High-hardness scratch-resistant ceramic tile and preparation method thereof

Abstract

The invention discloses a high-hardness scratch-resistant ceramic tile and a preparation method thereof, and belongs to the technical field of ceramic tile processing. According to the high-hardness scratch-resistant ceramic tile disclosed by the invention, the modified corundum and the modified magnesium borate whiskers are added, and a compact zirconium phosphate transition layer with excellent compatibility with a matrix is constructed on the surfaces of corundum particles, so that the capabilities of resisting surface indentation and superficial scratch can be maximized, initiation and expansion of cracks at an interface can be further hindered, and the toughness is improved; the rare earth elements Y and Ce are adopted to perform surface modification on the magnesium borate crystal whiskers, so that the crystal whiskers can effectively exert toughening mechanisms such as bridging and crack deflection under high stress, impact energy is greatly absorbed, deep crack propagation and material stripping are prevented, and the impact resistance and fracture toughness of the ceramic tile are remarkably improved. The kaolin, the quartz sand and the albite are used as raw materials, and the modified corundum, the modified magnesium borate whiskers and other materials are combined and sintered together to prepare the ceramic tile which has the characteristics of ultrahigh surface hardness, excellent scratch resistance, excellent impact resistance and the like.

Description

Technical Field

[0001] The invention belongs to the technical field of tile processing, and particularly relates to a high-hardness scratch-resistant tile and a preparation method thereof. Background Art

[0002] In modern architectural decoration, ceramic tiles have become one of the preferred materials due to their durability, ease of cleaning, and aesthetics. However, traditional ceramic tiles still face a series of technical bottlenecks during use. Scratch sensitivity is one of the most prominent issues, especially in crowded public places. The surface of ceramic tiles is easily scratched by hard objects such as gravel and metal debris, resulting in a loss of gloss and wear of the pattern. According to laboratory test data, the Mohs hardness of ordinary glazed tiles is usually between 5 and 6, which is lower than quartz sand. This is the root cause of scratches during daily use. In addition, the phenomenon of micro-crack propagation will further reduce the life of the tiles. Tiny scratches on the surface gradually extend under long-term stress, eventually causing the glaze layer to crack or fall off, seriously affecting the aesthetics and functionality.

[0003] Current technologies mainly increase surface hardness by adding high-hardness minerals or adjusting the firing system, or improve toughness by introducing fibers / whiskers. However, a single method is often difficult to achieve both: simply increasing hardness may increase brittleness and lead to a decrease in impact resistance; while improving toughness alone may not be enough to resist surface scratches. More importantly, the optimization of the interface between the reinforcing phase or toughening phase and the tile matrix is ​​often overlooked or insufficiently treated, greatly limiting its potential for performance improvement. Therefore, there is an urgent need to develop a comprehensive solution that can significantly improve the surface hardness and deep toughness of tiles at the same time, ensuring that the reinforcing phase and toughening phase can fully exert their synergistic effect in the matrix, thereby obtaining high-quality tiles with excellent scratch resistance, wear resistance and impact resistance. Summary of the Invention

[0004] The purpose of the present invention is to provide a high-hardness scratch-resistant ceramic tile. By adding modified corundum and modified magnesium borate whiskers, the two work synergistically to significantly improve the hardness and wear resistance of the ceramic tile.

[0005] In order to achieve the above technical objectives, the technical solution adopted by the present invention is: A high-hardness scratch-resistant ceramic tile comprises the following raw materials in parts by weight: 40-45 parts of kaolin, 20-25 parts of albite, 15-18 parts of quartz sand, 8-12 parts of surface-modified corundum, 4-6 parts of modified magnesium borate whiskers, 2.2-2.8 parts of glass powder, and 0.7-1.0 part of hydroxypropyl methylcellulose.

[0006] Furthermore, the preparation method of the surface-modified corundum is: Preparation of zirconium phosphate sol: Dissolve zirconium oxychloride in an ethanol-water mixed solvent to prepare a zirconium salt solution with a concentration of 0.1M. In another container, dilute phosphoric acid with deionized water to a concentration of 10wt%. Under magnetic stirring, add the phosphoric acid solution dropwise to the zirconium salt solution. After mixing, place the mixture in a 60°C constant temperature water bath and stir continuously for 4-6 hours. Then, adjust the pH to 3 with an ammonia solution and continue stirring and aging at 60°C for 2-4 hours, stirring until the sol becomes translucent or opalescent. Zirconium phosphate sol coating modification of corundum particles: Place the corundum particles in a ball mill, add deionized water and sodium hexametaphosphate, stir at 200rpm for 60 minutes, and ultrasonically disperse for 30 minutes to fully disperse the particles to form a uniform and stable suspension. Add the zirconium phosphate sol dropwise to the corundum suspension under continuous stirring at a dropping rate of 5mL / min. After the addition is completed, stir continuously at 50°C for 4-6 hours. After the reaction is completed, filter or centrifuge the suspension, collect the coated particles, wash them with deionized water 4-5 times to remove unabsorbed sol components and residual ions, dry the washed coated particles, and heat treat the dried coated particles in an air atmosphere at 550°C for 1.5 hours. After calcination, naturally cool to room temperature to obtain modified corundum.

[0007] Furthermore, during the preparation of the zirconium phosphate sol, the volume ratio of ethanol to water in the ethanol-water mixed solvent is 1:1; during the mixing of the phosphoric acid solution and the zirconium salt solution, the Zr / P molar ratio is 1:2.

[0008] Furthermore, during the zirconium phosphate sol coating modification process of the corundum particles, the solid-liquid ratio of the corundum particles to deionized water is 1kg:3L; the amount of sodium hexametaphosphate added is 1wt% of the corundum particles; the amount of zirconium phosphate sol added is 2-3wt% of the corundum mass; and the heating rate in the heat treatment stage is 2-5°C / min.

[0009] Furthermore, the preparation method of the modified magnesium borate whisker is: (1) Whisker pretreatment: immerse 1.0 g of magnesium borate whiskers in 50 mL of 0.1 M HCl, ultrasonically disperse for 10 min, stir at 60 °C for 30 min, filter, wash with deionized water until neutral, and dry at 110 °C for 2 h. (2) Preparation of precursor solution: Take 200 mL of deionized water, add cerium nitrate hexahydrate, yttrium nitrate hexahydrate, and urea, and stir until completely dissolved; (3) Loading: Add the pretreated whiskers to the precursor solution, ultrasonically disperse for 10 min, place in a constant temperature water bath at 90 °C, and magnetically stir at 300 rpm for 4-6 h; (4) Aging and washing: Aging was performed at room temperature for 12 h, followed by filtration, washing with deionized water three times, and then washing with anhydrous ethanol once to remove impurity ions and obtain the product; (5) Calcination and crystallization: The product was dried in an oven at 110°C for 12 hours, ground into uniform powder, and placed in an alumina crucible. The temperature was first raised to 300°C at a rate of 2°C / min, then raised to 550°C at a rate of 1°C / min, and finally kept at 550°C for 3 hours. Finally, the product was naturally cooled to room temperature to obtain the final product, modified magnesium borate whiskers.

[0010] Furthermore, the molar ratio of Y:Ce in the added cerium nitrate hexahydrate and yttrium nitrate hexahydrate is 1:9; the molar ratio of urea to Y+Ce is 10:1; and the molar ratio of magnesium borate whiskers to Y+Ce is 5.55:1.

[0011] Furthermore, the particle size of the albite is 200 mesh, the particle size of the quartz sand is 325 mesh, and the particle size of the surface-modified corundum is 5-20 μm.

[0012] A method for preparing high-hardness scratch-resistant ceramic tiles comprises the following steps: ball-milling dry components of kaolin, albite, quartz sand, surface-modified corundum, modified magnesium borate whiskers, glass powder, and hydroxypropyl methylcellulose for 30 minutes, then adding water and wet-milling for 2 hours, with an air inlet temperature of 280°C and an air outlet temperature of 110°C, performing press molding, first heating the temperature to 1150°C at a rate of 15°C / min and holding the temperature for 30 minutes, then heating the temperature to 1220°C at a rate of 25°C / min and holding the temperature for 10 minutes, air-cooling the temperature to 900°C, and slowly cooling the temperature in a kiln to room temperature.

[0013] Furthermore, the mass ratio of the dry material, balls and water is 1:2:0.6.

[0014] This invention incorporates surface-modified corundum, which acts as a hard particle dispersed throughout the ceramic tile mass. It forms the first line of defense against external scratches and abrasion, and serves as the primary load-bearing framework. Pretreatment (ball milling, sodium hexametaphosphate, and ultrasound) effectively disperses the corundum particles, preventing agglomeration. The zirconium phosphate sol coating provides a more compatible "bridge" between the corundum particles and the ceramic tile's glass matrix. This significantly reduces interfacial defects between the particles and the matrix, enabling more efficient stress transfer. Furthermore, the uniform, firmly bonded coating prevents cracks from initiating directly at the corundum / matrix interface under external forces. Even if a microcrack develops in the matrix, its propagation path is hindered or deflected when the crack tip encounters the coating, consuming more energy and thus improving the material's fracture toughness. Thus, the modified corundum provides the primary framework for ultra-high hardness, and surface modification significantly optimizes its dispersion and interfacial bonding strength within the matrix, maximizing its resistance to scratches and abrasion while enhancing the overall material's hardness and toughness.

[0015] The present invention also adds modified magnesium borate whiskers, which are single-crystal fiber materials with high strength, high modulus, and high heat resistance. In the ceramic tile matrix, they act like countless tiny steel bars, bridging, pulling out, and deflecting cracks, significantly absorbing and dissipating impact energy, preventing crack propagation, and thus improving the fracture toughness and impact resistance of the ceramic tile. Unmodified whiskers have a smooth and inert surface and tend to have a weak bond with the ceramic matrix. However, the coating of rare earth elements Y and Ce greatly improves the wettability and chemical compatibility between the whiskers and the matrix. Rare earth oxides can form stronger interfacial chemical bonds (such as YO-Si and Ce-O-Si) with the silicate components in the matrix, which is far superior to the physical or weak bonding of unmodified whiskers. This ensures that stress can be effectively transferred from the relatively fragile matrix to the high-strength whiskers. Therefore, as a high-efficiency toughening and reinforcing agent, rare earth element coating improves the interface bonding strength with the tile matrix, so that its toughening mechanisms such as bridging and crack deflection can be fully utilized, significantly improving the fracture toughness, impact resistance and ability to resist crack propagation of the tiles.

[0016] Beneficial effects The modified corundum and modified magnesium borate whiskers in the present invention are not isolated in improving the hardness and scratch resistance of ceramic tiles, but rather work synergistically: the modified corundum provides ultra-high hardness to resist surface indentation and superficial scratches, that is, it mainly resists scratches and wear; the modified magnesium borate whiskers provide high toughness to resist deep scratches, impacts and prevent material spalling caused by crack propagation, that is, it mainly resists crack initiation and propagation, preventing small scratches from evolving into large damage.

[0017] The present invention uses kaolin, quartz sand and albite as raw materials, and sinters them together with modified corundum, modified magnesium borate whiskers and other materials to prepare tiles with ultra-high surface hardness, excellent scratch resistance, excellent impact resistance and the like. DETAILED DESCRIPTION

[0018] The technical solution of the present invention will be further described below with reference to specific embodiments, but is not limited thereto.

[0019] Example 1 A high-hardness scratch-resistant ceramic tile comprises the following raw materials in parts by weight: 40 parts of kaolin, 20 parts of albite, 15 parts of quartz sand, 8 parts of surface-modified corundum, 4 parts of modified magnesium borate whiskers, 2.2 parts of glass powder, and 0.7 part of hydroxypropyl methylcellulose.

[0020] The preparation method of the surface-modified corundum is: Preparation of zirconium phosphate sol: zirconium oxychloride is dissolved in an ethanol-water mixed solvent to prepare a zirconium salt solution with a concentration of 0.1M. In another container, phosphoric acid is diluted with deionized water to a concentration of 10wt%. Under magnetic stirring, the phosphoric acid solution is added dropwise to the zirconium salt solution. After mixing, the mixture is placed in a 60°C constant temperature water bath and stirred continuously for 4 hours. The pH is then adjusted to 3 with an ammonia solution. Stirring and aging at 60°C for another 2 hours, stirring, until the sol becomes translucent or opalescent. Zirconium phosphate sol coating modification of corundum particles: Place the corundum particles in a ball mill, add deionized water and sodium hexametaphosphate, stir at 200rpm for 60 minutes, and ultrasonically disperse for 30 minutes to fully disperse the particles to form a uniform and stable suspension. Add the zirconium phosphate sol dropwise to the corundum suspension under continuous stirring at a dropping rate of 5mL / min. After the addition is completed, stir continuously at 50°C for 4 hours. After the reaction is completed, filter or centrifuge the suspension, collect the coated particles, wash them with deionized water 4 times to remove the unabsorbed sol components and residual ions, dry the washed coated particles, and heat treat the dried coated particles in an air atmosphere at 550°C for 1.5 hours. After calcination, naturally cool to room temperature to obtain modified corundum.

[0021] During the preparation of the zirconium phosphate sol, the volume ratio of ethanol to water in the ethanol-water mixed solvent is 1:1; during the mixing of the phosphoric acid solution and the zirconium salt solution, the Zr / P molar ratio is 1:2.

[0022] During the zirconium phosphate sol coating modification process of the corundum particles, the solid-liquid ratio of the corundum particles to deionized water is 1 kg:3 L; the amount of sodium hexametaphosphate added is 1 wt% of the corundum particles; the amount of zirconium phosphate sol added is 2 wt% of the corundum mass; and the heating rate in the heat treatment stage is 2°C / min.

[0023] The preparation method of the modified magnesium borate whisker is: (1) Whisker pretreatment: immerse 1.0 g of magnesium borate whiskers in 50 mL of 0.1 M HCl, ultrasonically disperse for 10 min, stir at 60 °C for 30 min, filter, wash with deionized water until neutral, and dry at 110 °C for 2 h. (2) Preparation of precursor solution: Take 200 mL of deionized water, add cerium nitrate hexahydrate, yttrium nitrate hexahydrate, and urea, and stir until completely dissolved; (3) Loading: Add the pretreated whiskers to the precursor solution, ultrasonically disperse for 10 min, place in a constant temperature water bath at 90 °C, and magnetically stir at 300 rpm for 4 h; (4) Aging and washing: Aging was performed at room temperature for 12 h, followed by filtration, washing with deionized water three times, and then washing with anhydrous ethanol once to remove impurity ions and obtain the product; (5) Calcination and crystallization: The product was dried in an oven at 110°C for 12 hours, ground into uniform powder, and placed in an alumina crucible. The temperature was first raised to 300°C at a rate of 2°C / min, then raised to 550°C at a rate of 1°C / min, and finally kept at 550°C for 3 hours. Finally, the product was naturally cooled to room temperature to obtain the final product, modified magnesium borate whiskers.

[0024] The molar ratio of Y:Ce in the added cerium nitrate hexahydrate and yttrium nitrate hexahydrate is 1:9; the molar ratio of urea to Y+Ce is 10:1; and the molar ratio of magnesium borate whiskers to Y+Ce is 5.55:1.

[0025] The particle size of the albite is 200 mesh, the particle size of the quartz sand is 325 mesh, and the particle size of the surface-modified corundum is 5-20 μm.

[0026] A method for preparing high-hardness scratch-resistant ceramic tiles comprises the following steps: ball-milling dry components of kaolin, albite, quartz sand, surface-modified corundum, modified magnesium borate whiskers, glass powder, and hydroxypropyl methylcellulose for 30 minutes, then adding water and wet-milling for 2 hours, with an air inlet temperature of 280°C and an air outlet temperature of 110°C, performing press molding, first heating the temperature to 1150°C at a rate of 15°C / min and holding the temperature for 30 minutes, then heating the temperature to 1220°C at a rate of 25°C / min and holding the temperature for 10 minutes, air-cooling the temperature to 900°C, and slowly cooling the temperature in a kiln to room temperature.

[0027] The mass ratio of the dry material, balls and water is 1:2:0.6.

[0028] Example 2 A high-hardness scratch-resistant ceramic tile comprises the following raw materials in parts by weight: 43 parts of kaolin, 22 parts of albite, 17 parts of quartz sand, 10 parts of surface-modified corundum, 5 parts of modified magnesium borate whiskers, 2.5 parts of glass powder, and 0.9 part of hydroxypropyl methylcellulose.

[0029] The preparation method of the surface-modified corundum is: Preparation of zirconium phosphate sol: zirconium oxychloride is dissolved in an ethanol-water mixed solvent to prepare a zirconium salt solution with a concentration of 0.1M. In another container, phosphoric acid is diluted with deionized water to a concentration of 10wt%. Under magnetic stirring, the phosphoric acid solution is added dropwise to the zirconium salt solution. After mixing, the mixture is placed in a 60°C constant temperature water bath and stirred continuously for 5 hours. Then, the pH is adjusted to 3 with an ammonia solution and stirred and aged at 60°C for another 3 hours, until the sol becomes translucent or opalescent. Zirconium phosphate sol coating modification of corundum particles: Place the corundum particles in a ball mill, add deionized water and sodium hexametaphosphate, stir at 200rpm for 60 minutes, and ultrasonically disperse for 30 minutes to fully disperse the particles to form a uniform and stable suspension. Add the zirconium phosphate sol dropwise to the corundum suspension under continuous stirring at a dropping rate of 5mL / min. After the addition is completed, stir continuously at 50°C for 5 hours. After the reaction is completed, filter or centrifuge the suspension, collect the coated particles, wash them with deionized water 5 times to remove the unabsorbed sol components and residual ions, dry the washed coated particles, and heat treat the dried coated particles in an air atmosphere at 550°C for 1.5 hours. After calcination, naturally cool to room temperature to obtain modified corundum.

[0030] During the preparation of the zirconium phosphate sol, the volume ratio of ethanol to water in the ethanol-water mixed solvent is 1:1; during the mixing of the phosphoric acid solution and the zirconium salt solution, the Zr / P molar ratio is 1:2.

[0031] During the zirconium phosphate sol coating modification process of the corundum particles, the solid-liquid ratio of the corundum particles to deionized water is 1 kg:3 L; the amount of sodium hexametaphosphate added is 1 wt% of the corundum particles; the amount of zirconium phosphate sol added is 3 wt% of the corundum mass; and the heating rate in the heat treatment stage is 5°C / min.

[0032] The preparation method of the modified magnesium borate whisker is: (1) Whisker pretreatment: immerse 1.0 g of magnesium borate whiskers in 50 mL of 0.1 M HCl, ultrasonically disperse for 10 min, stir at 60 °C for 30 min, filter, wash with deionized water until neutral, and dry at 110 °C for 2 h. (2) Preparation of precursor solution: Take 200 mL of deionized water, add cerium nitrate hexahydrate, yttrium nitrate hexahydrate, and urea, and stir until completely dissolved; (3) Loading: Add the pretreated whiskers to the precursor solution, ultrasonically disperse for 10 min, place in a constant temperature water bath at 90 °C, and magnetically stir at 300 rpm for 5 h; (4) Aging and washing: Aging was performed at room temperature for 12 h, followed by filtration, washing with deionized water three times, and then washing with anhydrous ethanol once to remove impurity ions and obtain the product; (5) Calcination and crystallization: The product was dried in an oven at 110°C for 12 hours, ground into uniform powder, and placed in an alumina crucible. The temperature was first raised to 300°C at a rate of 2°C / min, then raised to 550°C at a rate of 1°C / min, and finally kept at 550°C for 3 hours. Finally, the product was naturally cooled to room temperature to obtain the final product, modified magnesium borate whiskers.

[0033] The molar ratio of Y:Ce in the added cerium nitrate hexahydrate and yttrium nitrate hexahydrate is 1:9; the molar ratio of urea to Y+Ce is 10:1; and the molar ratio of magnesium borate whiskers to Y+Ce is 5.55:1.

[0034] The particle size of the albite is 200 mesh, the particle size of the quartz sand is 325 mesh, and the particle size of the surface-modified corundum is 5-20 μm.

[0035] A method for preparing high-hardness scratch-resistant ceramic tiles comprises the following steps: ball-milling dry components of kaolin, albite, quartz sand, surface-modified corundum, modified magnesium borate whiskers, glass powder, and hydroxypropyl methylcellulose for 30 minutes, then adding water and wet-milling for 2 hours, with an air inlet temperature of 280°C and an air outlet temperature of 110°C, performing press molding, first heating the temperature to 1150°C at a rate of 15°C / min and holding the temperature for 30 minutes, then heating the temperature to 1220°C at a rate of 25°C / min and holding the temperature for 10 minutes, air-cooling the temperature to 900°C, and slowly cooling the temperature in a kiln to room temperature.

[0036] The mass ratio of the dry material, balls and water is 1:2:0.6.

[0037] Example 3 A high-hardness scratch-resistant ceramic tile comprises the following raw materials in parts by weight: 45 parts of kaolin, 25 parts of albite, 18 parts of quartz sand, 12 parts of surface-modified corundum, 6 parts of modified magnesium borate whiskers, 2.8 parts of glass powder, and 1.0 part of hydroxypropyl methylcellulose.

[0038] The preparation method of the surface-modified corundum is: Preparation of zirconium phosphate sol: zirconium oxychloride is dissolved in an ethanol-water mixed solvent to prepare a zirconium salt solution with a concentration of 0.1M. In another container, phosphoric acid is diluted with deionized water to a concentration of 10wt%. Under magnetic stirring, the phosphoric acid solution is added dropwise to the zirconium salt solution. After mixing, the mixture is placed in a 60°C constant temperature water bath and stirred continuously for 6 hours. Then, the pH is adjusted to 3 with an ammonia solution and stirred and aged at 60°C for another 4 hours, until the sol becomes translucent or opalescent. Zirconium phosphate sol coating modification of corundum particles: Place the corundum particles in a ball mill, add deionized water and sodium hexametaphosphate, stir at 200rpm for 60 minutes, and ultrasonically disperse for 30 minutes to fully disperse the particles to form a uniform and stable suspension. Add the zirconium phosphate sol dropwise to the corundum suspension under continuous stirring at a dropping rate of 5mL / min. After the addition is completed, stir continuously at 50°C for 6 hours. After the reaction is completed, filter or centrifuge the suspension, collect the coated particles, wash them with deionized water 5 times to remove the unabsorbed sol components and residual ions, dry the washed coated particles, and heat treat the dried coated particles in an air atmosphere at 550°C for 1.5 hours. After calcination, naturally cool to room temperature to obtain modified corundum.

[0039] During the preparation of the zirconium phosphate sol, the volume ratio of ethanol to water in the ethanol-water mixed solvent is 1:1; during the mixing of the phosphoric acid solution and the zirconium salt solution, the Zr / P molar ratio is 1:2.

[0040] During the zirconium phosphate sol coating modification process of the corundum particles, the solid-liquid ratio of the corundum particles to deionized water is 1 kg:3 L; the amount of sodium hexametaphosphate added is 1 wt% of the corundum particles; the amount of zirconium phosphate sol added is 3 wt% of the corundum mass; and the heating rate in the heat treatment stage is 3°C / min.

[0041] The preparation method of the modified magnesium borate whisker is: (1) Whisker pretreatment: immerse 1.0 g of magnesium borate whiskers in 50 mL of 0.1 M HCl, ultrasonically disperse for 10 min, stir at 60 °C for 30 min, filter, wash with deionized water until neutral, and dry at 110 °C for 2 h. (2) Preparation of precursor solution: Take 200 mL of deionized water, add cerium nitrate hexahydrate, yttrium nitrate hexahydrate, and urea, and stir until completely dissolved; (3) Loading: Add the pretreated whiskers to the precursor solution, ultrasonically disperse for 10 min, place in a constant temperature water bath at 90 °C, and magnetically stir at 300 rpm for 6 h; (4) Aging and washing: Aging was performed at room temperature for 12 h, followed by filtration, washing with deionized water three times, and then washing with anhydrous ethanol once to remove impurity ions and obtain the product; (5) Calcination and crystallization: The product was dried in an oven at 110°C for 12 hours, ground into uniform powder, and placed in an alumina crucible. The temperature was first raised to 300°C at a rate of 2°C / min, then raised to 550°C at a rate of 1°C / min, and finally kept at 550°C for 3 hours. Finally, the product was naturally cooled to room temperature to obtain the final product, modified magnesium borate whiskers.

[0042] The molar ratio of Y:Ce in the added cerium nitrate hexahydrate and yttrium nitrate hexahydrate is 1:9; the molar ratio of urea to Y+Ce is 10:1; and the molar ratio of magnesium borate whiskers to Y+Ce is 5.55:1.

[0043] The particle size of the albite is 200 mesh, the particle size of the quartz sand is 325 mesh, and the particle size of the surface-modified corundum is 5-20 μm.

[0044] A method for preparing high-hardness scratch-resistant ceramic tiles comprises the following steps: ball-milling dry components of kaolin, albite, quartz sand, surface-modified corundum, modified magnesium borate whiskers, glass powder, and hydroxypropyl methylcellulose for 30 minutes, then adding water and wet-milling for 2 hours, with an air inlet temperature of 280°C and an air outlet temperature of 110°C, performing press molding, first heating the temperature to 1150°C at a rate of 15°C / min and holding the temperature for 30 minutes, then heating the temperature to 1220°C at a rate of 25°C / min and holding the temperature for 10 minutes, air-cooling the temperature to 900°C, and slowly cooling the temperature in a kiln to room temperature.

[0045] The mass ratio of the dry material, balls and water is 1:2:0.6.

[0046] Comparative Example 1 A high-hardness scratch-resistant ceramic tile comprises the following raw materials in parts by weight: 45 parts of kaolin, 25 parts of albite, 18 parts of quartz sand, 12 parts of corundum, 6 parts of modified magnesium borate whiskers, 2.8 parts of glass powder, and 1.0 part of hydroxypropyl methylcellulose.

[0047] The preparation method of the modified magnesium borate whisker is: (1) Whisker pretreatment: immerse 1.0 g of magnesium borate whiskers in 50 mL of 0.1 M HCl, ultrasonically disperse for 10 min, stir at 60 °C for 30 min, filter, wash with deionized water until neutral, and dry at 110 °C for 2 h. (2) Preparation of precursor solution: Take 200 mL of deionized water, add cerium nitrate hexahydrate, yttrium nitrate hexahydrate, and urea, and stir until completely dissolved; (3) Loading: Add the pretreated whiskers to the precursor solution, ultrasonically disperse for 10 min, place in a constant temperature water bath at 90 °C, and magnetically stir at 300 rpm for 6 h; (4) Aging and washing: Aging was performed at room temperature for 12 h, followed by filtration, washing with deionized water three times, and then washing with anhydrous ethanol once to remove impurity ions and obtain the product; (5) Calcination and crystallization: The product was dried in an oven at 110°C for 12 hours, ground into uniform powder, and placed in an alumina crucible. The temperature was first raised to 300°C at a rate of 2°C / min, then raised to 550°C at a rate of 1°C / min, and finally kept at 550°C for 3 hours. Finally, the product was naturally cooled to room temperature to obtain the final product, modified magnesium borate whiskers.

[0048] The molar ratio of Y:Ce in the added cerium nitrate hexahydrate and yttrium nitrate hexahydrate is 1:9; the molar ratio of urea to Y+Ce is 10:1; and the molar ratio of magnesium borate whiskers to Y+Ce is 5.55:1.

[0049] The particle size of the albite is 200 mesh, the particle size of the quartz sand is 325 mesh, and the particle size of the surface-modified corundum is 5-20 μm.

[0050] A method for preparing high-hardness scratch-resistant ceramic tiles comprises the following steps: ball-milling dry components of kaolin, albite, quartz sand, corundum, modified magnesium borate whiskers, glass powder, and hydroxypropyl methylcellulose for 30 minutes, then adding water and wet-milling for 2 hours, with an air inlet temperature of 280°C and an air outlet temperature of 110°C, performing press molding, first heating the temperature to 1150°C at a rate of 15°C / min and holding for 30 minutes, then heating the temperature to 1220°C at a rate of 25°C / min and holding for 10 minutes, air-cooling the temperature to 900°C, and slowly cooling the temperature in a kiln to room temperature.

[0051] The mass ratio of the dry material, balls and water is 1:2:0.6.

[0052] Compared with Example 3, this comparative example has the same raw materials and steps as Example 3 except that the corundum is not surface-modified.

[0053] Comparative Example 2 A high-hardness scratch-resistant ceramic tile comprises the following raw materials in parts by weight: 45 parts of kaolin, 25 parts of albite, 18 parts of quartz sand, 12 parts of surface-modified corundum, 6 parts of magnesium borate whiskers, 2.8 parts of glass powder, and 1.0 part of hydroxypropyl methylcellulose.

[0054] The preparation method of the surface-modified corundum is: Preparation of zirconium phosphate sol: zirconium oxychloride is dissolved in an ethanol-water mixed solvent to prepare a zirconium salt solution with a concentration of 0.1M. In another container, phosphoric acid is diluted with deionized water to a concentration of 10wt%. Under magnetic stirring, the phosphoric acid solution is added dropwise to the zirconium salt solution. After mixing, the mixture is placed in a 60°C constant temperature water bath and stirred continuously for 6 hours. Then, the pH is adjusted to 3 with an ammonia solution and stirred and aged at 60°C for another 4 hours, until the sol becomes translucent or opalescent. Zirconium phosphate sol coating modification of corundum particles: Place the corundum particles in a ball mill, add deionized water and sodium hexametaphosphate, stir at 200rpm for 60 minutes, and ultrasonically disperse for 30 minutes to fully disperse the particles to form a uniform and stable suspension. Add the zirconium phosphate sol dropwise to the corundum suspension under continuous stirring at a dropping rate of 5mL / min. After the addition is completed, stir continuously at 50°C for 6 hours. After the reaction is completed, filter or centrifuge the suspension, collect the coated particles, wash them with deionized water 5 times to remove the unabsorbed sol components and residual ions, dry the washed coated particles, and heat treat the dried coated particles in an air atmosphere at 550°C for 1.5 hours. After calcination, naturally cool to room temperature to obtain modified corundum.

[0055] During the preparation of the zirconium phosphate sol, the volume ratio of ethanol to water in the ethanol-water mixed solvent is 1:1; during the mixing of the phosphoric acid solution and the zirconium salt solution, the Zr / P molar ratio is 1:2.

[0056] During the zirconium phosphate sol coating modification process of the corundum particles, the solid-liquid ratio of the corundum particles to deionized water is 1 kg:3 L; the amount of sodium hexametaphosphate added is 1 wt% of the corundum particles; the amount of zirconium phosphate sol added is 3 wt% of the corundum mass; and the heating rate in the heat treatment stage is 3°C / min.

[0057] The particle size of the albite is 200 mesh, the particle size of the quartz sand is 325 mesh, and the particle size of the surface-modified corundum is 5-20 μm.

[0058] A method for preparing high-hardness scratch-resistant ceramic tiles comprises the following steps: ball-milling dry components of kaolin, albite, quartz sand, surface-modified corundum, magnesium borate whiskers, glass powder, and hydroxypropyl methylcellulose for 30 minutes, then adding water and wet-milling for 2 hours, with an air inlet temperature of 280°C and an air outlet temperature of 110°C, performing press molding, first heating the temperature to 1150°C at a rate of 15°C / min and holding the temperature for 30 minutes, then heating the temperature to 1220°C at a rate of 25°C / min and holding the temperature for 10 minutes, air-cooling the ceramic tiles to 900°C, and slowly cooling the ceramic tiles to room temperature in a kiln.

[0059] The mass ratio of the dry material, balls and water is 1:2:0.6.

[0060] Compared with Example 3, this comparative example uses the same raw materials and steps as Example 3, except that the magnesium borate whiskers are not modified.

[0061] Comparative Example 3 A high-hardness scratch-resistant ceramic tile comprises the following raw materials in parts by weight: 45 parts of kaolin, 25 parts of albite, 18 parts of quartz sand, 12 parts of corundum, 6 parts of magnesium borate whiskers, 2.8 parts of glass powder, and 1.0 part of hydroxypropyl methylcellulose.

[0062] The particle size of the albite is 200 mesh, the particle size of the quartz sand is 325 mesh, and the particle size of the corundum is 5-20 μm.

[0063] A method for preparing high-hardness scratch-resistant ceramic tiles comprises the following steps: ball-milling dry components of kaolin, albite, quartz sand, corundum, magnesium borate whiskers, glass powder, and hydroxypropyl methylcellulose for 30 minutes, then adding water and wet-milling for 2 hours, with an air inlet temperature of 280°C and an air outlet temperature of 110°C, performing press molding, first heating the temperature to 1150°C at a rate of 15°C / min and holding the temperature for 30 minutes, then heating the temperature to 1220°C at a rate of 25°C / min and holding the temperature for 10 minutes, air-cooling the ceramic tiles to 900°C, and slowly cooling the ceramic tiles to room temperature in a kiln.

[0064] The mass ratio of the dry material, balls and water is 1:2:0.6.

[0065] Compared with Example 3, this comparative example uses the same raw materials and steps as Example 3, except that neither the corundum nor the magnesium borate whiskers are modified.

[0066] Comparative Example 4 A high-hardness scratch-resistant ceramic tile comprises the following raw materials in parts by weight: 45 parts of kaolin, 25 parts of albite, 18 parts of quartz sand, 12 parts of corundum + zirconium phosphate sol, 6 parts of modified magnesium borate whiskers, 2.8 parts of glass powder, and 1.0 parts of hydroxypropyl methylcellulose.

[0067] Preparation of zirconium phosphate sol: zirconium oxychloride is dissolved in an ethanol-water mixed solvent to prepare a zirconium salt solution with a concentration of 0.1M. In another container, phosphoric acid is diluted with deionized water to a concentration of 10wt%. Under magnetic stirring, the phosphoric acid solution is added dropwise to the zirconium salt solution. After mixing, the mixture is placed in a 60°C constant temperature water bath and stirred continuously for 6 hours. Then, the pH is adjusted to 3 with an ammonia solution and stirred and aged at 60°C for another 4 hours, until the sol becomes translucent or opalescent. During the preparation of the zirconium phosphate sol, the volume ratio of ethanol to water in the ethanol-water mixed solvent is 1:1; during the mixing of the phosphoric acid solution and the zirconium salt solution, the Zr / P molar ratio is 1:2.

[0068] The addition amount of zirconium phosphate sol is 3wt% of the mass of corundum, and it is directly added during the dry material preparation process.

[0069] The preparation method of the modified magnesium borate whisker is: (1) Whisker pretreatment: immerse 1.0 g of magnesium borate whiskers in 50 mL of 0.1 M HCl, ultrasonically disperse for 10 min, stir at 60 °C for 30 min, filter, wash with deionized water until neutral, and dry at 110 °C for 2 h. (2) Preparation of precursor solution: Take 200 mL of deionized water, add cerium nitrate hexahydrate, yttrium nitrate hexahydrate, and urea, and stir until completely dissolved; (3) Loading: Add the pretreated whiskers to the precursor solution, ultrasonically disperse for 10 min, place in a constant temperature water bath at 90 °C, and magnetically stir at 300 rpm for 6 h; (4) Aging and washing: Aging was performed at room temperature for 12 h, followed by filtration, washing with deionized water three times, and then washing with anhydrous ethanol once to remove impurity ions and obtain the product; (5) Calcination and crystallization: The product was dried in an oven at 110°C for 12 hours, ground into uniform powder, and placed in an alumina crucible. The temperature was first raised to 300°C at a rate of 2°C / min, then raised to 550°C at a rate of 1°C / min, and finally kept at 550°C for 3 hours. Finally, the product was naturally cooled to room temperature to obtain the final product, modified magnesium borate whiskers.

[0070] The molar ratio of Y:Ce in the added cerium nitrate hexahydrate and yttrium nitrate hexahydrate is 1:9; the molar ratio of urea to Y+Ce is 10:1; and the molar ratio of magnesium borate whiskers to Y+Ce is 5.55:1.

[0071] The particle size of the albite is 200 mesh, the particle size of the quartz sand is 325 mesh, and the particle size of the surface-modified corundum is 5-20 μm.

[0072] A method for preparing high-hardness scratch-resistant ceramic tiles comprises the following steps: ball-milling dry components of kaolin, albite, quartz sand, corundum, zirconium phosphate sol, modified magnesium borate whisker, glass powder, and hydroxypropyl methylcellulose for 30 minutes, then adding water and wet-milling for 2 hours, with an air inlet temperature of 280°C and an air outlet temperature of 110°C, performing press molding, first heating the temperature to 1150°C at a rate of 15°C / min and holding for 30 minutes, then heating the temperature to 1220°C at a rate of 25°C / min and holding for 10 minutes, then air-cooling to 900°C, and slowly cooling the temperature in a kiln to room temperature.

[0073] The mass ratio of the dry material, balls and water is 1:2:0.6.

[0074] Compared with Example 3, this comparative example uses the same raw materials and steps as Example 3, except that the corundum is not modified and the zirconium phosphate sol is directly added during the dry material mixing process.

[0075] Performance Testing The high-hardness scratch-resistant ceramic tiles prepared in Examples 1-3 and Comparative Examples 1-4 were subjected to performance tests. The wear resistance of the samples was determined with reference to GB / T3810.7-2016 "Test Methods for Ceramic Tiles"; the flexural strength was tested with reference to GB / T 3810.4-2016 "Test Methods for Ceramic Tiles - Part 4: Determination of Modulus of Rupture and Destructive Strength"; and the Mohs hardness test was performed using a Mohs hardness pen.

[0076] Table 1 Test results of tiles prepared in each treatment group Experimental results show that the high-hardness, scratch-resistant tiles of the present invention exhibit excellent wear resistance, a high Mohs hardness rating, and high flexural strength. In contrast, the hardness and wear resistance of Comparative Examples 1-4, which modified the tile composition, decreased significantly. This demonstrates that the modification of corundum and magnesium borate crystals in the present invention significantly improves hardness and wear resistance, and that both modifications are essential.

[0077] It should be noted that the above embodiments are only some of the preferred embodiments of the present invention, and not all of them. Obviously, based on the above embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative work should fall within the scope of protection of the present invention.

Claims

1. A high hardness anti-scratch tile, characterized in that: The invention comprises the following raw materials in parts by weight: 40-45 parts of kaolin, 20-25 parts of albite, 15-18 parts of quartz sand, 8-12 parts of surface-modified corundum, 4-6 parts of modified magnesium borate whiskers, 2.2-2.8 parts of glass powder and 0.7-1.0 part of hydroxypropyl methylcellulose.

2. The high-hardness scratch-resistant ceramic tile according to claim 1, characterized in that: The preparation method of the surface-modified corundum is: Preparation of zirconium phosphate sol: Dissolve zirconium oxychloride in an ethanol-water mixed solvent to prepare a zirconium salt solution with a concentration of 0.1M. In another container, dilute phosphoric acid with deionized water to a concentration of 10wt%. Under magnetic stirring, add the phosphoric acid solution dropwise to the zirconium salt solution. After mixing, place the mixture in a 60°C constant temperature water bath and stir continuously for 4-6 hours. Then, adjust the pH to 3 with an ammonia solution and continue stirring and aging at 60°C for 2-4 hours, stirring until the sol becomes translucent or opalescent. Zirconium phosphate sol coating modification of corundum particles: Place the corundum particles in a ball mill, add deionized water and sodium hexametaphosphate, stir at 200rpm for 60 minutes, and ultrasonically disperse for 30 minutes to fully disperse the particles to form a uniform and stable suspension. Add the zirconium phosphate sol dropwise to the corundum suspension under continuous stirring at a dropping rate of 5mL / min. After the addition is completed, stir continuously at 50°C for 4-6 hours. After the reaction is completed, filter or centrifuge the suspension, collect the coated particles, wash them with deionized water 4-5 times to remove unabsorbed sol components and residual ions, dry the washed coated particles, and heat treat the dried coated particles in an air atmosphere at 550°C for 1.5 hours. After calcination, naturally cool to room temperature to obtain modified corundum.

3. The high-hardness anti-scratch ceramic tile according to claim 2, characterized in that: During the preparation of the zirconium phosphate sol, the volume ratio of ethanol to water in the ethanol-water mixed solvent is 1:1; during the mixing of the phosphoric acid solution and the zirconium salt solution, the Zr / P molar ratio is 1:

2.

4. The high-hardness scratch-resistant ceramic tile according to claim 2, characterized in that: During the zirconium phosphate sol coating modification process of the corundum particles, the solid-liquid ratio of the corundum particles to deionized water is 1 kg:3 L; the amount of sodium hexametaphosphate added is 1 wt% of the corundum particles; the amount of zirconium phosphate sol added is 2-3 wt% of the corundum mass; and the heating rate in the heat treatment stage is 2-5°C / min.

5. The high-hardness scratch-resistant ceramic tile according to claim 1, characterized in that: The preparation method of the modified magnesium borate whisker is: (1) Whisker pretreatment: immerse 1.0 g of magnesium borate whiskers in 50 mL of 0.1 M HCl, ultrasonically disperse for 10 min, stir at 60 °C for 30 min, filter, wash with deionized water until neutral, and dry at 110 °C for 2 h. (2) Preparation of precursor solution: Take 200 mL of deionized water, add cerium nitrate hexahydrate, yttrium nitrate hexahydrate, and urea, and stir until completely dissolved; (3) Loading: Add the pretreated whiskers to the precursor solution, ultrasonically disperse for 10 min, place in a constant temperature water bath at 90 °C, and magnetically stir at 300 rpm for 4-6 h; (4) Aging and washing: Aging was performed at room temperature for 12 h, followed by filtration, washing with deionized water three times, and then washing with anhydrous ethanol once to remove impurity ions and obtain the product; (5) Calcination and crystallization: The product was dried in an oven at 110°C for 12 hours, ground into uniform powder, and placed in an alumina crucible. The temperature was first raised to 300°C at a rate of 2°C / min, then raised to 550°C at a rate of 1°C / min, and finally kept at 550°C for 3 hours. Finally, the product was naturally cooled to room temperature to obtain the final product, modified magnesium borate whiskers.

6. The high-hardness scratch-resistant ceramic tile according to claim 5, characterized in that: The molar ratio of Y:Ce in the added cerium nitrate hexahydrate and yttrium nitrate hexahydrate is 1:9; the molar ratio of urea to Y+Ce is 10:1; and the molar ratio of magnesium borate whiskers to Y+Ce is 5.55:

1.

7. The high-hardness scratch-resistant ceramic tile according to claim 1, characterized in that: The particle size of the albite is 200 mesh, the particle size of the quartz sand is 325 mesh, and the particle size of the surface-modified corundum is 5-20 μm.

8. A method for preparing the high-hardness scratch-resistant ceramic tile according to any one of claims 1 to 7, characterized in that: The following steps are involved: The dry components of kaolin, albite, quartz sand, surface modified corundum, modified magnesium borate whisker, glass powder and hydroxypropyl methylcellulose were ball-milled for 30 minutes, then wet-milled for 2 hours with water added, with the inlet air temperature at 280°C and the outlet air temperature at 110°C. The materials were pressed and molded, firstly heated to 1150°C at a rate of 15°C / min and kept warm for 30 minutes, then heated to 1280°C at a rate of 25°C / min and kept warm for 10 minutes, then air-cooled to 900°C, and slowly cooled to room temperature in a kiln.

9. The method for preparing high-hardness scratch-resistant ceramic tiles according to claim 8, characterized in that: The mass ratio of the dry material, balls and water is 1:2:0.6.

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