Pearlescent colorful glitter frit and preparation method thereof

Abstract

The present invention discloses a pearlescent iridescent frit, which comprises the following raw materials, calculated by weight: 8-20 parts perlite, 25-35 parts quartz, 8-15 parts alumina, 10-18 parts fused magnesia, 3-8 parts potassium fluorosilicate, 8-15 parts potassium nitrate, 5-10 parts phase separator, 5-10 parts cerium oxide, and 6-16 parts flux. The pearlescent iridescent frit and its preparation method proposed in the present invention not only produce a strong and uniform pearlescent iridescent effect without affecting the original pattern of the tile's decorative layer, but also effectively maintain the pearlescent iridescent effect even during high-temperature firing, thereby overcoming the shortcomings of the prior art.

Description

Technical Field

[0001] The present invention relates to the technical field of building ceramics, in particular to a pearlescent colorful sparkling frit and a preparation method thereof. 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 the selection of raw materials and the preparation process, the existing pearlescent iridescent frits result in technical problems such as weak pearlescent iridescent effect and uneven distribution of iridescent points on the glaze of most produced ceramic tiles. In addition, the existing technology generally uses high-refractive-index oxides (such as iron oxide) to wrap the surface of low-refractive-index mica minerals to create a pearlescent iridescent effect. However, since iron oxide is dark in color and easily turns red, it can cover the original pattern of the ceramic tile decorative layer and affect its decorative effect. In addition, the high-temperature decomposition of mica minerals can easily cause the pearlescent iridescent frit to lose its pearlescent iridescent effect, so that the pearlescent iridescent frit can only be used under low-temperature calcination conditions. Therefore, the limitations of the above-mentioned factors have led to a very limited scope of application of the existing pearlescent iridescent frit. Summary of the Invention

[0005] The purpose of the present invention is to propose a pearlescent iridescent frit and a preparation method thereof, which can not only form a strong and uniform pearlescent iridescent effect without affecting the pattern effect of the original decorative layer of the tile, but also effectively maintain its pearlescent iridescent effect under high-temperature firing, so as to overcome the shortcomings of the existing technology.

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

[0007] A pearlescent iridescent frit comprises the following raw materials, calculated by weight: 8 to 20 parts of perlite, 25 to 35 parts of quartz, 8 to 15 parts of aluminum oxide, 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 a phase separator, 5 to 10 parts of cerium oxide, and 6 to 16 parts of a flux.

[0008] 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.

[0009] Furthermore, the flux includes zinc oxide and lithium carbonate, and calculated by mass ratio, the mixing ratio of the zinc oxide to the lithium carbonate is (0.8-1.2):1.

[0010] Furthermore, the phase separation agent is calcium phosphate.

[0011] Furthermore, calculated by mass percentage, the chemical composition of the pearlescent iridescent 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%.

[0012] Furthermore, calculated by mass, the pearlescent colorful sparkling frit includes the following raw materials: 10 parts of perlite, 32 parts of quartz, 10 parts of alumina, 15 parts of fused magnesia, 5 parts of potassium fluorosilicate, 10 parts of potassium nitrate, 8 parts of phase separator, 6 parts of cerium oxide and 9 parts of flux.

[0013] A method for preparing a pearlescent colorful glitter frit, for preparing the above-mentioned pearlescent colorful glitter frit, comprises the following steps:

[0014] 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;

[0015] 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;

[0016] 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.

[0017] Furthermore, in step C, the temperature curve of the high temperature firing is:

[0018] It takes 1.5 to 3 hours to heat from room temperature to 500°C;

[0019] From 500℃ to 1100℃, it takes 1.5 to 2.5 hours;

[0020] From 1100℃ to 1530℃, it takes 0.2~0.4h;

[0021] 1530℃, keep warm for 0.1~0.2h;

[0022] It takes 0.05 to 0.2 hours to reduce the temperature from 1500°C to 1400°C;

[0023] 1400℃, keep warm for 0.2~0.4h.

[0024] Furthermore, in step C, the temperature curve of the high temperature firing is as follows:

[0025] It takes 2 hours to heat from room temperature to 500℃;

[0026] It takes 2 hours to increase the temperature from 500°C to 1100°C;

[0027] From 1100℃ to 1530℃, it takes 0.3h;

[0028] 1530℃, keep warm for 0.16h;

[0029] It takes 0.1h to reduce the temperature from 1500℃ to 1400℃;

[0030] 1400℃, keep warm for 0.3h.

[0031] The technical solution provided by the present invention can have the following beneficial effects:

[0032] 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.

[0033] 2. Because the pearlescent iridescent frit is essentially fluorphlogopite glass coated with cerium oxide, the fluorphlogopite is coated with cerium oxide, which has excellent high-temperature resistance, to form a high-temperature protective layer. This further ensures the high-temperature resistance of the fluorphlogopite, allowing the pearlescent iridescent frit to be used even under high-temperature firing, thus expanding its application range. Furthermore, the cerium oxide used in this technical solution is white, which, compared to the darker iron oxide, is less likely to obscure the original ceramic pattern, thus ensuring the decorative effect.

[0034] 3. 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. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 This is a surface microstructure diagram of a ceramic obtained by applying a glaze made from the pearlescent iridescent frit in Example 1 of the present invention to the ceramic surface.

[0036] Figure 2 This is a glaze effect diagram of a ceramic obtained by applying a glaze made from the pearlescent colorful sparkling frit in Example 1 of the present invention to a ceramic surface. DETAILED DESCRIPTION

[0037] The present technical solution provides a pearlescent colorful sparkling frit, which includes the following raw materials, calculated by mass: 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 a phase separator, 5 to 10 parts of cerium oxide and 6 to 16 parts of a flux.

[0038] In order to solve the technical problems in the prior art that the pearlescent iridescent glitter frit has weak iridescent effect, uneven distribution of iridescent points, and is easily lost under high-temperature firing, the present technical solution proposes a pearlescent iridescent glitter frit, the raw materials of which include perlite, quartz, alumina, fused magnesia, potassium nitrate, a phase separator, cerium oxide, and a flux.

[0039] Specifically, the prior art generally uses high-refractive-index oxides (such as iron oxide) to wrap the surface of low-refractive-index mica minerals to form a pearlescent iridescent effect. However, since iron oxide is dark in color and easily turns red, it 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 iridescent frit to no longer have a pearlescent iridescent effect, so that the pearlescent iridescent frit can only be used under low-temperature calcination conditions.

[0040] 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.

[0041] It should be noted that fused magnesia is a general term for products produced by high-temperature treatment of magnesium raw materials such as magnesia ore to reach a molten state. Calculated by mass percentage, the chemical composition of fused magnesia includes MgO ≥ 98%, SiO2 ≤ 0.6% and CaO ≤ 1.2%.

[0042] 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.

[0043] 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.

[0044] 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.

[0045] 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.

[0046] When the mesh size of cerium oxide is too large, the roughness of the pearlescent particles coated with fluorphlogopite mica increases, affecting the uniformity of the iridescent effect. When the mesh size of 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 cerium oxide is limited to ensure the uniformity of the pearlescent iridescent effect at a lower cost.

[0047] 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.

[0048] It is further explained that the flux includes zinc oxide and lithium carbonate, and calculated by mass ratio, the mixing ratio of the zinc oxide and the lithium carbonate is (0.8-1.2):1.

[0049] 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 flux 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, facilitating the crystallization of cerium oxide, thereby further enhancing the pearlescent and iridescent effect; it can also improve anti-fouling properties.

[0050] It is further specified that the phase separation agent is calcium phosphate.

[0051] Calcium phosphate calcination produces phosphorus pentoxide. 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 frit, making it easier for cerium oxide crystals to precipitate, further enhancing the frit's pearlescent, iridescent, and shimmering effect. Furthermore, calcium oxide, also produced during the calcination of calcium phosphate, also acts as a flux, helping to lower the frit's calcination temperature and ensure complete calcination, ensuring the frit's iridescent, iridescent, and shimmering effect.

[0052] It is further explained that, calculated by mass percentage, the chemical composition of the pearlescent colorful sparkling frit includes SiO247~48%, Al2O319~22%, Fe2O30.2~0.5%, CaO 5~6%, MgO 10~12%, K2O 7~8.5%, ZnO4.4~4.5%, Na2O 0.02~0.03%, CeO 6~8% and P2O53.5~4.5%.

[0053] In another preferred embodiment of the present technical solution, a pearlescent colorful sparkling frit is selected, whose chemical composition includes SiO247-48%, Al2O319-22%, Fe2O30.2-0.5%, CaO 5-6%, MgO 10-12%, K2O 7-8.5%, ZnO4.4-4.5%, Na2O 0.02-0.03%, CeO 6-8% and P2O53.5-4.5% calculated by mass percentage, wherein 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.

[0054] It is further explained that, calculated by mass, the pearlescent colorful sparkling frit includes the following raw materials: 10 parts of perlite, 32 parts of quartz, 10 parts of alumina, 15 parts of fused magnesia, 5 parts of potassium fluorosilicate, 10 parts of potassium nitrate, 8 parts of phase separator, 6 parts of cerium oxide and 9 parts of flux.

[0055] In a preferred embodiment of the present technical solution, the formula of the pearlescent colorful glitter frit is further optimized to optimize the high temperature resistance of the pearlescent colorful glitter frit and the intensity and uniformity of the pearlescent colorful glitter effect.

[0056] A method for preparing a pearlescent colorful glitter frit, for preparing the above-mentioned pearlescent colorful glitter frit, comprises the following steps:

[0057] 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;

[0058] 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;

[0059] 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.

[0060] 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.

[0061] 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.

[0062] Further explanation, in step C, the temperature curve of the high temperature firing is:

[0063] It takes 1.5 to 3 hours to heat from room temperature to 500°C;

[0064] From 500℃ to 1100℃, it takes 1.5 to 2.5 hours;

[0065] From 1100℃ to 1530℃, it takes 0.2~0.4h;

[0066] 1530℃, keep warm for 0.1~0.2h;

[0067] It takes 0.05 to 0.2 hours to reduce the temperature from 1500°C to 1400°C;

[0068] 1400℃, keep warm for 0.2~0.4h.

[0069] In a preferred embodiment of the present technical solution, the temperature curve of the high-temperature firing of the frit is optimized, which is helpful to ensure the pearlescent and colorful sparkling effect of the frit.

[0070] Specifically, the 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 and colorful sparkle effect will deteriorate; if the holding time is too short, the amount of fluorophlogopite synthesized will be small, and the pearlescent and colorful sparkle effect will also deteriorate.

[0071] More specifically, it takes 0.05 to 0.2 hours for the frit to cool from 1500°C to 1400°C during the high-temperature firing process. If the cooling time is too short, the fluorophlogopite is not completely wrapped, the precipitation amount of pearlescent particles of cerium oxide wrapped fluorophlogopite is reduced, and the pearlescent colorful sparkle effect is deteriorated; if the cooling time is too long, the long-term cooling causes the viscosity of the frit to decrease uniformly, which is not conducive to the cerium oxide crystals wrapping the fluorophlogopite. The precipitation amount of pearlescent particles of cerium oxide wrapped fluorophlogopite is also reduced, and the pearlescent colorful sparkle effect is also deteriorated.

[0072] Further explanation, in step C, the temperature curve of the high temperature firing is as follows:

[0073] It takes 2 hours to heat from room temperature to 500℃;

[0074] It takes 2 hours to increase the temperature from 500°C to 1100°C;

[0075] From 1100℃ to 1530℃, it takes 0.3h;

[0076] 1530℃, keep warm for 0.16h;

[0077] It takes 0.1h to reduce the temperature from 1500℃ to 1400℃;

[0078] 1400℃, keep warm for 0.3h.

[0079] In a 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 conducive to ensuring that the pearlescent and colorful flashing effect of the frit is optimal.

[0080] The technical solution of the present invention is further illustrated below through specific implementation methods.

[0081] Example 1

[0082] A. 6 parts of cerium oxide with a mesh size of 300 and 10 parts of perlite with a mesh size of 325 were mixed evenly, and water was added to mix to obtain mixture I; mixture I was fed into a pelletizer and dried to obtain granules I;

[0083] B. 32 parts of quartz, 10 parts of alumina, 15 parts of 400-mesh fused magnesia, 5 parts of potassium fluorosilicate, and 10 parts of potassium nitrate were mixed uniformly, and water was added to mix to obtain a mixture II; the mixture II was fed into a pelletizer and dried to obtain granules II;

[0084] C. After evenly mixing particles I and II, 8 parts of calcium phosphate, 4 parts of zinc oxide and 5 parts of lithium carbonate are added, mixed and fired at high temperature. After water quenching, cooling and drying, a pearlescent colorful sparkling frit is obtained; wherein, the temperature curve of high temperature firing is as follows: from room temperature to 500°C, it takes 1.5 to 3 hours; from 500°C to 1100°C, it takes 1.5 to 2.5 hours; from 1100°C to 1530°C, it takes 0.2 to 0.4 hours; at 1530°C, keep warm for 0.1 to 0.2 hours; from 1500°C to 1400°C, it takes 0.05 to 0.2 hours; at 1400°C, keep warm for 0.2 to 0.4 hours.

[0085] The pearlescent iridescent frit prepared in this embodiment is mixed with kaolin, sodium carboxymethyl cellulose solution, sodium tripolyphosphate and water to form a pearlescent iridescent glaze. The pearlescent iridescent glaze is applied to the surface of a ceramic having a base glaze layer to form a ceramic having a pearlescent iridescent glaze layer. The surface microstructure of the ceramic is shown in FIG. Figure 1 As shown in the figure, a large number of pearlescent particles of fluorphlogopite wrapped in cerium oxide can be clearly seen distributed in the glass phase of the glaze layer. In addition, the glaze effect is shown in the figure below. Figure 2 As shown, it can be seen that its glaze can present a strong pearlescent and colorful sparkling effect under light conditions, and the sparkling effect is uniform.

[0086] Example 2

[0087] A. After uniformly mixing 10 parts of cerium oxide with a mesh size of 325 and 20 parts of perlite with a mesh size of 325, water was added and mixed to obtain a mixture I; the mixture I was fed into a pelletizer and dried to obtain granules I;

[0088] B. 25 parts of quartz, 8 parts of alumina, 18 parts of 380-mesh fused magnesia, 8 parts of potassium fluorosilicate, and 8 parts of potassium nitrate were mixed uniformly, and water was added to mix to obtain a mixture II; the mixture II was fed into a pelletizer and dried to obtain granules II;

[0089] C. After evenly mixing particles I and II, 10 parts of calcium phosphate, 6 parts of zinc oxide and 5 parts of lithium carbonate are added, mixed and fired at high temperature. After water quenching, cooling and drying, a pearlescent colorful sparkling frit is obtained; wherein, the temperature curve of high temperature firing is as follows: from room temperature to 500°C, it takes 1.5 to 3 hours; from 500°C to 1100°C, it takes 1.5 to 2.5 hours; from 1100°C to 1530°C, it takes 0.2 to 0.4 hours; at 1530°C, keep warm for 0.1 to 0.2 hours; from 1500°C to 1400°C, it takes 0.05 to 0.2 hours; at 1400°C, keep warm for 0.2 to 0.4 hours.

[0090] Example 3

[0091] A. After uniformly mixing 6 parts of cerium oxide with a mesh size of 325 and 10 parts of perlite with a mesh size of 300, water was added and mixed to obtain a mixture I; the mixture I was fed into a pelletizer and dried to obtain granules I;

[0092] B. 30 parts of quartz, 15 parts of alumina, 10 parts of 400-mesh fused magnesia, 5 parts of potassium fluorosilicate, and 15 parts of potassium nitrate were uniformly mixed, and water was added to mix to obtain a mixture II; the mixture II was fed into a pelletizer and dried to obtain granules II;

[0093] C. After evenly mixing particles I and II, 5 parts of calcium phosphate, 8 parts of zinc oxide and 7 parts of lithium carbonate are added, mixed and fired at high temperature. After water quenching, cooling and drying, a pearlescent colorful sparkling frit is obtained; wherein, the temperature curve of high temperature firing is as follows: from room temperature to 500°C, it takes 1.5 to 3 hours; from 500°C to 1100°C, it takes 1.5 to 2.5 hours; from 1100°C to 1530°C, it takes 0.2 to 0.4 hours; at 1530°C, keep warm for 0.1 to 0.2 hours; from 1500°C to 1400°C, it takes 0.05 to 0.2 hours; at 1400°C, keep warm for 0.2 to 0.4 hours.

[0094] Comparative Example 1

[0095] The preparation method and raw materials of Comparative Example 1 are the same as those of Example 1, except that cerium oxide is not added to the raw materials in Comparative Example 1.

[0096] Comparative Example 2

[0097] The preparation method and raw materials of Comparative Example 2 are the same as those of Example 1, except that the phase separation agent calcium phosphate is not added to the raw materials in Comparative Example 2.

[0098] Comparative Example 3

[0099] The preparation method and raw materials of Comparative Example 3 are the same as those of Example 1, except that quartz, alumina, fused magnesia, potassium fluorosilicate and potassium nitrate are not added to the raw materials in Comparative Example 3.

[0100] Comparative Example 4

[0101] The preparation method and raw materials of Comparative Example 4 are the same as those of Example 1, except that mineral mica is used to replace the quartz, alumina, fused magnesia, potassium fluorosilicate and potassium nitrate that form fluorphlogopite in Example 1 in Comparative Example 4, that is, the pearlescent iridescent frit in Comparative Example 4 includes the following raw materials calculated by mass: 10 parts of perlite, 72 parts of mineral mica, 8 parts of phase separator, 6 parts of cerium oxide and 9 parts of flux.

[0102] The pearlescent iridescent frits prepared in Examples 1-3 and Comparative Examples 1-4 were mixed with kaolin, sodium carboxymethyl cellulose solution, sodium tripolyphosphate, and water to form a pearlescent iridescent glaze. The pearlescent iridescent glaze was applied to the surface of a ceramic tile having a base glaze layer to form a ceramic tile having a pearlescent iridescent glaze layer. The ceramic tile was subjected to conventional hardness, glossiness, and antifouling grade tests in the field of architectural ceramics. The results are shown in Table 1 below:

[0103] Table 1 Performance test results of glazed tiles of Examples 1-3 and Comparative Examples 1-4

[0104]

[0105] It can be seen from the performance test results in Table 1 that the tiles obtained from the pearlescent iridescent frit of this scheme not only have a strong and uniform pearlescent iridescent effect, but also have good hardness and anti-fouling properties, so that the tiles obtained using the pearlescent iridescent frit are both decorative and practical, which is more conducive to meeting the usage needs of consumers.

[0106] In Comparative Example 1, since cerium oxide is not added, pearlescent particles of fluorphlogopite coated with cerium oxide cannot be formed, resulting in a weak pearlescent glitter effect on the glaze of the ceramic tile obtained using the pearlescent glitter frit of Comparative Example 1.

[0107] In Comparative Example 2, since the phase separator calcium phosphate is not added, it is not conducive to the precipitation of cerium oxide crystals, that is, it is not conducive to the formation of pearlescent particles of cerium oxide-coated fluorphlogopite. Although the glaze surface still has a certain pearlescent and colorful sparkling effect, compared with the glaze effect of Example 1, the pearlescent and colorful sparkling effect of the glaze surface of the ceramic tile prepared in Comparative Example 1 is average.

[0108] In Comparative Example 3, since quartz, alumina, fused magnesia, potassium fluorosilicate and potassium nitrate were not added, fluorophlogopite could not be formed, that is, pearlescent particles of fluorophlogopite wrapped with cerium oxide could not be formed, resulting in the ceramic tile glaze obtained using the pearlescent iridescent frit of Comparative Example 3 having a weak pearlescent iridescent effect.

[0109] Although mineral mica is used in Comparative Example 4 to replace the quartz, alumina, fused magnesia, potassium fluorosilicate and potassium nitrate that form fluorphlogopite in Example 1, the decomposition temperature of mineral mica is between 800 and 900°C, resulting in the decomposition of the pearlescent iridescent frit during the high-temperature firing process, and the formation of cerium oxide-wrapped mineral mica pearlescent particles cannot be formed, resulting in the glaze pearlescent iridescent effect of the tiles obtained using the pearlescent iridescent frit of Comparative Example 4 being weak.

[0110] 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 colorful glitter frit, characterized by: Calculated by mass, the raw materials include: 8 to 20 parts of perlite, 25 to 35 parts of quartz, 8 to 15 parts of aluminum oxide, 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; the essence of the pearlescent colorful sparkling frit is cerium oxide wrapped in fluorphlogopite glass.

2. The pearlescent colorful glitter frit 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.

3. The pearlescent colorful glitter frit according to claim 1, characterized in that: The flux includes zinc oxide and lithium carbonate, and calculated by mass ratio, the mixing ratio of the zinc oxide to the lithium carbonate is (0.8-1.2):

1.

4. The pearlescent colorful glitter frit according to claim 3, characterized in that: The phase separation agent is calcium phosphate.

5. The pearlescent colorful glitter frit according to claim 1, characterized in that: Calculated by mass, the pearlescent colorful sparkling frit includes the following raw materials: 10 parts of perlite, 32 parts of quartz, 10 parts of alumina, 15 parts of fused magnesia, 5 parts of potassium fluorosilicate, 10 parts of potassium nitrate, 8 parts of phase separator, 6 parts of cerium oxide and 9 parts of flux.

6. A method for preparing a pearlescent colorful glitter frit, characterized in that: The method for preparing the pearlescent colorful glitter frit according to any one of claims 1 to 5 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.

7. The method for preparing a pearlescent colorful glitter frit according to claim 6, characterized in that: In step C, the temperature curve of the high temperature firing is: It takes 1.5 to 3 hours to heat from room temperature to 500°C; From 500℃ to 1100℃, it takes 1.5 to 2.5 hours; From 1100℃ to 1530℃, it takes 0.2~0.4h; 1530℃, keep warm for 0.1~0.2h; It takes 0.05 to 0.2 hours to reduce the temperature from 1500°C to 1400°C; 1400℃, keep warm for 0.2~0.4h.

8. The method for preparing a pearlescent colorful glitter frit according to claim 7, characterized in that: In step C, the temperature curve of the high temperature firing is as follows: It takes 2 hours to heat from room temperature to 500℃; It takes 2 hours to increase the temperature from 500°C to 1100°C; From 1100℃ to 1530℃, it takes 0.3h; 1530℃, keep warm for 0.16h; It takes 0.1h to reduce the temperature from 1500℃ to 1400℃; 1400℃, keep warm for 0.3h.

Images