Flashing dry particles, flashing marble porcelain tile and preparation method of flashing dry particles and flashing marble porcelain tile

Abstract

The invention belongs to the field of architectural ceramics, and particularly discloses a flash dry particle, a flash marble porcelain tile and a preparation method thereof, the flash ceramic dry particle comprises the following raw material components: a basic dry particle material, CeO2 and PbO, and the initial melting temperature of the flash ceramic dry particle is 1100-1150 DEG C. According to the invention, CeO2 and PbO are added into the basic dry granules at the same time to prepare the flash ceramic dry granules, so that the secondary glaze firing temperature of CeO2 is reduced, the flatness of a glaze surface and the orientation degree and uniformity of CeO2 crystal grains are improved, and the flash effect of the glaze surface is improved; pbO is used as a strong fluxing agent, so that the high-temperature viscosity of a glaze melt can be greatly reduced, the smoothness of a fired glaze surface is improved, the reflectivity of the glaze surface is improved, the flashing effect of the glaze surface is improved, and the antifouling property of the glaze surface is improved. Meanwhile, PbO has a high refractive index, has a large difference value with the refractive index of glass glaze, and has a good enhancement effect on the flashing effect of the glaze surface.

Description

Technical Field

[0001] The present invention belongs to the technical field of building ceramics, and particularly relates to a flash dry granule, a flash marble porcelain tile and a preparation method thereof. Background Art

[0002] In daily life and work, people pay more and more attention to the comfort and beauty of the living and working environment. Whether it is a family residence or an office, people strive to create a harmonious and beautiful artistic atmosphere. This pursuit of spatial aesthetics not only meets people's material needs, but also gives great spiritual nourishment and comfort. As one of the main decorative materials, ceramic tiles have received extensive attention and application. For example, marble porcelain tile products imitating the texture, effect and texture of natural marble are very popular, especially the flash effect of natural marble, which has a diamond-like flash effect under light irradiation.

[0003] In the prior art, the preparation and production of ceramic tiles with a flash effect are mainly carried out in the following ways. For example, the Chinese invention patent with the publication number CN 111423113A discloses a diamond dry granule, a positioning diamond flash effect polished glazed tile and a preparation method thereof. The raw materials of the diamond dry granule include, by mass: 8-13% kaolin, 23-30% albite, 10-20% orthoclase, 20-25% calcite, 5-10% alumina, 3-6% calcined talc, 3-5% zinc oxide, and 15-25% zircon sand with a particle size of 150-250 mesh. The particle size distribution between 150-250 mesh of zircon sand is used for iron removal screening to solve the problem of dirt on the white brick surface. Without destroying the crystal structure, diamond dry granules with a particle size between 40-150 mesh are made. Through the difference in refractive index between it and the glaze surface, a diamond-like flash effect is achieved on the polished glazed tile according to the pattern positioning. However, due to the small expansion coefficient of zircon sand and high temperature of the raw materials, the glaze surface is prone to defects such as peeling, cracking and glaze chipping during the firing process after adding the glaze or dry granules, and the high content of zircon sand is likely to cause the radioactivity of the product to exceed the standard. The Chinese invention patent with the publication number CN 116395969A discloses a flash ceramic dry granule glaze, a ceramic tile and a preparation method thereof. The raw material composition of the flash ceramic dry granule includes frit dry granules and a flash material. Among them: the flash material includes CeO2, and the chemical composition of the frit dry granules contains ZrO2; and the particle size distribution of the frit dry granules is 15-20 wt% with a particle size of 10-30 mesh, 45-55 wt% with a particle size of 30-60 mesh, and 30-35 wt% with a particle size of 60-120 mesh. CeO2 and zircon crystals are precipitated during the firing process of the flash ceramic dry granule, and a flash dry granule with uneven texture is obtained. However, the melting point of CeO2 is high, and directly using it as a glaze component is likely to cause the glaze surface to be rough and have poor flatness, which not only affects the overall effect of the product, but also has poor stain resistance.

[0004] Therefore, there is an urgent need to develop a new flash ceramic glaze. On the premise of ensuring a smooth glaze surface, imitate marble porcelain tiles with good flash effect can be obtained, and the anti-fouling performance of the glaze surface is excellent. Summary of the Invention

[0005] The present invention aims to solve at least one of the technical problems existing in the above-mentioned prior art. For this purpose, the present invention provides a flash dry granule, a flash marble porcelain tile and a preparation method thereof. The flash dry granule improves the flash effect of the glaze surface by enhancing the specular reflection of the glaze surface and the crystal plane reflection of CeO2 grains in the glaze layer at the same time. When it is applied to ceramic tiles, flash marble porcelain tiles with excellent smoothness and anti-fouling properties can be obtained.

[0006] The inventive concept of the present invention is as follows: for flash materials (such as flash dry granules), their flash effect is mainly generated by the directional reflection of the materials to light. This reflection mainly consists of two parts. The first part is the specular reflection of the incident light on the surface of the glaze layer, and the second part is the reflection generated by the high-reflectivity crystals in the glaze layer. Among them: among the light reflected by the glaze surface in the first part, only the specular reflection with good directivity is beneficial to the formation of the flash effect. The smoother the glaze surface is, the better the flash effect is. Therefore, to improve the specular reflection of the glaze surface and increase the contribution of this part of the reflection to the flash effect, raw materials with high refractive index or those that can improve the high-temperature viscosity and the smoothness of the glaze surface can be used to increase the refractive index of the glass mechanism of the flash glaze layer. Based on this, CeO2 and PbO are added to the flash ceramic dry granule at the same time in the present invention. The two interact with each other to jointly improve the specular reflection of the glaze surface and the crystal plane reflection of CeO2 grains in the glaze layer, thereby enhancing the flash effect of the glaze surface.

[0007] Specifically, the CeO2 crystal has a face-centered cubic structure, and its

[200] plane is a singular plane with a low interfacial energy. At the same time, it is also an atomically close-packed plane and a smooth interface of the crystal grain. When the crystal grows from the glaze melt, the

[200] plane becomes the main exposed surface. The singular plane has smoothness at the atomic scale and has good crystal plane reflection characteristics for visible light. When the CeO2 grains are preferentially oriented with the

[200] plane, its refractive index is as high as 2.44. The surface of the crystal with a high refractive index has a high reflectivity, causing the glaze surface to form a strong specular reflection on the incident light, and thus the flash effect can be generated. However, the melting temperature of CeO2 is relatively high and it is not easy to melt. When it is directly added to the glaze, it is easy to cause the glaze surface to be rough, with poor flatness, and the overall flash effect is not ideal.

[0008] On the one hand, CeO2 is added to the dry granules in the present invention for high-temperature melting, reducing the secondary glaze firing temperature of CeO2, thereby improving the flatness of the glaze surface, the orientation degree and uniformity of CeO2 grains, and further improving the flash effect. On the other hand, PbO is introduced into the dry granules. As a strong flux, PbO can greatly reduce the high-temperature viscosity of the glaze melt, improve the smoothness of the fired glaze surface, increase the reflectivity, thereby improving the flash effect of the glaze surface, and is beneficial to improving the stain resistance of the glaze surface. At the same time, PbO itself has a high refractive index (2.4 - 2.6), and the difference from the refractive index of the glass glaze (about 1.50) is large, which is conducive to further enhancing the flash effect of the glaze surface. Therefore, by adding CeO2 and PbO simultaneously in the flash dry granules in the present invention, the two interact with each other, not only improving the smoothness and stain resistance of the glaze surface, but also obtaining an excellent flash effect.

[0009] To solve the above technical problems, a first aspect of the present invention provides a flash ceramic dry granule, and the raw material components of the flash ceramic dry granule include a basic dry granule material, cerium oxide, and lead oxide, and the initial melting temperature of the flash ceramic dry granule is 1100 - 1150 °C.

[0010] Specifically, the flash ceramic dry granule of the present invention is prepared by adding a certain amount of cerium oxide and lead oxide to the basic dry granule material. By utilizing the strong fluxing effect of lead oxide and its high refractive index, the high-temperature viscosity of the glaze melt is reduced, thereby achieving the improvement of the flash effect of the glaze surface while improving the smoothness and stain resistance of the glaze surface. At the same time, by adjusting the components of the basic dry granule material, the flash ceramic dry granule has a relatively high initial melting temperature, so as to improve the high-temperature fluidity of the glaze melt, improve the smoothness of the glaze surface, and further improve the flash effect of the glaze surface; and it is beneficial to reduce the generation of defects such as glaze surface pinholes and orange peel, and further improve the stain resistance of the glaze surface.

[0011] In some embodiments of the present invention, the mass ratio of cerium oxide to lead oxide is (1 - 4):1. By controlling the dosage relationship between cerium oxide and lead oxide, while improving the smoothness of the glaze surface, the flash effect of the glaze surface is improved.

[0012] In some embodiments of the present invention, by weight, it includes: 60 - 130 parts of basic dry granule material, 6 - 8 parts of cerium oxide, and 2 - 5 parts of lead oxide.

[0013] In some embodiments of the present invention, the raw material components of the basic dry granule material, by weight, include: 2 - 8 parts of potassium feldspar, 2 - 8 parts of sodium feldspar, 15 - 30 parts of calcite, 5 - 7 parts of zinc oxide, 4 - 8 parts of alumina, 30 - 50 parts of quartz, and 8 - 10 parts of zircon powder.

[0014] Specifically, the present invention increases the content of quartz in the basic dry granules to raise the initial melting temperature of the flash ceramic dry granules; meanwhile, a certain amount of zircon powder (1.9 - 2.0) with a high refractive index is added. During the high-temperature firing process, zircon crystals will precipitate from the zircon powder, forming reflections with CeO2 crystals on different crystal planes, thereby achieving the flash effect with multiple refractive surfaces.

[0015] The second aspect of the present invention provides a flash marble porcelain tile, comprising a body and a flash glaze layer provided on the upper surface of the body. The raw material components of the flash glaze layer include dry granule polishing dry granules and the above-mentioned flash ceramic dry granules.

[0016] In some embodiments of the present invention, the mass ratio of the dry granule polishing dry granules to the flash ceramic dry granules is 1:(0.2 - 0.3).

[0017] Specifically, the flash marble porcelain tile of the present invention uses the dry granule polishing dry granules as the base, and by adding a certain amount of flash ceramic dry granules, a flash imitation natural marble effect with uniform distribution can be obtained.

[0018] In some embodiments of the present invention, the initial melting temperature of the dry granule polishing dry granules is 1050 - 1120 °C, and the initial melting temperature of the dry granule polishing dry granules is lower than that of the flash ceramic dry granules.

[0019] Specifically, the present invention controls the initial melting temperature of the dry granule polishing dry granules to be lower than that of the flash ceramic dry granules. During the firing process, the dry granule polishing dry granules with a lower initial melting temperature will first present a liquid phase, which will fill between the flash ceramic dry granules, forming a flat and uniform glaze structure. The formation of this structure not only helps to improve the density of the glaze surface, thereby enhancing the stain resistance and wear resistance of the glaze surface, but also helps to obtain a glaze surface with higher flatness and smoothness, thereby improving the flash effect of the glaze surface.

[0020] In some embodiments of the present invention, the chemical composition of the dry granule polishing dry granules, by weight percentage, includes: SiO2 45 - 60%, Al2O3 8 - 15%, CaO 10 - 15%, MgO 0.5 - 5%, K2O 2 - 6%, Na2O 1 - 4%, ZnO 10 - 15%, BaO 0 - 10%.

[0021] In some embodiments of the present invention, the particle size of the dry granule polishing dry granules is 20 - 200 mesh, and the particle size of the flash ceramic dry granules is 30 - 100 mesh.

[0022] In some embodiments of the present invention, the particle size distribution of the dry granule polishing dry granules is: the mass ratio of 20 - 100 mesh is 70 - 80%, the mass ratio of 100 - 150 mesh is 10 - 15%, and the mass ratio of 150 - 200 mesh is 5 - 20%.

[0023] In some embodiments of the present invention, the particle size distribution of the flash ceramic dry particles is as follows: the mass ratio of particles with a size of 30 - 60 mesh is 70 - 80%, and the mass ratio of particles with a size of 60 - 100 mesh is 20 - 30%.

[0024] Specifically, dry particles for dry granule polishing and flash ceramic dry particles with different particle sizes and particle size distributions are filled with each other to obtain a smoother glaze surface, thereby further enhancing the flash effect of the glaze surface.

[0025] The third aspect of the present invention provides a method for preparing the above-mentioned flash marble porcelain tiles, comprising the following steps:

[0026] (1) Mix the raw materials for preparing the flash ceramic dry particles, after melting, pour them into water for quenching to obtain frit particles; then crush and screen the frit particles to obtain the flash ceramic dry particles;

[0027] (2) Add the flash ceramic dry particles and dry particles for dry granule polishing to a suspending agent and mix to obtain a dry particle slurry;

[0028] (3) Apply the dry particle slurry onto the green body to form a flash glaze layer, and after drying and firing, obtain the flash marble porcelain tiles.

[0029] Specifically, most traditional flash ceramic tiles adopt the method of dry cloth application, successively applying flash ceramic dry particles and dry particles for dry granule polishing on the surface of the green body. However, this preparation method is not conducive to the flatness of the glaze surface. Its flash effect only comes from the reflection formed by the flash crystals, the flash degree is limited to a certain extent, and the smoothness and stain resistance of the glaze surface are not good. The present invention adopts a wet glazing process. First, the flash ceramic dry particles and dry particles for dry granule polishing are made into a dry particle slurry, and then it is applied onto the surface of the green body by the method of pouring glaze, so as to obtain a smoother glaze surface, thereby enhancing the specular reflection of the glaze surface for incident light. Therefore, it has a stronger flash effect, and the smoothness and stain resistance of the glaze surface are also improved.

[0030] In some embodiments of the present invention, in step (1), the melting temperature is 1500 - 1600 °C, and the heat preservation time is 2 - 3 hours.

[0031] In some embodiments of the present invention, in step (2), the raw material components of the suspending agent, by weight, include 3 - 8 parts of polyacrylic acid, 0.5 - 2 parts of bentonite, 0.5 - 2 parts of defoaming agent, 0.1 - 0.3 parts of surfactant, 0.5 - 2 parts of thickening agent, and 90 - 95 parts of water.

[0032] In some embodiments of the present invention, in step (2), the mass ratio of the mixed dry particles of the flash ceramic dry particles and dry particles for dry granule polishing to the suspending agent is 1:(0.5 - 1.5).

[0033] In some embodiments of the present invention, in step (2), the specific gravity of the dry granule slurry is 1.20 - 1.25 g / cm 3 .

[0034] In some embodiments of the present invention, in step (3), the application amount of the dry granule slurry is 1000 - 1100 g / m 2 .

[0035] In some embodiments of the present invention, in step (3), the highest firing temperature is 1180 - 1220 °C, and the firing cycle is 50 - 70 minutes.

[0036] In some embodiments of the present invention, in step (3), before applying the dry granule slurry, it further includes the steps of applying a surface glaze, inkjet printing a pattern, and forming a surface glaze layer and a pattern decoration layer.

[0037] The above technical solution of the present invention has at least the following technical effects or advantages compared with the prior art:

[0038] (1) In the present invention, CeO2 and PbO are simultaneously added to the base dry granule material to prepare the flash ceramic dry granule, which is beneficial to reducing the secondary glaze firing temperature of CeO2, improving the flatness of the glaze surface, the orientation degree and uniformity of CeO2 grains, thereby improving the flash effect of the glaze surface; PbO, as a strong flux, can greatly reduce the high-temperature viscosity of the glaze melt, improve the smoothness of the fired glaze surface, increase the reflectivity of the glaze surface, thereby improving the flash effect of the glaze surface, and is beneficial to improving the stain resistance of the glaze surface. At the same time, PbO itself has a high refractive index, and the refractive index difference from the glass glaze is large, which has a good enhancing effect on the flash effect of the glaze surface.

[0039] (2) The present invention utilizes the interaction between CeO2 and PbO to jointly improve the flash effect of the flash ceramic dry granule from two aspects: improving the specular reflection of the glaze surface and the crystal plane reflection of CeO2 grains in the glaze layer. When it is applied to ceramic tiles, a flash marble porcelain tile with a smooth glaze surface, good stain resistance, and excellent flash effect is obtained. Description of the Drawings

[0040] Figure 1 It is a physical picture of the flash marble porcelain tile prepared in Example 1. Detailed Embodiments

[0041] The present invention will be specifically described below in conjunction with embodiments to facilitate the understanding of those skilled in the art. It is necessary to specifically point out here that the embodiments are only used to further illustrate the present invention and cannot be construed as a limitation on the protection scope of the present invention. Those skilled in the art, based on the above-mentioned invention content, make non-essential improvements and adjustments to the present invention, which should still fall within the protection scope of the present invention. At the same time, for the raw materials not detailed below, they are all commercially available products; for the process steps or preparation methods not detailed, they are all process steps or preparation methods known to those skilled in the art.

[0042] The chemical composition of the green body used in the examples and comparative examples of the present invention, by percentage, includes: SiO2 65%, Al2O3 22%, CaO 0.8%, MgO 0.9%, K2O 2.5%, Na2O 2.5%, Fe2O3 0.2%, TiO2 0.05%, loss on ignition 6.05%.

[0043] The chemical composition of the surface glaze layer, by percentage, includes: SiO2 59%, Al2O3 28%, CaO 0.5%, MgO 1.2%, K2O 1.3%, Na2O 4.2%, Fe2O3 0.2%, TiO2 0.05%, loss on ignition 5.55%.

[0044] The raw material components of the suspending agent, by weight, include: 5 parts of polyacrylic acid, 1 part of bentonite, 1 part of defoaming agent (octylphenol polyoxyethylene ether), 0.1 part of surfactant (sodium dodecyl sulfate), 1 part of thickening agent (sodium carboxymethyl cellulose), and 93 parts of water.

[0045] Example 1

[0046] A kind of flash ceramic dry granules, the raw material components of which, by weight, include: 2 parts of potassium feldspar, 2 parts of sodium feldspar, 15 parts of calcite, 1 part of zinc oxide, 4 parts of alumina, 30 parts of quartz, 8 parts of zircon powder, 6 parts of cerium oxide and 2 parts of lead oxide. The initial melting temperature of the flash ceramic dry granules is 1150 °C, and the particle size distribution is: the mass ratio of 30 - 60 mesh is 80%, and the mass ratio of 60 - 100 mesh is 20%.

[0047] A kind of flash marble porcelain tile, including a green body and a surface glaze layer, a pattern decoration layer and a flash glaze layer successively arranged on the surface of the green body, wherein: the raw material components of the flash glaze layer include dry granulation dry granules and the flash ceramic dry granules of this example.

[0048] Among them: The chemical composition of the dry granule for dry granule throwing, by weight percentage, includes: SiO2 56%, Al2O3 12%, CaO 12.5%, MgO 1.5%, K2O 3.5%, Na2O 2.5%, ZnO 12%. The initial melting temperature of the dry granule for dry granule throwing is 1100 °C, and the particle size distribution is: the mass ratio of 20-100 mesh is 80%, the mass ratio of 100-150 mesh is 15%, and the mass ratio of 150-200 mesh is 5%.

[0049] The preparation method of the above-mentioned flash marble porcelain tile includes the following steps:

[0050] (1) According to the raw material ratio, mix the raw materials for preparing the flash ceramic dry granule, melt at 1530 °C, keep warm for 2 hours, then pour into water for quenching to obtain molten block granules; then crush the molten block granules to obtain flash ceramic dry granules with a particle size of 30-100 mesh;

[0051] (2) Weigh the dry granule for dry granule throwing and the flash ceramic dry granule prepared in step (1) according to a mass ratio of 1:0.25, add to the suspending agent (the mass ratio of the mixed dry granules of the dry granule for dry granule throwing and the flash ceramic dry granule to the suspending agent is 1:1), stir evenly, and adjust the specific gravity to 1.2 g / cm 3 to obtain dry granule slurry;

[0052] (3) After mixing the raw materials of the bottom glaze layer according to the ratio, add water for ball milling (the mass ratio of the material to water is 100:40) to obtain a surface glaze with a fineness of 0.4 wt% residue on a 325-mesh sieve;

[0053] (4) Sequentially apply the surface glaze prepared in step (3), inkjet print the decorative pattern on the green body, and then apply the dry granule slurry prepared in step (2) (the application amount is 1000 g / m 2 ) to sequentially form a surface glaze layer, an inkjet printed pattern layer and a flash glaze layer. After drying and firing, the flash marble porcelain tile of this example is obtained. Among them: The highest firing temperature is 1200 °C, and the firing cycle is 60 minutes.

[0054] Example 2

[0055] A kind of flash ceramic dry granule, the raw material components of which, by weight parts, include: 4 parts of potassium feldspar, 6 parts of sodium feldspar, 20 parts of calcite, 6 parts of zinc oxide, 5 parts of alumina, 40 parts of quartz, 10 parts of zircon powder, 9 parts of cerium oxide and 3 parts of lead oxide. The initial melting temperature of the flash ceramic dry granule is 1120 °C, and the particle size distribution is: the mass ratio of 30-60 mesh is 80%, and the mass ratio of 60-100 mesh is 20%.

[0056] A flash marble porcelain tile, comprising a green body and a surface glaze layer, a pattern decoration layer and a flash glaze layer sequentially provided on the surface of the green body, wherein: the raw material components of the flash glaze layer include dry granulated abrasive dry granules and the flash ceramic dry granules of this embodiment.

[0057] Wherein: the chemical composition of the dry granulated abrasive dry granules, by weight percentage, includes: SiO2 59%, Al2O3 8%, CaO 12.5%, MgO 0.5%, K2O 3.5%, Na2O 1.5%, ZnO 12%, BaO 3%. The initial melting temperature of the dry granulated abrasive dry granules is 1080 °C, and the particle size distribution is: the mass ratio of 20-100 mesh is 80%, the mass ratio of 100-150 mesh is 15%, and the mass ratio of 150-200 mesh is 5%.

[0058] The preparation method of the above-mentioned flash marble porcelain tile comprises the following steps:

[0059] (1) According to the raw material ratio, mix the raw materials for preparing the flash ceramic dry granules, melt at 1530 °C, keep warm for 2 hours, then pour into water for quenching to obtain frit granules; then crush the frit granules to obtain flash ceramic dry granules with a particle size of 30-100 mesh;

[0060] (2) Weigh the dry granulated abrasive dry granules and the flash ceramic dry granules prepared in step (1) according to a mass ratio of 1:0.25, add to the suspending agent (the mass ratio of the mixed dry granules of the dry granulated abrasive dry granules and the flash ceramic dry granules to the suspending agent is 1:1), stir evenly, and adjust the specific gravity to 1.25 g / cm 3 to obtain dry granule slurry;

[0061] (3) After mixing the raw materials of the base glaze layer according to the ratio, add water for ball milling (the mass ratio of the material to water is 100:40) to obtain a surface glaze with a fineness of 0.4 wt% residue on a 325-mesh sieve;

[0062] (4) Sequentially apply the surface glaze prepared in step (3) and inkjet print the decorative pattern on the green body, and then apply the dry granule slurry prepared in step (2) (the application amount is 1100 g / m 2 ) to sequentially form a surface glaze layer, an inkjet printed pattern layer and a flash glaze layer. After drying and firing, the flash marble porcelain tile of this embodiment is obtained. Wherein: the highest firing temperature is 1220 °C, and the firing cycle is 50 minutes.

[0063] Example 3

[0064] A kind of flash ceramic dry granules, the raw material components of which by weight include: 8 parts of potassium feldspar, 8 parts of sodium feldspar, 30 parts of calcite, 7 parts of zinc oxide, 8 parts of alumina, 50 parts of quartz, 10 parts of zircon powder, 8 parts of cerium oxide and 5 parts of lead oxide. The initial melting temperature of the flash ceramic dry granules is 1100 °C, and the particle size distribution is: the mass ratio of 30-60 mesh is 80%, and the mass ratio of 60-100 mesh is 20%.

[0065] A kind of flash marble porcelain tile, comprising a body and a surface glaze layer, a pattern decoration layer and a flash glaze layer sequentially arranged on the surface of the body, wherein: the raw material components of the flash glaze layer include dry granule polishing dry granules and the flash ceramic dry granules of this embodiment.

[0066] Among them: the chemical composition of the dry granule polishing dry granules, by weight percentage, includes: 48% of SiO2, 8.5% of Al2O3, 14.4% of CaO, 3.4% of MgO, 3.5% of K2O, 1% of Na2O, 12% of ZnO, and 9.2% of BaO. The initial melting temperature of the dry granule polishing dry granules is 1050 °C, and the particle size distribution is: the mass ratio of 20-100 mesh is 80%, the mass ratio of 100-150 mesh is 15%, and the mass ratio of 150-200 mesh is 5%.

[0067] The preparation method of the above-mentioned flash marble porcelain tile includes the following steps:

[0068] (1) According to the raw material ratio, mix the raw materials for preparing the flash ceramic dry granules, melt them at 1530 °C, keep them warm for 2 hours, then pour them into water for quenching to obtain molten block granules; then crush the molten block granules to obtain flash ceramic dry granules with a particle size of 30-100 mesh;

[0069] (2) Weigh the dry granule polishing dry granules and the flash ceramic dry granules prepared in step (1) according to a mass ratio of 1:0.2, add them to a suspending agent (the mass ratio of the mixed dry granules of the dry granule polishing dry granules and the flash ceramic dry granules to the suspending agent is 1:1), stir evenly, and adjust the specific gravity to 1.25 g / cm 3 , to obtain dry granule slurry;

[0070] (3) After mixing the raw materials of the bottom glaze layer according to the ratio, add water for ball milling (the mass ratio of the material to water is 100:40) to obtain a surface glaze with a fineness of 0.4 wt% of the 325-mesh sieve residue;

[0071] (4) Sequentially apply the surface glaze prepared in step (3) and inkjet print the decorative pattern on the body, and then apply the dry granule slurry prepared in step (2) (the application amount is 1100 g / m 2 ), sequentially forming a surface glaze layer, an inkjet printed pattern layer and a flash glaze layer. After drying and firing, the flash marble porcelain tile of this embodiment is obtained. Among them: the highest firing temperature is 1180 °C, and the firing cycle is 65 minutes.

[0072] Comparative Example 1

[0073] The difference between Comparative Example 1 and Example 1 lies only in the type of flux in the flash ceramic dry granules. In the raw material components of the flash ceramic dry granules of Comparative Example 1, an equal amount of boric acid is used to replace lead oxide in Example 1.

[0074] Comparative Example 2

[0075] The difference between Comparative Example 2 and Example 1 lies only in the addition method of cerium oxide. The raw material components of the flash ceramic dry granules of Comparative Example 2 do not contain cerium oxide. Instead, the flash ceramic dry granules, dry granule polishing dry granules and cerium oxide are jointly added to the suspending agent to prepare a dry granule slurry.

[0076] Comparative Example 3

[0077] The difference between Comparative Example 3 and Example 1 lies only in that the initial melting temperature of the flash ceramic dry granules is lower. The raw material components of the flash ceramic dry granules of Comparative Example 3 include, by weight: 2 parts of potassium feldspar, 2 parts of sodium feldspar, 25 parts of calcite, 1 part of zinc oxide, 4 parts of alumina, 15 parts of quartz, 8 parts of zircon powder, 6 parts of cerium oxide and 2 parts of lead oxide; the initial melting temperature of the flash ceramic dry granules is 1080 °C.

[0078] Comparative Example 4

[0079] The difference between Comparative Example 4 and Example 1 lies only in the preparation method of the flash marble porcelain tile. The preparation method of the flash marble porcelain tile of Comparative Example 4 includes the following steps:

[0080] (1) According to the raw material ratio, the raw materials for preparing the flash ceramic dry granules are mixed, melted at 1530 °C, kept warm for 2 hours, and then poured into water for quenching to obtain molten block granules; then the molten block granules are crushed to obtain flash ceramic dry granules with a particle size of 30-100 mesh;

[0081] (2) After the raw materials of the bottom glaze layer are mixed according to the ratio, they are ball-milled with water (the mass ratio of the material to water is 100:40) to obtain a surface glaze with a fineness of 0.4 wt% residue on a 325-mesh sieve;

[0082] (4) The surface glaze prepared in step (2) and an inkjet-printed decorative pattern are sequentially applied to the green body to form a surface glaze layer and an inkjet-printed pattern layer; then a layer of the flash ceramic dry granules prepared in step (1) is first applied by a dry granule fabricator, and the application amount is 300 g / m 2 , to form a flash dry granule glaze layer with a thickness of 1-2 mm; continue to apply dry granule polishing dry granules, and the application amount is 1.3 kg / m 2 , to form a dry granule polishing glaze layer with a thickness of 4-8 mm; after drying and firing, the flash marble porcelain tile of this comparative example is obtained. Among them: the highest firing temperature is 1180 °C, and the firing cycle is 65 minutes.

[0083] Performance test

[0084] The samples of the flash marble porcelain tiles prepared in the above Examples 1-3 and Comparative Examples 1-4 were tested for flatness, abrasion resistance and stain resistance, and the flash effect of the glaze surface was observed, and the smooth feeling of the glaze surface when touched was recorded. The test standards were respectively GB / T 3810.2-2016 "Test methods for ceramic tiles - Part 2: Inspection of dimensions and surface quality", GB / T 3810.7-2016 "Test methods for ceramic tiles - Part 7: Determination of abrasion resistance of glazed tile surfaces". The abrasion resistance was divided into grades 0-5, with grade 0 indicating the worst abrasion resistance and grade 5 indicating the best abrasion resistance. GBT 3810.14-2016 "Test methods for ceramic tiles - Part 14: Determination of stain resistance", and the stain resistance was divided into grades 0-5, with grade 0 indicating the worst stain resistance and grade 5 indicating the best stain resistance. At the same time, according to the flash degree of the flash particles, they were divided into grades 1-5, with grade 5 having the best flash effect, shining like a diamond; grade 1 having the worst flash effect, and the flash particles being dull.

[0085] The test results are shown in Table 1.

[0086] Table 1: Performance comparison table of the samples prepared in Examples 1-3 and Comparative Examples 1-4

[0087]

[0088] As can be seen from Table 1, for the samples of the flash marble porcelain tiles prepared in Examples 1-3 of the present invention, the flash particles on the glaze surface are evenly distributed, with an obvious flash effect, and the flash degree can reach grade 5, see Figure 1 ; and the glaze surface has high flatness, smooth hand feeling; and has good abrasion resistance and stain resistance.

[0089] Compared with Example 1, in Comparative Example 1 and Comparative Example 3, due to using an equal amount of boric acid to replace lead oxide in the raw material components of the flash ceramic dry particles and the initial melting temperature of the flash ceramic dry particles being lower, the melting performance of the dry particles is poor and the refractive index decreases, resulting in a decrease in both the flash effect and flatness of the glaze surface, and the abrasion resistance and stain resistance also decrease accordingly.

[0090] Compared with Example 1, in Comparative Example 2, due to adding the flash ceramic dry particles, the dry particles and cerium oxide together into the suspending agent, the melting degree of cerium oxide is not high, which not only causes the glaze surface to be rough and the flatness to decrease, but also the flash effect of the glaze surface is poor, and the abrasion resistance and stain resistance also decrease significantly.

[0091] Compared with Example 1, in Comparative Example 4, due to using the dry method to apply the flash ceramic dry particles, it is difficult to ensure the smoothness of the glaze surface, and the flash effect only comes from the reflection formed by the flash crystals, resulting in a poor flash effect of the glaze surface, rough hand feeling, and poor abrasion resistance and stain resistance.

[0092] For those of ordinary skill in the art to which the present invention pertains, several simple deductions or substitutions can be made without departing from the concept of the present invention, without having to go through creative efforts. Therefore, any simple improvements made by those skilled in the art based on the disclosure of the present invention should fall within the protection scope of the present invention. The above embodiments are the preferred embodiments of the present invention, and all processes similar to the present invention and equivalent changes made thereto shall fall within the protection scope of the present invention.

Claims

1. A flash ceramic dry granule, characterized in that, The raw material components of the flash ceramic dry granules include a basic dry granule material, cerium oxide, and lead oxide, and the initial melting temperature of the flash ceramic dry granules is 1100 - 1150 °C.

2. The flash ceramic dry granules according to claim 1, characterized in that, The mass ratio of the cerium oxide to the lead oxide is (1 - 4):

1.

3. The flash ceramic dry granules according to claim 1, characterized in that, The raw material components of the flash ceramic dry granules, by weight, include: 60 - 130 parts of the basic dry granule material, 6 - 8 parts of cerium oxide, and 2 - 5 parts of lead oxide.

4. The flash ceramic dry granule according to claim 1 or 3, characterized in that, The components of the basic dry granule material, by weight, include: 2 - 8 parts of potassium feldspar, 2 - 8 parts of sodium feldspar, 15 - 30 parts of calcite, 5 - 7 parts of zinc oxide, 4 - 8 parts of alumina, 30 - 50 parts of quartz, and 8 - 10 parts of zircon powder.

5. A flash marble porcelain tile, characterized in that, It includes a green body and a flash glaze layer provided on the upper surface of the green body, and the raw material components of the flash glaze layer include dry - granulated dry granules and the flash ceramic dry granules according to any one of claims 1 - 4.

6. The flash marble porcelain tile according to claim 5, characterized in that, The mass ratio of the dry - granulated dry granules to the flash ceramic dry granules is 1:(0.2 - 0.3).

7. The flash marble porcelain tile according to claim 5, characterized in that, The initial melting temperature of the dry - granulated dry granules is 1050 - 1120 °C, and the initial melting temperature of the dry - granulated dry granules is less than that of the flash ceramic dry granules.

8. The flash marble porcelain tile according to claim 5 or 7, characterized in that, The chemical composition of the dry - granulated dry granules, by weight percentage, includes: SiO2 45 - 60%, Al2O3 8 - 15%, CaO 10 - 15%, MgO 0.5 - 5%, K2O 2 - 6%, Na2O 1 - 4%, ZnO 10 - 15%, BaO 0 - 10%; And / or, the particle size of the dry - granulated dry granules is 20 - 200 mesh, and the particle size of the flash ceramic dry granules is 30 - 100 mesh.

9. A method for preparing a flash marble porcelain tile according to any one of claims 5-8, characterized in that, It includes the following steps: (1) Mix the raw materials for preparing the flash ceramic dry granules, after melting, pour them into water for quenching to obtain molten block granules; then crush the molten block granules and screen them to obtain the flash ceramic dry granules; (2) Add the flash ceramic dry granules and the dry - granulated dry granules into a suspending agent and mix them to obtain a dry granule slurry; (3) Apply the dry granule slurry onto the green body to form a flash glaze layer, and after drying and firing, obtain the flash marble porcelain tile.

10. The preparation method of the flash marble porcelain tile according to claim 9, characterized in that, The application amount of the dry granule slurry is 1000 - 1100 g / m 2 ; And / or, the highest temperature of the firing is 1180 - 1220 °C, and the firing cycle is 50 - 70 minutes.

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