Technological evolution of ceramic glazes in the renaissance: In situ analysis of tiles in the Alcazar (Seville,Spain)

The Alcazar Palace (Seville, Spain) is famous for its ceramic decorations; 16th century wall tiles of different typologies have been analyzed in order to relate the manufacturing process of their colored glazes to the evolving technologies of the Renaissance. Chemical and mineralogical compositions have been determined in situ by nondestructive X-ray fluorescence and X-ray diffraction on arista ceramics in the Cenador de Carlos Quinto, and majolica ceramics in the Palacio Gotico and the Royal oratory. The arista style belongs to the local Hispano-Moresque ceramic tradition. Majolica tiles have the complex microstructures of glazes from Italy. The two types are clearly differentiated by their typology, morphology (curved vs flat surface), and also microstructure (single vs multi-layers), glaze chemistry, and use of different coloring agents. Moreover, we found different glaze chemistries in the investigated majolicas, which correspond to different artists and/or practices.     

The birth of copper-red glaze: Optical property and firing technology of the glaze from Changsha Kiln (8th–9th century)

Changsha Kiln rose and flourished alongside the development of China's Maritime Silk Road (8th–9th century). The kiln occupies an important place in the development of China's ceramic science and technology, notably as the source of high-temperature copper-red glaze. A variety of lime-colored glaze was one product of Changsha Kiln. Its surface was decorated with both copper-green and copper-red, and is the earliest known example of the successful firing of a copper-red glaze. This ware is representative of the birth of high-temperature copper-red glaze, but there has been a lack of research on its optical properties and the technology’s origin. In this paper, OM, SEM, TEM, optical coherence tomography (OCT), XRF, fiber optic spectrometry, and other analytical techniques were used to investigate the red and green glazes of Changsha Kiln. The key result of this paper is to reveal the optical properties of copper-green and copper-red in combination with colloidal absorption, ion absorption, and scattering, and to study the key factors for the origin of the high-temperature copper red glaze.     

Technological features of Renaissance pottery from Deruta (Umbria, Italy): An experimental study

This work is focused on the assessment of the basic technological features of the pottery production in Deruta in the Renaissance period. For this purpose, clay samples and two kinds of ceramic products (tiles and wares) dating back to the XVIth century were characterized using different analytical techniques: optical, cathodoluminescence and electron microscopy on thin sections, X-ray fluorescence and X-ray diffraction on the bulk powdered samples. Then two clays best representing the chemical composition of the ceramic products underwent laboratory experimental firing tests at different conditions following the procedure of firing applied in the XVIth century as reported in the ancient historical documents. The firing products underwent textural, chemical and mineralogical characterization by the same analytical techniques in order to be compared with the clays and the shards. Archaeometric investigation of the ceramic bodies led to the identification of two different clay raw materials, both of local provenance, for the tile and the ware production. Archaeometric investigation of the glazes showed some differences between the wares from different workshops. In this respect the typology and the quality of the glaze resulted to be much more effective than the texture and composition of the ceramic body in characterizing the wares from different coeval workshops. Results of the experimental tests evidenced the firing products result from a complex mix of physical and chemical variables strictly correlated to one another. Above all, the heating rate and the amount of calcite in the clay raw material are crucial driving forces of the kinetics of firing. Comparison between the original and the experimental ceramic products indicated ranges of biscuit firing temperature of 850–1050 °C and of 950–1050 °C for the tiles and the wares, respectively, and a low heating rate in both cases.     

Zircon-free frits suitable for single fast-firing opaque wall tile glazes and their industrial productions

Wall tile glazes with a smooth surface texture, high glossiness, and whiteness are usually based on zirconium containing frits. However, these frits are quite expensive and therefore, there have recently been certain attempts to lower the production cost such as taking suitable glass–ceramic glaze systems into an account. With the present work, the frit-based glaze compositions belonging to the K₂O–MgO–CaO–ZnO–Al₂O₃–B₂O₃–SiO₂ glass–ceramic system were studied to prepare newly synthesized wall tile glazes for industrial single fast-firing. The design of a glass–ceramic glaze for this type of tiles should ensure that the selected frit precursor is technically and commercially compatible with the manufacturing conditions generally used in the production of glazed ceramic wall tiles. The aim of the study is to develop zircon-free, frit-based, glossy opaque glass–ceramic glazes for wall tiles by optimizing the CaO/MgO and adjusting the Al₂O₃/alkali ratios in the starting frit compositions. Frit production, glaze preparation, application, and single fast-firing of wall tiles were, first of all, conducted under laboratory working conditions and then, successful recipes were adapted to the relevant industry. The frit crystallization capability and crystallization temperature range were determined by differential thermal analysis (DTA). Thermal expansion coefficient values of glazes were determined by a dilatometer. Characterization of single fast-fired glass–ceramic glazes was made by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) techniques. Colour and gloss analyses of the final glazes were measured with a spectrophotometer and a gloss meter, respectively.     

Colour-generating mechanism of copper-red porcelain from Changsha Kiln (A.D. 7th–10th century), China

Changsha Kiln, located at Changsha in Hunan Province, south of China, is famous for exported and coloured porcelain during the Tang Dynasty (A.D. 7th-10th century) period. Although the opinion that copper-red porcelain originates from Changsha Kiln is widely accepted in academic circles, chemical characters of glaze and colour mechanism of its copper-red porcelain have not been fully investigated and studied. Therefore, a shard of opaque glaze porcelain with red pigments which excavated at Changsha Kiln (A.D. 7th-10th century) was analyzed by Energy dispersive X-ray fluorescence (EDXRF), Synchrotron X-ray absorption near-edge spectroscopy (XANES), micro X-ray diffraction (μ-XRD), microscopy and scanning electron microscopy (SEM) methods. Combining with XANES and μ-XRD results, it indicates that metal copper is the major colouring-generation element status of the red hue. On the other hand, for the first time the study demonstrates that glaze of the sample from Changsha kiln is a typical phase separated-crystalline glaze with large particles surrounding acicular crystals which lead the opaque appearances. Because the sample from Changsha Kiln is Chinese ancient early stage copper-red porcelain relic, it will help to understand the origin of copper-red porcelain in China and enrich the knowledge of Chinese ancient ceramic culture.     

超耐磨高硬度全抛釉的制备研究

针对目前全抛釉砖产品存在的釉面耐磨性差、硬度小、坯釉结合性差及防污能力差的不足,通过采用成熟温度高的生料釉作为面釉和烧成温度低的熔块釉作为底釉制备了全抛釉。通过底釉和面釉釉料的配方组成优化和调整釉料熔融性能及制备工艺等,研制出超耐磨、高硬度的全抛釉,有效提升了全抛釉砖产品质量。     

Materials and technological evolution of ancient cobalt-blue-decorated ceramics: Pigments and work patterns in tin-glazed objects from Aragon (Spain) from the 15th to the 18th century AD

Cobalt-blue-decorated ceramics with tin glazes have been produced in the Iberian Peninsula since the 14th century AD and in Aragon region since the 15th century until the present time. An important ceramic trade was developed and relations with potters of other important production centres were established. Representative objects from archaeological findings could help in drawing conclusions on the technology used in the manufacture of blue-decoration ceramics. In this work, the composition of bodies and glazes of more than fifty samples of blue-decorated ceramics from Aragon was determined by ICPAES and EDX–Scanning Electron Microscopy (SEM). Based on this information, different ceramic groups could be appreciated and reference values valuable for the subsequent study of the blue decorations by means of other techniques, such as laser ablation (LA)–ICPMS, were also obtained. In particular, the data obtained permitted to unequivocally establish the use of three different types of cobalt pigments, with clear changes between areas and periods. Moreover, it is demonstrated that this evolution in the nature of the blue pigments was related to a different procedure when decorating the object, namely the application of the pigments and the drawing the designs before (under glaze) or after (on glaze) covering the ceramic with the tin glaze.     

物理化学在陶瓷科技史研究中的应用

综述了物理化学的原理和物理化学的方法在古陶瓷科学技术研究中的应用成果,特别是在古陶瓷釉的呈色、分相釉、陶瓷釉中的气泡和坯釉过度层形成等的机理研究,并介绍了古陶瓷烧成温度和烧制年代测量的原理。随着物理化学的发展,新理论和新方法不断涌现,努力掌握这些新方法和新理论,并探索将其应用于陶瓷科学技术史研究中,将有可能出现更加显著的成果。     

抗菌功能陶瓷釉面砖的研究

通过在釉中引入银系无机抗菌剂,研制了低温一次快烧的具有抗菌功能的陶瓷釉面砖。采用陶瓷试验系统（ｃｅｒａｍｉｃ ｍｅｃｈａｎｉｃａｌ ｔｅｓｔ ｓｙｓｔｅｍ,ＭＴＳ）用ＳＥＭ,ＥＰＭＡ等测定了材料的理化性能及微观结构。结果表明,该材料具有良好的抗菌性、耐久性及坯釉结合性,其他技术性能均达到国标。     

Copper and silver nanocrystals in lustre lead glazes: Development and optical properties

In the early 9th century AD ancient potters of Iraq discovered that after firing some copper oxides and silver salts with clay, iron oxides and some sulphur compounds applied on a ceramic glaze produced a beautiful layer with a wide range of colours, from reddish to yellowish or even greenish, and some with a characteristic metallic copper or purplish shine. Modern studies of these layers showed that they are formed by nanocrystals of copper and silver embedded in a glass matrix. Some attempts have been performed to understand ancient lustre coloration and characteristic gloss but have failed to give a clear correlation between chemical composition and colour, and generally make some assumptions on the shape and the size of the nanoparticles and the lustre nanostructure. The aim of this paper is to establish a basis for understanding lustre nanostructure linked to its optical properties from a sequence of lustre reproductions on traditional lead glazed tiles. These modern lustre decorations have been studied by means of optical microscopy, transmission electron microscopy and electron energy loss spectroscopy, UV–vis spectroscopy, low irradiation angle X-ray diffraction, synchrotron radiation X-ray diffraction and electron microprobe analysis. These results show that changes in the lustre nanostructure affect the glaze colour and shine during the lustre formation process. Lustre nanostructure showed crystal size range as a function of depth, that subsequently disappeared followed by an increase of nanoparticles mean diameter and reduction of the interparticle distances. Consequently, the dipole plasmon coupling between copper nanoparticles appeared, and seems to be responsible for the metallic shine and copper metal like coloration of the copper lustre. However, colour from the glaze surface differs when calculated for diffuse or reflected light. Diffuse coloration appears strongly affected by the copper nanocrystals, while specular coloration is not only affected by copper but also by the presence of an inhomogeneous distribution of silver nanocrystals which gives the lustre a characteristic purplish shine.     

Solar reflective ink-jet printed porcelain stoneware tiles as an alternative for Urban Heat Island mitigation

Digital ink-jet printing is a decoration system for ceramic tiles that requires the application of engobes with high whiteness and opacity, characteristics that can be used to design solar reflective ink-jet decorated tiles. These materials can help to mitigate Urban Heat Island (UHI) phenomenon. Here, the fabrication of ink-jet printed solar reflective tiles using an engobe with high solar reflectance was investigated. Two printing modalities (binary (BIN) and grayscale (GS)), five printing intensities, and four colours were tested. It was found that some of the prepared tiles can be used for mitigating the UHI phenomenon. The solar reflective properties were mainly derived from the reflective engobe, and in some grade, from the mineral composition of the inks. The colour and roughness measurements revealed that the GS modality could prepare ink-jet decorated tiles with good solar reflective properties with a smaller quantity of inks and good soiling resistance.     

大规格球磨机球磨釉料的探讨

8吨球磨机应用氧化铝刚玉质异形砖与普通瓷质砖砌筑成具有过渡圆角及不连续螺旋的新结构内衬（以下简称为新内衬），在广东某大型企业的生产线上球磨陶瓷耐磨地砖釉料，并就釉料颗粒大小及粒度分布、电耗、介质磨耗等与1．5吨球磨机进行对比，进行了实验研究。结果表明：配有新内衬的8吨球磨机可磨出颗粒较小、粒度分布较窄的质量好的釉料，且具有好的经济效益；在墙地砖大批量生产的条件下，采用新内衬的8吨等大规格球磨机替代1．5吨球磨机球磨普通釉料切实可行。     

简述釉面砖的胶辊印花工艺

为了提高陶瓷墙地砖的装饰艺术效果,通常采用印花技术在墙地砖表面印刷一些图案等。本文对近年来常用的胶辊印花技术进行介绍,主要介绍了胶辊印刷的图版制作、胶辊花釉的配制和胶辊印花机的操作,希望对墙地砖企业生产有一定的指导作用。     

Recycling in ceramic glazes of zirconia overspray from thermal barrier coatings manufacturing

Glazed ceramic tiles are the most common building material for floor and wall covering. Glazes are produced from frits. The aim of this work is to make a total or partial replacement of a raw material, zircon, widely used in ceramic tiles manufacturing, with a waste material, in order to prepare ceramic frits. The waste material used in this work, is the overspray zirconia, which is produced during the deposition process by atmospheric plasma spraying (APS) of thermal barrier coatings (TBC) on turbine blades. In particular, a replacement of 100 wt%, 1 wt% and 0.2 wt% of zirconium silicate with zirconia has been studied. Ceramic glazes prepared mixing frits and other raw materials are applied on a single-fired tile. The glazes obtained were characterized with different analytical techniques. This study has revealed that the substitution of zircon with waste zirconia is possible in small percentages due to the presence of small amount of chromophore ions in the overspray zirconia, which tend to colour the glaze.     

Non-Destructive Determination of the Structure and Composition of Glazes by Raman Spectroscopy

The utility of Raman spectroscopy as a non-destructive technique for the characterization of glassy (alumino)silicates (modern or ancient glazes and glasses) is demonstrated. The addition of fluxing ions breaks the Si–O linkages and the degree of (de)polymerization determines the relative intensity of the Si–O bending and stretching modes and hence the degree of polymerization could be classified. The analysis can be used to predict the processing temperature of glasses. Bending ( Q ^{' n} ) and stretching ( Qⁿ ) spectral components assigned to isolated ( Q ⁰ or SiO₄), and more or less connected SiO₄ vibrational units with one, two three/four bridging oxygen allow more precise analysis. The method is applied to reference modern porcelain glazes and selected ancient ceramic glazes and glasses, representative of the different production technologies used in the Asian, Islamic, and European worlds from Roman Empire to 19th century.     

简述耀州瓷的绘画装饰艺术

耀州窑陶瓷装饰技法是以青瓷刻画誉贯古今,并且成为一种特色,此外还有印花、划画、贴塑、等多种绘画装饰手法。然而耀州瓷的绘画装饰艺术也是别具特色。耀州陶瓷绘画装饰技法源于唐代,经过五代、两宋而盛传于金元,所饰陶瓷种类累计有白釉绿彩、白釉褐彩、素胎黑花、青瓷釉下绘白彩、白釉褐花多种,本文就以历史发展脉络论述其绘画装饰技法在耀州窑的发展和演变,从而阐述耀州窑绘画的装饰艺术与各个时期绘画艺术的关系。     

On-site pXRF analysis of body,glaze and colouring agents of the tiles at the excavation site of Iznik kilns

The excavation at Iznik tiles kilns continues as the third period of the field mission. We present here the first on-site, non-invasive analyses performed with portable XRF instrument on twenty-five excavated tiles and two residue materials of the kiln. The shards studied were attributed to the productions from 14th- to 17th-centuries. The comparison was made by the discussion of characteristic elemental ratios selected from the ceramic technology criteria and PCA/Euclidean distances analysis. Three groups of body and glaze technologies were evidenced. We encountered that the amount of tin oxide in the glaze decreased over the centuries. Besides, two different types of fluxes were used in the glaze, some containing only potassium, and the others having potassium and calcium. The decors, which were investigated in this study were blue, turquoise, green, red colours, and black lines. A copper-iron mixture in the red areas was documented, which reflects the use of bornite.     

窑系的命名模式与标准--兼论钧窑系和仿钧窑口的关系

"窑系"是指不同地方生产的具有相同釉色、装饰技法或使用同一生产工艺的窑址的集合体。这一概念最初来源于西方陶瓷收藏家,为的是方便识别和定义那些相似度高但窑口产地信息缺失的藏品。我国系统的陶瓷考古起步较晚,工作量大,任务紧迫,所以20世纪以来,以陈万里先生为代表的陶瓷学者为了方便研究,开始接受并使用这一概念。随着窑址和相关遗迹的出土,以及新的文献资料的不断发现,传统的"窑系"概念值得再审视。     

浅谈古代绞胎瓷与"绞釉"瓷

绞胎瓷与绞釉瓷是我国古代陶瓷装饰中两种不同的特殊产品。随着收藏热的升温，它们越来越受到人们的关注，但由于它们的制作工艺复杂，产量少，目前仍有很多人将二者混淆，误认为是同一种产品。本文通过对二者原料、制作方法、纹理的比较从而试图廓清两者之间的关系。     

包裹法国红色料在陶瓷领域应用的探索

探索包裹法国红色料在建筑陶瓷工业釉料、坯体中应用的工艺技术条件，采用正交实验方法找出包裹法国红色料在陶瓷釉料、外墙砖、地砖中的最佳发色条件：在釉料中一价的钾、钠离子特别利于该色料的发色；二价离子钡较好、钙次之、镁最差；法国红色料在普通熔块中发色不理想，在特制的熔块中发色良好。