Glaze Composition Research Articles

Investigation of the Usage Properties of Steel Slag as Pigment in Low-Temperature Glaze

The evaluation of industrial wastes in the ceramics industry has been the subject of research studies in recent years. This study investigated the use of steel slag as a colouring pigment in ceramic glazes. The colour effects of 45 compositions created with a triple-phase diagram with steel slag, CoO, and Cr2O3 on low-temperature glaze composition were determined. The microstructural evaluation of the selected colours by SEM and EDX analysis were carried out.The prepared glaze compositions were applied by pouring on the high silica ceramic body. Glazed tiles were sintered in a muffle furnace at 950 ℃ and then L*a*b colour and gloss brightness values were measured. By using steel slags instead of Fe2O3, black glazes were obtained in the triple diagram.

METALLIZED GLAZES FOR THE DECORATION OF PORCELAIN STONEWARE USING RAW MATERIALS OF THE REPUBLIC OF BELARUS

The aim of this research was to study the possibility of obtaining metallic (metallized) raw glazes for porcelain stoneware using the raw materials of the Republic of Belarus. Fusible clay, quartz sand, dolomite, kaolin and copper oxide were used to prepare the glazes. The glazed porcelain stoneware obtained under the industrial conditions of Berezastroimaterialy JSC had dark grey surface with a metallic appearance. The research on the physico-chemical properties of the synthesized samples was carried out under the requirements of existing international standards. The temperature coefficient of linear expansion of glazes was (65.9–73.4)∙10–7 K–1, resistance to surface abrasion (PEI) – 1–2, resistance to thermal shock – 150±5 °C. The structure of glaze coatings was characterized by X-ray diffraction analysis and scanning electron microscopy. The glassy matrix was established to be the predominant phase. Anorthite and tenorite were the crystalline components. Their amount varied depending on the glaze composition. Due to the crystalline phases, glazed porcelain stoneware has a relatively high degree of resistance to surface abrasion. A hot-stage microscope and differential scanning calorimeter were used to study the melting behavior of the experimental glazes. The characteristic temperatures (sintering, sphere, half-sphere, fusion), as well as the contact angle and shrinkage of glazes in the temperature range of 500–1400 ℃ were determined. It was found that an increase in the content of copper oxide from 12.5 to 22.5 % contributes to a decrease in the sintering temperature by 10–50 ℃. However, the prevailing influence on the surface tension of the glazes at temperatures 1050–1200 °C had the percentage of dolomite. For citation: Shymanskaya H.M., Popov R.Yu., Pospelov A.V. Metallized glazes for the decoration of porcelain stoneware using raw materials of the Republic of Belarus. ChemChemTech [Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol.]. 2023. V. 66. N 6. P. 69-75. DOI: 10.6060/ivkkt.20236606.6808.

Procena upotrebe otpada pri sečenju bazalta u bojenju različitih kompozicija keramičkih glazura

Color effects in ceramic glazes play a decisive role in the aesthetic and attractiveness of ceramic pieces. The colorants used in glazes interact with the ceramic materials during the firing process, resulting in a wide range of fascinating colors and effects. Due to the natural properties of basalt such as high compressive strength and wear resistance, this natural volcanic rock is attracting a lot of attention when used in ceramic production processes. The aim of this study is to evaluate the effects of basalt cutting waste (BCW) obtained from a stone company in Kayseri, Turkey, on the color effect of ceramic glazes in combination with different frits. For this purpose, glazes were prepared in which BCW was incorporated in different weight percentages of 0-20 % together with different frits. The glazes were characterized by analyzing chemical, phase, and thermal behavior of BCW using X-ray fluorescence (XRF), X-ray diffraction (XRD), and thermal microscopy, respectively. The prepared glazes were then applied to engobed wall tiles and fired at a temperature of 1,200 °C in a laboratory furnace. After firing, the glazed surfaces were subjected to color analysis, while the phase composition was analyzed by XRD. The microstructure analysis was carried out using electron microscopy (SEM/EDS). Increasing the proportion of BCW in the glaze compositions resulted in a change of the color of the finished surfaces from cream to yellow-beige tones. This study sheds light on the potential use of BCW as a coloring agent in the production of ceramic glazes.

Study on firing process of silicon zinc magnesium crystal glaze

It is complicated to control the technological conditions of silica-zinc crystalline glaze, and research on the technological conditions is an important subject in ceramic art and science. The artistic effect of silicon, zinc, and magnesium crystalline glaze is influenced by many factors, scientific and reasonable glaze composition and glaze application method are the basis of crystal formation, firing condition is the key to controlling crystal flower, and the colorant is the key factor of color presentation. This paper introduces the preparation process of crystalline art glaze of silicon, zinc, and magnesium, discusses the key factors that affect the performance of crystalline glaze and crystal formation, and determines the best glaze application method and firing technology.

Petrochemical attributes of glazed architectural elements from Middle-Elamite to Achaemenid excavation sites in Iran

Glazed decoration in Iran from the Middle Elamite to the Achaemenid periods includes world art milestones. With the exception of Hasanlu IVB, for most sites, comprehensive chemical and mineralogical data are lacking, owing to the generally profound alteration of the vitreous material. To bridge the information gap, and to enable to reconstruct operation production chains in a diachronic fashion, thirty-six glazed artefacts from Qalaichi, Rabat, Hasanlu, Ziwiye, Chogha Zanbil, Susa and Persepolis are studied. The microstructural make-up and alteration phenomena of glazes are characterized by petrographic microscopy, back-scattered electron (BSE) imaging and electron probe microanalysis (WDS-EPMA) on high-quality polished thin sections. Pristine glaze domains at all sites show plant ash soda-lime glass compositions and indicate the use of regionally specific halophyte species for soda production. A distinct feature in the composition of white and turquoise glazes from Qalaichi, Ziwiye and Achaemenid Susa is the employment of sodium-antimonate as white colourant and opacifier. Inter-diffusion and dissolution-precipitation are identified as regionally and temporally contrasting alteration processes.

Development of prototype fritting furnace for small scale pottery producers in Nigeria

Frit is an essential material required in the composition of low temperature glazes. Unfortunately, up till the year 2020 appropriate furnace for local production of frit is scarce in Nigeria. This may be due to the prohibitive prices of customary refractory materials, exorbitant cost for construction of a standard frit furnace, and the epileptic power supply to run a frit producing plant. Consequently, previous attempts to produce frit locally ended up in losses and products froth with impurities. In this work, the continuous-flow frit kiln with a sloping floor design was modified and a prototype was constructed using locally sourced refractory. The working section was lined with highly corrosion resistance monolith produced with a ramming mass composed of zircon and kaolinite. It has a volume of 10.62 litre. The furnace runs on butane gas, it is fed with pre-treated precursor in granules form and capable of continuous production of 30 kg of frit per hour (kg/h) at 1100 oC. With the appropriate burner, the furnace achieved the optimum operation temperature of 1100oC within two hours. The design is suitable for private studio, research and educational institutions. It can also be scaled up for industrial uses.

Study of sauce glazed wares from Yaozhou kilns (Northern Song Dynasty, 960–1127 CE): Probing the morphology and structure of crystals in the glazes

Sauce glaze is one of the main varieties of glazes produced in the Yaozhou kilns during the Song Dynasty. It is famous for its reddish-brown color and high gloss. In this work, the elemental composition, morphology, structure, and light reflectivity of glazes of archeological sherds were systematically studied. A large number of ε-Fe2O3 dendritic crystals were observed in the glazes. Alkali etching was implemented to remove the glassy matrix surrounding these crystals to further investigate their microstructure. SEM observations emphasize that they are composed of well-arranged parallel branches separated by about 230 nm, each of which consisting of offset stacks of many small flake-shaped crystals, with the offset ranging from 100 to 110 nm. Based on these results, the origin of the reddish-brown color and high gloss was discussed. In addition, cordierite crystals were observed for the first time in the sauce glaze from Yaozhou kilns.

MECHANICAL AND MICROSTRUCTURAL PROPERTIES OF OPAQUE CERAMIC TILES GLAZED WITH SOME INDUSTRIAL WASTES

The primary goal of this research is to determine the mechanical properties of opaque glazed ceramic tiles containing fly ash, tincal waste, and recycled red clay, including to assess if the results meet international requirements. Opaque glaze and tincal waste were the main components of all glaze compositions of four groups, which were named OG (original), FA (fly ash), RC (red clay), and FC (mixture) according to the additive. The ceramic tiles were prepared by dipping the biscuits in the glaze composition and firing them at 1150 ?C. The water absorption of the FA, RC, and FC tiles was less than that of the OG tiles (< 0.52 %) and the scratch hardness values were between 6 and 7. All the experimental groups were also resistant to thermal shock, chemicals, and staining showing high opacity (L* > 92) and having a light yellow-red color. The micro- and crystallographic structure of some selected tiles were determined by scanning electron microscopy and X-ray diffraction techniques. Zircon, diopside and augite phases were recognized.

PXRF Data Evaluation Methodology for On-Site Analysis of Precious Artifacts: Cobalt Used in the Blue Decoration of Qing Dynasty Overglazed Porcelain Enameled at Customs District (Guangzhou), Jingdezhen and Zaobanchu (Beijing) Workshops

In a noninvasive determination, Raman and XRF analyses showed the possibility of identifying specific phases and elements characteristic of the use of recipes and ingredients imported from Europe, according to the information documented in Chinese and European archives. Two sets of objects, supposed to have been produced during the Qing Dynasty (1662–1912) at the Forbidden City (‘imperial bowls’ of the Baur Foundation, Geneva) and in the customs district of Guangzhou (Musée Ariana, Geneva), were analyzed with pXRF and also for some objects with Raman microspectroscopy also on-site. The heterogeneity of the colored zones, in three spatial directions, requires the development of a new methodology. We focused particular attention on the cobalt used in the colored areas and marks, drawn either on the body layer (standard underglaze) or on the glaze itself (overglaze). Comparison is made with previous data on Chinese and Vietnamese porcelains from the Yuan (1271–1368) and Ming Dynasty (1368–1644) periods. Combined data for objects attributed to Guangzhou from the Kangxi and Yongzheng periods indicates the use of the same raw materials containing cobalt, associated with arsenic, nickel, zinc, copper and bismuth, according to the European sources. Similarity of the glaze composition and impurities promotes the production of the glazed body with the same raw materials as those used at Jingdezhen. A consistent shift in data for Qianlong style items, which are significantly richer in manganese, is compatible with their partial mixing with Asian cobalt. The deliberate selection of conflicting objects—namely, examples belonging to the other places of production or different periods—are well-observed outside the ‘Guangzhou’ cluster. Some artifacts have anachronistic purity characteristics that support a production after ca. 1850. For instance, two objects on which certain attributions had been made concerning the stylistic analysis are definitive examples of ceramics using a refined ‘cobalt’, and therefore now may be assigned to the later production period of the first half of the 19th century.

Organoleptic, rheological and crystallization properties of confectionery glaze with beet powder

The recipe composition of confectionary glaze determines its high caloricity upon the low content of physiologically significant substances. Introduction of fruit and vegetable raw materials makes it possible to increase a content of dietary fibers, vitamins, macro- and microelements in a product, as well as to reduce an amount of added sugar. This paper considers a technological possibility of introducing vegetable powders into the confectionary glaze recipe by the example of the beet powder. Physico-chemical indicators of the beet powder were studied in comparison with the classic recipe components of confectionary glaze. An effect of an amount of the beet powder (3–15%) introduced instead of part of sugar on the organoleptic, rheological and crystallization properties of glaze was studied. Organoleptic evaluation revealed that addition of the beet powder into the confectionary glaze recipe in an amount of more than 15% led to appearance of floury off-flavor. It was found that yield strength of glaze increased in the direct proportion to the content of beet powder in its composition (from 3.601 Pа to 4.446 Pa) and its value was in a range of the optimal values of 3÷7 Pа. Therefore, addition of the beet powder in an amount of up to 15% will not lead to technological difficulties. The study of the kinetics of the process of confectionary glaze structuring showed that addition of the beet powder led to a decrease in the solidification point and an increase in the time of glaze crystallization. The main crystallization parameters of the developed glaze were established: solidification point Tmax=28.0÷28.3°C, crystallization time τmax=8.2÷8.6 min. Based on the performed research, the following recipes were developed: vegetable-containing confectionary glaze with the beet powder content of 3 to 10%; vegetable confectionery glaze with the beet powder content of 13%.

Antibacterial persistence of hydrophobically glazed ceramic tiles

The antibacterial properties and durability of copper-glazed ceramic tiles were systematically investigated in detail in terms of the hydrophobicity change with glaze thickness. The water contact angle of the standard glaze without copper was 25.2° ± 0.2°, whereas the copper glaze showed hydrophobicity which was dependent on the glaze thickness. A maximum contact angle of 109.6° ± 0.4° was measured from the copper-glazed surface with thickness of 150–200 μm. As the contact angle and hydrophobicity of the copper glaze increased, the antibacterial efficiency against Staphylococcus aureus and Escherichia coli also increased. An antibacterial efficiency of 99.9% was demonstrated from the copper-glazed sample with the thickness of 150–200 μm. In addition, it was confirmed that 99.9% of the antibacterial efficiency of the copper-glazed ceramic tiles could be maintained for at least 2 years. In ion dissolution measurements of the standard and copper glazes, Ca, Na, Si, and K ions were observed, and Cu ion dissolution was only observed from the copper glaze. These results suggests that the hydrophobicity and strongly negative surface charge, which were contributed from Cu addition into the glaze composition, could block the access of bacteria to the glaze surface, and bacterial killing via Cu ion dissolution occurs.

Innovative Technology of Chocolate Covered Multi Layered Chips

Topicality. The assortment of chips in the world market and technologies of their production are analyzed in this article. The main tendency of chips market is the growing demand for products from local natural raw materials, which retain all the nutrients to the highest degree. Therefore, it is important to elaborate a technology for chips production, which is supposed to combine traditional methods of processing raw materials with some new technological solutions. As a result, an innovative product with various combinations of raw materials, as well as a high caloric content, can be obtained by this new technology. Aim and methods. The aim of the study is to substantiate and develop the technology of chocolate covered multi layered chips. Organoleptic research methods, the method of expert evaluations and the calculation method for determining quality and quantity indicators of chips are used to achieve the set purpose. Results. The organoleptic properties of chocolate covered multi layered chips are studied. It is obtained that chips have different shapes and sizes. The color of the chips surface depends on the composition of glaze and raw materials. Chips have a faint smell of chocolate and a sweet or sweet-sour taste. The inner layers of chips do not have a crispy and brittle consistency. In this research, some means of chips value quality indicators are calculated, their nutritional and energetical value is determined. Conclusions and discussion. It is obvious that adding berry powder to chocolate glaze improves taste properties of chips, the color of their surface and look in total. Chocolate covering of chips makes it possible to high their caloric content. The compositions of chips containing apple and berry powder have the highest values of quality, and the compositions of chips containing carrot and zucchini have the lowest ones. The scientific novelty of obtained results lies in the production technology elaboration of chocolate covered multi layered chips. The practical significance of the study results can be used in the expansion of chips assortment.

Factors influencing oxidative spoilage in glazed candies

The influence of nut raw materials and glaze composition on the peroxide value and the induction period during storage of glazed candies at different temperatures is investigated.

Development of Characteristics and Thermal Properties of Ash Celadon Glazes in Thailand

In this paper, we will study the development and comparison of characteristics and thermal properties of original celadon glazes and celadon glazes developed by adding black rice husk ash, Using Mae Rim black clay in Chiang Mai Province as raw material for the original celadon glaze (CG), including clay in the rice paddies, Kha wood ash and mixed wood ash. The raw materials for the development of celadon glazes formula were 14BR, 15BR, 20BR, 21BR, 27BR and 28BR, respectively. Using a triangular phase diagram system, Mae Taeng clay (MT), Kha wood ash (KWA) and black rice husk ash (BR) were used in the ratios of 40, 50, 60 and 70 wt.%, and using the red clay from Doi Saket, Chiang Mai as a coloring agent. Subsequently, the raw materials are ground and mixed to form a coating. Coated onto Mae Rim black clay test specimens. and fire the test specimen at 1250 °C in a reducing atmosphere. After that, the characteristics of the glazes after firing were tested, including crack, melt, flow, color appearance, and chemical composition. Thermal properties tests include the coefficient of thermal expansion and thermal shock resistance in temperature. The results showed that by comparing the original formula celadon glazes (CG) with the celadon glazes formula developed by adding black rice husk ash. crazing were reduced when adding more black rice husk ash. All formulations were melted at 1250 °C due to their CaO content of 55.0, 47.6, 41.0, 51.0, 47.9, 47.7 and 43.0 % respectively. From the chemical composition analysis with XRF, celadon glazes after firing in all formulas did not see any flow due to the content of SiO2 being 28.0, 28.8, 35.4, 26.7, 28.3, 27.9 and 31.1% respectively. The appearance of glazes after firing was more greenish-yellow when rice husk ash was added when using a color analyzer. Because the amount of Fe2O3 up to 4.6, 9.3, 10.4, 8.2, 9.1, 5.9 and 6.0% respectively from Mae Taeng clay and Doi Saket clay. The chemical composition of celadon glaze consists of CaO as the main component, followed by SiO2 and Fe2O3. The important thing is the chemical composition of the glazes was not found with lead and cadmium. The thermal expansion coefficient of celadon glazes at 25-1250°C decreased when adding more black rice husk ash. Finally, the percentage of strength loss after thermal shock temperature change was CG ˃ 20BR ˃ 21BR ˃ 27BR ˃ 28BR ˃ 14BR ˃ 15BR, respectively, using the Celadon Pottery Community Standards Test. (MorChor. 245/2013).

The coordination structure and optical property of iron ions in the traditional lead glazes

Iron could produce bright colors from yellow to brown in Tang Sancai lead glaze, a kind of important ceramic product from ancient China. The glaze color appearance is the most typical feature of Sancai wares, and it is a topic of great interest to scholars and potters. In this paper, we investigated the relationship between atomic-scale microstructure near iron ions and optical properties. The compositional analysis and X-ray absorption fine spectroscopy indicated that the iron ions in Sancai lead glazes were mainly in tetrahedral coordination structure, isolated [Fe3+O4]. The d-d absorption band of Fe3+ is the fundamental factor affecting the glaze color appearance. The tetrahedral coordination structure is the reason for the high intensity of this band. And, the adjustment of glaze composition (content of Pb and Fe) could change its width.

Thermophysical modeling of raw glaze liquidus temperature and viscosity

AbstractRaw glazes, which do not contain pre‐melted glass frits, are widely used due to their low cost. The natural variability of the mineral compositions used in raw glazes affects their viscosity during firing. Molten glaze viscosity plays an important role in determining the final surface quality; therefore, it is important to determine how raw glaze composition and firing conditions affect viscosity. Thermophysical modeling provides a way to evaluate the liquidus temperature and viscosity of molten glazes as a function of composition and oxygen activity. Equilibrium phase volume fraction and composition of 242 raw glaze recipes were evaluated under oxidizing and reducing conditions. Undissolved or precipitation of solid phases explains the secondary flux transition from anti‐fluxing to fluxing near the liquidus temperature. The liquidus temperature and viscosity of iron glazes decrease as a function of increasing iron content under a reducing atmosphere. The empirical probability distribution of molten glaze viscosity follows a lognormal distribution, with lead glazes having significantly lower viscosity compared with glazes without lead. The peak firing temperature viscosity of lead‐free glazes is near the working point of glass. Multiple linear regression analysis shows that the peak firing temperature viscosity and liquidus temperature significantly predict the viscosity factor.

Three-colored Sancai glazed ceramics excavated from Bohai sites in Primorye (Russia)

This paper presents the analytical results of polychrome and monochrome lead-glazed ceramic classified as Sancai that was excavated from the Bohai sites of Kraskino and Gorbatka walled towns, and the Chernyatino-2 settlement (Bohai layer) (Primorye, Russia). Thirty ceramic fragments were analyzed using non-destructive X-ray fluorescence analysis (pXRF), optical microscopy, and scanning electron microscopy (SEM) with energy-dispersive x-ray spectroscopy (EDS). This work presents new data on the elemental composition of lead glazes and discusses some aspects of their technology, including assumptions about the medieval potters' skill level and technological awareness. Data pertaining to the sample's elemental composition indicates their origin from various workshops practicing different approaches to pottery production. These ceramics have no slip layer with the glaze coating having been applied directly onto the surface of the ceramic vessels. The intensity of the lead component in the glaze composition varies significantly, in the range of concentration between 36 and 79 wt%. Surface features of filling and shine, as well as the nature of glaze defects demonstrates a low probability of the peak firing approach that was applied in the technological process. The results presented in this paper contribute to expanding our understanding of the Bohai (CE 698–926) and Tang (CE 618–907) periods for Sancai ceramics.

The early porcelain kilns of Arita: Identification of raw materials and their use from the 17th to the 19th century

Porcelain stone used at the early kilns of Arita, Japan, has never been identified due to the lack of written records. Ryumon and Shirakawa deposits are considered to have possibly been exploited before Izumiyama was discovered in the early 1630s, but there are no records or any previous scientific research aimed at resolving such crucial issue. This work presents the first systematic scientific study of clays from the three deposits and shards excavated at early kiln sites. Portable ED-XRF and SEM-EDS were used to identify the chemical compositions of bodies, glazes, and geochemical characteristics of clays. XRD, TG-DSC, and FTIR-ATR spectroscopy were also used for the mineralogical characterization of clay bodies. Results show that the earliest production was marked by the mineralogical characteristics of the available raw materials. A gradual improvement in material selection and processing will lead to the development of the nigoshide (milky-white) body in the mid-17th century.

Coloring effect of iron oxide content on ceramic glazes and their comparison with the similar waste containing materials

The effects of adding iron oxide to ceramic glaze formulations were studied in this study. Iron oxide was added in different weight ratios into the reactive transparent glaze, reactive opaque glaze, and transparent glaze formulations. The iron oxide content in the glaze composition, the coloring mechanisms, the phase distributions, and surface properties at temperatures of 950–1000-1050-1200 °C in the oxidation firing medium were investigated. Scanning Electron Microscopy (SEM) to determine the microstructural and morphological characterizations of the test glazes, X-Ray Diffractometry (XRD) to determine the crystallographic properties and phases, and X-Ray Fluorescence (XRF) analyses to determine the elemental and chemical composition were performed. In addition to these, surface images were examined with Digital Microscope (DM) and Commission Internationale de l'Eclairage (CIE) L*a*b, and water absorption values were compared. In addition, taking into account environmental factors, a comparison of ceramic glazes with the same amount of waste iron oxide was also performed for same purpose. As a result of the studies, it was observed that the addition of iron oxide and/or waste iron oxide did not have a negative effect, and coloring effects on the glaze layer were observed at different rates and firing temperatures.

Method for Qualitative and Quantitative Analysis of Ancient Lead Enamel Using Laser Inducted Breakdown Spectroscopy

The method of laser induced breakdown spectroscopy (LIBS) was used in analysis of the archaeological enamel samples from the ancient settlement of Jochi Khan (XIV century). During the qualitative analysis, it was found that the elements of the enamel matrix are Si, Pb, K, Na, Mg, Ca, Al. The glaze color is due to the presence of copper and iron. Clustering by the k-means method revealed two groups of samples similar in composition of enamel, but differing in place of origin within the settlement. For the studied samples the semi-quantitative composition of glazes was established from the spectra of LIBS using a method based on the hypothesis of local thermodynamic equilibrium (LTE) and a chemometric approach (Projection to Latent Structures, PLS). Probabilistic deterministic design of experiment was used to search for pairs of element lines that are not subject to changes when the conditions for spectra registration vary, and to determine the coefficients in the equations based on LTR. Calculations using the PLC method were carried out in the “R” programming environment. The following content of the matrix elements was obtained in terms of the most stable oxides, %: SiO2 — 49–61, PbO — 23–31, MgO — 1.7–2.3, CaO — 4.6–6.9, Na2O — 4.1–5.3, K2O — 5.1–6.4, Al2O3 — 0.8–1.7, CuO — 0.32–0.4, Fe2O3 — 0.09–0.16. The results of both methods are generally consistent with each other. The inaccuracy between 4 parallel determinations were 15-24 % for LTE, and 9–14 % for PLS. Taking into account the data of semi-quantitative analysis, it was concluded that the division into two groups is based on a different ratio of copper and iron in enamel.