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.     

Color matching algorithms in ceramic tile production

In the present work, the possibility of transferring in the ceramic tiles production the know-how developed in the field of the paints by using the Kubelka–Munk theory, in the form used for opaque surface coatings, have been evaluated. Five different target colors have been chosen as target and tried to reproduce with an industrial glaze in a cycle for fine porcelain stoneware tiles. Four industrial pigments have been chosen as basic stains for the formulations. The results show a good efficiency of the color matching algorithm applied to pigments for glazes for fine porcelain stoneware tiles. All the formulations, in fact, have allowed to obtain a value of ΔE^* lower to the accepted limit.     

Preparation and characterization of glazes from combinations of different industrial wastes

The work reported here involves the preparation and characterization of ceramic glazes made from combinations of different industrial wastes. The wastes were float glass, granite and lime shale (a raw material waste from the oil shale industry in São Mateus do Sul, state of Paraná, Brazil), which were used to replace natural raw materials in a proportion of up to 50% in weight. The compositions were formulated using the Seger method and prepared by conventional ceramic processing. The stabilized suspensions were applied in commercial wall tile and porcelain stoneware tile, which were sintered at temperatures of 1080 °C and 1150 °C, respectively, using two different heating cycle. Three compositions were developed, two of which yielded opaque glazes and one a transparent glaze. Linear thermal expansion coefficients (α) of 80.10^?7 °C^?1 to 100.10^?7 °C^?1, and glaze softening temperatures of 600–700 °C were characterized by dilatometric analysis. The glaze compositions showed chemical resistance against acid and alkaline attack after 96 h, showing a mass loss of less than 0.1% in weight. The surface hardness of the glazes determined by the Mohs scale, Vickers microhardness and abrasion resistance (PEI indices) were between 6–7, 3–3.7 GPa and 3–4, respectively. These properties are compatible with those of commercial glazes for wall tiles and porcelain stoneware ceramics.     

微晶玻璃釉的研究

用不同组成的微晶玻璃水淬料,施于陶瓷坯上经核化、晶化,同时完成烧成,而获得微晶玻璃釉层.其工艺制度可以结合DTA分析,通过实验来确定.微晶玻璃釉要和坯料相匹配:釉和坯的膨胀系数相近,微晶玻璃的晶化温度和坯的烧成温度要相一致.     

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.     

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.     

高档仿古砖全熔块无光釉的研制

近年来多数企业都生产无光釉仿古地砖,但由于釉料质量问题,导致生产质量很难控制。本文通过对比传统无光釉的特点,阐述了全熔块无光釉的特点、配制方法以及对生产高档仿古砖产生的积极影响。     

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.     

Microstructure and cleanability of uncoated and fluoropolymer,zirconia and titania coated ceramic glazed surfaces

The aim of this investigation was to examine the effect of surface topography of different compositions and surface coatings of glazed ceramic tiles on their cleanability. The cleanability was estimated with color measurements. Contact angle measurements were used to describe the surface properties and profilometry and electron microscopy to describe the topography. The effect of additional coatings on the surface properties was compared by applying experimental zirconia and titania coatings as well as a commercial fluoropolymer coating on one of the experimental and all reference glazes. The results show that there were clear differences between the soiling tendencies of the glazes. Generally the topography measurements show that the rougher was ceramic glaze, the more soil adhered on its surface.     

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.     

Influence of firing temperature on the color developed by a (Zr,V)SiO4 pigmented opaque ceramic glaze

The analysis of the physical interactions between pigments, opacifiers and glazes is fundamental to understand the optical behavior of ceramic glazes. Furthermore is important to verify if the glaze devitrifies because the crystallized phases can contribute to the optical properties of the system. The size and the quantity of the formed crystals can change significantly the glaze color. The mean goal of this study was to evaluate the influence of firing temperature on the color stability of an opaque ceramic glaze colored by a blue vanadium–zircon pigment taking into account all the optical components. Quantitative X-ray diffraction analysis was conducted in order to evaluate the pigment dissolution at the three studied temperature and the quantity of the in situ formed zircon crystals from the used frit. The reported study demonstrated the importance to consider all the components in a multicomponent optical system as a ceramic glaze.     

Cathode-Ray Tube panel glass replaces frit in transparent glazes for ceramic tiles

The disposal of Cathode Ray Tubes (CRT) from end-of-life personal computers and TV screens represents a serious problem in electronic-waste management. As an assembly of different materials, finding a use for each of a monitor's parts is a critical step forward a solution. However, the CRT panel is a silicate glass with a relatively high proportion of alkaline and alkaline-earth oxides, for which recycling is a natural task, and the replacement of frit in ceramic glazes arises as an interesting alternative. In this context, we investigated the effect of CRT panel glass in glazes for ceramic tiles based on a comparative analysis. We replaced up to 40?wt% of commercial transparent frit with CRT panel glass in the formulation of one reference slurry. Chemical analyses were conducted by X-ray fluorescence (XRF) and inductively coupled plasma optical emission (ICP-OES) spectrometry. The thermal expansion coefficient and the glass transition and dilatometric softening temperatures were characterized by dilatometry and compared to such properties calculated as a function of composition, using the SciGlass software and database. 20- and 30-min firing cycles were applied in a fast-firing roller kiln, replicating industrial conditions. The samples transparency was measured by spectrophotometry and compared to the colorimetric parameters of a standard glaze. The maximum content of panel glass possible to add in the transparent glaze formulation without affecting the expected properties was 20?wt%, above which transparency decreased due to heterogeneities. The reformulation of a ceramic glaze with waste CRT panel glass was successful, thus suggesting an interesting approach for disposal of other electronic wastes.     

The influence of particle size distribution on the surface appearance of glazed tiles

Matte glaze was milled in for different times (15–50 min) and the glazes obtained were applied over ceramic bodies which were then fired using an industrial cycle and the final surfaces were analyzed using a glossmeter. The same glazes were also uniaxially pressed, forming cylindrical samples; the specimens were placed on engobe surfaces and fired at 1100 °C in a laboratory oven. The contact angles between the melted specimens and the ceramic surfaces were measured to determine their wettability. The results showed a correlation between the glaze particle size distribution and the surface aspect of the final product.     

Potential fingerprints for the usage of botanic ash in the glaze recipes of the Jizhou tea bowl

A glaze slip made from a mixture of porcelain clay and flux was melted at high temperatures to form an amorphous glaze layer on a ceramic body. All information about the raw materials and recipes of the glaze was lost in this process, leading to difficulties in the reconstruction of the ceramic-making process performed in ancient China. Herein, the refiring experiment was performed and the thermal dilatometer (DIL), X-ray diffractometer (XRD), X-ray fluorescence (XRF) and field emission scanning electron microscope (SEM) were utilized to investigate the crystallization behavior in the glazes of an underfired Jizhou tea bowl. The results showed that diopside, fluorapatite, and anorthite crystallized from the heterogeneous glaze slip, induced by the inhomogeneity of the raw materials and the incomplete mixing process, during the firing process in the glazes of the Jizhou tea bowl. All these crystals melted with increasing temperature, indicating the importance of the underfired samples in reconstructing the ancient ceramic-making technique. Diopside and fluorapatite could be potential fingerprints to identify the usage of botanic ash in the glaze recipes.     

Development of sapphirine opaque glazes for ceramic tiles

The purpose of this work is to produce more excellent opaque wall tile glazes by using sapphirine instead of zirconium silicate as an opacifier. In order to achieve it, the chemical compositions were precisely adjusted in the system of SiO₂-Al₂O₃-MgO-K₂O-Na₂O-B₂O₃. The morphological characteristics of the glaze were determined by differential scanning calorimetry (DSC), X-ray powder diffraction (XRD) and scanning electron microscopy (SEM). And the optical properties of the glaze were characterized by a spectrophotometer and a gloss meter. The results reveal that well-shaped crystals of sapphirine (Mg₂Al₄SiO₁₀) with needle-like morphology were formed as only crystal phase. The glaze is provided with better opacity whiteness and gloss compared with commercial zircon-based glass-ceramic glazes, and it is mainly composed of cheap mineral raw materials. Those features make it as an alternative one for improving the properties of conventional opaque ceramic glazes.     

Reuse of glass waste in the manufacture of ceramic tableware glazes

Today, various studies are carried out to spread the understanding of sustainability. The sustainability of production processes gains importance in corporate areas. In this study, the use of glass waste instead of frit used in glaze compositions in the ceramic industry was evaluated. The chemical and physical properties of glass wastes on samples were examined. The glaze formulations were prepared using 3%, 5%, and 8% by weight of glass waste instead of frit. Glass wastes were added to glaze compositions and 12 different glaze formulation studies were carried out. Transparent, Opaque, and Matte test glazes were prepared with glass waste added glaze formulations, and these glazes were applied to ceramic bodies. SEM (scanning electron microscope) analysis of standard glaze and glass waste added glazes was performed to determine the microstructural and morphological characterizations. Also, surface whiteness, brightness, L*a*b values, glaze flows, harcort test results, and final water absorption values were compared. As a result of the studies, it has been determined that it is appropriate to use 3% glass waste by weight instead of the frit in the production of ceramic tableware.     

我国色釉料产业现状及发展趋势分析

从我国色釉料行业的现状、发展趋势、仿古砖色料、全抛釉技术、喷墨打印技术、原料标准化以及加强基础研究和技术创新等角度进行了分析评述。     

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.     

Characterization of blue CoAl2O4 nano-pigment synthesized by ultrasonic hydrothermal method

Nano-sized CoAl₂O₄ pigments, which have received significant attention as a coloring agent in glaze and bulk tile compositions, were successfully synthesized by substituting mechanical stirring during hydrothermal process with ultrasonic irradiation. Difference in physicochemical and optical properties of the CoAl₂O₄ pigments prepared by an ultrasonic-assisted-hydrothermal method was characterized using simultaneous thermo-gravimetric and differential thermal analysis (TG–DTA), X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), high-resolution transmission electron microscopy (HRTEM), diffuse reflectance spectroscopy, CIELAB colorimetric analysis, and testing in ceramic glazes and bodies. The ultrasonic-assisted CoAl₂O₄ pigments present a narrow particle size distribution with vivid blue color, and better thermal stability, allowing their use for ceramic inks processed at high temperature. Application of ultrasonic irradiation during the hydrothermal process produces nano-sized powders with better physicochemical and optical properties.     

Effect of ZnO/MgO ratio on the crystallization and optical properties of spinel opaque glazes

The effect of the ZnO/MgO ratio on the crystallization and optical properties of glass‐ceramic glazes from the SiO₂–Al₂O₃–ZnO–MgO–CaO–K₂O–Na₂O–B₂O₃ system was studied. The glazes with different ZnO/MgO ratios were characterized by differential scanning calorimetry, X‐ray powder diffraction, Raman spectroscopy, scanning electron microscopy, energy dispersive spectroscopy analysis and a spectrophotometer. The results reveal that the A glaze without ZnO content contains forsterite and sapphirine. The B and C glazes with intermediate ZnO/MgO ratio contain enstatite and spinel solid solution. The D to F glazes with higher ZnO/MgO ratio crystallize spinel solid solution as the only crystalline phase. The amount of spinel solid solution, lightness values (L*), gloss values and the reflectance of the studied glazes increase with the ZnO/MgO ratio.