A green-based crystalline glaze, ceramic tile and its preparation method

Abstract

This invention relates to the field of ceramic tile technology, and discloses a green-based flowing color crystalline glaze, ceramic tiles, and their preparation method. The green-based flowing color crystalline glaze includes a green-based crystalline surface glaze and a flowing color effect glaze. The raw material formula of the green-based crystalline surface glaze, by weight, includes: 34-45 parts of albite, 20-30 parts of quartz, 10-12 parts of limestone, 12-18 parts of zinc oxide, 2-5 parts of kaolin, 2-6 parts of copper oxide, and 3-8 parts of barium carbonate. The raw material formula of the flowing color effect glaze, by weight, includes: 30-35 parts of albite, 25-30 parts of quartz, 8-10 parts of limestone, 12-18 parts of zinc oxide, 2-6 parts of kaolin, 2-6 parts of manganese oxide, 5-10 parts of boric acid, 1-3 parts of red lead, and 5-10 parts of bone ash. This invention designs the composition of green-based crystalline glaze and flowing effect glaze, and improves the process to make the combination of green-based crystalline glaze and flowing effect glaze present a crystalline flowing glaze effect, enriching the glaze colors of ceramic tiles and meeting the market demand for ceramic tiles of different colors.

Description

Technical Field

[0001] This invention belongs to the field of ceramic tile technology, and specifically relates to a green-based flowing crystalline glaze, ceramic tiles, and their preparation methods. Background Technology

[0002] During the firing process, because the glaze contains sufficient crystalline substances (melt), it reaches a saturated state after melting and crystallizes during slow cooling, thus forming a crystalline glaze. Ancient crystalline glazes were all high-temperature iron-based. By the Song Dynasty, mature varieties of crystalline glazes such as hare's fur and oil-drop patterns existed, while Qing Dynasty varieties like tea dust and iron rust were increasingly exquisite. Modern crystalline glazes, in addition to iron, also contain zinc, manganese, and titanium as melts. The crystals in crystalline glazes can vary in size and number; some are visible to the naked eye, while others require a microscope to distinguish. The shapes of crystalline glazes include star-shaped, needle-shaped, and flower-shaped, among others.

[0003] Crystalline glazes can be classified according to the different crystallizing agents used. Zinc silicate crystalline glaze uses zinc oxide as the crystallizing agent, and its crystallizing mineral is zinc silicate. Zinc silicate crystalline glazes have low viscosity and high fluidity at high temperatures, resulting in rapid crystal growth, beautiful crystal shapes, and complex variations. The basic components of the glaze are ZnO and SiO2, and at high temperatures, the glaze melt precipitates crystals in the form of zinc silicate. Zinc silicate crystalline glazes crystallize in various shapes, including round, fan-shaped, and fibrous. At high temperatures, Fe... 2+ Co 2+ Cu 2+ and Mn 2+ It can undergo isomorphous substitution with zinc silicate crystals, but the amount of substitution is limited, and the substitution gives the crystals different lighter colors.

[0004] The fundamental characteristic that distinguishes crystalline glaze from ordinary glaze is that it contains a certain number of visible crystals. Currently, most crystalline glaze products on the market are found in everyday ceramics, handcrafted art tiles, and ceramic kiln-fired mosaics, but are less common in architectural ceramic wall and floor tiles. Patent document CN102936156A discloses a glaze and preparation process for high-temperature fast-firing crystalline glaze antique tiles. Patent document CN104829268A discloses a glaze for fast-firing crystalline glaze ceramic tiles and a method for preparing and applying the ceramic tiles. However, these crystalline kiln-fired products are too monotonous, with limited decorative techniques, failing to achieve higher visual effects and artistic quality in ceramic tiles, and thus failing to meet consumers' future demands and expectations for higher product value.

[0005] Therefore, existing technologies still need to be improved and developed. Summary of the Invention

[0006] In view of the shortcomings of the prior art, the purpose of this invention is to provide a green-based flowing crystalline glaze, ceramic tile and its preparation method, which aims to solve the problem of the single color of existing crystalline glaze ceramic tiles.

[0007] The technical solution of the present invention is as follows:

[0008] A green-based crystalline glaze with flowing colors, comprising a green-based crystalline glaze and a flowing color effect glaze. The raw material formula of the green-based crystalline glaze, by weight, includes: 34-45 parts of albite, 20-30 parts of quartz, 10-12 parts of limestone, 12-18 parts of zinc oxide, 2-5 parts of kaolin, 2-6 parts of copper oxide, and 3-8 parts of barium carbonate. The raw material formula of the flowing color effect glaze, by weight, includes: 30-35 parts of albite, 25-30 parts of quartz, 8-10 parts of limestone, 12-18 parts of zinc oxide, 2-6 parts of kaolin, 2-6 parts of manganese oxide, 5-10 parts of boric acid, 1-3 parts of red lead, and 5-10 parts of bone ash.

[0009] The green-based flowing crystalline glaze, wherein the molar ratio of Si to Al in the blue crystalline glaze is 8-11:1.

[0010] The green-based flowing crystalline glaze, wherein the molar ratio of Si to Ca in the blue crystalline glaze is 6-14:1.

[0011] In the aforementioned green-based crystalline glaze, copper oxide accounts for 2-4% of the total weight of the raw materials for the green-based crystalline glaze.

[0012] In the aforementioned green-based iridescent crystalline glaze, manganese oxide accounts for 2-6% of the total weight of the raw materials used in the iridescent effect glaze.

[0013] A method for preparing a green-based crystalline glaze with flowing colors, comprising the following steps:

[0014] Weigh out the raw materials for the green base crystalline glaze and the flowing color effect glaze according to the proportions of each component, and set aside.

[0015] The raw materials of the green crystalline glaze are mixed with water in a ball mill at a mass ratio of 1-1.5:2:1 and then ball milled. After that, the mixture is passed through an 80-120 mesh sieve to obtain a crystalline glaze slurry for later use.

[0016] The raw materials of the iridescent glaze are mixed with a ball mill and water in a mass ratio of 1-1.5:2:1 and then ball milled. After that, the mixture is passed through a 120-140 mesh sieve to obtain an iridescent glaze slurry for later use.

[0017] A method for preparing ceramic tiles using a green-based, iridescent crystalline glaze, comprising the following steps:

[0018] A crystalline glaze slurry is applied to the bisque-fired ceramic tile blank, and after drying, a glazed body is obtained.

[0019] Apply a flowing color effect glaze to the glazed body, and dry it again to obtain the effect glaze body.

[0020] The ceramic tile with the effect glaze is fired in a kiln. During firing, the temperature is raised from room temperature to 300℃ in 120-240 minutes, from 300℃ to 950℃ in 90-150 minutes, and from 950℃ to 1300℃ in 40-60 minutes. After holding at this temperature for 10-30 minutes, the temperature is lowered to 500℃-600℃. Finally, the power is turned off and the tile is allowed to cool naturally, resulting in a ceramic tile with a green base and flowing crystalline glaze.

[0021] In the method for preparing ceramic bricks, the step of applying a crystalline glaze slurry to the bisque-fired ceramic brick has a glaze thickness of 1.2-1.5 mm.

[0022] In the method for preparing ceramic tiles, in the step of applying a flowing glaze slurry to the glazed body, the glaze thickness is 1.0-1.2 mm.

[0023] A ceramic tile with a green base and flowing crystalline glaze, wherein the ceramic tile is prepared by the method described in this invention.

[0024] Beneficial effects: This invention designs the composition of green base crystalline glaze and flowing color effect glaze, and improves the process so that the combination of green base crystalline glaze and flowing color effect glaze presents a crystalline flowing glaze effect, enriching the glaze colors of ceramic tiles and meeting the market demand for ceramic tiles of different colors. Attached Figure Description

[0025] Figure 1 A flowchart of a method for preparing ceramic tiles using a green-based flowing crystalline glaze according to the present invention is shown;

[0026] Figure 2 The image shows a physical example of a ceramic tile with a green base and iridescent crystalline glaze prepared in Example 1.

[0027] Figure 3 A physical image of a ceramic tile with a green base and iridescent crystalline glaze prepared in Example 2. Detailed Implementation

[0028] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below in conjunction with the embodiments.

[0029] This invention provides a green-based crystalline glaze with flowing colors, comprising a green-based crystalline glaze and a flowing color effect glaze. The raw material formula of the green-based crystalline glaze, by weight, includes: 34-45 parts of albite, 20-30 parts of quartz, 10-12 parts of limestone, 12-18 parts of zinc oxide, 2-5 parts of kaolin, 2-6 parts of copper oxide, and 3-8 parts of barium carbonate. The raw material formula of the flowing color effect glaze, by weight, includes: 30-35 parts of albite, 25-30 parts of quartz, 8-10 parts of limestone, 12-18 parts of zinc oxide, 2-6 parts of kaolin, 2-6 parts of manganese oxide, 5-10 parts of boric acid, 1-3 parts of red lead, and 5-10 parts of bone ash.

[0030] In this invention, the crystallizing substances of zinc silicate crystalline glaze are ZnO and SiO2, which react at high temperature to form zinc silicate. The albite is a common feldspar mineral with the chemical formula Na2O·Al2O3·6SiO2 and a theoretical chemical composition of Na2O: 11.8%; Al2O3: 19.4%; SiO2: 68.8%. As a ceramic glaze material, albite can soften the glaze surface and lower its melting temperature. Simultaneously, as a solvent in the glaze glass, albite can promote the formation of zinc silicate crystals.

[0031] In this invention, quartz is a hard, wear-resistant, and chemically stable silicate mineral. Its main mineral component is SiO2. Quartz is a non-plastic raw material. When quartz and clay are reacted at high temperatures, the resulting mullite crystals give porcelain high mechanical strength and chemical stability, and can increase the translucency of the body. It is a good raw material for preparing white glaze.

[0032] In this invention, limestone is a calcium carbonate mineral with the main chemical formula CaCO3. Limestone is a common ingredient in glaze formulations, primarily used to adjust the alkalinity and viscosity of the glaze, ensuring its uniform adhesion to the porcelain surface. Simultaneously, limestone can regulate the melting point of the glaze and, together with other ingredients, comprehensively adjust its properties. Adding an appropriate amount of limestone to the glaze can significantly improve its brightness and transparency. The principle is that when limestone melts at high temperatures, it forms calcium oxide (CaO). This compound can combine with molten silicates and other materials to form a bright and transparent chemical substance, thereby improving the aesthetics of the glaze surface. Limestone can also react chemically with other ingredients at high temperatures to generate calcium oxide and calcium carbonate, which can increase the glaze's toughness and reduce cracking during firing. Furthermore, adding a certain amount of limestone to the glaze can increase its viscosity and ductility, thereby enhancing the glaze's smoothness and tactile feel. Limestone is a widely used material in ceramic glazes, playing a vital role in adjusting glaze formulations, improving glaze brightness and transparency, and increasing glaze toughness. In the production of high-quality porcelain and pottery, the proper use and control of limestone dosage can enhance glaze quality and improve the overall quality and value of ceramic products.

[0033] In this invention, the main components of kaolin are alumina and silicon dioxide. Its main function in the glaze is to increase the melting temperature of the glaze, and its auxiliary function is to improve the suspension of the glaze, making the glaze less prone to sedimentation.

[0034] In this invention, zinc oxide is the main nucleating substance for zinc silicate crystalline glaze, and its introduction also has a good effect on the chemical stability and gloss of the glaze. Zinc oxide can make the glaze more fusible, lower the firing temperature of high-temperature glazes, and also increase the gloss and whiteness of the glaze, expanding its maturation range. When zinc oxide reaches saturation, it crystallizes to form a crystalline glaze.

[0035] In this invention, barium carbonate decomposes with SiO2 or other alkaline substances below 700°C, because Ba... 2+ Its ionic radius is very large, and its fluxing effect is stronger than that of other alkaline earth metal oxides.

[0036] In this invention, boric acid is mainly introduced from boric acid, borax, and boron-containing minerals. B2O3 is a strong fluxing agent component, and its addition significantly reduces the melting temperature of the glaze, accelerates the melting of the glaze, reduces the coefficient of expansion of the glaze, and improves the hardness and elasticity of the glaze surface.

[0037] In this invention, the chemical formula of red lead is Pb3O4. Red lead has a significant fluxing effect, and when added to the glaze, it can increase the refractive index of the glaze surface and improve the gloss of the glaze surface.

[0038] In this invention, the chemical formula of bone ash is Ca3(PO4)2, which is mainly obtained by calcining animal bones. CaO acts as a flux, while P2O5 has an opacifying effect, promoting the phase separation effect of the glaze melt, and can be used to formulate decorative glazes.

[0039] In this invention, because zinc silicate crystalline glaze is characterized by its rich colors, to enhance its artistic value and aesthetic appeal, an appropriate amount of colorant is added to the glaze, resulting in crystals of different hues. Furthermore, different amounts of colorant result in different color hues and crystallization states in the crystalline glaze, as the color of the glaze depends on the metal elements it contains. This invention selects copper oxide and manganese oxide as colorants for the glaze, which can produce a richly colored green-based iridescent crystalline glaze.

[0040] For crystalline glaze formulations, different raw materials and varying proportions of components significantly impact the final appearance of the crystalline glaze surface. Therefore, this invention employs a combination of orthogonal experimental design and single-factor analysis to improve and adjust the glaze formulation, resulting in the aforementioned formulation of a green-based, iridescent crystalline glaze.

[0041] In some embodiments, the molar ratio of Si to Al in the blue crystalline glaze is 8-11:1. A lower Al₂O₃ content in the crystalline glaze can significantly increase the viscosity of the glaze, thereby affecting crystal growth; the SiO₂ content directly affects the growth of the zinc silicate crystalline glaze; in the crystalline glaze, crystal growth is a combined effect of Al₂O₃ / SiO₂, and a suitable molar ratio of Si to Al can improve the stability, hardness, and elasticity of the glaze surface, and reduce the coefficient of thermal expansion. The effects of different molar ratios of Si to Al on the glaze surface are shown in Table 1.

[0042] Table 1. Glaze effects with different silicon-to-aluminum ratios

[0043] Molar ratio of Si to Al Glazed effect 6:1 An opaque effect appears, and the glaze is uneven. 9:1 It has crystals, a uniform and transparent glaze, and a high gloss. 12:1 No crystallization, the glaze is transparent.

[0044] The experimental results showed that when the Al2O3 / SiO2 ratio was high (i.e., the molar ratio of Si to Al was less than 8:1), the glaze would form a spinel structure with an opaque effect, and no Zn2SiO4 crystals would precipitate. However, when the Al2O3 / SiO2 ratio was low (i.e., the molar ratio of Si to Al was greater than 11:1), a matte glaze would form. Therefore, adjusting the molar ratio of Al2O3 / SiO2 can improve the gloss and crystallization properties of the glaze. When the Al2O3 / SiO2 ratio is between 1:8 and 1:11, a bright glossy glaze is formed.

[0045] In some embodiments, the molar ratio of Si to Ca in the blue crystalline glaze is 6-14:1. In the crystalline glaze, crystal growth is also affected by the molar ratio of Si to Ca. This embodiment tested different molar ratios of Si to Ca, and the effects of the glaze are shown in Table 2.

[0046] Table 2 Glaze effects with different silicon-to-calcium ratios

[0047] Molar ratio of Si to Ca Glazed effect 5:1 The glaze is white, uneven, has low gloss, and a frosted appearance. 11:1 The glaze has a high gloss and is transparent. 15:1 The glaze becomes opaque, forming a matte glaze.

[0048] As shown in Table 2, when the silicon-calcium ratio is low, a matte glaze will form. When the silicon-calcium ratio is high, the glaze layer will become opaque, resulting in a matte glaze.

[0049] In some embodiments, the copper oxide accounts for 2-4% of the total weight of the raw materials in the green crystalline glaze. Within this range, the color of the crystalline glaze tends to be green. If the weight percentage of copper oxide is greater than 4%, a mirror-like glaze will appear with a significant reflective effect; if the weight percentage of copper oxide is less than 2%, the coloring effect will be poor, and the color of the crystalline glaze will be too light.

[0050] In some embodiments, the manganese oxide accounts for 2-6% of the total weight of the raw materials of the iridescent effect glaze. Within this proportion range, the color of the iridescent effect glaze tends to shift towards red and yellow, mixing with the color of the crystalline glaze on the green base to form an iridescent effect.

[0051] In some embodiments, a method for preparing a green-based crystalline glaze with flowing colors is also provided, such as... Figure 1 As shown, it includes the following steps:

[0052] S10. Weigh the raw materials for the green base crystalline glaze and the flowing color effect glaze according to the proportions of each component, and set aside.

[0053] S20. Mix the raw materials of the green crystalline glaze with a ball mill and water in a mass ratio of 1-1.5:2:1 and ball mill them. Then pass the mixture through an 80-120 mesh sieve to obtain a crystalline glaze slurry for later use.

[0054] S30. Mix the raw materials of the flowing color effect glaze with a ball mill and water in a mass ratio of 1-1.5:2:1 and ball mill them. Then pass the mixture through a 120-140 mesh sieve to obtain the flowing color effect glaze slurry for later use.

[0055] This invention obtains glaze slurries with predetermined particle sizes by ball milling and sieving the raw materials of green-based crystalline glaze and iridescent glaze, which helps the slurry form a crystalline glaze with better and more uniform morphology after sintering.

[0056] In some embodiments, a method for preparing ceramic tiles using a green-based flowing crystalline glaze is also provided, comprising the steps of:

[0057] A crystalline glaze slurry is applied to the bisque-fired ceramic tile blank, and after drying, a glazed body is obtained.

[0058] Apply a flowing color effect glaze to the glazed body, and dry it again to obtain the effect glaze body.

[0059] The ceramic tile with the effect glaze is fired in a kiln. During firing, the temperature is raised from room temperature to 300℃ in 120-240 minutes, from 300℃ to 950℃ in 90-150 minutes, and from 950℃ to 1300℃ in 40-60 minutes. After holding at this temperature for 10-30 minutes, the temperature is lowered to 500℃-600℃. Finally, the power is turned off and the tile is allowed to cool naturally, resulting in a ceramic tile with a green base and flowing crystalline glaze.

[0060] In this invention, the appropriate firing temperature and firing time directly affect the precipitation of crystal nuclei and crystal growth. The invention first preheats the effect glaze body to approximately 300°C. This preheating stage primarily aims to remove moisture from the body, preventing pinhole defects. Then, an oxidation decomposition process occurs between 300-950°C. During this stage, chemical changes include the removal of water of crystallization, oxidation of organic matter and sulfides, decomposition of carbonates, and transformation of the quartz crystal form. Next, a high-temperature firing stage is initiated between 950°C and 1300°C. During this stage, a liquid phase begins to appear in the body, and the glaze layer begins to melt. At this point, the glaze layer is essentially mature, and all reduction reactions have largely concluded. During the high-temperature stage, due to the increase in liquid phase and the decrease in porosity, the green body undergoes significant shrinkage. At this time, it is crucial to minimize the temperature difference within the furnace to prevent deformation or cracking caused by excessive shrinkage. Holding at this temperature for 10-30 minutes primarily reduces the temperature difference within the furnace, allowing the physicochemical reactions within the green body to proceed completely, resulting in a more uniform microstructure. This also allows the glaze melt to spread better on the green body, facilitating sufficient crystal growth. Finally, during the cooling stage, rapid cooling prevents liquid phase crystallization and crystal growth, thereby improving the strength, whiteness, and gloss of the green body and glaze. Different cooling procedures in the firing process can influence the shape of the zinc silicate crystalline glaze crystals. Holding at temperatures slightly above the crystallization temperature will result in radial or star-shaped crystals, as the crystals formed at higher temperatures will be dissolved by the latent heat. Holding at temperatures slightly below the crystallization range will create overlapping crystal zones. At lower temperatures, suitable dispersed crystal nuclei continue to grow, increasing the number of crystals and causing them to overlap. By maintaining the temperature within the suitable crystallization temperature range of this invention, and extending the holding time appropriately, followed by rapid cooling to 500℃-600℃, uniform crystals can be obtained, thereby forming ceramic tiles with green-based flowing crystalline glaze.

[0061] In some embodiments, in the step of applying a crystalline glaze slurry to the bisque-fired ceramic tile, the glaze thickness is 1.2-1.5 mm; in the step of continuing to apply a flowing effect glaze slurry to the glazed body, the glaze thickness is 1.0-1.2 mm. Specifically, as the glaze thickness increases, the degree of crystallization of the resulting crystalline glaze gradually increases, and the number of crystals increases. This is because different glaze thicknesses result in different amounts of glaze adhering to the body surface, and different contents of the crystallizing agent zinc oxide. If the glaze thickness is too low, the thin glaze layer increases the strain on the glaze surface, improving the adhesion between the body and the glaze, but failing to reach full saturation. This embodiment limits the glaze thickness to 1.2-1.5 mm because at high temperatures, the fluidity of the glaze layer formed within this range is better, crystals grow on the horizontal surface, and particles are suspended on the vertical surface, providing space for crystal precipitation, all of which are beneficial to crystal growth. Within this range, the thicker the glaze, the more zinc oxide and glaze adhere to the surface, making it more prone to saturation in the high-temperature molten state. After a large amount of saturation, the remaining zinc oxide adheres to the surface of the blank, acting as seed crystals to form crystal flowers.

[0062] In some embodiments, a ceramic tile with a green base and flowing crystalline glaze is also provided, which is prepared by the method for preparing ceramic tiles described in this invention.

[0063] The present invention will be further explained and illustrated below through specific embodiments:

[0064] Example 1

[0065] A method for preparing ceramic tiles using a green-based, iridescent crystalline glaze, comprising the following steps:

[0066] The raw materials of the green-based crystalline glaze are mixed with a ball mill and water in a mass ratio of 1.5:2:1 and then ball-milled. After passing through a 100-mesh sieve, a crystalline glaze slurry is obtained for later use. The raw materials of the green-based crystalline glaze include, by weight, 40 parts of albite, 25 parts of quartz, 11 parts of limestone, 15 parts of zinc oxide, 3 parts of kaolin, 4 parts of copper oxide, and 5 parts of barium carbonate.

[0067] The raw materials for the iridescent effect glaze are mixed with a ball mill and water in a mass ratio of 1.5:2:1 and then ball-milled. After passing through a 130-mesh sieve, an iridescent effect glaze slurry is obtained for later use. The raw material formula for the iridescent effect glaze includes, by weight, 32 parts of albite, 27 parts of quartz, 9 parts of limestone, 15 parts of zinc oxide, 4 parts of kaolin, 4 parts of manganese oxide, 7 parts of boric acid, 2 parts of red lead, and 8 parts of bone ash.

[0068] A crystalline glaze slurry is applied to the bisque-fired ceramic tile blank, and after drying, a glazed body is obtained.

[0069] Apply a flowing color effect glaze to the glazed body, and dry it again to obtain the effect glaze body.

[0070] The glaze blanks were fired in a kiln. During firing, the temperature was raised from room temperature to 300°C in 180 minutes, from 300°C to 950°C in 120 minutes, and from 950°C to 1300°C in 50 minutes. After holding at that temperature for 20 minutes, the temperature was lowered to 550°C, and finally the power was turned off for natural cooling, resulting in the desired glaze. Figure 2 The ceramic tile shown has a green base with flowing crystalline glaze.

[0071] Example 2

[0072] A method for preparing ceramic tiles using a green-based, iridescent crystalline glaze, comprising the following steps:

[0073] The raw materials of the green-based crystalline glaze are mixed with a ball mill and water in a mass ratio of 1:2:1 and then ball-milled. After passing through an 80-mesh sieve, a crystalline glaze slurry is obtained for later use. The raw materials of the green-based crystalline glaze include, by weight, 35 parts of albite, 20 parts of quartz, 12 parts of limestone, 12 parts of zinc oxide, 2 parts of kaolin, 6 parts of copper oxide, and 8 parts of barium carbonate.

[0074] The raw materials for the iridescent effect glaze are mixed with a ball mill and water in a mass ratio of 1.5:2:1 and then ball-milled. After passing through a 120-mesh sieve, an iridescent effect glaze slurry is obtained for later use. The raw material formula for the iridescent effect glaze includes, by weight, 30 parts of albite, 30 parts of quartz, 10 parts of limestone, 12 parts of zinc oxide, 2 parts of kaolin, 2 parts of manganese oxide, 5 parts of boric acid, 3 parts of red lead, and 10 parts of bone ash.

[0075] A crystalline glaze slurry is applied to the bisque-fired ceramic tile blank, and after drying, a glazed body is obtained.

[0076] Apply a flowing color effect glaze to the glazed body, and dry it again to obtain the effect glaze body.

[0077] The glaze blanks were fired in a kiln. During firing, the temperature was raised from room temperature to 300°C in 120 minutes, from 300°C to 950°C in 100 minutes, and from 950°C to 1300°C in 40 minutes. After holding at that temperature for 20 minutes, the temperature was lowered to 600°C, and finally the power was turned off for natural cooling, resulting in the desired glaze. Figure 3 The ceramic tile shown has a green base with flowing crystalline glaze.

[0078] Example 3

[0079] A method for preparing ceramic tiles using a green-based, iridescent crystalline glaze, comprising the following steps:

[0080] The raw materials of the green-based crystalline glaze are mixed with a ball mill and water in a mass ratio of 1:2:1 and then ball-milled. After passing through a 120-mesh sieve, a crystalline glaze slurry is obtained for later use. The raw materials of the green-based crystalline glaze include, by weight, 45 parts of albite, 30 parts of quartz, 10 parts of limestone, 18 parts of zinc oxide, 2 parts of kaolin, 2 parts of copper oxide, and 3 parts of barium carbonate.

[0081] The raw materials for the iridescent effect glaze are mixed with a ball mill and water in a mass ratio of 1.5:2:1 and then ball-milled. After passing through a 120-mesh sieve, an iridescent effect glaze slurry is obtained for later use. The raw material formula for the iridescent effect glaze includes, by weight, 35 parts of albite, 30 parts of quartz, 8 parts of limestone, 18 parts of zinc oxide, 2 parts of kaolin, 6 parts of manganese oxide, 10 parts of boric acid, 3 parts of red lead, and 5 parts of bone ash.

[0082] A crystalline glaze slurry is applied to the bisque-fired ceramic tile blank, and after drying, a glazed body is obtained.

[0083] Apply a flowing color effect glaze to the glazed body, and dry it again to obtain the effect glaze body.

[0084] The ceramic tile with the effect glaze was fired in a kiln. During firing, it took 240 minutes to go from room temperature to 300°C, 150 minutes to go from 300°C to 950°C, and 40 minutes to go from 950°C to 1300°C. After holding at that temperature for 20 minutes, the temperature was lowered to 500°C. Finally, the power was turned off and the tile was allowed to cool naturally, thus obtaining a ceramic tile with a green base and flowing crystalline glaze.

[0085] It should be understood that the application of the present invention is not limited to the examples above. Those skilled in the art can make improvements or modifications based on the above description, and all such improvements and modifications should fall within the protection scope of the appended claims.

Claims

1. A green-based, iridescent crystalline glaze, characterized in that, The product includes a green-based crystalline glaze and a flowing color effect glaze. The raw material formula of the green-based crystalline glaze, by weight, includes: 34-45 parts of albite, 20-30 parts of quartz, 10-12 parts of limestone, 12-18 parts of zinc oxide, 2-5 parts of kaolin, 2-6 parts of copper oxide, and 3-8 parts of barium carbonate. The molar ratio of Si to Al in the green-based crystalline glaze is 8-11:1, the molar ratio of Si to Ca is 6-14:1, and copper oxide accounts for 2-4% of the total weight of the raw materials in the green-based crystalline glaze. The raw material formula of the flowing color effect glaze, by weight, includes: 30-35 parts of albite, 25-30 parts of quartz, 8-10 parts of limestone, 12-18 parts of zinc oxide, 2-6 parts of kaolin, 2-6 parts of manganese oxide, 5-10 parts of boric acid, 1-3 parts of red lead, and 5-10 parts of bone ash. The manganese oxide accounts for 2-6% of the total weight of the raw materials in the flowing color effect glaze.

2. A method for preparing a green-based, iridescent crystalline glaze as described in claim 1, characterized in that, Including the following steps: Weigh out the raw materials for the green base crystalline glaze and the flowing color effect glaze according to the proportions of each component, and set aside. The raw materials of the green crystalline glaze are mixed with water in a ball mill at a mass ratio of 1-1.5:2:1 and then ball milled. After that, the mixture is passed through an 80-120 mesh sieve to obtain a crystalline glaze slurry for later use. The raw materials of the iridescent glaze are mixed with a ball mill and water in a mass ratio of 1-1.5:2:1 and then ball milled. After that, the mixture is passed through a 120-140 mesh sieve to obtain an iridescent glaze slurry for later use.

3. A method for preparing ceramic tiles using the green-based flowing crystalline glaze described in claim 1, characterized in that, Including the following steps: A crystalline glaze slurry is applied to the bisque-fired ceramic tile blank, and after drying, a glazed body is obtained. Apply a flowing color effect glaze to the glazed body and dry it again to obtain the effect glaze body. The ceramic tile with the effect glaze is fired in a kiln. During firing, the temperature is raised from room temperature to 300℃ in 120-240 minutes, from 300℃ to 950℃ in 90-150 minutes, and from 950℃ to 1300℃ in 40-60 minutes. After holding at this temperature for 10-30 minutes, the temperature is lowered to 500℃-600℃. Finally, the power is turned off and the tile is allowed to cool naturally, resulting in a ceramic tile with a green base and flowing crystalline glaze.

4. The method for preparing ceramic bricks according to claim 3, characterized in that, In the step of applying crystalline glaze slurry to the bisque-fired ceramic tile, the glaze thickness is 1.2-1.5 mm.

5. The method for preparing ceramic bricks according to claim 3, characterized in that, In the step of applying the flowing color effect glaze to the glazed body, the glaze thickness is 1.0-1.2 mm.

6. A ceramic tile with a green base and flowing crystalline glaze, characterized in that, The ceramic bricks are prepared using the method described in any one of claims 3-5.

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