Ceramic Glazes Research Articles

OBTAINING OF GARNET CERAMIC MATERIALS BY UTILIZATION OF RICE HUSK ASH AS SILICA SOURCE

The current research aims at the obtaining of new type pigments from the garnet mineral group by utilizationof rice husk ash as silica source (RHA). At the beginning, the mixtures prepared from the starting raw materials areground in a ball mill and then subjected to high temperature treatment. Green pigments were synthesized at twotemperatures: 1000°C and 1100°C. Using the tintometer RT 100 Lovibond the colour characteristics were measuredspectrophotometrically. The rice husk ash was investigated using scanning electron microscopy. The conducted hot-stage microscopic studies show that the pigments remain thermally stable when heated. The highest fire resistance - upto temperatures of 1380°C - 1400°C show the uvarovite pigments with main phase 3CaO.Cr2O3.3SiO2 or by a generalformula Ca3Cr2[SiO4 ]3. They are suitable for inserting into ceramic glazes without danger of decomposition or reaction.Keywords: ceramic pigments, SEM, colour determination, Hot-stage microscopy.

New group of glazed Anatolian Pottery from the Ottoman fortress of Azak

The article introduces a new group of glazed pottery of Anatolian production from the archaeological studies of different years (1962, 2004, 2020) on the territory of the former Ottoman fortress of Azak in the North-Eastern Azov Region. Among the finds, there are 20 fragments of open shaped vessels (bowls, plates) and one fragment of the lid which originate from redeposited cultural layer of the site dated back to the late Middle Ages – Modern period. Close analogies can be found on the Crimean peninsula in the materials from the excavations in Sudak, Aluston, Cembalo, Mangup, Partenit, Biyuk-Lambat (Maly Mayak), and Chufut-Kale where they are generally dated by the last quarter of 15th–17th century AD, as well as in South-Western Georgia (Gonio fortress in Adjara) and on the Taman Peninsula (the Taman fortified settlement) in the cultural layer of the 16th–17th centuries AD. Production centre for this group of Ottoman pottery has not yet been established. The group got its conventional name ‘thick-walled bichrome bowls’ due to the dominant archaeological remains of thick-walled bowls with the characteristic decor style in the Crimea.

Metallised Sol-Gel coatings on ceramic glazes with photocatalytic activity

Metallised Sol-Gel coatings on ceramic glazes with photocatalytic activity

Exploring circulation dynamics in Han Dynasty China: insights from isotopic analysis of lead glazed pottery

This study investigates lead provenance and circulation patterns in Han Dynasty (202BC-220AD) China through the analysis of lead glazed pottery. Four objects were studied using a combination of typological study, elemental chemistry and lead isotope ratio analysis. The results for each object were compared with databases of ‘lead mining districts’ (lead deposits) and ‘lead usage districts’ (lead-containing artifacts unearthed in different spatial and temporal ranges) to assess the lead sources used for each sample and offers a spatial-temporal range of the use of these lead resources. Three distinct groups of lead and their possible circulating spatial-temporal scales are identified across six samples in this study. A possible change in lead supply networks between the Western Han Dynasty (202BC-9AD) and the Eastern Han Dynasty (25AD-220AD) is proposed. This study also highlights the probable changes in the movement of lead resources from the Western Han Dynasty to the Tang Dynasty (618AD-690AD), suggesting improvements in long-distance transport capabilities, and the development of economic divisions and exchange connections in ancient Chinese society. Our findings contribute to a deeper understanding of the economic and political dynamics during the Han Dynasty and emphasize the significance of lead isotope analysis of glazed pottery in exploring resource movement.

Was bone used in the glaze of the ancient Qiong kilns for the production of tang dynasty opaque glaze celadon?

Being an important source of primary celadon in ancient China, the Qiong kiln is one of the few kilns that can skillfully produce opaque glaze celadon, which is of great significance in the history of Chinese ceramics. In this study, the chemical composition, microstructure, and crystalline phase of sixteen pieces of opaque glaze celadon excavated from the site of Qiong kiln Shifangtang dated at the Tang Dynasty were investigated by using ultra depth of field microscopy, scanning electron microscopy, energy spectrometry, and micro confocal Raman spectrometry. The findings indicate that Fe is the predominant coloring element in the ceramic glaze, and Cu is sometimes a secondary coloring element. During porcelain firing, washed plant ash was used to increase the phosphorus content of the glaze, while some wares incorporated animal ashes as a flux to improve glaze emulsification.

Sustainable Ceramic Glaze Development from Coal Power Plant Water Treatment Sludge: A Customer-Oriented Approach Using Delphi Method, QFD, and Mixture Design

This research delves into the sustainable utilization of waste materials, particularly chemical sludges from coal power plant water treatment processes, in ceramic glaze development. The study background underscores the growing interest in repurposing industrial waste for sustainability in the ceramics industry. To address this, this study employs innovative methods like the Delphi method and Quality Function Deployment (QFD) to understand customer needs and guide product development. The next step will be to design an experiment to find the optimization point of the mixture of chemical sludge, silica, and soda feldspar to obtain a prototype as desired from QFD. The experimental investigations in this study highlight that resistance to cracking is a crucial factor in glaze formulations. An analysis revealed that a formulation containing 15% sludge, 52% soda feldspar, and 22% silica emerged as the optimal combination for further development. The results indicate that the prototype holds promise for future development, as demonstrated by cracking tests accelerated in an autoclave and analyzed using image processing. These findings contribute to advancing sustainable practices in ceramics, aligning with broader goals of waste minimization, circular economy principles, and resource efficiency.

Characterization of hybrid silicate materials based on ceramic glazes and waste London underground dust

In “London Underground” stations, a high concentration of dust particles containing organic and inorganic matter of varying chemical composition. “London underground dust” is created from train wheels and brakes grinding against steel tracks and collected in filtration systems. The experiment will focus on using “London Underground Dust” to colour the ceramic facing tiles intended for re-use in newly built London Underground stations. The phase composition, particle size distribution surface area, morphology, and thermal behavior of collected dust were studied by XRD, XRF, SEM-EDS, BET, heating microscopy, STA-MS, UV–VIS spectroscopy. The substrate tiles for glazing experiments were prepared from local London clay. The mixtures of glazes and collected or milled dust were sprayed on the substrate tile's surface, dried and finally fired at 1060 °C. The influence of used materials weight ratio and dust milling time were shown as crucial parameters to obtain optimal final glaze colour.

In situ boro-mullite phase formation in Glass–Ceramic glazes: Anatase–rutile phase transformations and microstructure properties

‘‘Boro-mullite’’ is the name for mullites produced through the synthesis of boron-rich material and playing a critical role in producing high-performance materials. Also, the stability of the anatase phase in the glaze and against temperature has been addressed and improved by many studies. In situ boro-mullite crystals generated using various glass-ceramic glaze compositions that contain TiO2 and their impact on the transformation of anatase into a rutile phase were examined in this study. Additionally, the samples' water absorption, bulk density, apparent porosity and shrinkage, Vickers hardness, and optical properties were evaluated at various Al2O3 and B2O3 amounts at 700 °C, 800 °C, 900 °C, 1000 °C and 1100 °C. X-ray diffraction analysis revealed that as the temperature and Al2O3 ratio rose, it triggered the boro-mullite phase formation. On the other hand, increasing the Al2O3 ratio led to a rise in the samples' sintering temperature and delayed the anatase to rutile phase transformation. Furthermore, the presence of corundum crystals retarded the anatase crystal size growth during the remodelling process of the conversion of anatase to rutile. While the increase in the B2O3 ratio sharpened the peaks of albite crystals, the formation of rutile crystals accelerated with the increase in temperature and caused inhibition of albite formation. The albite phase's presence facilitated the creation of the liquid phase and achieved the 0.010 % water absorption and 0 % apparent porosity values as well the highest bulk density and microhardness with 2.476 g/cm3 and 550 H V. The yellowness (+b∗) values were found to be the highest at 1100 °C where the rutile crystals reached their maximum size. The anatase-rutile conversion is postponed and the increase in the yellowness value is prevented by the glaze's formation of boro-mullite. FESEM-EDS analysis showed that the temperature was the driving force in the transformation of acicular boro-mullite crystal into highly acicular prismatic needle crystal and spherical anatase crystals into the rod shape rutile.

Sustainable photocatalytic process using non-silver agent ZnO/P-g-C3N4/Sr2MgSi2O7:Eu2+,Dy3+ for antibacterial activity

Antimicrobials have become a necessity in the post-pandemic era. In contrast to traditional silver-based antimicrobial materials, which are sterilized by silver ions, photocatalytic materials are mainly sterilized by generating reactive oxygen species, but they are limited by light. In this study, the composite coupling of semiconductor photocatalysts with long afterglow materials was designed to form ZnO/P-g-C3N4/Sr2MgSi2O7:Eu2+,Dy3+ (ZPS) for antibacterial ceramics application. The morphological, chemical structure, and optical properties of ZPS were analyzed by scanning electron microscope (SEM), X-ray diffractometer (XRD), Fourier transform infrared spectroscopy (FT-IR), and UV visible diffuse reflectance spectroscopy (UV–vis DRS). The sustainable photocatalytic properties of as-synthesized composites were explored. Furthermore, the antimicrobial ceramics were prepared by incorporating this antibacterial agent into ceramic glazes, which were found to be highly effective against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus), with a suppression rate of more than 99 %. The results of active species capture and electron spin resonance (ESR) experiments suggested that •O2- was the significant active species of the photocatalytic antimicrobial agent with a contribution of 47.17 % and that ZPS could continuously produce active species in the dark state.

Exploring Colour Palette in Pottery from Western Anatolia and East Asia—Colour Schemes to Inspire

In the present case study, the manufacturing technology for glazed pottery was investigated, with particular focus on the great variety of colours and glaze recipes used in Western Anatolia and East Asia and observed in finds from rescue excavation sites in Greece. An assemblage of 40 ceramic fragments dating from the Late Byzantine and Islamic to the Ottoman/Venetian periods was examined for their decoration, surface treatment, and production technology. The peculiarities of the colour recipes applied on the glazed pottery of different assumed origins of production were investigated, focusing on glaze technology and employing colourants. This was achieved by the use of an analytical workflow that considered the compositional details of pigments, slip coatings, and glazes. The chemical evaluation was carried out utilising X-Ray Fluorescence Spectroscopy (pXRF) and Scanning Electron Microscopy with Energy Dispersive X-Ray Spectroscopy (SEM-EDS). Raman Spectroscopy provided information about the compositional variation, and the microscopic examination via Optical Microscopy (OM) and Scanning Electron Microscopy (SEM-EDS) yielded information about the sample stratigraphy of the examined ceramic sections. Through a wide range of colour and glaze recipes, this study of glazed ceramics was able to define and express the essential elements of each pottery workshop’s perception of colour.

Combined studies on glazed ceramic bodies from the Middle and Neo-Elamite periods (1500–539 BCE)

The Elamites have assigned specialized names for different types of ceramics, signaling a specialized approach to ceramic production during the Middle and Neo-Elamite periods. They were pioneers in the use of glazed ceramics on the Iranian Plateau. This investigation focuses on the examination of 29 samples of glazed ceramic bodies originating from the Middle-Elamite (~ 1500–1100 BCE) and Neo-Elamite periods (~ 1100–539 BCE). The objective of this analysis, centered on the earliest instances of glazed ceramic bodies in Iran, is to obtain a comparative examination of the ceramic bodies. Such an approach can be useful for understanding the diverse production techniques used by Elamites in the Middle-Elamite and Neo-Elamite periods. To achieve this purpose, X-ray diffraction and petrography was used to determine the mineralogical characteristics of the ceramic bodies. Further insight into the chemical analysis of the samples was obtained through Electron Probe Micro-Analysis. The experimental data allowed the classification of the samples into four distinct groups. Particularly noteworthy in this categorization is the diversity observed in the Neo-Elamite samples. This diversity of Neo-Elamite ceramic bodies can be attributed to two primary factors. Firstly, the Neo-Elamite period witnessed a more varied array of techniques for producing glazed ceramic bodies compared to the Middle-Elamite period. Unlike the Middle-Elamite glazed ceramics, which were solely utilized for architectural decoration (glazed bricks) and were locally produced, the Neo-Elamite period marked the first instance of glazed ceramic vessels being used in the southwest of Iranian plateau, leading to a higher technological diversity. Secondly, the frequency of trade and importation of glazed ceramics from other regions to the southwest of Iran was notably higher during the Neo-Elamite period compared to the Middle-Elamite one. A notable distinction emerges in the Middle-Elam period, where exclusively quartz-based ceramic bodies were referenced, setting it apart from other sample types.

Multi-functional ceramic glazes with nano ZnO/Cu–ZnO incorporation

The study successfully enabled the creation of ceramic surfaces with multi functionalities, including superhydrophilicity, self-cleaning, antibacterial properties, and photocatalytic activity, by applying a glaze composition rich in nano ZnO/Cu–ZnO and utilizing surface chemistry and unique texturing on porcelain tiles. The tiles, coated with unique glaze compositions, were fired in an industrial furnace and heat treated. The crystalline phases and surface morphology of glazed surfaces were systematically evaluated using XRD, SEM, FT-IR, drop shape analyzer, and surface roughness profilometer. Key-factors affecting the wettability, self-clean ability, photocatalytic activity and antibacterial efficacy were discussed. Adding nano Cu into the glaze mixture that is rich in ZnO improves the evolution of zincite crystals, increases the specific surface energy, decreases surface roughness, provide superhydrophilicity and promotes the antibacterial effectiveness and photocatalytic activity. Superhydrophilic surfaces doped with nano Cu–ZnO display antibacterial characteristics that do not require UV or visible light. The quick achievement of complete self-cleaning, up to 100 %, is due to the presence of nano Cu particles in its structure. Hydrophilicity has the ability to improve the efficiency of photocatalysis. If a surface exhibits superhydrophilic properties, it shows exceptional photocatalytic performance. A surface that is solely photohydrophilic may not maintain self-cleaning. Hydrophilicity may be more important than photocatalysis in the self-cleaning effect.

The influence of raw material changes on gamut colour volume of a matt ceramic glaze

This study aims to investigate the relationship between digital printing colour performance and the raw materials used in a matt glaze. Inkjet technology has enhanced the decorative properties of ceramic tiles in production. Improving the colour perception of the glaze is possible by optimizing the raw materials in the glaze, which results in less ink usage and thus lower costs. Investigation of the colour performance of glazes is possible by determining the L* a* b* values of the colours as well as the gamut colour volumes. Colour of the samples were evaluated by spectrophotometer and i1 profiler. Gamut volume was calculated by 3D CIE chromaticity diagrams of ICC profiles. It was observed that the colour saturation was higher in the samples where the pigment was homogeneously distributed in the glaze microstructure. SiO2 particles not embedded in the glass structure observed in the glaze microstructure disrupt the colour intensity. The low sphere temperature value of the composition made with wollastonite enabled the SiO2 particles to be embedded in the glaze. When wollastonite was used instead of dolomite as the source of calcium oxide in mat glaze, the colour gamut volume reached its highest value (11262), consequently increasing colour saturation. Conversely, the lowest colour gamut volume (6475) was obtained when dolomite was used instead of wollastonite.

Biofouling and biomineralization of tubular concretions attached to Longquan celadon from Shengbeiyu shipwreck, China (14th Century CE): a multi-analytical case study

A comprehensive multi-analytical investigation was conducted on a piece of Longquan celadon excavated from the Shengbeiyu shipwreck site in the East China Sea. This study focused on a representative type of tubular bio-concretions attached to the submerged celadon, believed to have been formed through the construction activities of a marine tubeworm belonging to the benthic phylum of Polychaeta Annelids. The research examined the microstructure, composition and adhesion form of these tubular bio-concretions, aiming to elucidate their developmental and attachment patterns from a biomineralization and biofouling perspective. The tubular bio-concretions were found to have a bimineralic composition, with notably higher content of aragonite than calcite, and display diverse yet highly ordered microstructures. The presence of organic matter within the bio-concretions indicates an organic matrix-controlled crystallization model, commonly observed in the construction of benthic calcareous tubes. Microscopic analyses revealed the primary degradation microstructures and corresponding phases of the glaze to which calcareous tubes attached. These findings closely resembled the corrosion characteristics observed in submerged ceramic glaze without bio-concretion attachments, as documented in earlier studies. OM and SEM observations also indicated that the calcareous tubes intricately intermeshed with the cracked glaze layer of the celadon. Additionally, Raman spectroscopic analysis detected the presence of proteins at the interface, likely residual adhesives secreted by fouling organisms to cement themselves to the settlement substrata, suggesting the occurrence of organic-mediated bio-adhesion mechanisms. These results shed new light on the formation process of bio-concretions and their interaction with attached underwater ceramics. A simplified formation mechanism of this biologically-induced degradation has been discussed.

Effect of particle size distribution on the properties of celsian based glazes

AbstractThe microstructure and surface properties of ceramic glaze are influenced by chemical composition, particle size distribution, glaze application conditions, and firing parameters. This study specifically focused on the influence of glaze particle size distribution on the thermal behavior, microstructure, and surface appearance of barium frit based ceramic glaze in the floor tile firing process. The investigation involved examining the impact of four distinct particle size dimensions (d50: 5.7 μm, 6.8 μm, 7.5 μm, 10.9 μm) on the glaze properties by using hot stage microscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), color and gloss measurements. The studies indicated that celsian is the dominant phase in the glaze structure. The sintering and softening temperatures of glazes decreased with the increase of milling time. A decrease in the particle size of the glaze slurry increased the whiteness index. As the average particle size (d50) of the glaze decreased, the number of crystals was also increased. The investigation results also suggested a relation between specular reflection and milling time. As the milling time extended, there was a corresponding increase in the magnitude of glossiness.

Influence of the composition and structure of sodium borosilicate glasses on the optical-color characteristics of chromium aventurine glass in the presence of cobalt (II) oxide

We investigated the influence of cobalt (II) oxide additive in the amount of 1–3 mol.% on the structure and optical-color characteristics of chromium-containing glass with the following composition (mol.%): 29.6 Na2O; 19.7 В2О3; 49.3 SiO2; and 1.5 Cr2O3. The dependence of the optical-color characteristics of the glasses under study on the thermal treatment of the glass melt at a temperature of 10500C for 20 minutes was established. The thermal treatment resulted in the volumetric crystallization with the subsequent development of the aventurine effect. According to X-ray phase analysis data, the decorative effect was caused by Cr2O3 crystals. By using IR spectroscopy and differential thermal analysis, the structure of the experimental glasses was studied, and the influence of thermal treatment of glass melts on the formation of the structure of glass-ceramic material was established. Aventurine glass of dark blue-green color was obtained with a color tone =490 nm, color purity P=11.35%, and lightness L=5.454 %. The nature of the influence of cobalt (II) oxide on the optical-color characteristics of chromium-containing aventurine glass based on the Na2O–В2О3–SiO2 system is of interest for further development of new compositions of decorative ceramic glazes and enamel coatings.

The high-hardness ceramic glazes based on basalt from Bali Province for ceramic body coatings

The ceramic glaze method is not only done to add color aesthetics but also to increase the hardness of the glaze. Basalt is one of the raw materials developed as a ceramic glaze material because it is cheap, easy to find, and has good characteristics. This research aims to determine glaze characteristics by varying the concentration of basalt rocks from the Ababi area, Karangasem Regency, Bali Province. The experiment used basalt at 45%-61%, Feldspar 27%-37%, Kaolin 3%-8%, and ZnO 7%-10% as raw materials for glaze, not frit glaze. Heating the glaze material layer at 1,250 °C for 3 hrs. The product characteristics of glaze ceramics include chemical composition, crystal phase, microhardness, porosity, density, thermal expansion coefficient, and surface morphology. Basalt from Bali is characterized by its high Fe2O3 content, reaching 20.07 wt%. Compared to basalt in generally, it has a different impact on the physical and mechanical characteristics of the ceramic glaze produced. Based on the observation of ceramic glaze products, the glaze composition with 56% basalt, 32% feldspar, 5% kaolin, and 7% ZnO showed the best coating, with a yellowish-brown color and an average thickness of 79.82µm. The hardness value of the glaze layer is 6.5 GPa, exceeding the standard hardness value of glazes on the market. Glazed ceramics contain the minerals Gahnite (ZnAl2O4) and Coesite (SiO2), which can increase the hardness of the glaze. This research demonstrates the tremendous potential and added value of using basalt from Bali Province as a raw material for glazed ceramics.

Ce doped (Y, Yb)3Al5O12 yellow cool pigment with high solar reflectance and enhanced colour performance

The high solar reflectance and good colour performance are requisite for the practical application of the colour-cool pigment. In this work, Ce-doped Yb3Al5O12 and (Y, Yb)3Al5O12 ceramic pigments were prepared by the sol-gel method. Both Ce3+ and Ce4+ ions coexist in the doped pigments. Due to the 4f→5d electron transition of Ce3+, the Ce-doped pigments have a selective absorption at around 400–520 nm, which is responsible for the yellow hue. The content of the Ce3+ ion determines the colour performance of the pigment. The size effect from the smaller Yb3+ ion results in an increased content of Ce3+ in the Ce-doped pigments, leading to an improved colour performance. The incorporation of Y3+ ion can effectively decrease the absorption at 975 nm, thereby enhancing the solar reflectance to 80.6 %, while maintaining good colour performance (Yb0.7Y2.1Ce0.2Al5O12, L* = 91.40, a* = -4.89, b* = 45.33). In a simulation experiment, the ceramic glaze coating based on the prepared pigment showed a temperature reduction of 5.2 °C compared to the commercial yellow pigment ceramic coating.

The possibility of modifying the mechanism of Seger's theory to calculate ceramic glaze

تهدف الدراسة الى محاولة لأجراء تعديلات على نظرية لحساب مكونات الزجاج والتي وضعت من قبل الكيميائي الألماني (H. Seger) (1839-1893م) منذ (130) عام وسميت باسمه وما زالت فاعلة بعد التطور العلمي والتكنلوجي وظهور البرامج الالكترونية لحسابات الزجاج والتي اعتمدت على اساسيات هذه النظرية، تعرضت هذه النظرية لعدد من التعديلات ولا زال هناك قصور في بعض تطبيقاتها. في هذا البحث تم اجراء "تعديلين" في الأول تم تحرير صيغة الزجاج (Formula unit) من ثوابت قيم المكافئات المولية وتسهيل إضافة المكونات بأي قيمة، وفي التعديل الثاني وضعت آلية لحساب العتمة بالقواعد الترابية (RO) والمواد الحامضية (RO2) وقد اقتصرت هذه النظرية على المواد المتعادلة (R2O3) في اظهار العتمة، وبالتطبيق أظهرت هذه التعديلات فعاليتها.

The influence of varying Cu doping concentrations on the microstructure, phase evolution and surface wettability of ceramic glazes modified with nano Cu-ZnO

This study intended to develop nano Cu-doped nano ZnO-modified ceramic glazes. In this scope, nano-sized ZnO and nano Cu powders were incorporated into a commercial glaze composition and then the modified glaze was applied to the surface using the spraying method. The glazed tiles were sintered in a laboratory furnace at 1210oC for 10 min. The surfaces of the sintered samples were analyzed using scanning electron microscopy. X-Ray diffractometer, surface profilometer and contact angle goniometer. The study examined the influence of varying levels of Cu doping on the microstructural evolution and formation of phases, surface roughness, as well as the contact angle. Additionally, wettability conversion experiments were conducted under UV light. As a result, the addition of Cu increased the presence of Willemite crystals and also increasing the quantity and size of Plagioclase crystals. The contact angle of the sintered commercial glaze coated surface was measured to be 51.8o. However, when nano ZnO was added, the contact angle reduced to 44.4o. Likewise, the contact angle of the Cu doped nano ZnO coated surfaces decreased even further to approximately 33o. The inclusion of nano ZnO in commercial glaze resulted in a decrease in the Ra value, while doping Cu led to a modest increase in the Ra value. UV irradiation resulted in a reduction in the contact angles of all surfaces.