Wear-resistant glaze, wear-resistant ceramic tile and preparation method

Abstract

The application belongs to the field of building ceramics, and discloses a wear-resistant glaze, a wear-resistant ceramic tile and a preparation method. The solid components of the wear-resistant glaze include combined dry particles, quartz powder, corundum powder and protective glaze. The ratio of the sum of the mass of the combined dry particles, the quartz powder and the corundum powder to the mass of the protective glaze is 1:(0.18-0.22). The combined dry particles include high-aluminum calcium dry particles, matte dry particles and low-temperature dry particles with a mass ratio of (0.95-1.05):1:(0.26-0.30). The wear-resistant glaze provided by the application has high wear resistance, excellent transparency and good stain resistance through the specific components and proportions of the combined dry particles, the quartz powder, the corundum powder and the protective glaze, and the synergistic effect of the components. The ceramic tile with the wear-resistant glaze as the surface glaze layer has outstanding wear resistance, good transparency and excellent stain resistance, and can meet the core use requirements of the glaze-throwing ceramic tile in terms of wear resistance, transparency and stain resistance, and is suitable for various home and public space application scenarios.

Description

Technical Field

[0001] This invention belongs to the field of building ceramics technology, and specifically relates to a wear-resistant glaze, wear-resistant ceramic bricks, and their preparation method. Background Technology

[0002] The glaze layer on the surface of existing glazed tiles is mainly composed of a glass phase. Although it has high transparency and can well present the rich patterns and colors under the tile body, the glass phase itself has poor wear resistance, which makes the surface of glazed tiles very easy to scratch during use, seriously affecting the product's service life and appearance integrity.

[0003] To balance the transparency and performance of the glaze, most existing polished glazes employ a high silica-to-alumina ratio formulation, typically controlling the alumina content below 10%. While this formulation ensures the glaze's transparency, the low alumina content further exacerbates the problem of insufficient wear resistance. Some technologies attempt to enhance the glaze's wear resistance by increasing the alumina content, but this easily triggers crystallization, leading to a cloudy glaze surface and directly damaging the presentation of patterns and colors. Furthermore, some solutions improve wear resistance by adding wear-resistant media such as corundum and zircon sand; however, the core components of these media are mostly alumina and zirconium oxide, which can also easily cause opacity during high-temperature firing, reducing the glaze's transparency and obscuring the clear display of tile patterns and colors.

[0004] In summary, the existing glaze design of polished glazed tiles has always struggled to balance wear resistance and transparency. How to significantly improve the wear resistance of the polished glaze while ensuring the transparency of the glaze and not affecting the color of the pattern has become a technical problem that the industry urgently needs to solve. Summary of the Invention

[0005] The present invention aims to improve at least one technical problem in the prior art.

[0006] The first aspect of the present invention provides a wear-resistant glaze, the solid components of which include a combination of dry granules, quartz powder, corundum powder and protective glaze.

[0007] The ratio of the total mass of the combined dry granules, quartz powder, and corundum powder to the mass of the protective glaze is 1:(0.18~0.22).

[0008] Among them, the combined dry granules include high-alumina calcium dry granules, matte dry granules and low-temperature dry granules with a mass ratio of (0.95~1.05):1:(0.26~0.30);

[0009] The high-alumina calcium dry granules, by mass percentage, comprise: SiO2 48.1%~53.0%, Al2O3 19.0%~21.6%, CaO 17.0%~19.6%, K2O 2.9%~3.5%, and ZnO 6.0%~7.2%.

[0010] The matte dry granules, by mass percentage, comprise: SiO2 51.5%~56.5%, Al2O3 15.5%~18.0%, CaO 6.5%~7.6%, MgO 2.3%~2.8%, K2O 3.2%~3.8%, Na2O 1.8%~2.2%, SrO 7.2%~8.6%, and ZnO 4.6%~5.5%.

[0011] The low-temperature dry granules, by mass percentage, comprise: SiO2 61.2%~66.5%, Al2O3 12.6%~14.8%, CaO 7.6%~9.0%, K2O 3.7%~4.5%, Na2O 1.1%~1.5%, and ZnO 7.7%~9.0%.

[0012] The particle size D97 of high-alumina calcium dry granules is 70µm~74µm, the particle size D97 of matte dry granules is 76µm~80µm, the particle size D97 of low-temperature dry granules is 73µm~77µm, the particle size D97 of quartz powder is 40µm~50µm, and the particle size D97 of corundum powder is 40µm~50µm.

[0013] In this application, the combined dry granules serve as the core functional component of the wear-resistant glaze. Their clinker properties reduce the violent reactions of the melt during firing, which helps improve the glaze's transparency and airtightness, reducing surface defects such as pores and blistering to ensure clear patterns and colors. Furthermore, they allow for the precipitation of more potassium and sodium feldspar crystal phases during heat preservation, further optimizing the glaze's transparency. The three types of dry granules also form a specific synergistic effect, constructing a multi-dimensional functional complementary system. The high-alumina calcium dry granules in the combined dry granules construct a core synergistic system with a specific ratio of Al2O3 and CaO. Al2O3, as a wear-resistant skeleton component, significantly increases the initial melting point and hardness of the glaze melt due to its high content, thereby enhancing the glaze's wear resistance and anti-fouling properties. CaO effectively alleviates the melting difficulties caused by high alumina, and synergistically with the silicon-aluminum components, imparts suitable high-temperature viscosity and surface tension to the glaze melt, achieving a "moderate crystallization" effect. This ensures the amount of crystal phase required for basic wear resistance while avoiding glaze cloudiness caused by crystal phase agglomeration, achieving a balance between high alumina wear resistance and transparency. In matte dry granules, SrO purifies the glaze by reducing surface tension and adsorbing microbubbles during the melting process. Its excellent refractive index matching with the glass phase ensures that bubble removal doesn't affect the glaze's transparency. Combined with magnesium oxide's effect of reducing the glass phase's refractive index, this results in a soft matte finish, balancing aesthetics and user experience. In low-temperature dry granules, ZnO effectively lowers the overall glaze melting temperature, making it suitable for conventional firing processes in polished glazed tiles. During cooling, it synergistically forms a dense glass phase with other components, optimizing the melting process and further enhancing the glaze's stain resistance. ZnO also participates in the melting reaction to form a high-hardness, angular zinc spinel crystal phase. This phase not only exhibits excellent wear resistance but also strong acid and alkali resistance, improving wear resistance while supplementing the glaze's chemical corrosion resistance.

[0014] In this application, quartz powder and corundum powder, as high-melting-point functional components, partially do not melt during firing, directly forming high-hardness quartz and corundum crystal phases. These phases synergistically interact with the zinc spinel and potassium-sodium feldspar crystal phases generated by the reaction of the combined dry granules, resulting in a sufficient quantity of high-hardness, wear-resistant crystal phases within the glaze layer. These crystal phases are uniformly distributed throughout the glaze layer, significantly improving its wear resistance. Simultaneously, thanks to the clinker characteristics of the combined dry granules, the viscosity control of the high-alumina-calcium dry granules, and the clarifying effect of the matte dry granules, the formation of these crystal phases does not lead to glaze opacity, effectively ensuring the glaze's transparency and not affecting the color development of the underlying pattern. The protective glaze fills and encapsulates the dry granules and micro-gaps in the glaze layer, further enhancing its anti-fouling properties, giving the product a combination of wear resistance, transparency, and excellent anti-fouling characteristics.

[0015] This application further forms a particle size combination of large-particle dry granules and small-particle hard powders (quartz powder and corundum powder), which is beneficial to constructing a dense packing structure to improve the density of the glaze layer, and can also achieve functional complementarity by means of particle size differences. Because the melting points of quartz and corundum are much higher than the conventional firing temperature of glazed tiles, they do not melt during firing. Instead, they remain as rigid particles, uniformly embedded in the glass phase formed by the melting of dry particles, creating uniformly dispersed rigid support points. This effectively avoids uneven wear resistance caused by localized stress concentration. Furthermore, the thickness of the three types of dry particles after melting and leveling is basically matched with the particle diameter of quartz and corundum powder. Combined with the high-temperature viscosity characteristics of the high-alumina-calcium dry particles, these rigid particles act as excellent network support points in the high-temperature fluidity of the glaze layer. This provides appropriate traction for the molten glaze and dry particles, reducing leveling pits during firing and helping to form a smoother glaze surface. This results in a more uniform crystal arrangement, ultimately ensuring the consistency of the product's surface physicochemical properties, further enhancing the hardness and wear resistance of the glaze layer without affecting its transparency or pattern color expression.

[0016] In summary, this invention, through the synergistic design of its components, especially the specific synergistic effect of the three combined dry granules and their combination with quartz powder, corundum powder, and protective glaze, constructs a composite glaze structure that combines a high content of wear-resistant crystalline phases with a transparent glassy phase. This not only solves the problem of insufficient wear resistance in polished glazed tiles through the synergistic effect of multiple wear-resistant crystalline phases, but also avoids the glaze opacity problem that may be caused by the high wear-resistant design through the precise control of each component, thus achieving a balance between wear resistance, transparent color development, and usability.

[0017] The ratio of the mass of the combined dry granules to the sum of the masses of quartz powder and corundum powder is 1:(0.07~0.09); the mass ratio of quartz powder to corundum powder is 1:(0.4~0.5).

[0018] Among them, the SiO2 content in quartz powder is >99%, and the Al2O3 content in corundum powder is >99%.

[0019] In some preferred embodiments, the wear-resistant glaze comprises, by weight percentage: 47.5%~52.0% SiO2, 23.6%~26.6% Al2O3, 6.3%~8.1% CaO, 0.8%~1.2% MgO, 3.0%~3.8% K2O, 1.0%~1.4% Na2O, 3.2%~4.3% BaO, and 5.7%~7.3% ZnO.

[0020] In some preferred embodiments, the contents of different phases in the wear-resistant glaze are as follows: potassium sodium feldspar crystal phase 11.5%~15.5%, corundum crystal phase 5%~7%, quartz crystal phase 4%~6%, zinc spinel crystal phase 1.5%~3.5%, and amorphous phase 70%~76%.

[0021] In some preferred embodiments, the raw materials for preparing high-alumina calcium dry granules include, by weight, 16.5-19.5 parts potassium feldspar, 13.5-16.5 parts quartz, 9-11 parts kaolin, 11-13 parts limestone, 23-27 parts wollastonite, 6.5-7.5 parts calcined kaolin, 5.5-6.5 parts alumina, and 6.5-7.5 parts zinc oxide.

[0022] In some preferred embodiments, the raw materials for preparing the matte dry granules include, by weight, 18-22 parts potassium feldspar, 9-11 parts sodium feldspar, 17-21 parts quartz, 6.3-7.8 parts kaolin, 12.5-15.5 parts limestone, 7-9 parts calcined talc, 2.5-3 parts alumina, 12.5-15.5 parts strontium carbonate, and 4.5-5.5 parts zinc oxide.

[0023] In some preferred embodiments, the raw materials for preparing the low-temperature dry granules include, by weight, 21-25 parts potassium feldspar, 6.5-7.5 parts sodium feldspar, 11-13 parts kaolin, 25-30 parts quartz, 7.5-8.5 parts wollastonite, 9-11 parts limestone, 3.5-4.5 parts alumina, and 8-9 parts zinc oxide.

[0024] In some preferred embodiments, the raw materials for preparing the protective glaze include, by weight, 28.5-32.5 parts potassium feldspar powder, 11-13 parts sodium feldspar powder, 18.5-21.5 parts kaolin, 5.5-6.5 parts barium carbonate, 4-5 parts strontium carbonate, 8.5-10.5 parts dolomite, 5.5-6.5 parts calcined talc, 6.5-7.5 parts calcined zinc oxide, and 4-5 parts color-developing frit.

[0025] The color-developing frit includes K2O, Na2O and ZnO; the sum of the masses of K2O and Na2O accounts for 5.5% to 5.7% of the color-developing frit, and the mass of ZnO accounts for 4.4% to 4.7% of the color-developing frit.

[0026] The protective glaze of this application contains a high proportion of feldspar raw materials, which can melt at a low temperature first, reducing the initial melting temperature of the glaze layer. This promotes the gradual melting of low-temperature dry particles, matte dry particles, and high-alumina-calcium dry particles in the glaze layer. At the same time, it effectively fills and coats the dry particles and micro-gaps in the glaze layer, thus better enhancing its stain resistance. The protective glaze contains color-developing frit. When it melts, due to its clinker characteristics, potassium and sodium ions do not participate in the reaction of the raw materials but directly regulate the uniformity and dispersion of the ceramic ink pigment, enhancing the vibrancy of the pattern. Meanwhile, zinc ions effectively improve the stability of the ink, making it less prone to oxidation and better restoring the pattern colors.

[0027] In some preferred embodiments, the protective glaze comprises, by weight percentage: 46.5%~50.8% SiO2, 17.5%~19.6% Al2O3, 3.2%~3.9% CaO, 4.5%~5.2% MgO, 5.2%~6.2% K2O, 1.5%~1.9% Na2O, 3.3%~4.0% SrO, 7.0%~9.0% ZnO, and 4.8%~5.7% BaO.

[0028] The above-mentioned method for preparing wear-resistant glaze includes the following steps:

[0029] High-alumina calcium dry granules, matte dry granules, low-temperature dry granules, quartz powder, corundum powder, protective glaze slurry, suspending agent, and water are mixed to obtain a wear-resistant glaze.

[0030] The protective glaze slurry is prepared from a protective glaze; the particle size D97 of the protective glaze slurry is 10µm~20µm.

[0031] The ratio of the mass of the solid component of the wear-resistant glaze to the sum of the masses of the suspending agent and water is 1:(0.86~0.90); the mass ratio of the suspending agent to water is 1:(0.20~0.30).

[0032] A second aspect of the present invention provides a wear-resistant ceramic tile, comprising, in sequence: a body layer, a surface glaze layer, a pattern layer, and a wear-resistant glaze layer; the wear-resistant glaze layer is formed by the aforementioned wear-resistant glaze.

[0033] A third aspect of the present invention provides a method for preparing the above-mentioned wear-resistant ceramic tile, wherein the surface glaze layer is formed by a surface glaze and the pattern layer is formed by colored ink; the preparation method includes the following steps:

[0034] A surface glaze is applied to the surface of the body layer, then colored ink is printed, followed by the application of a wear-resistant glaze, firing, and polishing to obtain a wear-resistant ceramic tile.

[0035] In some preferred embodiments, the coefficient of thermal expansion of the glaze at 400°C is (7.8~7.9)×10⁻¹⁰. -6 / ℃, the coefficient of thermal expansion of the wear-resistant glaze at 400℃ is (5.45~5.55)×10 -6 / ℃.

[0036] This application further controls the expansion coefficient of the lower layer glaze and the expansion coefficient of the surface wear-resistant glaze of the wear-resistant ceramic tile simultaneously. The surface wear-resistant glaze adopts a low expansion coefficient formula design, which has a more stable structure and produces fewer air bubbles and pinholes. At the same time, the total silica content in the wear-resistant glaze layer is controlled to effectively reduce the presence of free silica and avoid uneven melting of the glaze layer due to excessive fluidity. Meanwhile, the high expansion coefficient of the lower layer glaze forms a shrinkage and tightening trend during the curing process in the later stage of firing, which further tightens and densifies the upper wear-resistant glaze layer, making its wear-resistant glaze layer denser, harder, and more wear-resistant.

[0037] The beneficial effects of this invention: The wear-resistant glaze provided by this invention, through a specific combination and ratio of dry granules, quartz powder, corundum powder, and protective glaze, combined with the synergistic effect of each component, enables the wear-resistant glaze to possess high wear resistance while also ensuring excellent transparency and stain resistance. Ceramic tiles using this wear-resistant glaze as the surface glaze layer exhibit outstanding wear resistance, good transparency, and excellent stain resistance, thus meeting the core usage requirements of polished glazed ceramic tiles for wear resistance, transparency, and stain resistance, and is suitable for various home and public space application scenarios. Attached Figure Description

[0038] To more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0039] Figure 1 The image shows the XRD phase diagram of the wear-resistant glaze layer of the wear-resistant ceramic tile prepared in Example 1. Detailed Implementation

[0040] The present invention will be further described below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Furthermore, it should be understood that after reading the description of this invention, those skilled in the art can make various alterations or modifications to the invention, and these equivalent forms also fall within the scope defined by the appended claims.

[0041] Example 1

[0042] A wear-resistant glaze, the solid components of which include a combination of dry granules, quartz powder, corundum powder and protective glaze.

[0043] The ratio of the total mass of the combined dry granules, quartz powder, and corundum powder to the mass of the protective glaze is 1:0.205; the ratio of the mass of the combined dry granules to the total mass of quartz powder and corundum powder is 1:0.085; and the ratio of the mass of quartz powder to corundum powder is 1:0.444.

[0044] Among them, the combined dry granules include high-alumina calcium dry granules, matte dry granules and low-temperature dry granules with a mass ratio of 1:1:0.284;

[0045] The raw materials for preparing high-alumina calcium dry granules include, by weight, 18 parts potassium feldspar, 15 parts quartz, 10 parts kaolin, 12 parts limestone, 25 parts wollastonite, 7 parts calcined kaolin, 6 parts alumina, and 7 parts zinc oxide. These raw materials are mixed and calcined in a furnace at 1400℃ to melt and clarify the mixture. The molten glass is then rapidly cooled using a water bath or water-cooled metal rollers to form glass-like flakes or granular flocs, which are then crushed to obtain high-alumina calcium dry granules. The high-alumina calcium dry granules, by mass percentage, include: 50.36% SiO2, 20.21% Al2O3, 18.20% CaO, 3.20% K2O, and 6.6% ZnO, with the remainder being loss on ignition and impurities.

[0046] The raw materials for preparing matte dry granules, by weight, include: 20 parts potassium feldspar, 10 parts sodium feldspar, 19 parts quartz, 7 parts kaolin, 14 parts limestone, 8 parts calcined talc, 3 parts alumina, 14 parts strontium carbonate, and 5 parts zinc oxide. These raw materials are mixed and calcined in a furnace at 1400℃ to melt and clarify the mixture. The molten glass is then rapidly cooled using a water bath or water-cooled metal rollers to form glass-like flakes or granular flocs, which are then crushed to obtain the matte dry granules. The matte dry granules, by mass percentage, include: 53.65% SiO2, 16.76% Al2O3, 7.04% CaO, 2.58% MgO, 3.51% K2O, 2.02% Na2O, 7.92% SrO, and 5.07% ZnO, with the remainder being loss on ignition and impurities.

[0047] The raw materials for preparing low-temperature dry granules, by weight, include: 23 parts potassium feldspar, 7 parts sodium feldspar, 12 parts kaolin, 27.5 parts quartz, 8 parts wollastonite, 10 parts limestone, 4 parts alumina, and 8.5 parts zinc oxide. These raw materials are mixed and calcined in a furnace at 1400℃ to melt and clarify the mixture. The molten glass is then rapidly cooled using a water bath or water-cooled metal rollers to produce glass-like flakes or granular flocs, which are then crushed to obtain the low-temperature dry granules. The low-temperature dry granules, by mass percentage, include: 63.81% SiO2, 13.62% Al2O3, 8.24% CaO, 4.09% K2O, 1.30% Na2O, and 8.31% ZnO, with the remainder being loss on ignition and impurities.

[0048] Among them, the SiO2 content in quartz powder is >99%, and the Al2O3 content in corundum powder is >99%.

[0049] The raw materials for preparing the protective glaze, by weight, include: 30.5 parts potassium feldspar powder, 12 parts sodium feldspar powder, 20 parts kaolin, 6 parts barium carbonate, 4.5 parts strontium carbonate, 9.5 parts dolomite, 6 parts calcined talc, 7 parts calcined zinc oxide, and 4.5 parts color-developing frit (the color-developing frit includes K2O, Na2O, and ZnO; the sum of the masses of K2O and Na2O accounts for 5.6% of the color-developing frit, and the mass of ZnO accounts for 4.57% of the color-developing frit). These raw materials are crushed separately and mixed in proportion to obtain the protective glaze. The protective glaze, by mass percentage, includes: 48.66% SiO2, 18.56% Al2O3, 3.55% CaO, 4.88% MgO, 5.67% K2O, 1.68% Na2O, 3.6% SrO, 8.0% ZnO, and BaO. 5.22%, the remainder being loss on ignition and impurities.

[0050] Among them, the particle size D97 of high-alumina calcium dry granules is 72µm, the particle size D97 of matte dry granules is 76µm~80µm, the particle size D97 of low-temperature dry granules is 75µm, the particle size D97 of quartz powder is 45µm, and the particle size D97 of corundum powder is 45µm.

[0051] The wear-resistant glaze comprises, by weight percentage: 49.78% SiO2, 25.17% Al2O3, 7.16% CaO, 0.96% MgO, 3.38% K2O, 1.17% Na2O, 3.73% BaO, and 6.53% ZnO.

[0052] The preparation method of this wear-resistant glaze includes the following steps:

[0053] 17 parts of protective glaze were mixed with water, thickener (methylcellulose), and dispersant (sodium tripolyphosphate) (the mass ratio of protective glaze, water, thickener and dispersant was 100:30:0.15:0.35). The protective glaze slurry was then prepared by grinding, sieving and aging (the particle size D97 of the protective glaze slurry was 15µm).

[0054] 33.5 parts of high-alumina calcium dry granules, 33.5 parts of matte dry granules, 9.5 parts of low-temperature dry granules, 4.5 parts of quartz powder, 2 parts of corundum powder, the above protective glaze slurry, 70 parts of suspending agent, and 18 parts of water were mixed evenly (the mass ratio of the solid components of the wear-resistant glaze to the sum of the masses of the suspending agent and water was 1:0.88; the mass ratio of the suspending agent to water was 1:0.257) to obtain the wear-resistant glaze.

[0055] This embodiment also provides a wear-resistant ceramic tile, which includes, in sequence: a body layer, a surface glaze layer, a pattern layer, and a wear-resistant glaze layer; wherein, the surface glaze layer is formed by a surface glaze, the pattern layer is formed by colored ink, and the wear-resistant glaze layer is formed by the wear-resistant glaze of this embodiment.

[0056] The preparation method of this wear-resistant ceramic brick includes the following steps:

[0057] The pre-dried body layer (with moisture content controlled below 0.3%) is fed into the first glaze spraying equipment, and a top glaze (specific gravity 1.85 g / cm³) is applied to the surface of the body layer. 3 The application rate is 440 g / m 2 );

[0058] Enter the printing equipment and print with color ink;

[0059] The second glaze is applied using a second glaze spraying device to apply a wear-resistant glaze (specific gravity 1.53 g / cm³). 3 The application rate is 500g / m³ 2 )

[0060] It is then placed in a kiln for firing (the maximum firing temperature is 1150℃, and the firing time is 50 minutes).

[0061] Remove and polish to obtain wear-resistant ceramic tiles.

[0062] The raw materials for preparing the glaze, by weight, include: 11 parts potassium feldspar powder, 10.5 parts sodium feldspar powder, 12.5 parts calcined alumina, 5 parts calcined kaolin, 23 parts quartz powder, 10.5 parts kaolin, 18 parts nepheline powder, 1.5 parts calcined talc powder, and 8 parts zirconium silicate. The glaze, by mass percentage, includes: 57.81% SiO2, 27.24% Al2O3, 0.59% CaO, 0.60% MgO, 2.07% K2O, 3.51% Na2O, and 5.02% ZrO2, with the remainder being loss on ignition and impurities. The coefficient of thermal expansion of the glaze at 400℃ is 7.85 × 10⁻⁶. -6 / ℃. The coefficient of thermal expansion of the wear-resistant glaze at 400℃ is 5.5×10. -6 / ℃.

[0063] Example 2

[0064] A wear-resistant glaze, the solid components of which include a combination of dry granules, quartz powder, corundum powder and protective glaze.

[0065] The ratio of the total mass of the combined dry granules, quartz powder, and corundum powder to the mass of the protective glaze is 1:0.205; the ratio of the mass of the combined dry granules to the total mass of quartz powder and corundum powder is 1:0.085; and the ratio of the mass of quartz powder to corundum powder is 1:0.444.

[0066] Among them, the combined dry granules include high-alumina calcium dry granules, matte dry granules and low-temperature dry granules with a mass ratio of 1:1:0.284;

[0067] The raw materials for preparing high-alumina calcium dry granules include, by weight, 16.5 parts potassium feldspar, 14 parts quartz, 11 parts kaolin, 11 parts limestone, 27 parts wollastonite, 6.5 parts calcined kaolin, 6.5 parts alumina, and 7.5 parts zinc oxide. These raw materials are mixed and calcined in a furnace at 1400℃ to melt and clarify the mixture. The molten glass is then rapidly cooled using a water bath or water-cooled metal rollers to produce glass-like flakes or granular flocs, which are then crushed to obtain high-alumina calcium dry granules. The high-alumina calcium dry granules, by mass percentage, comprise: 48.5% SiO2, 21.12% Al2O3, 19.32% CaO, 2.93% K2O, and 6.87% ZnO, with the remainder being loss on ignition and impurities.

[0068] The raw materials for preparing matte dry granules, by weight, include: 22 parts potassium feldspar, 9 parts sodium feldspar, 17 parts quartz, 6.5 parts kaolin, 12.5 parts limestone, 8.5 parts calcined talc, 3.5 parts alumina, 15.5 parts strontium carbonate, and 5.5 parts zinc oxide. These raw materials are mixed and calcined in a furnace at 1400℃ to melt and clarify the mixture. The molten glass is then rapidly cooled using a water bath or water-cooled metal rollers to form glass-like flakes or granular flocs, which are then crushed to obtain the matte dry granules. The matte dry granules, by mass percentage, include: 51.86% SiO2, 17.6% Al2O3, 6.65% CaO, 2.73% MgO, 3.75% K2O, 1.82% Na2O, 8.51% SrO, and 5.37% ZnO, with the remainder being loss on ignition and impurities.

[0069] The raw materials for preparing low-temperature dry granules, by weight, include: 25 parts potassium feldspar, 6.5 parts sodium feldspar, 11 parts kaolin, 25.5 parts quartz, 7.5 parts wollastonite, 11 parts limestone, 4.5 parts alumina, and 9 parts zinc oxide. These raw materials are mixed and calcined in a furnace at 1400℃ to melt and clarify the mixture. The molten glass is then rapidly cooled using a water bath or water-cooled metal rollers to produce glass-like flakes or granular flocs, which are then crushed to obtain the low-temperature dry granules. The low-temperature dry granules, by mass percentage, include: 61.2% SiO2, 14.41% Al2O3, 8.62% CaO, 4.39% K2O, 1.15% Na2O, and 8.85% ZnO, with the remainder being loss on ignition and impurities.

[0070] Among them, the SiO2 content in quartz powder is >99%, and the Al2O3 content in corundum powder is >99%.

[0071] The raw materials for preparing the protective glaze, by weight, include: 32 parts potassium feldspar powder, 13 parts sodium feldspar powder, 18.5 parts kaolin, 6 parts barium carbonate, 5 parts strontium carbonate, 8.5 parts dolomite, 5.5 parts calcined talc, 6.5 parts calcined zinc oxide, and 5 parts color-developing frit (the color-developing frit includes K2O, Na2O, and ZnO; the sum of the masses of K2O and Na2O accounts for 5.67% of the color-developing frit, and the mass of ZnO accounts for 4.43% of the color-developing frit). These raw materials are crushed separately and mixed in proportion to obtain the protective glaze. The protective glaze, by mass percentage, includes: 50.33% SiO2, 17.8% Al2O3, 3.32% CaO, 4.67% MgO, 5.35% K2O, 1.82% Na2O, 3.85% SrO, 7.16% ZnO, and 5 parts BaO. 5.3%, the remainder being loss on ignition and impurities.

[0072] Among them, the particle size D97 of high-alumina calcium dry granules is 70µm, the particle size D97 of matte dry granules is 76µm~80µm, the particle size D97 of low-temperature dry granules is 73µm, the particle size D97 of quartz powder is 40µm~50µm, and the particle size D97 of corundum powder is 42µm.

[0073] The wear-resistant glaze comprises, by weight percentage: 47.8% SiO2, 26.9% Al2O3, 7.87% CaO, 1.14% MgO, 3.67% K2O, 1.08% Na2O, 4.21% BaO, and 7.27% ZnO.

[0074] The preparation method of this wear-resistant glaze includes the following steps:

[0075] 17 parts of protective glaze were mixed with water, thickener (methylcellulose), and dispersant (sodium tripolyphosphate) (the mass ratio of protective glaze, water, thickener and dispersant was 100:30:0.15:0.35). The protective glaze slurry was then prepared by grinding, sieving and aging (the particle size D97 of the protective glaze slurry was 12µm).

[0076] 33.5 parts of high-alumina calcium dry granules, 33.5 parts of matte dry granules, 9.5 parts of low-temperature dry granules, 4.5 parts of quartz powder, 2 parts of corundum powder, the above protective glaze slurry, 70 parts of suspending agent, and 18 parts of water were mixed evenly (the mass ratio of the solid components of the wear-resistant glaze to the sum of the masses of the suspending agent and water was 1:0.88; the mass ratio of the suspending agent to water was 1:0.257) to obtain the wear-resistant glaze.

[0077] This embodiment also provides a wear-resistant ceramic tile, which includes, in sequence: a body layer, a surface glaze layer, a pattern layer, and a wear-resistant glaze layer; wherein, the surface glaze layer is formed by a surface glaze, the pattern layer is formed by colored ink, and the wear-resistant glaze layer is formed by the wear-resistant glaze of this embodiment.

[0078] The preparation method of this wear-resistant ceramic brick includes the following steps:

[0079] The pre-dried body layer (with moisture content controlled below 0.3%) is fed into the first glaze spraying equipment, and a surface glaze (specific gravity 1.83 g / cm³) is applied to the surface of the body layer. 3 The application rate is 430 g / m 2 );

[0080] Enter the printing equipment and print with color ink;

[0081] The second glaze is applied using a second glaze spraying device to apply a wear-resistant glaze (specific gravity 1.51 g / cm³). 3 The application rate is 510 g / m 2 )

[0082] It is then placed in a kiln for firing (the maximum firing temperature is 1160℃, and the firing time is 45 minutes).

[0083] Remove and polish to obtain wear-resistant ceramic tiles.

[0084] The raw materials for preparing the glaze, by weight, include: 10 parts potassium-sodium feldspar powder, 11.5 parts sodium feldspar powder, 13.5 parts calcined alumina, 5.5 parts calcined kaolin, 21 parts quartz powder, 11.5 parts kaolin, 16.5 parts nepheline powder, 2 parts calcined talc powder, and 8.5 parts zirconium silicate. The glaze, by mass percentage, includes: 55.5% SiO2, 26.12% Al2O3, 0.7% CaO, 0.78% MgO, 1.82% K2O, 3.87% Na2O, and 5.34% ZrO2, with the remainder being loss on ignition and impurities. The coefficient of thermal expansion of the glaze at 400℃ is 7.8 × 10⁻⁶. -6 / ℃. The coefficient of thermal expansion of the wear-resistant glaze at 400℃ is 5.45×10. -6 / ℃.

[0085] Example 3

[0086] A wear-resistant glaze, the solid components of which include a combination of dry granules, quartz powder, corundum powder and protective glaze.

[0087] The ratio of the total mass of the combined dry granules, quartz powder, and corundum powder to the mass of the protective glaze is 1:0.205; the ratio of the mass of the combined dry granules to the total mass of quartz powder and corundum powder is 1:0.085; and the ratio of the mass of quartz powder to corundum powder is 1:0.444.

[0088] Among them, the combined dry granules include high-alumina calcium dry granules, matte dry granules and low-temperature dry granules with a mass ratio of 1:1:0.284;

[0089] The raw materials for preparing high-alumina calcium dry granules, by weight, include: 19.5 parts potassium feldspar, 16 parts quartz, 9 parts kaolin, 13 parts limestone, 23 parts wollastonite, 7.5 parts calcined kaolin, 5.5 parts alumina, and 6.5 parts zinc oxide. These raw materials are mixed and calcined in a furnace at 1400℃ to melt and clarify the mixture. The molten glass is then rapidly cooled using a water bath or water-cooled metal rollers to form glass-like flakes or granular flocs, which are then crushed to obtain high-alumina calcium dry granules. The high-alumina calcium dry granules, by mass percentage, include: 52.53% SiO2, 19.34% Al2O3, 17.18% CaO, 3.42% K2O, and 6.16% ZnO, with the remainder being loss on ignition and impurities.

[0090] The raw materials for preparing matte dry granules, by weight, include: 18 parts potassium feldspar, 11 parts sodium feldspar, 21 parts quartz, 7.5 parts kaolin, 15.5 parts limestone, 7.5 parts calcined talc, 2.5 parts alumina, 12.5 parts strontium carbonate, and 4.5 parts zinc oxide. These raw materials are mixed and calcined in a furnace at 1400℃ to melt and clarify the mixture. The molten glass is then rapidly cooled using a water bath or water-cooled metal rollers to form glass-like flakes or granular flocs, which are then crushed to obtain the matte dry granules. The matte dry granules, by mass percentage, include: 56.3% SiO2, 15.68% Al2O3, 7.47% CaO, 2.45% MgO, 3.23% K2O, 2.1% Na2O, 7.29% SrO, and 4.74% ZnO, with the remainder being loss on ignition and impurities.

[0091] The raw materials for preparing low-temperature dry granules, by weight, include: 21 parts potassium feldspar, 7.5 parts sodium feldspar, 13 parts kaolin, 29.5 parts quartz, 8.5 parts wollastonite, 9 parts limestone, 3.5 parts alumina, and 8 parts zinc oxide. These raw materials are mixed and calcined in a furnace at 1400℃ to melt and clarify the mixture. The molten glass is then rapidly cooled using a water bath or water-cooled metal rollers to produce glass-like flakes or granular flocs, which are then crushed to obtain the low-temperature dry granules. The low-temperature dry granules, by mass percentage, include: 66.16% SiO2, 12.72% Al2O3, 7.8% CaO, 3.81% K2O, 1.43% Na2O, and 7.84% ZnO, with the remainder being loss on ignition and impurities.

[0092] Among them, the SiO2 content in quartz powder is >99%, and the Al2O3 content in corundum powder is >99%.

[0093] The raw materials for preparing the protective glaze, by weight, include: 28.5 parts potassium feldspar powder, 11.5 parts sodium feldspar powder, 21.5 parts kaolin, 6 parts barium carbonate, 4 parts strontium carbonate, 10.5 parts dolomite, 6.5 parts calcined talc, 7.5 parts calcined zinc oxide, and 4 parts color-developing frit (the color-developing frit includes K2O, Na2O, and ZnO; the sum of the masses of K2O and Na2O accounts for 5.52% of the color-developing frit, and the mass of ZnO accounts for 4.67% of the color-developing frit). These raw materials are crushed separately and mixed in proportion to obtain the protective glaze. The protective glaze, by mass percentage, includes: 46.89% SiO2, 19.3% Al2O3, 3.78% CaO, 5.05% MgO, 6.05% K2O, 1.53% Na2O, 3.36% SrO, 8.78% ZnO, and 4 parts BaO. 5.18%, the remainder being loss on ignition and impurities.

[0094] Among them, the particle size D97 of high-alumina calcium dry granules is 74µm, the particle size D97 of matte dry granules is 76µm~80µm, the particle size D97 of low-temperature dry granules is 77µm, the particle size D97 of quartz powder is 40µm~50µm, and the particle size D97 of corundum powder is 48µm.

[0095] The wear-resistant glaze comprises, by weight percentage: 51.7% SiO2, 23.9% Al2O3, 6.47% CaO, 0.85% MgO, 3.13% K2O, 1.35% Na2O, 3.32% BaO, and 5.86% ZnO.

[0096] The preparation method of this wear-resistant glaze includes the following steps:

[0097] 17 parts of protective glaze were mixed with water, thickener (methylcellulose), and dispersant (sodium tripolyphosphate) (the mass ratio of protective glaze, water, thickener and dispersant was 100:30:0.15:0.35). The protective glaze slurry was then prepared by grinding, sieving and aging (the particle size D97 of the protective glaze slurry was 18µm).

[0098] 33.5 parts of high-alumina calcium dry granules, 33.5 parts of matte dry granules, 9.5 parts of low-temperature dry granules, 4.5 parts of quartz powder, 2 parts of corundum powder, the above protective glaze slurry, 70 parts of suspending agent, and 18 parts of water were mixed evenly (the mass ratio of the solid components of the wear-resistant glaze to the sum of the masses of the suspending agent and water was 1:0.88; the mass ratio of the suspending agent to water was 1:0.257) to obtain the wear-resistant glaze.

[0099] This embodiment also provides a wear-resistant ceramic tile, which includes, in sequence: a body layer, a surface glaze layer, a pattern layer, and a wear-resistant glaze layer; wherein, the surface glaze layer is formed by a surface glaze, the pattern layer is formed by colored ink, and the wear-resistant glaze layer is formed by the wear-resistant glaze of this embodiment.

[0100] The preparation method of this wear-resistant ceramic brick includes the following steps:

[0101] The pre-dried body layer (with moisture content controlled below 0.3%) is fed into the first glaze spraying equipment, and a surface glaze (specific gravity 1.87 g / cm³) is applied to the surface of the body layer. 3 The application rate is 440 g / m 2 );

[0102] Enter the printing equipment and print with color ink;

[0103] The second glaze is applied using a second glaze spraying device to apply a wear-resistant glaze (specific gravity 1.55 g / cm³). 3 The application rate is 500g / m³ 2 )

[0104] It is then placed in a kiln for firing (the maximum firing temperature is 1140℃, and the firing time is 55 minutes).

[0105] Remove and polish to obtain wear-resistant ceramic tiles.

[0106] The raw materials for preparing the glaze, by weight, include: 12 parts potassium-sodium feldspar powder, 9.5 parts sodium feldspar powder, 11.5 parts calcined alumina, 4.5 parts calcined kaolin, 25 parts quartz powder, 9.5 parts kaolin, 19.5 parts nepheline powder, 1 part calcined talc powder, and 7.5 parts zirconium silicate. The glaze, by mass percentage, includes: 60% SiO2, 28.3% Al2O3, 0.5% CaO, 0.41% MgO, 2.33% K2O, 3.21% Na2O, and 4.7% ZrO2, with the remainder being loss on ignition and impurities. The coefficient of thermal expansion of the glaze at 400℃ is 7.9 × 10⁻⁶. -6 / ℃. The coefficient of thermal expansion of the wear-resistant glaze at 400℃ is 5.55×10. -6 / ℃.

[0107] Example 4

[0108] This embodiment provides a wear-resistant glaze and the wear-resistant ceramic tile formed therefrom, which differs from Embodiment 1 in that:

[0109] The ratio of the total mass of the combined dry granules, quartz powder, and corundum powder in the wear-resistant glaze to the mass of the protective glaze is 1:0.183; the ratio of the mass of the combined dry granules to the total mass of quartz powder and corundum powder is 1:0.09; the mass ratio of quartz powder to corundum powder is 1:0.4; and the mass ratio of high-alumina calcium dry granules, matte dry granules, and low-temperature dry granules in the combined dry granules is 0.985:1:0.211.

[0110] The weight parts of each raw material in the preparation of wear-resistant ceramic tiles are as follows: 33.5 parts of high alumina-calcium dry granules, 34 parts of matte dry granules, 10 parts of low-temperature dry granules, 5 parts of quartz powder, 2 parts of corundum powder, 15.5 parts of protective glaze, 71 parts of suspending agent, and 15 parts of water.

[0111] Everything else is the same as in Example 1.

[0112] Example 5

[0113] This embodiment provides a wear-resistant glaze and the wear-resistant ceramic tile formed therefrom, which differs from Embodiment 1 in that:

[0114] The ratio of the total mass of the combined dry granules, quartz powder, and corundum powder in the wear-resistant glaze to the mass of the protective glaze is 1:0.22; the ratio of the mass of the combined dry granules to the total mass of quartz powder and corundum powder is 1:0.079; the mass ratio of quartz powder to corundum powder is 1:0.5; and the mass ratio of high-alumina calcium dry granules, matte dry granules, and low-temperature dry granules in the combined dry granules is 1.03:1:0.273.

[0115] The weight parts of each raw material in the preparation of wear-resistant ceramic tiles are as follows: 34 parts of high alumina-calcium dry granules, 33 parts of matte dry granules, 9 parts of low-temperature dry granules, 4 parts of quartz powder, 2 parts of corundum powder, 18 parts of protective glaze, 70 parts of suspending agent, and 20 parts of water.

[0116] Everything else is the same as in Example 1.

[0117] Comparative Example 1

[0118] This comparative example provides a wear-resistant glaze and the ceramic tile formed therefrom, which differs from Example 1 in that the solid component of the wear-resistant glaze does not contain quartz powder. Everything else is the same as in Example 1.

[0119] Comparative Example 2

[0120] This comparative example provides a wear-resistant glaze and the ceramic tile formed therefrom, which differs from Example 1 in that the solid component of the wear-resistant glaze does not contain corundum powder. Otherwise, it is the same as Example 1.

[0121] Comparative Example 3

[0122] This comparative example provides a wear-resistant glaze and the ceramic tile formed therefrom, which differs from Example 1 in that:

[0123] The weight parts of each raw material in the preparation of ceramic tiles are as follows: 30 parts of high alumina-calcium dry granules, 37 parts of matte dry granules, 9 parts of low-temperature dry granules, 4.5 parts of quartz powder, 2.5 parts of corundum powder, 17 parts of protective glaze, 70 parts of suspending agent, and 18 parts of water; the mass ratio of high alumina-calcium granules to matte dry granules is 0.81:1.

[0124] Everything else is the same as in Example 1.

[0125] Comparative Example 4

[0126] This comparative example provides a wear-resistant glaze and the ceramic tile formed therefrom, which differs from Example 1 in that:

[0127] The raw materials used in the preparation of ceramic tiles are as follows by weight: 37 parts high-alumina calcium dry granules, 30 parts matte dry granules, 9 parts low-temperature dry granules, 4.5 parts quartz powder, 2.5 parts corundum powder, 17 parts protective glaze, 70 parts suspending agent, and 18 parts water; the mass ratio of high-alumina calcium granules to matte dry granules is 1.23:1.

[0128] Everything else is the same as in Example 1.

[0129] Comparative Example 5

[0130] This comparative example provides a wear-resistant glaze and the ceramic tile formed therefrom, which differs from Example 1 in that:

[0131] The raw materials used in the preparation of ceramic tiles are as follows by weight: 34.5 parts of high-alumina calcium dry granules, 34.5 parts of matte dry granules, 7 parts of low-temperature dry granules, 4.5 parts of quartz powder, 2.5 parts of corundum powder, 17 parts of protective glaze, 70 parts of suspending agent, and 18 parts of water; the mass ratio of matte dry granules to low-temperature dry granules is 1:0.203.

[0132] Everything else is the same as in Example 1.

[0133] Comparative Example 6

[0134] This comparative example provides a wear-resistant glaze and the ceramic tile formed therefrom, which differs from Example 1 in that:

[0135] The raw materials used in the preparation of ceramic tiles are as follows by weight: 32.5 parts of high-alumina calcium dry granules, 32.5 parts of matte dry granules, 11 parts of low-temperature dry granules, 4.5 parts of quartz powder, 2.5 parts of corundum powder, 17 parts of protective glaze, 70 parts of suspending agent, and 18 parts of water; the mass ratio of matte dry granules to low-temperature dry granules is 1:0.338.

[0136] Everything else is the same as in Example 1.

[0137] Comparative Example 7

[0138] This comparative example provides a wear-resistant glaze and the ceramic tile formed therefrom, which differs from Example 1 in that:

[0139] The raw materials used in the preparation of ceramic tiles are as follows by weight: 34.5 parts high-alumina calcium dry granules, 34.5 parts matte dry granules, 10 parts low-temperature dry granules, 4.5 parts quartz powder, 2.5 parts corundum powder, 14 parts protective glaze, 70 parts suspending agent, and 18 parts water; the ratio of the total mass of the combined dry granules, quartz powder, and corundum powder to the mass of the protective glaze is 1:0.163.

[0140] Everything else is the same as in Example 1.

[0141] Comparative Example 8

[0142] This comparative example provides a wear-resistant glaze and the ceramic tile formed therefrom, which differs from Example 1 in that:

[0143] The raw materials used in the preparation of ceramic tiles are as follows by weight: 32.5 parts high-alumina calcium dry granules, 32.5 parts matte dry granules, 8 parts low-temperature dry granules, 4.5 parts quartz powder, 2.5 parts corundum powder, 20 parts protective glaze, 70 parts suspending agent, and 18 parts water; the ratio of the total mass of the combined dry granules, quartz powder, and corundum powder to the mass of the protective glaze is 1:0.25.

[0144] Everything else is the same as in Example 1.

[0145] Comparative Example 9

[0146] This comparative example provides a wear-resistant glaze and the ceramic tile formed therefrom, which differs from Example 1 in that the particle size D97 of both the quartz powder and corundum powder is greater than 50µm. Everything else is the same as in Example 1.

[0147] Comparative Example 10

[0148] This comparative example provides a wear-resistant glaze and the ceramic tile formed therefrom, which differs from Example 1 in that the particle size D97 of both the quartz powder and corundum powder is less than 40µm. Everything else is the same as in Example 1.

[0149] Performance testing

[0150] (1) Semi-quantitative phase analysis

[0151] The wear-resistant glaze layers of the wear-resistant ceramic tiles prepared in Examples 1-5 and the wear-resistant glaze layers of the ceramic tiles prepared in Comparative Examples 1-2 were analyzed by X-ray diffraction (XRD) for semi-quantitative phase determination. The test results are shown in Table 1. The XRD phase diagram of the wear-resistant glaze layer of the wear-resistant ceramic tile prepared in Example 1 is shown in Table 1. Figure 1 As shown.

[0152] Table 1

[0153]

[0154] (2) Tests for abrasion resistance, stain resistance, transparency and surface quality

[0155] The wear-resistant ceramic tiles prepared in Examples 1-5 and the ceramic tiles prepared in Comparative Examples 1-10 were tested for wear resistance, transparency, and surface quality. Wear resistance was tested using the method in GB / T 3810.7; stain resistance and surface quality were tested using the method in GB / T 3810.14-2016; transparency was tested using the method for determining the direct transmittance of sunlight through architectural glass in GB / T 2680-94. The linear transmittance of sunlight was measured after the wear-resistant glaze was made into glaze sheets (1 mm) and fired. The test results are shown in Table 2.

[0156] Table 2

[0157]

[0158] As can be seen from the test data in Table 2 above, the ceramic tiles prepared using the technical solution of this invention have a wear resistance of up to level 4 at 6000 revolutions, a stain resistance of up to level 5, and good color development, high transparency, and excellent quality.

[0159] Referring to Table 2, a comparison of Example 1 and Comparative Examples 1-2 shows that when quartz powder is lacking, there is no quartz crystal phase in the glaze layer, resulting in poor wear resistance and transparency; when corundum powder is lacking, there is no corundum crystal phase in the glaze layer, resulting in significantly poor wear resistance.

[0160] Referring to Table 2, a comparison of Example 1 and Comparative Examples 3-4 shows that when there are fewer high-alumina calcium dry particles, under the same firing conditions, the high-alumina calcium dry particles are fired at a higher temperature, while the matte dry particles are fired at a slightly lower temperature. The lower proportion of high-alumina calcium dry particles and the higher proportion of matte dry particles will result in a lower firing temperature. The overall low temperature will lead to poor sintering, and the surface is prone to glaze flow pits, resulting in poor stain resistance, wear resistance, and transparency. When there are more high-alumina calcium dry particles, under the same firing conditions, the high-alumina calcium dry particles are fired at a higher temperature, while the matte dry particles are fired at a slightly lower temperature. The higher proportion of high-alumina calcium dry particles requires a higher firing temperature, resulting in a matte glaze, poor transparency, and incomplete pore sealing, leading to poor stain resistance.

[0161] Referring to Table 2, a comparison of Example 1 and Comparative Examples 5-6 shows that when the proportion of low-temperature dry particles is relatively small, under the same firing conditions, the low-temperature dry particles, being at a lower temperature, have insufficient fluxing power, thus reducing the sintering degree of the glaze layer and resulting in poor wear resistance, stain resistance, and color development. When the proportion of low-temperature dry particles is relatively large, under the same firing conditions, the low-temperature dry particles, being at a lower temperature, further enhance the fluxing power, causing the glaze layer to melt prematurely, resulting in lower glaze viscosity and easier crystallization, and decreased transparency.

[0162] Referring to Table 2, a comparison of Example 1 and Comparative Examples 7-8 shows that when the protective glaze accounts for a small proportion, under the same firing conditions, the dry granules and other materials lack filling between each other, resulting in insufficient low-temperature melting and a glaze layer that is too hot. This leads to poor meltability, reduced anti-fouling performance, decreased transparency, and poor pattern color development. When the protective glaze accounts for a large proportion, under the same firing conditions, the melting temperature is lower, causing the dry granules and other materials to melt prematurely. This can easily lead to overfiring, resulting in uneven glaze surface effects. At the same time, the precipitated crystals are of varying sizes and unevenly distributed, resulting in poor anti-fouling and wear resistance, and reduced transparency.

[0163] Referring to Table 2, a comparison of Example 1 and Comparative Examples 9-10 shows that when the particle size of both quartz powder and corundum powder is relatively large, the particle content decreases accordingly, resulting in uneven particle distribution, a larger particle size distribution range, a rougher glaze surface, and poor stain resistance and wear resistance. When the particle size of both quartz powder and corundum powder is relatively small, the particle content increases accordingly, resulting in a smaller particle size distribution range, causing the quartz powder to basically melt, and thus reducing wear resistance.

[0164] In the description of this specification, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of indicated technical features. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one of that feature.

[0165] The above description is only a preferred embodiment of the present invention. It should be noted that those skilled in the art can make several improvements and additions without departing from the method of the present invention, and these improvements and additions should also be considered within the scope of protection of the present invention.

Claims

1. A wear-resistant glaze layer, characterized in that, The wear-resistant glaze layer is obtained by firing a wear-resistant glaze. The solid components of the wear-resistant glaze include a combination of dry granules, quartz powder, corundum powder, and protective glaze. The ratio of the total mass of the combined dry granules, the quartz powder, and the corundum powder to the mass of the protective glaze is 1:(0.18~0.22). The combined dry granules include high-alumina calcium dry granules, matte dry granules, and low-temperature dry granules in a mass ratio of (0.95~1.05):1:(0.26~0.30); The high-alumina calcium dry granules comprise, by mass percentage: SiO2 48.1%~53.0%, Al2O3 19.0%~21.6%, CaO 17.0%~19.6%, K2O 2.9%~3.5%, and ZnO 6.0%~7.2%; The matte dry granules comprise, by mass percentage: SiO2 51.5%~56.5%, Al2O3 15.5%~18.0%, CaO 6.5%~7.6%, MgO 2.3%~2.8%, K2O 3.2%~3.8%, Na2O 1.8%~2.2%, SrO 7.2%~8.6%, and ZnO 4.6%~5.5%; The low-temperature dry granules comprise, by mass percentage: SiO2 61.2%~66.5%, Al2O3 12.6%~14.8%, CaO 7.6%~9.0%, K2O 3.7%~4.5%, Na2O 1.1%~1.5%, and ZnO 7.7%~9.0%; The particle size D97 of the high-alumina calcium dry granules is 70µm~74µm, the particle size D97 of the matte dry granules is 76µm~80µm, the particle size D97 of the low-temperature dry granules is 73µm~77µm, the particle size D97 of the quartz powder is 40µm~50µm, and the particle size D97 of the corundum powder is 40µm~50µm. The mass ratio of the combined dry granules to the sum of the masses of the quartz powder and the corundum powder is 1:(0.07~0.09); the mass ratio of the quartz powder to the corundum powder is 1:(0.4~0.5). The contents of different phases in the wear-resistant glaze are as follows: potassium-sodium feldspar crystal phase 11.5%~15.5%, corundum crystal phase 5%~7%, quartz crystal phase 4%~6%, zinc spinel crystal phase 1.5%~3.5%, and amorphous phase 70%~76%.

2. The wear-resistant glaze layer according to claim 1, characterized in that, The raw materials for preparing the high-alumina calcium dry granules include, by weight, 16.5-19.5 parts potassium feldspar, 13.5-16.5 parts quartz, 9-11 parts kaolin, 11-13 parts limestone, 23-27 parts wollastonite, 6.5-7.5 parts calcined kaolin, 5.5-6.5 parts alumina, and 6.5-7.5 parts zinc oxide. The raw materials for preparing the matte dry granules include, by weight, 18-22 parts potassium feldspar, 9-11 parts sodium feldspar, 17-21 parts quartz, 6.3-7.8 parts kaolin, 12.5-15.5 parts limestone, 7-9 parts calcined talc, 2.5-3 parts alumina, 12.5-15.5 parts strontium carbonate, and 4.5-5.5 parts zinc oxide. The raw materials for preparing the low-temperature dry granules include, by weight, 21-25 parts potassium feldspar, 6.5-7.5 parts sodium feldspar, 11-13 parts kaolin, 25-30 parts quartz, 7.5-8.5 parts wollastonite, 9-11 parts limestone, 3.5-4.5 parts alumina, and 8-9 parts zinc oxide.

3. The wear-resistant glaze layer according to claim 1, characterized in that, The raw materials for preparing the protective glaze, by weight, include: 28.5-32.5 parts potassium feldspar powder, 11-13 parts sodium feldspar powder, 18.5-21.5 parts kaolin, 5.5-6.5 parts barium carbonate, 4-5 parts strontium carbonate, 8.5-10.5 parts dolomite, 5.5-6.5 parts calcined talc, 6.5-7.5 parts calcined zinc oxide, and 4-5 parts color-developing frit; The color-developing frit comprises K2O, Na2O, and ZnO; the sum of the masses of K2O and Na2O accounts for 5.5% to 5.7% of the color-developing frit, and the mass of ZnO accounts for 4.4% to 4.7% of the color-developing frit.

4. The wear-resistant glaze layer according to claim 3, characterized in that, The protective glaze comprises, by mass percentage: 46.5%~50.8% SiO2, 17.5%~19.6% Al2O3, 3.2%~3.9% CaO, 4.5%~5.2% MgO, 5.2%~6.2% K2O, 1.5%~1.9% Na2O, 3.3%~4.0% SrO, 7.0%~9.0% ZnO, and 4.8%~5.7% BaO.

5. A wear-resistant ceramic tile, characterized in that, In order, they include: The body layer, the surface glaze layer, the pattern layer, and the wear-resistant glaze layer as described in any one of claims 1 to 4.

6. A method for preparing wear-resistant ceramic bricks as described in claim 5, characterized in that, The surface glaze layer is formed by a surface glaze, and the pattern layer is formed by colored ink; the preparation method includes the following steps: The surface glaze is applied to the surface of the body layer, then the color ink is printed, followed by the application of the wear-resistant glaze, firing, and polishing to obtain the wear-resistant ceramic tile.

7. The method for preparing wear-resistant ceramic bricks according to claim 6, characterized in that, The coefficient of thermal expansion of the glaze at 400℃ is (7.8~7.9)×10⁻¹⁰. -6 / ℃, the coefficient of thermal expansion of the wear-resistant glaze at 400℃ is (5.45~5.55)×10 -6 / ℃.

Images