圆明园琉璃瓦表面釉层变色机理的研究

主要利用光学显微镜、能量色散(EDXRF)、XPS、SEM、TEM对圆明园出土的部分绿色琉璃瓦釉-绿中泛红现象进行分析,以研究圆明园出土琉璃瓦的变色机理和烧制过程.通过以上分析表明,琉璃瓦的釉层属于一种铅硅系玻璃,其绿色和红色是由于釉中Cu元素存在价态与含量不同所致,并且绿色区域是以Cu2+形式存在,黑红色和鲜红色区域主要以Cu+和Cu0并存形式存在,而且黑红色区域Cu0的含量要高于鲜红色,所以Cu0对于呈红色起到主要作用.绿色到红色转变是釉层中Cu2+被圆明园遭到火烧时产生的C和CO还原为Cu0和Cu2O析出富集到表面所致,其本质与铜红釉呈色机理相同.     

Relationship between certain ceramic roofing tile characteristics and biodeterioration

This paper examines the relationship of certain red ceramic roofing tile properties to roofing tile biodeterioration. The following properties were studied: apparent porosity, roughness, and the presence or absence of two types of coatings.The effect of apparent porosity was studied by varying the peak firing temperature of a standard industrial red ceramic roofing tile composition and by preparing several clay mixtures, of different chemical and mineralogical composition, that were fired at various peak temperatures. The effect of roofing tile roughness was determined by either polishing or sanding fired standard red roofing tiles. A waterproof ceramic glaze coating and a photocatalytic coating were formulated to analyse the effect of the presence of different types of coatings. Roofing tile bioreceptivity was evaluated with a method developed in a previous study using the cyanobacteria Oscillatoria sp, which enabled roofing tile resistance to microbial colonization to be determined.As expected, bioreceptivity rose as apparent porosity (measured as water absorption) increased, enabling possible water retention, which favours biological growth. Similarly, greater roughness encouraged micro-organism adhesion and raised bioreceptivity. It was found that, after prolonged exposure periods (several months) under very favourable conditions for biological colonization, roofing tiles coated with the waterproof ceramic glaze were colonized. However, glazed standard red roofing tiles covered with a TiO₂ photocatalytic coating exhibited practically no biological growth under the test conditions used, even after long exposure times, owing to the chemical-physical effect of the TiO₂-based coating.     

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。     

琉璃瓦用园子红釉的工艺条件探索

实验主要采用单因素实验法考察了工艺条件对琉璃瓦用园子红釉的影响。制备出了在1170℃,保温30min琉璃瓦用园子红釉。     

Compositional modifications to floor tile glazes opacified with zircon

Abstract

In the ceramic tile industry opaque glazes with considerable zircon content are widely used. However, the high cost of zircon limits its wide use in relevant glaze compositions. In the present study, a model opaque glaze was modified by changing the alumina/silica ratio, adding potassium oxide, or using a higher content of opaque frit while gradually eliminating the zircon content in the glaze batch. After glaze preparation, application, and single firing of glazed floor tiles under industrial conditions glazes were characterised by XRD, SEM, and EDX. The optimum alumina/silica ratio was found to be 0·26. Colour parameters L, a, and b of starting and final glazes showed that an increase in opaque frit content gives more positive improvement in opacity and in dry abrasion resistance than potassium oxide addition. Removal of zircon from the glazes resulted in a decrease of ～13–18% in glaze cost without detrimental effect on opacity.     

Ascertaining the degradation state of ceramic tiles: A preliminary non-destructive step in view of conservation treatments

Conserving the cultural heritage is a general concern and the use of non-destructive techniques to characterize ancient materials is important. Serious deterioration effects in environmentally exposed ancient glazed ceramic tiles arise from the development of micro-organisms (algae/fungi) within the pore system. Subsequent biodegradation processes are particularly harmful once the decorated glaze is damaged by exfoliation/detachment.Three case studies will be addressed: Portuguese polychrome decorated tiles from the interior of two churches (16th–17th century) and from the outdoor of a Palace (18th century). Small tile fragments were directly irradiated in a wavelength-dispersive X-ray fluorescence spectrometer for glaze chemical characterization and subsequently irradiated in a powder diffractometer to assess the phase constitution of both glaze and ceramic body.Cleaning and conserving these ancient cultural artifacts involve a decontamination process applying innovative non-destructive techniques. The present work is intended as a contribution to diagnose the actual degradation state of ancient tiles in view of future decontamination actions using gamma radiation.     

On-site pXRF analysis of glaze composition and colouring agents of “Iznik” tiles at Edirne mosques (15th and 16th-centuries)

The production of the tiles in Ottoman Empire had begun as a continued workshop of Seldjuk ceramic art, and after this initial phase, its own technology was introduced into Ottoman art by local craftsmen. Iznik tiles are among the most appreciated pottery masterpieces, and wall decoration in tiles is a significant asset of Unesco World Heritage Edirne mosques. Rare glaze composition studies have been made, which justify the need for more comprehensive studies. We present here the first on-site elemental analyses performed with portable XRF instrument in four of the most representative mosques in Edirne (?ah Melek Pa?a (1429), Muradiye (1435–1436), Üç ?erefeli (1410–1447) and Selimiye (1569–1575)). A handheld 785?nm Raman spectrometer was used as a complementary technique to identify some pigments. About forty tiles have been analysed in this research. Additionally, two tiles from Ye?ilce Mosque (1442, Edirne) have been analysed at the Selimiye Foundation Museum. The weight percent of the elements measured with pXRF are normalized by Si amount in order to eliminate the variation due to the positioning shifts. Different glazing technologies are evidenced (Master of Tabriz Sn-free glazed tiles, Hünkar Mahfili Sn-poor glazed tiles, and Sn-(Bi) rich ones). At least three different cobalt ores have been used (with characteristic Cu, Ni, Mn and Bi content) in blue decors. Use of a chromium-based ore is demonstrated for some Selimiye Hünkar Mahfili tiles. The link between ?ah Melek Pa?a and polychrome (mihrab) Muradiye tiles and Seldjuk production is established. On the contrary, the technology of Üç ?erefeli and blue-and-white Muradiye tiles is unique and appears a precursor of 16th-century Iznik production. Bismuth, Sn/Pb, Co/Mn, and Co/Ni ratio appears very useful to compare the different glazes and to identify mining sources of cobalt.     

Lead Free Cu-Containing Frit for Modern Metallic Glaze

A lead-free frit containing high amount of copper and its glaze conceived for fine porcelain stoneware tiles were investigated. The glazes obtained under industrial firing were studied using X-ray photoelectron spectroscopy, X-ray diffraction, optical and scanning electron microscopy with energy dispersion spectroscopy. The mechanism of the red color formation on the surface was explained. The results indicated that the glaze presents a metallic gloss and iridescent colors on the surface, mainly associated to the formation of CuO crystallites and Cu metallic particles. Moreover, the Cu glaze showed a good chemical durability; this is particularly interesting because commercial Cu frits usually present poor chemical properties.     

低温快烧琉璃瓦的研制

利用丰富的红页岩、花岗岩风化砂、劣质粘土和硅灰石等原料,采用半干压成型和一次低温快烧工艺,代替传统生产工艺,制备高质量琉璃瓦,研究其工艺条件、坯釉配方以及釉坯显微结构.     

A glaze for construction ceramics

A new glaze for facing tiles, tiles, and sanitary-technical products was developed. The glaze, which has a high concentration of quartz materials, is characterized by good technical and operational properties.Translated from Steklo i Keramika, Nos. 3–4, p. 26, March–April, 1994.     

化妆土及其在红坯体墙地砖中的应用

论述了化妆土的函义、作用与种类。提出了化妆土的技术要求。以生产实际例子说明了化妆土在黄灰色墙面砖和红坯体无光釉地砖中的应用情况。详细论述了化妆土在上述坯体中应用的原料配比、化学组成及有关工艺参数。     

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。     

低成本一次低温快烧生料无光釉的研制

以工业废渣为主要原料研制了低温一次快烧生料无光釉，分析探讨了废渣无光釉的化学组成和烧成条件，该釉不仅适于一次低温快烧工艺，而且可显著降低釉料成本，在墙地砖生产中有较大应用价值。     

Anorthite-based transparent glass-ceramic glaze for ceramic tiles: Preparation and crystallization mechanism

A series of high hardness anorthite-based transparent glass-ceramic glaze was successfully developed for ceramic tiles. These glazes were prepared by mixing a high-calcium frit (denoted as HCa) that can crystallize anorthite with other fluxes. The effect of HCa content on the crystalline phase, microstructure and properties of the glaze was studied. In addition, the phase transformation, microstructure evolution and crystallization kinetics of anorthite from frit glaze were investigated in detail. The results revealed that when the HCa content was 45–55 wt%, the glazes had excellent transparency with a hardness of 6.4–7.3 GPa, which was higher than conventional glazes. The XRD and SEM tests showed the crystallization of single-phase lamellar-shaped anorthite crystals up to 20–40 μm in length. Anorthite was found to crystallize directly from the frit glaze at 850 °C. The laminated anorthite was composed of thinner lamellae, and cracks were observed inside the large crystals. The activation energy of anorthite crystallization was about 420 kJ/mol, and the Avrami index (n) was 2.03?2.36. The n value indicates that the crystal is grown in two dimensions, which explains the formation of lamellar-shaped anorthite in SEM.     

墙地砖无光釉的研究

通过大量实验，研制出适用于墙地砖快速烧成的多组份无光基础釉，经分析测试，该釉性能良好，成本较低，对墙地砖生产厂家降低生产成本，提高产品档次，增强产品市场竞争力具有一定的参考价值。     

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。     

Melting behaviour of raw glazes

Melting behaviour of raw and inhomogeneous glazes influences the appearance and the properties of the final glaze surface. The melting behaviour was estimated from the sintering curves and characteristic samples measured with hot-stage microscopy. The glaze compositions were statistically chosen to cover the glaze-forming systems used in traditional ceramic industries. Altogether seventy-five compositions were mixed and ball-milled from seven different raw materials. The temperatures describing the sintering and melting of the glazes were mathematically modelled as functions of the raw material compositions. All the compositions were then also applied on raw floor tiles and fired in an industrial kiln for fast-firing (50 min) of dense floor tiles. The gloss of the fired glazes was mathematically modelled as a function of both the raw material and the oxide compositions. The resistance to abrasion and the crystalline phases of the fired surfaces were also determined.     

用鄂东原料研制仿石砖

仿石砖是表面凸凹不平,酷似天然石材的瓷质外墙砖。用鄂东当地开采的风化长石、瓷石、瓷砂、瓷土等为原料,控制恰当的生产工艺,可制备具有良好性能的一次快烧仿石砖。     

高铝瓷质抛光砖特殊渗花釉的研制

本文将瓷质抛光砖坯体中的铝含量提高到28%左右,同时引入适量活性氢氧化铝,以实现一些以氧化铝作为色料化学成分之一的特殊渗花颜色。     

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.