A pearlescent colorful glazed tile

Abstract

The present invention discloses a pearlescent iridescent glazed tile, comprising, from bottom to top, a body layer, a base glaze layer, an inkjet printing layer, a dry particle positioning layer, and a pearlescent iridescent glaze layer. The dry particle positioning frit glaze comprises the following raw materials, calculated by weight: 8-15 parts quartz, 5-12 parts alumina, 10-15 parts zircon powder, 5-10 parts lead carbonate, and 49-87 parts flux I. The pearlescent iridescent glaze comprises the following raw materials, calculated by weight: 4-8 parts kaolin, 92-96 parts pearlescent iridescent frit, 0.2-0.5 parts sodium carboxymethyl cellulose, 0.2-0.4 parts sodium tripolyphosphate, and 35-45 parts water. The pearlescent iridescent glazed tile proposed by the present invention is advantageous for presenting a strong and uniform pearlescent iridescent effect on the surface of the glazed tile while ensuring the decorative effect of the inkjet printing layer.

Description

Technical Field

[0001] The present invention relates to the technical field of building ceramics, in particular to a pearlescent colorful glittering glazed tile. Background Art

[0002] In the vast ceramics market, consumer demands are becoming increasingly diverse and personalized. Consumers not only pursue practicality and durability but also have high expectations for artistic value and visual beauty. This shift in market demand is driving the ceramics industry to continuously innovate technology and develop products to meet these growing aesthetic and practical needs.

[0003] During the production process of ceramic tiles, the blending of glazes is extremely important. The same ceramic tile body can produce different glaze effects depending on the glaze. The varying tactile and visual qualities of the glazes can influence consumer choices. Pearlescent Sparkle Frit is a special type of frit. When applied to the ceramic tile body and fired at high temperatures, the glaze imparts a pearlescent, iridescent effect. This not only meets market demand for aesthetically pleasing ceramic tile appearance, but also provides new insights and directions for technological innovation and product upgrades in the ceramic industry, avoiding homogenization and enhancing the added value of ceramic tile products.

[0004] Due to differences in raw material selection and manufacturing processes, existing pearlescent iridescent frits often produce ceramic tile glazes with weak iridescent effects and uneven iridescent distribution. Furthermore, to control production costs, existing glazed tiles with a pearlescent iridescent effect typically consist of a body layer, a base glaze layer, an inkjet-printed layer, and a pearlescent iridescent layer. However, since each glaze layer is a flat decorative layer, the relatively flat surface of the decorative layer hinders the glitter effect of the pearlescent iridescent glaze layer, resulting in a poor pearlescent iridescent effect. Summary of the Invention

[0005] The purpose of the present invention is to propose a pearlescent iridescent glazed tile. By adding a dry particle positioning layer with both a sense of transparency and a concave-convex effect to the bottom of the pearlescent iridescent glaze layer, while ensuring the decorative effect of the inkjet printing layer, the dry particle positioning layer and the pearlescent iridescent glaze layer cooperate with each other, which is conducive to presenting a strong and uniform pearlescent iridescent effect on the surface of the glazed tile, so as to effectively solve the technical problems of the existing pearlescent iridescent glaze, such as the weak pearlescent iridescent effect and uneven distribution of the iridescent points, and overcome the shortcomings of the existing technology.

[0006] To achieve this object, the present invention adopts the following technical solutions:

[0007] A pearlescent iridescent glazed tile comprises a body layer, a base glaze layer, an inkjet printing layer, a dry particle positioning layer, and a pearlescent iridescent glaze layer, which are arranged in sequence from bottom to top; wherein the dry particle positioning layer is obtained by calcining dry particle positioning frit glaze, and the pearlescent iridescent glaze layer is obtained by calcining pearlescent iridescent glaze;

[0008] Calculated by weight, the dry particle positioning frit glaze includes the following raw materials: 8 to 15 parts of quartz, 5 to 12 parts of alumina, 10 to 15 parts of zircon powder, 5 to 10 parts of lead carbonate and 49 to 87 parts of flux I;

[0009] Calculated by weight, the pearlescent iridescent glaze comprises the following raw materials: 4 to 8 parts of kaolin, 92 to 96 parts of pearlescent iridescent frit, 0.2 to 0.5 parts of sodium carboxymethyl cellulose, 0.2 to 0.4 parts of sodium tripolyphosphate, and 35 to 45 parts of water;

[0010] Calculated by mass, the pearlescent iridescent frit includes the following raw materials: 8 to 20 parts of perlite, 25 to 35 parts of quartz, 8 to 15 parts of alumina, 10 to 18 parts of fused magnesia, 3 to 8 parts of potassium fluorosilicate, 8 to 15 parts of potassium nitrate, 5 to 10 parts of phase separator, 5 to 10 parts of cerium oxide and 6 to 16 parts of flux II.

[0011] Furthermore, calculated as a percentage by mass, the content of zirconium oxide in the zircon powder is 70-85%.

[0012] Furthermore, the particle size distribution of the dry particle positioning frit glaze is as follows: the residue on a 100-mesh sieve is 0.1-0.5%, the residue on a 120-mesh sieve is 40-50%, and the residue on a 140-mesh sieve is 70-80%.

[0013] Furthermore, the firing curve of the dry particle positioning frit glaze is:

[0014] It takes 1.5 to 3 hours to heat up from room temperature to 500°C;

[0015] It takes 0.5 to 1.5 hours to heat up from 500°C to 1100°C;

[0016] It takes 0.4 to 1 hour to heat up from 1100°C to 1530°C;

[0017] 1530℃, keep warm for 0.5~1.2h.

[0018] Furthermore, the flux I comprises potassium feldspar, sodium feldspar, calcined talc, barium carbonate, wollastonite and zinc oxide;

[0019] Calculated by mass, the dry particle positioning frit glaze includes the following raw materials: 8 to 15 parts of quartz, 5 to 12 parts of aluminum oxide, 10 to 15 parts of zircon powder, 30 to 40 parts of potassium feldspar, 8 to 15 parts of sodium feldspar, 2 to 5 parts of calcined talc, 1 to 4 parts of barium carbonate, 5 to 15 parts of wollastonite, 3 to 8 parts of zinc oxide, and 5 to 10 parts of lead carbonate.

[0020] Furthermore, the thickness of the dry particle positioning layer is 5 to 8 μm, and the thickness of the pearlescent iridescent glaze layer is 2 to 5 μm.

[0021] Furthermore, the specific gravity of the pearlescent iridescent glaze is 1.28 to 1.32, and in terms of mass percentage, the residue of the pearlescent iridescent glaze after passing through a 325-mesh sieve is 0.3 to 0.5%.

[0022] Furthermore, the mesh number of the cerium oxide is 300-325 meshes, the mesh number of the perlite is 300-325 meshes, and the mesh number of the fused magnesia is 380-400 meshes.

[0023] Furthermore, the flux II includes zinc oxide and lithium carbonate, and the mixing ratio of the zinc oxide and the lithium carbonate is (0.8-1.2):1 according to the mass ratio;

[0024] The phase separation agent is calcium phosphate;

[0025] Calculated by mass percentage, the chemical composition of the pearlescent colorful sparkling frit includes SiO2 47-48%, Al2O3 19-22%, Fe2O3 0.2-0.5%, CaO 5-6%, MgO 10-12%, K2O 7-8.5%, ZnO 4.4-4.5%, Na2O 0.02-0.03%, CeO 6-8% and P2O5 3.5-4.5%.

[0026] Furthermore, the preparation method of the pearlescent colorful glitter frit comprises the following steps:

[0027] A. After uniformly mixing cerium oxide and perlite according to the proportion, water is added and mixed to obtain mixture I; mixture I is fed into a pelletizer and dried to obtain granules I;

[0028] B. After uniformly mixing quartz, alumina, fused magnesia, potassium fluorosilicate and potassium nitrate according to the proportion, adding water and mixing to obtain mixture II; feeding mixture II into a pelletizer, and drying to obtain granules II;

[0029] C. After evenly mixing granules I and II, add the formulated amount of phase separator and flux, mix and sinter at high temperature, quench with water, cool and dry to obtain a pearlescent colorful glittering frit.

[0030] The technical solution provided by the present invention can have the following beneficial effects:

[0031] 1. The essence of the pearlescent iridescent frit of this technical solution is cerium oxide wrapped in fluorphlogopite glass, and the refractive index of the cerium oxide crystal is 2.44, and the refractive index of the fluorphlogopite is 1.6. At the same time, the refractive index of the glass phase generated by the glass in the frit is 1.54, so that the glaze surface formed by the glaze with the addition of the pearlescent iridescent frit has three crystals with different refractive indices. Since the cerium oxide crystal has a face-centered cubic crystal structure, its crystal plane parallel to the glaze surface has a low interfacial energy, and thus exhibits strong anisotropy during the growth process, and has good specular reflection properties for visible light, thus forming a strong specular reflection. When the incident light shines on the glaze surface formed by the glaze with the addition of the pearlescent iridescent frit, the glaze surface can simultaneously undergo refraction, reflection and interference. Moreover, since fluorphlogopite is translucent and cerium oxide is white, the glaze surface forms a strong and uniform pearlescent iridescent effect.

[0032] 2. This technical solution adds a dry particle positioning layer between the inkjet printing layer and the pearlescent iridescent glaze layer, which has both a sense of transparency and a concave-convex effect and matches the pearlescent iridescent glaze layer. Without affecting the decorative effect of the inkjet printing layer, this technical solution effectively promotes the pearlescent particles of fluorphlogopite wrapped in cerium oxide with different refractive indices in the inner and outer layers to produce stronger reflection, refraction and interference under light conditions, thereby presenting a stronger pearlescent iridescent effect. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 This is a glaze effect diagram of the glazed tile prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0034] The present technical solution provides a pearlescent iridescent glazed tile, comprising a body layer, a base glaze layer, an inkjet printing layer, a dry particle positioning layer, and a pearlescent iridescent glaze layer, which are sequentially arranged from bottom to top; wherein the dry particle positioning layer is obtained by calcining dry particle positioning frit glaze, and the pearlescent iridescent glaze layer is obtained by calcining pearlescent iridescent glaze;

[0035] Calculated by weight, the dry particle positioning frit glaze includes the following raw materials: 8 to 15 parts of quartz, 5 to 12 parts of alumina, 10 to 15 parts of zircon powder, 5 to 10 parts of lead carbonate and 49 to 87 parts of flux I;

[0036] Calculated by weight, the pearlescent iridescent glaze comprises the following raw materials: 4 to 8 parts of kaolin, 92 to 96 parts of pearlescent iridescent frit, 0.2 to 0.5 parts of sodium carboxymethyl cellulose, 0.2 to 0.4 parts of sodium tripolyphosphate, and 35 to 45 parts of water;

[0037] Calculated by mass, the pearlescent iridescent frit includes the following raw materials: 8 to 20 parts of perlite, 25 to 35 parts of quartz, 8 to 15 parts of alumina, 10 to 18 parts of fused magnesia, 3 to 8 parts of potassium fluorosilicate, 8 to 15 parts of potassium nitrate, 5 to 10 parts of phase separator, 5 to 10 parts of cerium oxide and 6 to 16 parts of flux II.

[0038] In order to solve the technical problems in the prior art that the pearlescent iridescent glazed tiles have weak pearlescent iridescent effect and uneven distribution of iridescent points, the present technical solution proposes a pearlescent iridescent glazed tile, comprising a body layer, a base glaze layer, an inkjet printing layer, a dry particle positioning layer and a pearlescent iridescent glaze layer arranged in sequence from bottom to top; wherein the dry particle positioning layer is obtained by calcining the dry particle positioning frit glaze, and the pearlescent iridescent glaze layer is obtained by calcining the pearlescent iridescent glaze, by adding a dry particle positioning layer with both a sense of transparency and a concave-convex effect between the inkjet printing layer and the pearlescent iridescent glaze layer, and optimizing the formulas of the dry particle positioning frit glaze and the pearlescent iridescent glaze, while ensuring the decorative effect of the inkjet printing layer, the dry particle positioning layer and the pearlescent iridescent glaze layer cooperate with each other, which is conducive to presenting a strong and uniform pearlescent iridescent effect on the surface of the glazed tile to meet usage requirements.

[0039] It should be noted that the green body layer in this scheme is made by pressing and drying the conventional ceramic green body in the ceramic field; the base glaze layer is obtained by calcining the conventional base glaze in the ceramic field, and the inkjet printing layer is printed with the conventional color ink in the ceramic field. The ceramic green body, base glaze and inkjet printing layer are not further described here.

[0040] First, the existing technology generally uses high-refractive-index oxides (such as iron oxide) to coat the surface of low-refractive-index mica minerals to create a pearlescent effect. However, due to the dark color of iron oxide, it easily turns red, which can easily cover the original pattern of the ceramic, affecting its decorative effect. In addition, the high-temperature decomposition of mica minerals can easily cause the pearlescent frit to lose its pearlescent effect, making it only applicable to the field of artistic ceramics and difficult to apply to the field of architectural ceramics. Therefore, the pearlescent glaze of this technical solution cannot be designed based on the above principles.

[0041] Therefore, in order to solve the defects in the above-mentioned prior art, the present technical solution uses perlite as a layered structure carrier, uses quartz to increase the silicon element, fused magnesia to provide magnesium element, potassium fluorosilicate to provide potassium and fluorine elements, alumina to provide aluminum element and potassium nitrate to provide potassium element, so that quartz, fused magnesia, potassium fluorosilicate, alumina and potassium nitrate react with each other to generate fluorophlogopite with a layered structure, and cerium oxide is wrapped around the outside of the fluorophlogopite to form pearlescent particles of cerium oxide wrapped fluorophlogopite, that is, the essence of the pearlescent iridescent frit is cerium oxide wrapped fluorophlogopite glass, and the refractive index of cerium oxide crystals is 2.44, and the refractive index of fluorophlogopite is 1.6. At the same time, the refractive index of the glass phase generated by the glass in the frit is 1.54, so that the glaze formed by the glaze with the addition of pearlescent iridescent frit has three crystals with different refractive indices. Because cerium oxide crystals have a face-centered cubic structure, their crystal faces parallel to the glaze surface have low interfacial energy. Consequently, they exhibit strong anisotropy during growth, resulting in excellent specular reflection properties for visible light, resulting in intense specular reflection. When incident light strikes the glaze surface formed by the addition of pearlescent iridescent frit, the glaze undergoes simultaneous refraction, reflection, and interference. Furthermore, due to the translucency of fluorphlogopite and the white color of cerium oxide, the glaze surface creates a strong and uniform pearlescent iridescent effect. Furthermore, compared to mica, fluorphlogopite exhibits excellent high-temperature resistance. Furthermore, because the pearlescent iridescent frit is essentially fluorphlogopite glass encapsulated by cerium oxide, the highly heat-resistant cerium oxide forms a protective layer around the fluorphlogopite, further ensuring the fluorphlogopite's high-temperature resistance. This allows the pearlescent iridescent frit to be used even at high firing temperatures, expanding its application range. In addition, the cerium oxide in this technical solution is white, and compared with the darker iron oxide, it is not easy to cover the original pattern of the ceramic, thereby ensuring its decorative effect.

[0042] It should be noted that fused magnesia is a general term for the product of magnesia raw materials such as magnesia that are molten after high-temperature treatment. Calculated by mass percentage, the chemical composition of fused magnesia includes MgO ≥ 98%, SiO2 ≤ 0.6% and CaO ≤ 1.2%.

[0043] In order to further enhance the pearlescent and iridescent effect of the pearlescent and iridescent frit, the present technical solution also adds a phase separation agent to the frit formula. The phase separation agent is easily separated from the glass phase network structure during the heat treatment process, resulting in phase separation. Phase separation can promote the enrichment of cerium oxide in the frit, making it easier for cerium oxide crystals to precipitate and be wrapped around the outside of the layered fluorphlogopite. This not only helps to increase the precipitation amount of pearlescent particles of cerium oxide-wrapped fluorphlogopite, forming a strong and uniform pearlescent and iridescent effect, but also helps to improve the hardness of the frit.

[0044] Furthermore, since the increase in fluorine content will hinder the weakening of hydroxyl groups and lattice at high temperature, thereby delaying the dehydration and decomposition of fluorophlogopite, that is, the fluorine element in fluorophlogopite plays an important role in stabilizing the lattice structure, significantly improving the thermal stability of fluorophlogopite, and within a certain range, the higher the fluorine content, the greater the degree to which the decomposition temperature of fluorophlogopite can be increased. Therefore, in this technical solution, the amount of potassium fluorosilicate added is limited to 3 to 8 parts to ensure the formation of fluorophlogopite and improve its high temperature resistance at a lower cost.

[0045] In addition, it should be noted that the frit of the present technical solution utilizes the reaction of quartz, alumina and flux to generate a silicate network structure, thereby forming a glass phase, which is beneficial to improving the hardness and wear resistance of the frit. However, due to the high melting points of quartz and alumina, and the large amount of both added, when no flux is added or the amount of flux added is too little, it is easy to cause the frit to fail to be completely calcined during the firing process, affecting the amount of pearlescent particles of cerium oxide-coated fluorphlogopite that are precipitated, and thus affecting the pearlescent and colorful sparkling effect of the frit. Therefore, in the present technical solution, the amount of flux added is limited to 6 to 16 parts, which is beneficial to ensure the pearlescent and colorful sparkling effect of the frit.

[0046] Therefore, the pearlescent iridescent frit in this technical solution is made of perlite, quartz, alumina, fused magnesia, potassium nitrate, phase separator, cerium oxide and flux II, so that the pearlescent iridescent frit can not only form a strong and uniform pearlescent iridescent effect without affecting the decorative effect of the inkjet printing layer, but also effectively maintain its pearlescent iridescent effect under high-temperature firing, so that it can be applied to the field of building ceramics and expand its scope of use.

[0047] Furthermore, the raw materials of the pearlescent iridescent glaze of the present technical solution also include kaolin, sodium carboxymethyl cellulose, sodium tripolyphosphate and water. Among them, kaolin can effectively improve the suspension and water retention of the glaze slurry, so that the glaze slurry does not produce precipitation during the glazing process; sodium carboxymethyl cellulose is beneficial to improving the fluidity of the glaze slurry, making it easier to glaze, and at the same time, sodium carboxymethyl cellulose can improve the bonding performance of the body and glaze, and prevent deglazing; sodium tripolyphosphate is beneficial to increasing the fluidity of the pearlescent iridescent glaze while reducing the water content of the pearlescent iridescent glaze, thereby improving the fluidity and stability of the pearlescent iridescent glaze; water, as a solvent, helps to dissolve and mix the various components evenly, ensuring the effect of the pearlescent iridescent glaze. That is, the raw materials in the pearlescent iridescent glaze in the present technical solution cooperate with each other to ensure its performance.

[0048] Secondly, in order to best present the glittering effect of the pearlescent iridescent glaze on the surface of the glazed tiles, this technical solution adds a dry particle positioning layer with both translucency and concave-convex effects between the inkjet printing layer and the pearlescent iridescent glaze layer. Without affecting the decorative effect of the inkjet printing layer, this technical solution effectively promotes the pearlescent particles of fluorphlogopite wrapped in cerium oxide with different refractive indices in the inner and outer layers to produce stronger reflection, refraction and interference under light conditions, thereby presenting a stronger pearlescent iridescent effect.

[0049] Specifically, existing conventional dry-grained fixed frit glazes typically utilize a silicon-aluminum-calcium-magnesium-potassium-sodium-barium system, with alumina as the primary crystalline phase. However, this system does not easily create a glaze with a concave-convex effect. Therefore, the dry-grained fixed frit glaze in this technical solution cannot be based on this principle. Furthermore, existing zirconium white frit glazes generally utilize the high whiteness of zirconium oxide, but their transparency is extremely poor, easily obscuring the inkjet print layer and affecting its decorative effect. Therefore, the dry-grained fixed frit glaze in this technical solution cannot be based on this principle either.

[0050] In order to make the dry particle positioning frit glaze have both transparency and low high temperature fluidity, the technical solution introduces zircon powder and lead carbonate to form a high-lead and high-zirconium system. On the one hand, it is beneficial to promote the color development of the inkjet printing layer, thereby improving the decorative effect of the glazed tiles. On the other hand, it is also beneficial to make zirconium oxide crystals as the main crystal phase. Zirconium oxide has high high temperature viscosity and low high temperature fluidity, so that the dry particle positioning frit glaze is not easy to melt flat after being fired in the kiln, and still maintains its original state and has the original thickness, thereby achieving the concave and convex effect of the dry particle positioning layer. The concave and convex effect of the dry particle positioning layer can cause the pearlescent iridescent glaze layer to have a thickness deviation, that is, the pearlescent iridescent glaze layer is relatively thin at the convex parts of the dry particle positioning layer, and thinner at the concave parts of the dry particle positioning layer. The thickness is relatively thick. The above thickness deviation is conducive to promoting the inner and outer layers of cerium oxide-wrapped fluorphlogopite pearlescent particles with different refractive indices to produce stronger reflection, refraction and interference under light conditions, thereby enhancing the pearlescent fantasy and sparkling effect of the glaze. At the same time, the more obvious the concave and convex effect of the dry particle positioning layer is, the more conducive it is to promoting the inner and outer layers of cerium oxide-wrapped fluorphlogopite pearlescent particles with different refractive indices to produce reflection, refraction and interference under light conditions, and the more conducive it is to enhancing the pearlescent fantasy and sparkling effect of the glaze. In addition, the refractive index of zirconium oxide crystals is 2.14, and they themselves can also produce reflection, refraction and interference with the cerium oxide-wrapped fluorphlogopite pearlescent particles under light conditions, which is conducive to further enhancing the pearlescent fantasy and sparkling effect.

[0051] Furthermore, due to the high melting point of zircon powder, adding only zircon powder to a high-lead, high-zirconium system to form zirconium oxide crystals after calcination can easily lead to underfiring of the dry-grain positioning frit glaze. Therefore, the dry-grain positioning frit glaze of this technical solution also incorporates alumina, which has better high-temperature fluidity than zirconium oxide formed by calcining zircon powder. By combining alumina with zircon powder and limiting the addition amounts of these two raw materials, the dry-grain positioning frit glaze maintains low high-temperature fluidity while also avoiding underfiring, thereby ensuring the performance of the dry-grain positioning layer.

[0052] At the same time, to ensure the transparency of the high-lead, high-zirconium system, this technical solution adds flux I to the high-lead, high-zirconium system, and the amount of flux I added is limited to 48 to 83 parts. A large amount of flux I reacts with quartz and lead carbonate to form a silicate glass network structure, forming a glass phase, thereby giving the high-lead, high-zirconium system a sense of transparency. In addition, due to the high content of zircon powder in the high-lead, high-zirconium system in this technical solution, the shrinkage rate and porosity of the dry particle positioning layer are increased, resulting in the formation of micropores in the dry particle positioning layer and a poorer embossing effect. The glass phase of the high-lead, high-zirconium system in this technical solution can fill the microporous defects in the dry particle positioning layer, ensuring the embossing effect. In addition, the reaction of lead carbonate with quartz and other substances to form a silicate glass phase helps significantly reduce the toxicity of lead.

[0053] It should be noted that, since the pearlescent iridescent glaze layer in this scheme forms a sealing layer for the dry particle positioning layer, that is, the pearlescent iridescent glaze layer reacts with lead carbonate and quartz and other substances to form a silicate glass phase to form a sealing layer, the toxicity of lead is further reduced. According to the standard "GB / T3810.15-2016 Ceramic Tile Test Method Part 15: Determination of Lead and Cadmium Dissolution from Glazed Tiles", the lead dissolution amount of the glazed tiles is <0.003 mg / dm2, which is in line with the national standard.

[0054] Further, calculated by mass percentage, the content of zirconium oxide in the zircon powder is 70-85%.

[0055] This solution preferably uses zircon powder with a zirconium oxide content of 70-85% as the formula raw material for the dry particle positioning frit glaze, which is more conducive to promoting the formation of zirconium oxide crystals in the glaze layer and more conducive to improving the pearlescent and colorful sparkling effect.

[0056] It is further explained that the particle size distribution of the dry particle positioning frit glaze is as follows: the residue on a 100-mesh sieve is 0.1-0.5%, the residue on a 120-mesh sieve is 40-50%, and the residue on a 140-mesh sieve is 70-80%.

[0057] In a preferred embodiment of the present technical solution, by optimizing the particle grading of the dry particle positioning frit glaze, the following effects are achieved: first, it is beneficial to improve the fluidity of the dry particle positioning frit glaze, and improve the convenience and stability of its application; second, it is beneficial to increase the calcination temperature of the dry particle positioning frit glaze, thereby lowering the melting boundary and enhancing the three-dimensional concave and convex effect of the dry particle positioning, thereby enhancing the pearlescent and colorful sparkling effect.

[0058] It should be noted that the particle gradation of dry particle positioning frit glaze refers to the particle gradation formed after the dry particle positioning frit glaze is dried and crushed into powder by a crusher.

[0059] Further explanation, the firing curve of the dry particle positioning frit glaze is:

[0060] It takes 1.5 to 3 hours to heat up from room temperature to 500°C;

[0061] It takes 0.5 to 1.5 hours to heat up from 500°C to 1100°C;

[0062] It takes 0.4 to 1 hour to heat up from 1100°C to 1530°C;

[0063] 1530℃, keep warm for 0.5~1.2h.

[0064] In a preferred embodiment of the present technical solution, the firing curve of the dry particle positioning frit glaze is optimized to help ensure its relevant performance.

[0065] It is further stated that the flux I comprises potassium feldspar, sodium feldspar, calcined talc, barium carbonate, wollastonite and zinc oxide;

[0066] Calculated by mass, the dry particle positioning frit glaze includes the following raw materials: 8 to 15 parts of quartz, 5 to 12 parts of aluminum oxide, 10 to 15 parts of zircon powder, 30 to 40 parts of potassium feldspar, 8 to 15 parts of sodium feldspar, 2 to 5 parts of calcined talc, 1 to 4 parts of barium carbonate, 5 to 15 parts of wollastonite, 3 to 8 parts of zinc oxide, and 5 to 10 parts of lead carbonate.

[0067] Potassium feldspar, sodium feldspar, calcined talc, wollastonite, and zinc oxide all have the effect of lowering firing temperatures and promoting sintering. Furthermore, barium carbonate increases the transparency and glossiness of the frit, while zinc oxide acts as a nucleating agent, lowering the crystallization activation energy and peak crystallization temperature, thus facilitating oxidative crystallization. Therefore, in a preferred embodiment of this technical solution, flux I includes potassium feldspar, sodium feldspar, calcined talc, barium carbonate, wollastonite, and zinc oxide. The amounts of these raw materials added to the dry-grained fixed frit glaze are limited to ensure high-temperature viscosity and translucency of the dry-grained fixed layer.

[0068] Preferably, calculated by mass, the dry particle positioning frit glaze includes the following raw materials: 10 parts of quartz, 8 parts of aluminum oxide, 12 parts of zircon powder, 35 parts of potassium feldspar, 10 parts of sodium feldspar, 3 parts of calcined talc, 2 parts of barium carbonate, 8 parts of wollastonite, 6 parts of zinc oxide and 6 parts of lead carbonate.

[0069] It is further explained that the thickness of the dry particle positioning layer is 5 to 8 μm, and the thickness of the pearlescent iridescent glaze layer is 2 to 5 μm.

[0070] The thickness of the dry particle positioning layer is related to the amount of dry particle positioning frit glaze applied. The greater the amount of dry particle positioning frit glaze applied, the thicker the dry particle positioning layer, the rougher its surface, the more obvious the concave-convex effect, the more obvious the thickness deviation of the pearlescent iridescent glaze layer, and the more conducive it is to improving the pearlescent iridescent effect of the glaze surface. Similarly, the thickness of the pearlescent iridescent glaze layer is related to the amount of pearlescent iridescent glaze applied. The greater the amount of dry pearlescent iridescent glaze applied, the thicker the pearlescent iridescent glaze layer, the more obvious the thickness deviation of the pearlescent iridescent glaze layer, and the more conducive it is to improving the pearlescent iridescent effect of the glaze surface. Therefore, in a preferred embodiment of the present technical solution, by limiting the amount of dry particle frit glaze applied and the amount of pearlescent iridescent glaze applied, the thickness of the dry particle positioning layer is 5 to 8 μm, and the thickness of the pearlescent iridescent glaze layer is 2 to 5 μm. By coordinating the thicknesses of the two, the pearlescent iridescent effect is improved at a lower cost.

[0071] It is further explained that the specific gravity of the pearlescent iridescent glaze is 1.28 to 1.32, and in terms of mass percentage, the residue of the pearlescent iridescent glaze after passing through a 325-mesh sieve is 0.3 to 0.5%.

[0072] In a preferred embodiment of the present technical solution, by limiting the specific gravity and fineness of the pearlescent iridescent glaze, the pearlescent iridescent glaze layer and the dry particle positioning layer cooperate with each other to form a better pearlescent iridescent effect and improve the glaze quality of the glazed tiles.

[0073] It is further described that the mesh number of the cerium oxide is 300-325 meshes, the mesh number of the perlite is 300-325 meshes, and the mesh number of the fused magnesia is 380-400 meshes.

[0074] When the mesh size of the cerium oxide is too large, the roughness of the pearlescent particles coated with fluorphlogopite mica increases, thereby affecting the uniformity of the pearlescent, iridescent, and shimmering effect. When the mesh size of the cerium oxide is too small, it increases the difficulty of grinding, reduces production efficiency, and increases production costs. Therefore, in a preferred embodiment of this technical solution, the mesh size of the cerium oxide is limited to ensure the uniformity of the pearlescent, iridescent, and shimmering effect at a lower cost.

[0075] Furthermore, by limiting the mesh size of perlite and fused magnesia, it is beneficial to improve the intensity and uniformity of the pearlescent colorful glitter effect.

[0076] It is further described that the flux II includes zinc oxide and lithium carbonate, and the mixing ratio of the zinc oxide and the lithium carbonate is (0.8-1.2):1 according to the mass ratio;

[0077] The phase separation agent is calcium phosphate;

[0078] Calculated by mass percentage, the chemical composition of the pearlescent colorful sparkling frit includes SiO2 47-48%, Al2O3 19-22%, Fe2O3 0.2-0.5%, CaO 5-6%, MgO 10-12%, K2O 7-8.5%, ZnO 4.4-4.5%, Na2O 0.02-0.03%, CeO 6-8% and P2O5 3.5-4.5%.

[0079] Both zinc oxide and lithium carbonate have a good effect of lowering the firing temperature and promoting sintering. Therefore, in a preferred embodiment of the present technical solution, the fluxing agent II includes zinc oxide and lithium carbonate, and the mixing ratio of zinc oxide and lithium carbonate is limited to promote high-temperature calcination of the frit, thereby ensuring its pearlescent and iridescent effect. In addition, in addition to its fluxing effect, zinc oxide can also act as a nucleation agent, reducing the crystallization activation energy and crystallization peak temperature, which is beneficial to the crystallization of cerium oxide, thereby further enhancing the pearlescent and iridescent effect; on the other hand, it can also improve anti-fouling performance.

[0080] Calcium phosphate produces phosphorus pentoxide during calcination. Due to its high coordination number and strong cationic field, phosphorus pentoxide easily separates from the glassy network during heat treatment, leading to phase separation. This phase separation promotes the enrichment of cerium oxide in the pearlescent frit, making it easier for cerium oxide crystals to precipitate, further enhancing the pearlescent effect of the frit. Furthermore, calcium oxide, also produced during the calcination of calcium phosphate, also acts as a flux, helping to lower the calcination temperature and ensure complete calcination, ensuring the pearlescent effect of the frit.

[0081] In another preferred embodiment of the present technical solution, a pearlescent colorful sparkling frit is selected, whose chemical composition includes SiO2 47-48%, Al2O3 19-22%, Fe2O3 0.2-0.5%, CaO 5-6%, MgO 10-12%, K2O 7-8.5%, ZnO 4.4-4.5%, Na2O 0.02-0.03%, CeO 6-8% and P2O5 3.5-4.5%, calculated in mass percentage. The SiO2 content is as high as 47-48%, which is a high-silicon frit, which is beneficial to ensure the hardness and wear resistance of the frit.

[0082] Further description, the preparation method of the pearlescent colorful glitter frit comprises the following steps:

[0083] A. After uniformly mixing cerium oxide and perlite according to the proportion, water is added and mixed to obtain mixture I; mixture I is fed into a pelletizer and dried to obtain granules I;

[0084] B. After uniformly mixing quartz, alumina, fused magnesia, potassium fluorosilicate and potassium nitrate according to the proportion, adding water and mixing to obtain mixture II; feeding mixture II into a pelletizer, and drying to obtain granules II;

[0085] C. After evenly mixing granules I and II, add the formulated amount of phase separator and flux, mix and sinter at high temperature, quench with water, cool and dry to obtain a pearlescent colorful glittering frit.

[0086] This technical solution also proposes a method for preparing pearlescent iridescent frit, which has simple steps and strong operability, and is conducive to ensuring the relevant properties of soft porcelain during the preparation process.

[0087] Specifically, in the present technical solution, cerium oxide and perlite are first mixed evenly according to a ratio, water is added for mixing to obtain mixture I, mixture I is fed into a pelletizer, and granules I are obtained after drying, and then quartz, alumina, fused magnesia, potassium fluorosilicate and potassium nitrate are mixed evenly according to a ratio, water is added for mixing to obtain mixture II, mixture II is fed into a pelletizer, and granules II are obtained after drying, thereby reducing the interface contact area between different raw materials and reducing the mutual penetration between glass phases during the sintering process of the frit, thereby ensuring the precipitation amount of pearlescent particles of cerium oxide-coated fluorphlogopite and ensuring the pearlescent and colorful sparkling effect of the frit.

[0088] Preferably, in step C, the temperature curve of the high temperature firing is:

[0089] It takes 1.5 to 3 hours to heat from room temperature to 500°C;

[0090] From 500℃ to 1100℃, it takes 1.5 to 2.5 hours;

[0091] From 1100℃ to 1530℃, it takes 0.2~0.4h;

[0092] 1530℃, keep warm for 0.1~0.2h;

[0093] It takes 0.05 to 0.2 hours to reduce the temperature from 1500°C to 1400°C;

[0094] 1400℃, keep warm for 0.2~0.4h.

[0095] In a preferred embodiment of the present technical solution, the temperature curve of the high-temperature firing of the pearlescent colorful glitter frit is optimized, which is helpful to ensure the pearlescent colorful glitter effect of the pearlescent colorful glitter frit.

[0096] Specifically, the pearlescent iridescent frit is kept at 1530°C for 0.1 to 0.2 hours during the high-temperature firing process. If the holding time is too long, the glass content of the frit will increase significantly, destroying the layered structure of perlite and fluorophlogopite, and the pearlescent iridescent effect will deteriorate; if the holding time is too short, the amount of fluorophlogopite synthesized will be small, and the pearlescent iridescent effect will also deteriorate.

[0097] More specifically, it takes 0.05 to 0.2 hours for the pearlescent iridescent frit to cool from 1500°C to 1400°C during the high-temperature firing process. If the cooling time is too short, the fluorphlogopite is not completely wrapped, the amount of pearlescent particles of cerium oxide wrapped fluorphlogopite is reduced, and the pearlescent iridescent effect is deteriorated; if the cooling time is too long, the long-term cooling causes the viscosity of the pearlescent iridescent frit to decrease uniformly, which is not conducive to the wrapping of fluorphlogopite by cerium oxide crystals. The amount of pearlescent particles of cerium oxide wrapped fluorphlogopite is also reduced, and the pearlescent iridescent effect is also deteriorated.

[0098] More preferably, in step C, the temperature curve of the high temperature firing is as follows:

[0099] It takes 2 hours to heat from room temperature to 500℃;

[0100] It takes 2 hours to increase the temperature from 500°C to 1100°C;

[0101] From 1100℃ to 1530℃, it takes 0.3h;

[0102] 1530℃, keep warm for 0.16h;

[0103] It takes 0.1h to reduce the temperature from 1500℃ to 1400℃;

[0104] 1400℃, keep warm for 0.3h.

[0105] In a more preferred embodiment of the present technical solution, the temperature curve of the high-temperature firing of the frit is further optimized so that the temperature curve of the high-temperature firing is optimized, which is beneficial to ensure that the pearlescent and colorful sparkling effect of the frit is optimal.

[0106] The technical solution of the present invention is further illustrated below through specific implementation methods.

[0107] Example 1

[0108] A pearlescent iridescent glazed tile comprises, arranged in order from bottom to top, a body layer, a base glaze layer, an inkjet printing layer, a dry particle positioning layer with a thickness of 6 μm, and a pearlescent iridescent glaze layer with a thickness of 3 μm; wherein the dry particle positioning layer is obtained by calcining a dry particle positioning frit glaze having a particle gradation of 0.1% on a 100-mesh sieve, 40% on a 120-mesh sieve, and 80% on a 140-mesh sieve; and the pearlescent iridescent glaze layer is obtained by calcining a pearlescent iridescent glaze having a specific gravity of 1.3 and a mass percentage of 0.3% on a 325-mesh sieve.

[0109] The dry particle positioning frit glaze includes the following raw materials, calculated by weight: 10 parts of quartz, 8 parts of aluminum oxide, 12 parts of zircon powder with a zirconium oxide content of 70%, 35 parts of potassium feldspar, 10 parts of sodium feldspar, 3 parts of calcined talc, 2 parts of barium carbonate, 8 parts of wollastonite, 6 parts of zinc oxide and 6 parts of lead carbonate;

[0110] Calculated in parts by mass, the pearlescent iridescent glaze includes the following raw materials: 5 parts of kaolin, 95 parts of pearlescent iridescent frit, 0.2 parts of sodium carboxymethyl cellulose, 0.3 parts of sodium tripolyphosphate and 40 parts of water; calculated in parts by mass, the pearlescent iridescent frit includes the following raw materials: 10 parts of perlite with a mesh size of 300 mesh, 32 parts of quartz, 10 parts of alumina, 15 parts of fused magnesia with a mesh size of 400 mesh, 5 parts of potassium fluorosilicate, 10 parts of potassium nitrate, 8 parts of calcium phosphate, 6 parts of cerium oxide with a mesh size of 325 mesh, 4 parts of zinc oxide and 5 parts of lithium carbonate.

[0111] Example 2

[0112] A pearlescent iridescent glazed tile comprises, arranged in order from bottom to top, a body layer, a base glaze layer, an inkjet printing layer, a dry particle positioning layer with a thickness of 5 μm, and a pearlescent iridescent glaze layer with a thickness of 4 μm; wherein the dry particle positioning layer is obtained by calcining a dry particle positioning frit glaze having a particle gradation of 0.5% on a 100-mesh sieve, 50% on a 120-mesh sieve, and 70% on a 140-mesh sieve; and the pearlescent iridescent glaze layer is obtained by calcining a pearlescent iridescent glaze having a specific gravity of 1.28 and a mass percentage of 0.5% on a 325-mesh sieve.

[0113] The dry particle positioning frit glaze includes the following raw materials, calculated by weight: 8 parts of quartz, 12 parts of aluminum oxide, 13 parts of zircon powder with a zirconium oxide content of 75%, 38 parts of potassium feldspar, 15 parts of sodium feldspar, 5 parts of calcined talc, 4 parts of barium carbonate, 8 parts of wollastonite, 6 parts of zinc oxide and 7 parts of lead carbonate;

[0114] Calculated in parts by mass, the pearlescent iridescent glaze includes the following raw materials: 4 parts of kaolin, 96 parts of pearlescent iridescent frit, 0.5 parts of sodium carboxymethyl cellulose, 0.2 parts of sodium tripolyphosphate and 45 parts of water; calculated in parts by mass, the pearlescent iridescent frit includes the following raw materials: 20 parts of perlite with a mesh size of 325 mesh, 25 parts of quartz, 8 parts of alumina, 18 parts of fused magnesia with a mesh size of 380 mesh, 8 parts of potassium fluorosilicate, 8 parts of potassium nitrate, 10 parts of calcium phosphate, 10 parts of cerium oxide with a mesh size of 325 mesh, 6 parts of zinc oxide and 5 parts of lithium carbonate.

[0115] Example 3

[0116] A pearlescent iridescent glazed tile comprises, arranged in order from bottom to top, a body layer, a base glaze layer, an inkjet printing layer, a dry particle positioning layer with a thickness of 8 μm, and a pearlescent iridescent glaze layer with a thickness of 2 μm; wherein the dry particle positioning layer is obtained by calcining a dry particle positioning frit glaze having a particle gradation of 0.3% on a 100-mesh sieve, 45% on a 120-mesh sieve, and 75% on a 140-mesh sieve; and the pearlescent iridescent glaze layer is obtained by calcining a pearlescent iridescent glaze having a specific gravity of 1.28 and a mass percentage of 0.4% on a 325-mesh sieve.

[0117] The dry particle positioning frit glaze includes the following raw materials, calculated by weight: 15 parts of quartz, 8 parts of aluminum oxide, 15 parts of zircon powder with a zirconium oxide content of 85%, 30 parts of potassium feldspar, 8 parts of sodium feldspar, 2 parts of calcined talc, 1 part of barium carbonate, 15 parts of wollastonite, 8 parts of zinc oxide and 10 parts of lead carbonate;

[0118] Calculated by mass, the pearlescent iridescent glaze includes the following raw materials: 4 to 8 parts of kaolin, 92 parts of pearlescent iridescent frit, 0.3 part of sodium carboxymethyl cellulose, 0.4 part of sodium tripolyphosphate and 3545 parts of water; calculated by mass, the pearlescent iridescent frit includes the following raw materials: 20 parts of perlite with a mesh size of 325 mesh, 25 parts of quartz, 8 parts of alumina, 18 parts of fused magnesia with a mesh size of 380 mesh, 8 parts of potassium fluorosilicate, 8 parts of potassium nitrate, 10 parts of calcium phosphate, 10 parts of cerium oxide with a mesh size of 325 mesh, 6 parts of zinc oxide and 5 parts of lithium carbonate.

[0119] Comparative Example 1

[0120] The brick surface structure and raw materials of Comparative Example 1 are the same as those of Example 1, except that no dry particle positioning layer is provided in Comparative Example 1.

[0121] Comparative Example 2

[0122] The brick surface structure and raw materials of Comparative Example 2 are the same as those of Example 1, except that zircon powder is not added to the dry particle positioning frit glaze in Comparative Example 2.

[0123] The glazed tiles prepared in Examples 1-3 and Comparative Examples 1-2 were subjected to conventional hardness, glossiness and antifouling grade tests in the field of architectural ceramics. The results are shown in Table 1 below:

[0124]

[0125] It can be seen from the performance test results in Table 1 that the glazed tiles obtained by this technical solution not only have a strong and uniform pearlescent and colorful glittering effect, but also have good hardness and anti-fouling properties, and are both decorative and practical, which is more conducive to meeting the usage needs of consumers.

[0126] In Comparative Example 1, since no dry particle positioning layer is set, and since the remaining glaze layers are all flat decorative layers, and the relatively flat surface of the decorative layer is not conducive to the glittering effect of the pearlescent iridescent glaze layer, the pearlescent iridescent effect of the glazed tiles obtained using Comparative Example 1 is weak.

[0127] In Comparative Example 2, the absence of zircon powder hindered the precipitation of zirconium oxide crystals and limited the concavo-convex effect of the dry particle positioning layer. Therefore, despite the provision of a dry particle positioning layer in Comparative Example 2, the resulting glazed tile still exhibited a weak pearlescent, iridescent effect.

[0128] The technical principles of the present invention have been described above with reference to specific embodiments. These descriptions are intended solely to illustrate the principles of the present invention and are not to be construed in any way as limiting the scope of protection of the present invention. Based on the explanations herein, those skilled in the art will readily conceive of other specific embodiments of the present invention without inventive effort, and such embodiments will fall within the scope of protection of the present invention.

Claims

1. A pearlescent iridescent glazed tile, characterized by: The invention comprises a body layer, a base glaze layer, an inkjet printing layer, a dry particle positioning layer and a pearlescent colorful glitter glaze layer, which are sequentially arranged from bottom to top; wherein the dry particle positioning layer is obtained by calcining the dry particle positioning frit glaze, and the pearlescent colorful glitter glaze layer is obtained by calcining the pearlescent colorful glitter glaze; Calculated by weight, the dry particle positioning frit glaze includes the following raw materials: 8 to 15 parts of quartz, 5 to 12 parts of alumina, 10 to 15 parts of zircon powder, 5 to 10 parts of lead carbonate and 49 to 87 parts of flux I; Calculated by weight, the pearlescent iridescent glaze comprises the following raw materials: 4 to 8 parts of kaolin, 92 to 96 parts of pearlescent iridescent frit, 0.2 to 0.5 parts of sodium carboxymethyl cellulose, 0.2 to 0.4 parts of sodium tripolyphosphate, and 35 to 45 parts of water; Calculated by mass, the pearlescent iridescent frit includes the following raw materials: 8 to 20 parts of perlite, 25 to 35 parts of quartz, 8 to 15 parts of alumina, 10 to 18 parts of fused magnesia, 3 to 8 parts of potassium fluorosilicate, 8 to 15 parts of potassium nitrate, 5 to 10 parts of phase separator, 5 to 10 parts of cerium oxide and 6 to 16 parts of flux II; the essence of the pearlescent iridescent frit is cerium oxide wrapped in fluorphlogopite glass.

2. The pearlescent iridescent glazed tile according to claim 1, characterized in that: Calculated by mass percentage, the content of zirconium oxide in the zircon powder is 70-85%.

3. The pearlescent iridescent glazed tile according to claim 1, characterized in that: The particle size distribution of the dry particle positioning frit glaze is as follows: the residue on a 100-mesh sieve is 0.1-0.5%, the residue on a 120-mesh sieve is 40-50%, and the residue on a 140-mesh sieve is 70-80%.

4. The pearlescent iridescent glazed tile according to claim 1, characterized in that: The firing curve of the dry particle positioning frit glaze is: It takes 1.5 to 3 hours to heat up from room temperature to 500°C; It takes 0.5 to 1.5 hours to heat up from 500°C to 1100°C; It takes 0.4 to 1 hour to heat up from 1100°C to 1530°C; 1530℃, keep warm for 0.5~1.2h.

5. The pearlescent iridescent glazed tile according to claim 1, characterized in that: The flux I comprises potassium feldspar, sodium feldspar, calcined talc, barium carbonate, wollastonite and zinc oxide; Calculated by mass, the dry particle positioning frit glaze includes the following raw materials: 8 to 15 parts of quartz, 5 to 12 parts of aluminum oxide, 10 to 15 parts of zircon powder, 30 to 40 parts of potassium feldspar, 8 to 15 parts of sodium feldspar, 2 to 5 parts of calcined talc, 1 to 4 parts of barium carbonate, 5 to 15 parts of wollastonite, 3 to 8 parts of zinc oxide, and 5 to 10 parts of lead carbonate.

6. The pearlescent iridescent glazed tile according to claim 1, characterized in that: The thickness of the dry particle positioning layer is 5 to 8 μm, and the thickness of the pearlescent colorful glaze layer is 2 to 5 μm.

7. The pearlescent iridescent glazed tile according to claim 1, characterized in that: The specific gravity of the pearlescent iridescent glaze is 1.28-1.32, and according to mass percentage, the residue of the pearlescent iridescent glaze after passing through a 325-mesh sieve is 0.3-0.5%.

8. The pearlescent iridescent glazed tile according to claim 1, characterized in that: The mesh number of the cerium oxide is 300-325 meshes, the mesh number of the perlite is 300-325 meshes, and the mesh number of the fused magnesia is 380-400 meshes.

9. The pearlescent iridescent glazed tile according to claim 1, characterized in that: The flux II includes zinc oxide and lithium carbonate, and the mixing ratio of the zinc oxide to the lithium carbonate is (0.8-1.2):1 according to the mass ratio; The phase separation agent is calcium phosphate.

10. The pearlescent iridescent glazed tile according to claim 1, characterized in that: The preparation method of the pearlescent colorful glitter frit comprises the following steps: A. After uniformly mixing cerium oxide and perlite according to the proportion, water is added and mixed to obtain mixture I; mixture I is fed into a pelletizer and dried to obtain granules I; B. After uniformly mixing quartz, alumina, fused magnesia, potassium fluorosilicate and potassium nitrate according to the proportion, adding water and mixing to obtain mixture II; feeding mixture II into a pelletizer, and drying to obtain granules II; C. After evenly mixing granules I and II, add the formulated amount of phase separator and flux, mix and sinter at high temperature, quench with water, cool and dry to obtain a pearlescent colorful glittering frit.

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