were measured by scanning electron microscopy and their mineralogical compositions were determined using a particular technique of X‐ray small‐angle scattering (SAS) optimized for studies of thin films. Moreover, the material used for decoration was studied using micro‐Raman spectroscopy. The archaeometric results confirmed the distinction into two different ceramic classes, already individuated from archaeological analysis: the Altilia objects belong to the protomajolica class, whereas the objects from Terravecchia are RMR (ramina‐manganese‐red) ceramics. A comparison between the chemical and mineralogical compositions of good‐quality ceramic objects and those of waste products indicated local production of the ceramics. A sharp distinction was found in the chemical composition of the coatings: the Altilia products have tin‐opacified lead glazes, while the Terravecchia ones have transparent high‐lead glazes. Among the Altilia products, the unsuccessful process that produced a large quantity of discarded materials was attributed to the high lead content of the glazes. In fact, the principal advantage of the high lead content was to make the preparation and application of the glaze suspension easier, but the risk of reduction of lead oxide to metallic lead was greatly increased. Using micro‐Raman spectroscopy, the following minerals were identified as pigments: pyrolusite for the dark colour, malachite for green, lepidocrocite for yellow and hematite for red.     

福建六朝墓葬出土青瓷研究

通过造型、纹饰、胎釉、工艺等的分析与比较,证明福建两晋青瓷与浙湘赣粤所出共性较多,而南朝青瓷则有明显的地域差异,其文化成因应与历史沿革、地理环境、经济发展、宗教信仰和文化传统有关联。     

元代青花釉里红楼阁式谷仓赏析

青花釉里红楼阁式谷仓,是一件极为珍贵的元代瓷器。1979年它入藏江西省博物馆以来,专家和学者对其独特的造型,复杂的工艺,丰富的内涵、珍贵的价值给予了高度的肯定,名列2002年国家文物局发布的《首批禁止出国（境）展览文物目录》64件（组）国家一级文物之中,禁止出国出境展览。三十年来,许多专家和学者对其进行了多方面的研究,其中的文物价值和文化内涵仍有进一步深入研究的空间。     

The Chemical Composition and Production Area of Early Western Zhou Proto‐Porcelain Unearthed from Yejiashan Cemetery,Suizhou, China

The bodies and glazes of 27 early Western Zhou proto‐porcelain samples from Yejiashan cemetery, Hubei Province, were analysed using LA‐ICP–AES, SEM, XRD, a thermal expansion instrument and other analytical methods. The results indicated that the bodies of all samples were characterized by high silicon and low aluminium, and were made with porcelain stone raw materials found in the south of China. The glazes are typical of high‐temperature calcium glazes of the CaO (MgO) – K₂O (Na₂O) – Al₂O₃ – SiO₂ series, with relatively high Mn and P content, which was probably caused by the addition of plant ashes. The physical properties and phase compositions of Yejiashan proto‐porcelain show that firing processes were still in the early stages of development in ancient China. Multivariate statistical analyses indicated that Yejiashan proto‐porcelain might have come from the Deqing area, in Zhejiang Province. These results provide new archaeological evidence for research on issues related to material flow in the Western Zhou dynasty.     

历代耀州窑釉料渊源关系的初步分析

耀州窑是我国古代名瓷窑。为了探讨历代耀州窑釉料之间的渊源关系,用中子活化分析(NAA)技术测定古耀州瓷釉样品和耀州窑博物馆附近粘土矿样品中29种元素的含量,将这批NAA数据进行模糊聚类分析,得到动态模糊聚类分析图。结果表明：唐代的黑瓷釉原料产地非常集中,矿料成分单纯。宋代青瓷釉料配方比较稳定,五代青瓷具有承前启后的作用。金代月白釉料成分和宋代青瓷釉料接近。唐三彩蓝釉料与其他耀州瓷釉料来源明显不同。     

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。     

Chemical Composition and Manufacturing Technology of a Collection of Various Types of Islamic Glazes Excavated from Jordan

A collection of Islamic glazed pottery shards that were excavated from the archaeological site of Dohaleh/Northern Jordan were chemically analysed. The glazes belong to three different decorative styles. The chemical analysis of the glazes was carried out using energy dispersive x-ray fluorescence. The chemical analysis results enable the classification of the glazes into the three distinct compositional groups with reference to their principal modifier, these are: the alkaline glazes, the high lead glazes and the lead–alkali glazes. In some cases the body fabric was analysed by a combination of petrographic and chemical analysis techniques. The study show that inherited traditional techniques were combined with innovative Islamic techniques were used for the production of the glazes.     

DISCOVERY,PRODUCTION AND USE OF TIN‐BASED OPACIFIERS IN GLASSES,ENAMELS AND GLAZES FROM THE LATE IRON AGE ONWARDS: A REASSESSMENT*

Tin‐based opacifiers (lead stannate yellow and tin oxide white) were first used in glass production for a short period in Europe from the second to the first centuries bc , and then again throughout the Roman and Byzantine Empires from the fourth century ad onwards. Tin oxide was also used in the production of Islamic opaque glazes from the ninth century ad , and subsequently in enamels applied to Islamic and Venetian glasses from the 12th century ad onwards. A selection of published analytical data for the tin‐opacified glasses, enamels and glazes is summarized, and the methods used in their production are reassessed. The phase transformations occurring when mixtures of lead oxide, tin oxide and silica are fired are investigated with high temperature X‐ray diffraction (XRD) using a synchrotron radiation source, and these results are used to explain the observed differences in the glass, enamel and glaze compositions. Possible reasons for the use of tin‐based opacifiers in the second to first centuries bc , and for the switch from antimony‐ to tin‐based opacifiers in the fourth century ad are suggested, and the possible contexts in which tin‐based opacifiers might have been discovered are considered. The introduction of tin‐opacified glazes by Islamic potters in the ninth century ad is discussed in terms of technological transfer or independent invention.     

A Technological Study of the Elamite Polychrome Glazed Bricks at Susa,South‐Western Iran

This study investigated the technological features of the Neo‐Elamite glazed bricks discovered at the Acropolis of Susa, south‐western Iran, by conducting micro‐Raman spectroscopy, differential thermal analysis/thermogravimetry (DTA/TG), X‐ray diffraction (XRD) and scanning electron microscopy–energy‐dispersive X‐ray spectroscopy (SEM–EDS). The results showed that calcium antimonate white and lead antimonate yellow were used as opacifiers in the white, yellow and green glazes, and that green and turquoise glazes were achieved using copper. Coloured glazes were separated by a Si‐rich brown glaze to prevent them from running together during firing. The glazed bricks most probably were not fired at temperatures higher than 900°C.     

Chemical durability of lead-bearing glazes in sulphuric acid solutions — Laboratory experiments performed on Zsolnay architectural ceramics from Budapest (Hungary)

This study aims to simulate the long-term deterioration of architectural glazes exposed to open air in a highly polluted urban environment. A laboratory experiment—a 14-day long accelerated weathering test—on glazed roof tiles has been performed to reveal the damaging influence of contacting acid solutions originating from dissolved gaseous pollutants, mainly SO₂. The studied tiles are made by the Hungarian Zsolnay factory and applied on two buildings in Budapest in the 19th and 20th century. The ceramics were covered mainly by lead glazes in the construction and lead-bearing alkali glazes in the renovation periods.

The solution of pH2 induced a greater dissolution, especially of alkali and alkaline earth metals (up to 2886 ppm), but less lead (up to 21 ppm) from the lead glazes of the construction periods. Newly formed lead sulphate (anglesite) on the corroded glaze parts precipitated on some lead-bearing alkali glazes, with moderate dissolution of alkali and alkaline earth metals (up to 396 ppm) accompanied by higher amount of lead (28–39 ppm). Based on the results, the main determining factor in the durability of glazes is mostly their chemical composition and less their preliminary degradation state.     

A TECHNOLOGICAL EXAMINATION OF NINTH–TENTH CENTURY AD ABBASID BLUE‐AND‐WHITE WARE FROM IRAQ,AND ITS COMPARISON WITH EIGHTH CENTURY AD CHINESE BLUE‐AND‐WHITE SANCAI WARE*

Eight sherds of ninth–tenth century ad Abbaesid blue‐and‐white glazed earthenware, excavated in 1931 at Hira in western Iraq, were analysed using, variously, quantitative wavelength‐dispersive spectrometry (WDS) and energy‐dispersive spectrometry (EDS) in association with scanning electron microscopes (SEM), and semi‐quantitative X‐ray fluorescence spectrometry (XRF). In order to compare the compositions of the cobalt pigments used, the glazes of seven complete vessels of eighth century ad Chinese Tang blue‐and‐white sancai were also analysed semi‐quantitatively using XRF. The Abbasid wares were shown to have used traditional Mesopotamian alkali–lime glazes applied to calcareous clay bodies. Half the glazes examined were opacified with tin oxide. Three types of blue decoration (i.e., raised; spreading; and flat, non‐spreading) were produced using a variety of formulations, including a mixture of cobalt pigment with lead oxide. The sources of the ores used for the cobalt pigments have not been identified. However, the analytical data showed that the cobalt ore used for the Abbasid blue‐and‐white ware could be distinguished from that used for the Tang blue‐and‐white sancai by its higher iron content and by the presence of a significant amount of zinc. The use of cobalt‐blue decoration on the ninth–tenth century ad Abbasid ware was anticipated in China by eighth century ad Tang blue‐and‐white sancai wares. However, whether its introduction by the Abbasid potters should be seen as an independent invention that followed the introduction of tin‐opacified glazes in Iraq, or whether it was influenced in some way by Chinese originals, is still unresolved.     

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.     

云南昆明石寨山出土汉代青铜器的初步分析

云南昆明的石寨山墓葬是汉代滇池区域的土著文化,为了了解该地汉代铜器的制作工艺水平,本研究通过金相显微镜观察、扫描电镜及能谱分析的现代分析手段来对M3、M5、M6、M7、M10、M12这6个墓葬群的31件青铜器展开探讨。结果显示在31件铜器样品中,有30件为铜锡合金,1件为红铜,所有器物均为铸造,其中有1件铜戈的刃部经历过热锻加工。这一分析结果丰富了石寨山文化的铜器研究,为器物的保护修复提供科学依据,同时也为云南汉代时期的铜器考古学以及金属技术史补充部分资料。     

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.