Three-Dimensional Microstructure of ε-Fe2O3 Crystals in Ancient Chinese Sauce Glaze Porcelain Revealed by Focused Ion Beam Scanning Electron Microscopy.

Ancient Chinese sauce glaze porcelain has recently received growing attention for the discovery of epsilon iron oxide (ε-Fe2O3) crystals in glaze. In this work, we first confirm the presence of ε-Fe2O3 microcrystals, in large quantiteis, in sauce glaze porcelain fired at the Qilizhen kiln in Jiangxi province during the Southern Song dynasty. We then employed focused ion beam scanning electron microscopy (FIB-SEM) to investigate the three-dimensional microstructure of ε-Fe2O3 microcrystals, which revealed three well-separated layers (labeled, respectively, as LY1, LY2, and LY3 from the glaze surface to inside) under the glaze surface. Specifically, LY1 consists of well-defined dendritic fractal structure with high ordered branches at micrometers scale, LY2 has spherical or irregular-shaped particles at nanometers scale, while LY3 consists of dendrites with four, six, or eight primary branches ranging from several nanometers to around 1 µm. Given these findings, we proposed a process for the possible growth of ε-Fe2O3 microcrystals in ancient Chinese sauce glaze.

[Raman and EDXRF Study on Overglaze Decorations of Jingdezhen Ceramics].

Overglaze decoration porcelain is an important category of ancient Chinese ceramics, which has significant artistic value and scientific value. Nondestructive analysis methods such as Raman spectroscopy and EDXRF were used to analyze the overglaze decorations on the Jingdezhen ceramic samples of Yuan, Ming and Qing Dynasty. The recipe and color mechanism of the overglaze pigments were discussed according to the chemical composition and phase composition analysis. The study found that dark red overglaze decorations of ancient Honglvcai, Wucai and famille rose in Jingdezhen are colored by hematite, yellow color is lead tin yellow, carmine decoration is colored by gold less than 0. 1 % in concentration, and green decorations are colored by bivalent copper ion. The result also indicates that the effective combination of Raman spectroscopy and EDXRF can play an important role in the deep research on ceramic artifacts, especially for the overglaze decoration pigments which are interveined each other.

[Chemical composition and chromaticity characteristic of purple-gold glaze of Jingdezhen imperial kiln].

Color glaze is one of the four famous traditional ceramics of Jingdezhen, especially for the products from Ming and Qing Dynasties' official kilns which have rich connotation of technology and culture. The chemical composition and chromaticity characteristic of glaze and body of purple-gold glaze samples from Jingdezhen Ming and Qing Dynasties' official kilns were analyzed by energy dispersive X ray fluorescence (EDXRF) and colorimeter. Preliminary study on the composition, formula and chromaticity characteristic of glaze of purple-gold glaze samples of different period was carried out and the intrinsic causes of ifferences were discussed. The result shows that the concentration of magnesium and calcium in purple-gold glaze is different from the other glazes in Jingdezhen in the same time, probably due to the addition of auburn or brown limestone which is rich in magnesium. The purple-gold glaze sample of Ming Dynasty is darker chiefly because the concentration of magnesium and calcium is higher than the sample of Ming Dynasty which led to iron crystal separated, reducing the brightness and glossiness of glaze. In addition, the body of purple-gold glaze samples from Jingdezhen Ming and Qing Dynasties' official kilns has the characteristics of high silicon and low aluminum and the molar ratio of silicon to aluminum of samples from Ming Dynasty to Qing Dynasty declined, showing that the concentration of kaolin of sample's body of Ming dynasty was increased. The result of this experiment fill deficiency in the ceramic science and technology research in our country about purple-gold glaze from Ming and Qing Dynasties' official kilns and provides scientific material for comprehensive understanding of porcelain marking technology and intrinsic value of Jingdezhen official kiln.

Study on the Influence of Calcination Temperature of Iron Vitriol on the Coloration of Ancient Chinese Traditional Iron Red Overglaze Color.

Iron red, a traditional Jingdezhen overglaze color, is primarily colored with iron oxide (Fe2O3). In traditional processes, the main ingredient for the iron red overglaze color, raw iron red, is produced by calcining iron vitriol (FeSO4·7H2O). Analysis of ancient iron red porcelain samples indicates that the coloration is unstable, ranging from bright red to dark red and occasionally to black. Addressing this, the present study, from a ceramic technology standpoint, conducts a series of calcination experiments on industrial iron vitriol at varying temperatures. Utilizing methodologies such as differential scanning calorimetry-thermogravimetry (DSC-TG), Raman spectroscopy, X-ray diffraction (XRD), scanning electron microscopy with X-ray energy dispersive spectrometry (SEM-EDS), and optical microscopy (OM), this research scientifically explores the impact of iron vitriol's calcination temperature on the coloration of traditional Jingdezhen iron red overglaze color. The findings indicate that from room temperature to 550 °C, the dehydration of iron vitriol resulted in the formation of Fe2(SO4)3 and a minimal amount of α-Fe2O3, rendering the iron red overglaze color a yellowish-red shade. At 650 °C, the coexistence of Fe2(SO4)3 and α-Fe2O3 imparted a brick-red color to the iron red. As the temperature was elevated to 700 °C, the desulfurization of Fe2(SO4)3 produced α-Fe2O3, transitioning the iron red to an orange red. With further temperature increase to 750 °C, the particle size of α-Fe2O3 grew and the crystal reflectivity decreased, resulting in a purplish-red hue. Throughout this stage, the powder remained in a single α-Fe2O3 phase. Upon further heating to 800 °C, the crystallinity of α-Fe2O3 enhanced, giving the iron red overglaze color a dark red or even black appearance.

Processing, Microstructure, and Performance of Robocast Clay-Based Ceramics Incorporating Hollow Alumina Microspheres.

The restoration of ancient ceramics has attracted widespread attention as it can reveal the overall appearance of ancient ceramics as well as the original information and artistic charm of cultural relics. However, traditional manual restoration is constrained due to its time-consuming nature and susceptibility to damaging ancient ceramics. Herein, a three-dimensional (3D) printing technique was employed to accurately restore Chinese Yuan Dynasty Longquan celadon using hollow Al2O3 microsphere-modified 3D printing paste. The results show that the hollow Al2O3 microsphere content plays a vital role in the printability, physical properties, and firing performance of the modified 3D printing paste. The printed green bodies show no noticeable spacing or voids under moderate rheological conditions. The as-prepared ceramic body modified with 6 wt.% hollow Al2O3 microspheres and fired at 1280 °C exhibits optimal bending strength of 56.66 MPa and a relatively low density of 2.16 g∙cm-3, as well as a relatively uniform longitudinal elastic modulus and hardness along the interlayer. This 3D printing technique based on hollow Al2O3 microsphere-modified paste presents a promising pathway for achieving non-contact and damage-free restoration of cultural relics.

[Research on the composition characteristics of imitated Longquan celadon in Jingdezhen and Longquan celadon].

Longquan celadon not only has been loved widely by the domestic and international ceramic lovers, but also imitated by the kiln workers from different places. Among all of the imitated celadons, the most representative products appeared in Ming and Qing dynasties. This paper used EDXRF to test 38 pieces of Longquan celadon of Song, Yuan and Ming dynasty and imitated Longquan celadon in Jingdezhen of Ming dynasty, combined with firing temperature in order to analyze the different composition characteristics of the bodies and the glaze, evolution rule and formation reasons of these samples in the two different places from the views of time and space. It will be contributed to realising the evolution development, mutual communication and influence of the southern celadon and also provide a scientific basis to get the exact information of the celadon including its time and place of origin and so on.

[EDXRF study on the chemical composition and raw material recipe of Jindezhen porcelains in the five dynasties].

Early crafts of porcelain making in Jindezhen were an important issue in ceramic history of China. The chemical composition of white porcelain and celadon samples excavated from Xianghu Kiln in the five dynasties was analyzed using energy dispersive X-ray fluorescence (EDXRF). Raw material recipes of the samples were discussed. The results showed that white porcelain bodies of Xianghu Kiln in the Five Dynasties were made from porcelain stone, while celadon bodies were made from porcelain stone and Zijin clay. Glaze ash and glaze stone were both used in the formula of white porcelain and celadon glaze, and the amount of glaze ash in the celadon was higher than that in the white porcelain samples.

[Chemical composition and chromaticity characteristic of Jilan glaze of Ming and Qing official kilns].

Color glazes of Ming and Qing official kilns are excellent representatives of the famous ancient Chinese porcelains. The study of official ware with Jilan glaze has been an important topic. But it made slow progress due to the rarity of samples with strict production management and using system. The recipes, chemical composition and chromaticity characteristic of the Jilan samples excavated from official kilns in the Ming and Qing dynasties were first discussed by systematical testing with the energy dispersive X-ray fluorescence (EDXRF) and color difference meter. The results showed that the porcelain stone content in Jilan bodies of official kiln in the Ming dynasty is higher than the samples of the Qing dynasty. The manganese content in Jilan glazes of the Ming dynasty is higher than that in the Qing dynasty, while the glaze ash addition and the lightness value in the glaze are opposite.

[Research on the composition characteristics of Chinese ancient southern white porcelain].

The southern white porcelain is the rise in our country's pottery, it is later than the development of northern white porcelain, but it is rising stars, blockbuster, well-grounded, keeping continuous. Jingdezhen kiln and Dehua kiln are the most representative kilns among the southern white porcelain kilns. the present paper used EDXRF to test 30 pieces of Song, Yuan and Ming period' Dehua white porcelains and Jingdezhen Yuan dynasty Shufu white porcelains samples to analyze the different characteristics of the bodies and the glaze of these samples in terms of time and space. The results show that in the bodies and the glaze of Jingdezhen Shufu white porcelains the iron content is obviously on the high side, and the Dehua white porcelains' potassium content is obviously on the high side, and along with time development they have been in a rising trend, which should be the main reason for the sudden rise of Dehua white porcelain sculptures.