Porcelain Stone Research Articles

The earliest stamped hard pottery and high-firing technology dating back to 5000 BP: Evidence from two sites in southeastern China

This study focuses on the technological origin of stamped hard pottery, one of the precursors to Chinese porcelain, developed in the Late Neolithic period of China. 160 ceramic sherds of stamped hard wares from the Nanshan site (5300–4300 cal. BP) and Yanzaidong site (5000–4300 cal. BP) were investigated through water absorption, Vickers hardness, petrography, ED-XRF, thermodilatometry, XRD, and SEM-EDS. The results indicate that two categories of samples exhibit commendable physical properties, comparable to stoneware, attributed to specific high-alumina clay with low fluxing elements (porcelain stone), fired at high temperatures ranging from 1100 to 1250 °C. The other categories of samples appear to be defective products during firing process, or have another raw material source, contributing to a diversity of pottery at the two sites. Nanshan and Yanzaidong unequivocally emerge as the earliest known production of stamped hard pottery, dating back to 5000 cal. BP, marking a revolutionary advancement in high-firing technology during the Late Neolithic China.

Study of the manufacture of high‐fired ceramics from Fujian (China) during the Shang and Zhou dynasties

AbstractIn recent years, some kiln sites from Shang and Zhou dynasties have been excavated in Fujian province in southeastern China, and substantial high‐quality ceramic shards were unearthed. The research conducted by archaeologists indicates that these shards are likely the earliest high‐fired ceramic products in this area, characterised by unique appearance features and are therefore valuable for exploring the development and manufacture of early high‐fired ceramics in Fujian. In this study, we gathered some proto‐celadon and stamped stoneware shards from three kiln sites dating back to the Shang and Western Zhou dynasties. We analysed the chemical composition of the ceramic body and glaze, firing temperature, and mineral phase to investigate the selection of raw materials, firing, and glazing technology of these early ceramic products. The results indicate that the bodies of these high‐fired ceramic shards were made of locally weathered porcelain stone, and the glazes are lime glaze. During the Western Zhou dynasty, the potter utilised different raw materials for proto‐celadon and stamped stoneware, which was not the case during the Shang Dynasty. The firing temperatures of the majority of shards exceeded 1,000°C, and the bodies had been completed phase transformation.

Koryŏ inlay celadon from Taicang Port of the Yuan Dynasty, China

Inlay celadon was a type of high-end ceramics of the Koryŏ dynasty (918–1392 AD) produced in the Korean Peninsula. It was conveyed to China during the Yuan dynasty (1279–1368 AD) as tribute or trade goods. In this study, the authors analyzed six samples of inlay celadon recently discovered at the prosperous Taicang Port of the Yuan and Ming dynasties in the lower Yangtze River, China. With scanning electron microscopy coupled with energy dispersive spectroscopy (SEM–EDS) and X-ray diffraction (XRD), the authors investigated the production technique, and compositional characteristics of these samples for the purpose of tracking their provenances. While the bodies are made of porcelain stone, the glazes are of porcelain stone and calcium-rich flux. The white inlay material in these samples is kaolinite-dominant, and the black one is made of quartz with high Fe content or a compound of quartz and raw materials with high Fe content. The results link the samples uncovered at the Taicang Port to the Samhǔngni Kiln in Kangjin-gun and the Uch'ǒlli and Chinsǒri Kilns in Buan-gun in Southern Korea. The products from these kilns were shipped to China in several shipments.

Study on the ceramic wares from the Leizhou kiln of the Tang and Song dynasties

The Leizhou kiln in Guangdong Province was ever famous for porcelain manufacturing. High-quality porcelain products were produced for export, a core business of the Maritime trade. However, there has been little research on the Leizhou kiln in the past, particularly, regarding the manufacturing technology for porcelain in local areas. In this work, by using portable X-ray fluorescence (p-XRF), optical microscopy (OM), scanning electron microscopy (SEM) and dilatometry (DIL), the samples from the Leizhou kiln dating back to the Tang and Song dynasties were systematically analyzed. The major emphasis was placed on analysis of the technological characteristics employed in the manufacturing process from the aspects of the raw materials, microstructure and firing temperature, etc. As indicated by the research findings, during the Tang Dynasty, the main raw materials used for the body were locally sourced porcelain stone alone, while the porcelain stone mixed with sort a kaolinite could have been added to the body during the Song Dynasty. The body of the samples from the Tang Dynasty contained low levels of Fe2O3. The body of the samples from the Song Dynasty were more compact, so the raw materials used for the body were more refine and had been carefully processed. The samples from these two periods all belonged to transparent glaze and calcium glaze. Moreover, the polychrome ceramics from the Song Dynasty were typically of high-temperature over-glazed craftsmanship, and the brown color was caused by iron ions. The “dragon kiln” and sagger were used both in the Tang and Song dynasties. The firing temperature of the sample was approsximately 1080 °C during the Tang Dynasty and 1150 °C during the Song Dynasty.

НЕТРАДИЦИОННОЕ ПРИРОДНОЕ СЫРЬЁ ДЛЯ ПРОИЗВОДСТВА ФАРФОРА

The accumulated knowledge about the structure of a substance makes it possible to control its properties, including the purposeful selection of raw materials and materials for its creation, and vice versa, based on the natural or artificial material composition, predict its physical and chemical properties. This approach allows choosing a replacement for rare or even scarce types of mineral raw materials to produce a particular product. The analysis of literature data and sources, a comparative analysis of the Middle Amur Lowland loess-like rocks chemical composition, and one of the white porcelain recipes for the manufacture of laboratory glassware showed a high degree of their similarity. In this connection, it is proposed to consider loess-like loams as one of the porcelain stone types. At the same time, there are some differences – an increased content of coloring oxides in loess-like loam: TiO2 twice and Fe2O3 more than 10 times; reduced content of SiO2 and Al2O3 by 6–7%; the content of CaO and MgO is twice as high as in porcelain; Na2O is 1,7 less, and K2O is 3.4 more than in porcelain. Evaluating loess-like loams as a kind of porcelain stone, we can conclude that the rocks are alkaline according to the total content of alkalis (Na2O + K2O) - more than 3%. Potassium module (K2O/Na2O) is 1,54 – i.e. the rocks are suitable for the manufacture of porcelain. Thus, loess-like rocks are potentially applicable to use them as a corrective raw material in the production of ceramic masses, including coarse building ceramics, colored porcelain and porcelain-like products, with appropriate adjustment of chemical and granulometric compositions. At the same time, in order to clarify the proposed loess-like rocks options feasibility, it is necessary to conduct additional manufacture and technological tests.

The early porcelain kilns of Arita: Identification of raw materials and their use from the 17th to the 19th century

Porcelain stone used at the early kilns of Arita, Japan, has never been identified due to the lack of written records. Ryumon and Shirakawa deposits are considered to have possibly been exploited before Izumiyama was discovered in the early 1630s, but there are no records or any previous scientific research aimed at resolving such crucial issue. This work presents the first systematic scientific study of clays from the three deposits and shards excavated at early kiln sites. Portable ED-XRF and SEM-EDS were used to identify the chemical compositions of bodies, glazes, and geochemical characteristics of clays. XRD, TG-DSC, and FTIR-ATR spectroscopy were also used for the mineralogical characterization of clay bodies. Results show that the earliest production was marked by the mineralogical characteristics of the available raw materials. A gradual improvement in material selection and processing will lead to the development of the nigoshide (milky-white) body in the mid-17th century.

An AAS study of Chinese imperial yellow porcelain bodies and their place in the history of Jingdezhen's porcelain development

The bodies of 12 examples of imperial yellow Chinese porcelain dating from the early sixteenth century to the early twentieth century have been studied by atomic absorption spectroscopy. The yellow lead glaze was reserved for imperial use, and these fine monochrome porcelains played important roles in imperial rites at the summer solstice and as court wares within Beijing's Forbidden City. The project's aim has been to understand more fully the technologies used to make imperial yellow porcelains, which were significant ceramics in the history and culture of imperial China.This paper concerns the porcelain body material, particularly the nature and use of Jingdezhen's two prime body materials — porcelain stone (cishi) and kaolin (gaoling). The 12 samples studied span four centuries of imperial porcelain production and include a major change in kaolin usage at Jingdezhen in the early seventeenth century, when the proportions of kaolin used in fine porcelain bodies rose abruptly from some 20% to 50%. This study explores the natures of both prepared rocks and looks particularly at kaolin, about which some long-standing problems remain.

Colour and composition characteristics of beige-glazed porcelain from Jingdezhen Imperial Kiln, early and middle Qing Dynasty (18th century)

The Jingdezhen Imperial Kiln made unprecedented achievements in the firing of colour glazed porcelain during the Qing Dynasty (1636–1912). Among these, beige-glazed porcelain became an imperial porcelain variety reserved for the exclusive use of the imperial household. To reveal details of the manufacturing process, Energy Dispersive X-ray Fluorescence (EDXRF) and spectrophotometry, combined with the records of ancient Chinese documents were used to analyse samples of beige-glazed porcelain fired at the Jingdezhen Imperial Kiln in the early and middle Qing Dynasty (18th century) and unearthed from the Nandaku area of the Forbidden City. The results show that the colour of beige glaze in the Qing Dynasty was similar to that in the Song Dynasty (960–1279), which is consistent with ancient literature records reflecting the former's imitation of ‘Beige Song Glaze’. The beige-glazed porcelain body is made of a binary formula of porcelain stone and kaolin clay, in a ratio between 5:5 and 4:6. Based on the glaze layer formula of purple-gold imperial porcelain, the beige glaze layer was fired by innovatively adjusting the ratio of glaze stone, glaze ash and purple-gold clay. The imitation of ‘beige Song glaze’ and the innovation of purple-gold glaze reflected the exacting production and high technology of the Jingdezhen Imperial Kiln in the Qing Dynasty.

Isotopic investigations of Chinese ceramics

This chapter provides insights into Chinese ceramic technologies of both bodies and glazes as well as provenance by using isotopes applied to a number of case studies. The use of Sr isotopes to investigate Chinese high-fired Celadon wares and blue-and-white Jingdezhen porcelain (Jiangxi province) has revealed a clear distinction associated with the fluxes used in the glazes: plant ash in celadons and limestone in Jingdezhen glazes, something that is not clear from major element analysis. Furthermore, the technique is able to suggest by implication the nature of the silica source used in the glazes—normally weathered granitic rocks or metamorphic rocks (porcelain stone) which also contains Sr. This leads to an isotopic mixing line of the 2 Sr-rich components and is proof that 2 Sr-rich components were mixed in the manufacture of limestone glaze. This is not the case for plant ash glazes. Eventually, the technique may be used in provenance studies. Like Sr isotope analysis, lead isotope analysis relies on there being a lack of or a minimal change in the isotope ratios when the raw materials are heated. Lead isotope analysis links the use of lead in glazes to the original metal ore and if a kiln uses a distinctive lead source in its glazes, it can provide a provenance for the pottery. This has been very successful in distinguishing Chinese Tang sancai wares made in the Huangye, Huangbao, Liquanfang and Qionglai kilns.

Solvent Extraction of Copper and Zinc from Sulfate Leach Solution Derived from a Porcelain Stone Tailings Sample with Chemorex CP-150 and D2EHPA

This research investigates the extraction behavior of copper and zinc from the sulfate leachate of a porcelain stone tailings sample with Chemorex CP-150 and D2EHPA in detail. The findings demonstrated that Chemorex had greater ability and selectivity in the extraction of copper, while D2EHPA was better in the extraction of zinc. 97.88% copper and 78.2% zinc were extracted, respectively, with Chemorex and D2EHPA within 10 min contact time at an 1:1 aqueous/organic ratio, 10% (v/v) extractant concentration, and ambient temperature. The appropriate solution pH levels for Chemorex and D2EHPA were found to be 2.5 and 2, respectively. Also, a McCabe–Thiele diagram was drawn and one single-step extraction for copper and a two-stage process for zinc were needed to achieve the highest extraction efficiency. Additionally, the mechanism study indicated the association of ~ 1.5 and 1 mol of Chemorex CP-150 and D2EHPA for the extraction of one mole of Cu and Zn from the leach solution. Moreover, thermodynamic parameters, including ΔH, ΔG and ΔS were found to be 65.29 kJ/mol, 9.83 kJ/mol, and 186.14 J/mol K for copper and − 18.71 kJ/mol, 17.80 kJ/mol, and − 122.53 J/mol K for zinc, respectively, indicating that the extraction process was endothermic for copper and exothermic for zinc. The effect of contact time, pH, and extractants concentration on the extraction efficiency of Cu and Zn by Chemorex CP-150 and D2EHPA and also the number moles required for extractants

Selective Extraction of Li, Rb, and Cs and Precipitation of Lithium Carbonate Directly from Lithium Porcelain Stone

The expected increase in demand for alkali metal raises a concern over the difficulty in extracting Li, Rb, and Cs from hard rock ores. A four-step process is discussed to extract alkali metal from lithium porcelain stone. The process consists of roasting, leaching, evaporation and purification of lixivium, and precipitation of lithium salts. Two types of additives are used to enhance selective conversion into salts. The Li, Rb, Cs extraction efficiencies are determined to be 98.70, 97.27, 98.40%. An Na2SO4/CaCl2/ore mass ratio of 0.2/0.2/1 at 850°C for 60 min is used for the roasting step. Analysis of calcine and leach residue shows the cation ions from the reagents promote highly-chemo selective ion-exchange extraction of the alkali metals in the ores. After this process, the Li+ in lixivium is concentrated from 3.43 to 9.50 g/L by evaporation. A controlled amount of H2O2, NaOH, and Li3PO4 is added to the lixivium to remove the impurities. Precipitation of 94.09% of the Li in the purified solution by Na2CO3 is achieved. Further precipitation using Na3PO4 · 12H2O is done, leaving a solution from which Rb, Cs could be recovered. This proves the process is possible and practical.

Leaching of copper and zinc from the tailings sample obtained from a porcelain stone mine: feasibility, modeling, and optimization.

This research was aimed to investigate the leaching behavior of zinc and copper from a porcelain stone tailings sample using RSM-CCD modeling. The synergetic and individual effects of five main factors including liquid/solid ratio, sulfuric acid concentration, agitation speed, leaching time, and temperature were examined on the recoveries of zinc and copper. For this purpose, two 2F1 models with R2 values of 0.9341 and 0.8693 were developed for the relationship between the leaching efficiencies of copper and zinc and effective terms, respectively. The results indicated that the leaching process was significantly influenced by the interactive effects between factors. The leaching recoveries increased by increasing all factors in the range studied. However, the recoveries were nearly independent of the agitation rate, indicating surface chemical reaction as the leaching kinetics controlling step. It was also found that the linear effect of temperature, the interaction effect of leaching time with liquid/solid ratio, and the interactive effect between sulfuric acid concentration and agitation rate had the greatest impact on the leaching rate of copper. Additionally, the linear effect of temperature and the interactive effect of temperature with agitation speed and liquid/solid ratio were distinguished to be the most effective factors on the recoveries of zinc. Moreover, the optimization was performed using desirability function approach, and the highest recoveries of copper (73.95%) and zinc (81.02%) were obtained at an acid concentration of 10%, 300rpm agitation rate, 10mL/g liquid/solid ratio, 35°C temperature, and 75min leaching time.

Extraction of lithium, rubidium and cesium from lithium porcelain stone

The anticipated increase in demand for Li, Rb, and Cs raises growing concern due to the expected shortage in alkali metals available for extraction from ores. In this study, two kinds of additives (Na2SO4 and CaCl2) were used to selectively extract alkali metals from lithium porcelain stone. HSC modelling was used to simulate the process of roasting the ore in the presence of these additives, and to predict the temperature effect in addition to the ore/Na2SO4/CaCl2 mass ratio. Under the optimized conditions, the Li, Na, K, Rb, and Cs extraction efficiencies were 98.70, 49.80, 37.90, 97.27, and 98.40%, respectively. The optimal roasting conditions were found to be an ore/Na2SO4/CaCl2 mass ratio of 1/0.2/0.2 with heating at 850 °C for 60 min, while the optimal water leaching conditions were a liquid/solid ratio of 1/1 and a stirring speed of 300 rpm at room temperature for 60 min. Upon analysis of the calcined and leaching residues, the extraction mechanism was demonstrated to involve a highly chemoselective ion-exchange process between the alkali metals present in the ore, the Na+ in Na2SO4, and the Ca2+ in CaCl2. After this process, the concentrations of the alkali metals in lixivium were approximately 3.43 g/L Li, 25.50 g/L Na, 11.00 g/L K, 1.35 g/L Rb, and 0.56 g/L Cs, thereby indicating the feasibility of this process.

Comparative study on old white porcelains produced in Gwangju (Korea) and Arita (Japan) in the 15th to 19th centuries

The production technology of white porcelains was introduced in Arita, Japan, from the Korean Peninsula in the beginning of the 17th century. The production of clay for Arita white porcelain from porcelain stone was strongly influenced by the production technology for old Korean white porcelain. To compare the chemical and mineral properties of old Korean and Arita white porcelains and the raw clay materials, old white porcelain shards excavated from some kilns at Gwangju-si (Korea) and Arita were evaluated by X-ray diffraction, X-ray fluorescence analysis, and scanning electron microscopy. From the chemical analysis, it was found that white clay derived from weathered granite was used as raw clay for old Korean porcelain and white clay produced from rhyolite stone was used for old Arita porcelain. Old Korean porcelain had higher content of Al2O3 compared with old Arita porcelain, and it was estimated that kaolin was added to the white clay used in Korean white porcelains. The molar ratio of Fe2O3/MgO against SiO2/Al2O3 in old Korean porcelains was approximately 0.8, and cristobalite was not formed in all old Korean white porcelains studied. The average particle sizes of quartz in old Korean and Arita white porcelains were 8–13 μm.

Unveiling the science behind the tea bowls from the Jizhou kiln. Part I. Chemical compositions and the two-layer glazing technique

The Jizhou kiln, a folk kiln of ancient China, is well-known for the production of black-glazed tea bowls. Polished cross sections showed a white opaque glazed surface covering a black lower layer and a light brown opaque layer existed between them. Analysis by X-ray fluorescence yielded two different calcia-alkali glaze compositions-a black ground glaze and a white cover glaze. Using multi-variable factor-loading analysis, the two-layer glazes were compared to those on white, greenish-white and white-rim black porcelains, in order to understand the variability. In addition, compositions of bodies were compared to the glaze compositions to determine if the same porcelain stone was used along with ash to form the glaze. Based on the physicochemical foundation of the glazes, the opacification of the white cover glazes was due to the phase separation between SiO2 and CaO. It is the combined contribution of melting, bubbling, flowing and diffusion between the cover and ground glazes, as well as the development of phase separation during the firing process, that bring about the “Yao Bian” tea bowls.

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.

シンクロトロン蛍光X線分析法による世界文化遺産三重津海軍所跡（佐賀市）出土磁器の胎土分析 ─第1報，陶石，佐賀城跡出土磁器との比較─

A lot of porcelains were found at the Mietsu Naval Facility Site in Saga, Japan, which was approved as a World Heritage by UNESCO in July, 2015. We determined the X-ray fluorescence intensity ratios of Fe, Rb, Sr, Y and Zr involved in the body clay of the porcelains by synchrotron X-ray fluorescence analysis, and compared them with those excavated from the Saga castle site and with Amakusa or Izumiyama porcelain stones. The X-ray fluorescence intensity ratio of each element was the highest for Fe in all samples, but other chemical elements depended on the kind of porcelain and the porcelain stone. Sr was the lowest for porcelain stones, but increased greatly for porcelains. A plot of log {Intensity ratio (Rb/Sr)} vs. log {Intensity ratio (Zr/Sr)} gave a good straight line. The data for the porcelain stones gathered in the 1st quadrant and those of the porcelains of the Saga castle site shifted a little to the left lower side, but those of porcelains of the Mietsu Naval Facility site shifted to the more left and lower side. The change in the intensity ratio of elements was ascribed to the porcelain stones used and to the manufacturing process of the clay.

Возможность использования природного фарфорового камня месторождения «Джаны-Джол» (Учкурт) в ортопедической стоматологии (после обогащения)

Возможность использования природного фарфорового камня месторождения «Джаны-Джол» (Учкурт) в ортопедической стоматологии (после обогащения)

Study on the compositional features of Longquan celadon with black body and Southern Song Guan wares from Laohudong using EDXRF

The celadon with black body is a special and famous type of ceramic artifact in the Chinese history. They have crackled celadon glaze that was a notable typological features. Their bodies are noticeably darker in color than regular celadon wares. This type of ceramic wares mainly includes Southern Song Guan wares from Hangzhou and Longquan celadon with black body that might be classed as Ge wares. They were the top ceramic artifacts in ancient China and have been attracting many attentions. The wares from Longquan and Hangzhou have the similar appearance so that it is difficult to distinguish them from each other. In this paper, we collected some ceramic fragments of Longquan celadon with black body from two kiln sites (Xiaomei Town and Wayaoyang) and Southern Song Guan wares from Laohudong, Hangzhou. We applied the energy dispersive X-ray fluorescence analysis to find the similarities and differences in chemical composition between them. The results indicated that the bodies of Longquan and Southern Song Guan samples were made from porcelain stone. Although all their bodies look darker, the contents of coloring elements (iron and titanium) in them were different. The bodies from Laohudong have lower iron and higher titanium than Longquan samples. Their glazes are rich in lime, and the data indicated that the wood ash was the most likely source of the lime-rich component. Depending on the chemical composition of the sample, such as the concentration of manganese and rubidium, one can determine the provenance of samples produced in these three manufacturing sites.

Hydrothermal synthesis of tobermorite nanowires from porcelain stone

A facile and efficient hydrothermal process was explored to obtain tobermorite nanowires using porcelain stone and CaO powders as raw materials. The as-synthesised nanowires have a diameter of 50–100 nm and a length of tens of micrometres under conditions of a porcelain stone/CaO weight ratio of 3, a water/solid weight ratio of 22, a reaction temperature of 240°C and a reaction time of 24 h. The results indicate that the weight ratio of porcelain stone/CaO and hydrothermal temperature play important roles regarding the morphology and structure of tobermorite. Furthermore, a possible growth mechanism of the tobermorite nanowires is proposed. This approach might open up a simple and economic route to prepare tobermorite nanowires using inexpensive porcelain stone as the silicon source.