Silicon-aluminum-boron mullite for improving wear resistance of cover glaze, preparation method of silicon-aluminum-boron mullite, wear-resistant ceramic tile and preparation method of wear-resistant ceramic tile

Abstract

The invention relates to the field of architectural ceramics, and discloses silicon-aluminum-boron mullite for improving the wear resistance of cover glaze, a preparation method of the silicon-aluminum-boron mullite, a wear-resistant ceramic tile and a preparation method of the wear-resistant ceramic tile. The preparation method of the silicon-aluminum-boron mullite comprises the following steps: S1, weighing a silicon source, an aluminum source and a boron source according to a ratio, adding the silicon source, the aluminum source and the boron source into a solvent, and stirring at 40-60 DEG C for 12-20 hours; filtering, cooling to room temperature, and aging for at least 3 days; s2, stirring and concentrating the mixed solution obtained in the step S1 at 60-80 DEG C, drawing and collecting, drying at 60-80 DEG C for more than 2 hours, taking out and grinding into powder; and S3, calcining the powder collected in the step S2, firstly heating to 160-170 DEG C, keeping the temperature for 1.5-2.5 hours, then heating to 680-700 DEG C, and keeping the temperature for 2-4 hours to obtain the silicon-aluminum-boron mullite. The silicon-aluminum-boron mullite prepared by adopting the preparation process can be suitable for a firing process of a conventional 1200 DEG C kiln, and in the firing process, the silicon-aluminum-boron mullite is crystallized to form a high-hardness mullite microchip, so that the wear resistance can be remarkably enhanced.

Description

Technical Field

[0001] This invention relates to the field of building ceramics, and in particular to a silicon-aluminum-boron mullite for improving the wear resistance of surface glaze, its preparation method, and wear-resistant ceramic bricks and their preparation methods. Background Technology

[0002] Ceramic tiles are widely used in home and commercial space decoration due to their advantages such as good durability, strong decorative properties, and easy maintenance. As consumers' demands for product quality continue to rise, wear resistance has become one of the key factors influencing tile selection. Market research shows that most consumers consider wear resistance as one of the core indicators for evaluating tile quality, reflecting the growing market demand for highly wear-resistant tiles, especially dark-colored tiles with more visually appealing wear resistance.

[0003] However, the overall wear resistance of ceramic tiles in the industry is still limited. According to the national standard for ceramic wear resistance levels, light-colored tiles can usually reach level 4 (≥2100 revolutions), while dark-colored tiles, due to the significant color difference between the underlying material and the glaze after wear, show more obvious visual wear marks. Their wear resistance level is mostly maintained at level 3 (≥750 revolutions), which is difficult to meet the needs of high-end decoration and high-traffic scenarios.

[0004] To improve the wear resistance of ceramic tile surfaces, the industry has mainly explored two technical approaches: one is "hardness-rigidity" reinforcement, which involves introducing high-hardness particles such as silicon carbide and corundum into the glaze layer, or preparing a high-hardness crystalline layer (such as microcrystalline glass or diamond coating) on ​​its surface to directly increase surface hardness and resist wear; the other is "energy dissipation" toughening, which involves adjusting the glaze formula or structural design to give the glaze a certain degree of toughness, allowing some energy to be dissipated through elastic deformation under external loads, thereby reducing material loss. However, both approaches have significant bottlenecks in practical application: the process of coating the surface with a high-hardness crystalline layer is complex and costly, making it difficult to adapt to large-scale industrial production; while relying solely on glaze toughening contributes little to energy dissipation, resulting in a small improvement in wear resistance, and may affect the glaze's gloss and texture.

[0005] Therefore, current research focuses on adding rigid phases to glazes to improve wear resistance. However, when applied to dark-colored ceramic tiles, simply adding conventional rigid particles can easily lead to changes in hue after firing and difficulties in controlling color difference. Furthermore, issues such as the bonding strength and dispersion uniformity of the hard particles with the glaze matrix directly affect the final product's wear resistance and surface quality. Existing technologies have not yet been able to significantly and economically improve the wear resistance of dark-colored ceramic tiles without compromising their decorative effect, which has become a significant technical obstacle restricting the development of this type of product into the high-end market.

[0006] Therefore, it is necessary to develop a high wear-resistant rigid filler and its preparation process suitable for dark-colored ceramic tiles, which can significantly improve wear resistance while ensuring the stability of glaze color and decorative effect, so as to make up for the current market and technological deficiencies. Summary of the Invention

[0007] The main objective of this invention is to propose a silicon aluminum boron mullite and its preparation method for improving the wear resistance of the surface glaze, as well as wear-resistant ceramic tiles and their preparation method, thereby improving the wear resistance of ceramic tiles, especially the wear resistance of dark-colored ceramic tiles.

[0008] To achieve the above objectives, in a first aspect, the present invention proposes a method for preparing silica-alumina-boron mullite to improve the wear resistance of surface glaze, comprising the following steps: S1. Weigh out the silicon source, aluminum source and boron source according to the ratio, add them to the solvent, and stir at 40~60 ℃ for 12~20 h; filter and cool to room temperature, then age for at least 3 days. S2. The mixed solution obtained in step S1 is stirred and concentrated at 60~80 ℃, collected by drawing into fibers, dried at 60~80 ℃ for more than 2 hours, and then ground into powder. S3. The powder collected in step S2 is calcined. First, the temperature is raised to 160~170 ℃ and held for 1.5~2.5 h, then the temperature is raised to 680~700 ℃ and held for 2~4 h to obtain the silica-alumino-boron mullite.

[0009] The present invention uses the above-mentioned preparation process to prepare silicon aluminum boron mullite with a specific component ratio, which can be adapted to the conventional 1200℃ kiln firing process. During the firing process, silicon aluminum boron mullite crystallizes to form high-hardness mullite microcrystals, which can significantly enhance wear resistance.

[0010] Preferably, the silicon source is at least one selected from tetraethoxysilane, methyltriethoxysilane, tetramethoxysilane, and trimethoxysilane; The aluminum source is at least one of aluminum acetate and aluminum dihydroxyaminoacetate; The boron source is at least one of low-viscosity polyethylene glycol borate and triethyl borate; The solvent includes ethanol and water, wherein the mass ratio of ethanol to water is 1:1.

[0011] Preferably, the molar ratio of silicon source: aluminum source: boron source is 0.32~0.43:0.82~1.00:0.23~0.38.

[0012] Preferably, in step S3, the heating rate is 1.5 ± 0.5 °C / min.

[0013] Secondly, the present invention provides a silicon-aluminum-boron mullite for improving the wear resistance of surface glaze, which is prepared by the preparation method described above; the silicon-aluminum-boron mullite comprises the following components by mass percentage of oxides: SiO2 20~25%, Al2O3 60~70% and B2O3 10~18%.

[0014] Thirdly, the present invention provides a wear-resistant ceramic tile, comprising, from bottom to top: a body layer, a base glaze layer, a pattern layer, and a top glaze layer; the raw materials of the top glaze layer include a base glaze and the silicon-aluminum-boron mullite as described above; based on the total mass of the base glaze oxides being 100%, the Al2O3 content in the base glaze is < 24%. Limiting the aluminum content in the base glaze can reduce the impact on mullite crystallization.

[0015] Preferably, the amount of silicon-aluminum-boron mullite added accounts for 20-30% of the total mass of the raw materials in the glaze layer. By controlling the amount of silicon-aluminum-boron mullite added, the mullite microcrystals formed during the firing process can reach a certain quantity and density, thereby reducing the overall wear on the tile surface and improving the wear resistance of the tile.

[0016] Preferably, the amount of the silica-alumina-boron mullite added accounts for 28% of the total mass of the raw materials of the glaze layer.

[0017] Fourthly, the present invention also provides a method for preparing the above-mentioned wear-resistant ceramic brick, comprising the following steps: pressing a green body, applying a base glaze to the green body layer, printing color ink, applying a surface glaze, drying, and firing to obtain the wear-resistant ceramic brick.

[0018] Preferably, in the above preparation method, the firing regime is as follows: the temperature is increased to 400-450℃ at a rate of 1-1.3℃ / min and held for 20 min; then the temperature is increased to 850-900℃ at a rate of 2.5-3℃ / min and held for 30 min; then the temperature is increased to 1250-1280℃ at a rate of 1-1.3℃ / min and held for 20-30 min; then the temperature is decreased to 1200±10℃ at a rate of 1-1.3℃ / min and held for 40-45 min; then the temperature is decreased to 700℃ at a rate of 5℃ / min and held for 5-10 min; finally, the temperature is reduced to room temperature.

[0019] Compared with existing technologies, this invention has the following advantages: This invention selects suitable silicon, aluminum, and boron sources in specific ratios, and through reaction, concentration, and calcination processes, forms a silicon-aluminum-boron mullite with a specific component ratio. This silicon-aluminum-boron mullite enhances wear resistance. When mixed into a base glaze and sintered at high temperature, it forms high-hardness mullite microcrystals distributed on the surface of the ceramic tile, thereby ultimately improving the wear resistance of the tile. Attached Figure Description

[0020] To more clearly illustrate the technical solutions in the embodiments of this application or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this application. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0021] Figure 1 This is a microscopic view (50 μm) of the glaze surface structure of Example 5. Figure 2 This is a microscopic view of the glaze surface structure of Example 5 (20 μm). Figure 3 This is a 3D fitting image of the ceramic tile surface obtained in Example 5 (before the abrasion resistance test). Figure 4 This is a 3D fitting image of the ceramic tile surface obtained in Example 5 (after abrasion resistance test).

[0022] The realization of the purpose, functional features and advantages of this application will be further explained in conjunction with the embodiments and with reference to the accompanying drawings. Detailed Implementation

[0023] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention. It should be noted that, in the absence of conflict, the embodiments and features in the embodiments of this application can be combined with each other. At the same time, the raw materials mentioned below, unless otherwise specified, are all commercially available products; the process steps or preparation methods not mentioned in detail are all process steps or preparation methods known to those skilled in the art.

[0024] This embodiment discloses a method for preparing silica-alumina-boron mullite to improve the wear resistance of surface glaze, comprising the following steps: S1. Weigh out the silicon source, aluminum source and boron source according to the ratio, add them to the solvent, and stir at 40~60 ℃ for 12~20 h; filter and cool to room temperature, then age for at least 3 days. S2. The mixed solution obtained in step S1 is stirred and concentrated at 60~80 ℃, collected by drawing into fibers, dried at 60~80 ℃ for more than 2 hours, and then ground into powder. S3. The powder collected in step S2 is calcined. First, the temperature is raised to 160~170 ℃ and held for 1.5~2.5 h, then the temperature is raised to 680~700 ℃ and held for 2~4 h to obtain the silica-alumino-boron mullite.

[0025] The present invention uses the above-mentioned preparation process to obtain silicon aluminum boron mullite with a specific component ratio. The silicon aluminum boron mullite can effectively improve wear resistance and can be adapted to the current kiln firing process above 1200℃. With high-temperature sintering, the silicon aluminum boron mullite crystallizes to form high-hardness mullite microcrystals, thus improving the overall wear resistance level.

[0026] In some preferred embodiments, the silicon source is at least one of tetraethoxysilane, methyltriethoxysilane, tetramethoxysilane, and trimethoxysilane; the aluminum source is at least one of aluminum acetate and aluminum dihydroxyaminoacetate; the boron source is at least one of low-viscosity polyethylene glycol borate and triethyl borate; and the solvent includes ethanol and water, wherein the mass ratio of ethanol to water is 1:1.

[0027] In some preferred embodiments, the molar ratio of silicon source: aluminum source: boron source is 0.32~0.43:0.82~1.00:0.23~0.38.

[0028] The present invention prepares silicon-aluminum-boron mullite by adjusting the ratio of silicon, aluminum and boron sources and combining the reaction process, concentration process and calcination process. The mullite comprises the following components by mass percentage of oxides: SiO2 20~25%, Al2O3 60~70% and B2O3 10~18%.

[0029] It should be noted that in the above preparation method, the filtration in step S1 uses 100~120μm precision filter paper to filter out obviously large particles. Aging for at least 3 days can increase the silica particle size. In step S3, the heating rate is 1.5±0.5 ℃ / min.

[0030] Adding the aforementioned silicon-aluminum-boron mullite to the glaze system and sintering it at high temperature increases the surface hardness of the glaze, thereby improving wear resistance. In some preferred embodiments, the amount of silicon-aluminum-boron mullite added accounts for 20-30% of the total mass of the raw materials in the glaze layer. When the amount of silicon-aluminum-boron mullite added is within a suitable range, the mullite microcrystals formed after sintering can be evenly distributed and reach a certain threshold, thereby uniformly improving the overall wear resistance of the tile surface. More preferably, the amount of silicon-aluminum-boron mullite added accounts for 28% of the total mass of the raw materials in the glaze layer.

[0031] This embodiment also provides a wear-resistant ceramic tile, comprising, from bottom to top: a body layer, a base glaze layer, a pattern layer, and a top glaze layer; the raw materials of the top glaze layer include a base glaze and the silicon-aluminum-boron mullite as described above; based on the total mass of the base glaze oxides as 100%, the Al2O3 content in the base glaze is < 24%. The top glaze layer of this invention can significantly improve the wear resistance of ceramic surfaces, especially for dark-colored ceramic tiles, solving the key pain point of poor wear resistance in dark-colored tiles in the industry. Limiting the aluminum content in the base glaze can reduce the impact on mullite crystallization.

[0032] Furthermore, this embodiment provides a method for preparing the above-mentioned wear-resistant ceramic tile, including the following steps: pressing the green body, applying a base glaze to the green body layer, printing color ink, then applying a top glaze, drying, and firing to obtain the wear-resistant ceramic tile. The firing regime is as follows: heating to 400-450℃ at a rate of 1-1.3℃ / min and holding for 20 min; then heating to 850-900℃ at a rate of 2.5-3℃ / min and holding for 30 min; then heating to 1250-1280℃ at a rate of 1-1.3℃ / min and holding for 20-30 min; then cooling to 1200±10℃ at a rate of 1-1.3℃ / min and holding for 40-45 min; then cooling to 700℃ at a rate of 5℃ / min and holding for 5-10 min; finally cooling to room temperature. Using the above firing process, after reaching the highest temperature and holding it at that temperature, slowly cooling it to 1200℃ and then holding it at that temperature for a period of time helps to stably form the mullite microcrystalline structure.

[0033] In the above preparation method, both the green body and the base glaze can adopt well-known green body formulas, base glaze formulas, and their preparation processes. The top glaze can be prepared by directly adding silica-alumina-boron mullite to the base glaze, mixing and ball milling to form a top glaze slurry.

[0034] The following examples further illustrate the present invention in detail. It should also be understood that the following examples are only for further explanation of the present invention and should not be construed as limiting the scope of protection of the present invention. Any non-essential improvements and adjustments made by those skilled in the art based on the above description of the present invention are within the scope of protection of the present invention. The specific process parameters in the following examples are merely one example within a suitable range; that is, those skilled in the art can make appropriate selections within the range based on the description herein, and are not intended to be limited to the specific values ​​in the examples below. Where specific conditions are not specified in the examples, conventional conditions or conditions recommended by the manufacturer shall apply.

[0035] For example, the body formulations in the following embodiments and comparative examples are as follows (by weight percentage): 7.94% virgin clay, 3.97% albite powder, 3.97% pressed clay, 1.99% polished clay, 5.96% recycled clay powder, 15.89% kaolin, 5.96% alumina sand, 17.87% stone powder, 2.98% bentonite, 5.96% quartz powder, 1.99% wollastonite, 9.93% red sand, 10.92% potassium alumina sand, 3.97% talc, 0.2% deflocculant, and 0.5% water glass. The base glaze is model 1096 glaze from Foshan Yuanda Glaze Technology Co., Ltd.

[0036] Example 1 A method for preparing silica-alumina-boron mullite to improve the wear resistance of surface glaze includes the following steps: S1. Weigh 7.2g tetraethoxysilane, 11.3g aluminum dihydroxyaminoacetate, and 3.7g triethyl borate, add them to a mixed solvent of 38.9g anhydrous ethanol and 38.9g distilled water, stir at 40 ℃, reflux under condensation, and react for 12h; filter and cool to room temperature, then let stand and age for 3 days. S2. The mixed solution obtained in step S1 is stirred and concentrated at 80 °C. The solution is collected by drawing it into a thin string with a glass rod, and then dried in an oven at 60 °C for 2 h. The solution is then taken out and ground into powder. S3. The powder collected in step S2 is calcined. First, the temperature is raised to 160 ℃ and held for 2 h, then raised to 700 ℃ and held for 2 h. The heating rate is 1.5 ± 0.5 ℃ / min to obtain the silica-alumina-boron mullite. The composition ratio of the prepared silica-alumina-boron mullite is shown in Table 1.

[0037] Preparation of wear-resistant ceramic bricks: 20g of silica-alumina-boron mullite was weighed and added to 80g of base glaze (the amount of silica-alumina-boron mullite added was 20%), and then dispersed by ball milling to obtain the surface glaze. The base glaze used was model 386 glaze from Foshan Yuanda Glaze Technology Co., Ltd., with an Al2O3 content of 23.27%.

[0038] The green body is pressed, a base glaze is applied to the green body layer, pure black ceramic ink is printed, and then the aforementioned top glaze is applied. After drying, it is fired. The firing regime is as follows: the temperature is increased to 450℃ at a rate of 1℃ / min and held for 20 min; then increased to 850℃ at a rate of 2.5℃ / min and held for 30 min; then increased to 1280℃ at a rate of 1℃ / min and held for 30 min; then decreased to 1200℃ at a rate of 1℃ / min and held for 45 min; then decreased to 700℃ at a rate of 5℃ / min and held for 7 min; finally, it is cooled to room temperature. The wear-resistant ceramic tile is obtained.

[0039] Example 2 A method for preparing silica-alumina-boron mullite to improve the wear resistance of surface glaze includes the following steps: S1. Weigh 7.2g tetraethoxysilane, 11.3g aluminum dihydroxyaminoacetate, and 5g triethyl borate, add them to a mixed solvent of 38.9g anhydrous ethanol and 38.9g distilled water, stir at 40 ℃, reflux under condensation, and react for 12 h; filter and cool to room temperature, then let stand and age for 3 days. S2. The mixed solution obtained in step S1 is stirred and concentrated at 80 °C. The solution is collected by drawing it into a thin string with a glass rod, and then dried in an oven at 60 °C for 2 h. The solution is then taken out and ground into powder. S3. The powder collected in step S2 is calcined. First, the temperature is raised to 160 ℃ and held for 2 h, then raised to 700 ℃ and held for 2 h. The heating rate is 1.5 ± 0.5 ℃ / min to obtain the silica-alumina-boron mullite. The composition ratio of the prepared silica-alumina-boron mullite is shown in Table 1.

[0040] Preparation of wear-resistant ceramic bricks: 20g of silica-alumina-boron mullite was weighed and added to 80g of base glaze (the amount of silica-alumina-boron mullite added was 20%), and then dispersed by ball milling to obtain the surface glaze. The base glaze used was model 386 glaze from Foshan Yuanda Glaze Technology Co., Ltd., with an Al2O3 content of 23.27%.

[0041] The green body is pressed, a base glaze is applied to the green body layer, pure black ceramic ink is printed, and then the aforementioned top glaze is applied. After drying, it is fired. The firing regime is as follows: the temperature is increased to 420℃ at a rate of 1.3℃ / min and held for 20 min; then increased to 880℃ at a rate of 3℃ / min and held for 30 min; then increased to 1250℃ at a rate of 1.3℃ / min and held for 25 min; then decreased to 1200℃ at a rate of 1.3℃ / min and held for 40 min; then decreased to 700℃ at a rate of 5℃ / min and held for 10 min; finally, it is cooled to room temperature. The wear-resistant ceramic tile is obtained.

[0042] Example 3 A method for preparing silica-alumina-boron mullite to improve the wear resistance of surface glaze includes the following steps: S1. Weigh 7.2g tetraethoxysilane, 13.1g aluminum dihydroxyaminoacetate, and 3.7g triethyl borate, add them to a mixed solvent of 38.9g anhydrous ethanol and 38.9g distilled water, stir at 40 ℃, reflux under condensation, and react for 12h; filter and cool to room temperature, then let stand and age for 3 days. S2. The mixed solution obtained in step S1 is stirred and concentrated at 80 °C. The solution is collected by drawing it into a thin string with a glass rod, and then dried in an oven at 60 °C for 2 h. The solution is then taken out and ground into powder. S3. The powder collected in step S2 is calcined. First, the temperature is raised to 160 ℃ and held for 2 h, then raised to 700 ℃ and held for 2 h. The heating rate is 1.5 ± 0.5 ℃ / min to obtain the silica-alumina-boron mullite. The composition ratio of the prepared silica-alumina-boron mullite is shown in Table 1.

[0043] Preparation of wear-resistant ceramic bricks: 20g of silica-alumina-boron mullite was weighed and added to 80g of base glaze (the amount of silica-alumina-boron mullite added was 20%), and then dispersed by ball milling to obtain the surface glaze. The base glaze used was model 386 glaze from Foshan Yuanda Glaze Technology Co., Ltd., with an Al2O3 content of 23.27%.

[0044] The green body is pressed, a base glaze is applied to the green body layer, pure black ceramic ink is printed, and then the aforementioned top glaze is applied. After drying, it is fired. The firing regime is as follows: the temperature is increased to 400℃ at a rate of 1.3℃ / min and held for 20 min; then increased to 850℃ at a rate of 2.7℃ / min and held for 30 min; then increased to 1280℃ at a rate of 1℃ / min and held for 20 min; then decreased to 1200℃ at a rate of 1.3℃ / min and held for 45 min; then decreased to 700℃ at a rate of 5℃ / min and held for 5 min; finally, it is cooled to room temperature. The wear-resistant ceramic tile is obtained.

[0045] Comparative Example 1 A method for preparing silica-alumina-boron mullite to improve the wear resistance of surface glaze includes the following steps: S1. Weigh 7.2g of tetraethoxysilane and 15g of aluminum dihydroxyaminoacetate, add them to a mixed solvent of 38.9g of anhydrous ethanol and 38.9g of distilled water, stir at 40 ℃, reflux under condensation, and react for 12 h; filter and cool to room temperature, then let stand and age for 3 days. S2. The mixed solution obtained in step S1 is stirred and concentrated at 80 °C. The solution is collected by drawing it into a thin string with a glass rod, and then dried in an oven at 60 °C for 2 h. The solution is then taken out and ground into powder. S3. The powder collected in step S2 is calcined. First, the temperature is raised to 160 ℃ and held for 2 h, then raised to 700 ℃ and held for 2 h. The heating rate is 1.5 ± 0.5 ℃ / min to obtain the silica-alumina-boron mullite. The composition ratio of the prepared silica-alumina-boron mullite is shown in Table 1.

[0046] Preparation of wear-resistant ceramic bricks: 30g of silica-alumina-boron mullite was weighed and added to 70g of base glaze (the amount of silica-alumina-boron mullite added was 30%), and the mixture was ball-milled and dispersed to obtain the surface glaze. The base glaze used was model 386 glaze from Foshan Yuanda Glaze Technology Co., Ltd., with an Al2O3 content of 23.27%.

[0047] The green body is pressed, a base glaze is applied to the green body layer, pure black ceramic ink is printed, and then the aforementioned top glaze is applied. After drying, it is fired. The firing regime is as follows: the temperature is increased to 450℃ at a rate of 1℃ / min and held for 20 min; then increased to 850℃ at a rate of 2.5℃ / min and held for 30 min; then increased to 1280℃ at a rate of 1℃ / min and held for 30 min; then decreased to 1200℃ at a rate of 1℃ / min and held for 45 min; then decreased to 700℃ at a rate of 5℃ / min and held for 7 min; finally, it is cooled to room temperature. The wear-resistant ceramic tile is obtained.

[0048] Comparative Example 2 A method for preparing silica-alumina-boron mullite to improve the wear resistance of surface glaze includes the following steps: S1. Weigh 7.2g tetraethoxysilane, 7.2g aluminum dihydroxyaminoacetate, and 3.7g triethyl borate, add them to a mixed solvent of 38.9g anhydrous ethanol and 38.9g distilled water, stir at 40 ℃, reflux under condensation, and react for 12 h; filter and cool to room temperature, then let stand and age for 3 days. S2. The mixed solution obtained in step S1 is stirred and concentrated at 80 °C. The solution is collected by drawing it into a thin string with a glass rod, and then dried in an oven at 60 °C for 2 h. The solution is then taken out and ground into powder. S3. The powder collected in step S2 is calcined. First, the temperature is raised to 160 ℃ and held for 2 h, then raised to 700 ℃ and held for 2 h. The heating rate is 1.5 ± 0.5 ℃ / min to obtain the silica-alumina-boron mullite. The composition ratio of the prepared silica-alumina-boron mullite is shown in Table 1.

[0049] Preparation of wear-resistant ceramic bricks: 30g of silica-alumina-boron mullite was weighed and added to 70g of base glaze (the amount of silica-alumina-boron mullite added was 30%), and the mixture was ball-milled and dispersed to obtain the surface glaze. The base glaze used was model 386 glaze from Foshan Yuanda Glaze Technology Co., Ltd., with an Al2O3 content of 23.27%.

[0050] The green body is pressed, a base glaze is applied to the green body layer, pure black ceramic ink is printed, and then the aforementioned top glaze is applied. After drying, it is fired. The firing regime is as follows: the temperature is increased to 450℃ at a rate of 1℃ / min and held for 20 min; then increased to 850℃ at a rate of 2.5℃ / min and held for 30 min; then increased to 1280℃ at a rate of 1℃ / min and held for 30 min; then decreased to 1200℃ at a rate of 1℃ / min and held for 45 min; then decreased to 700℃ at a rate of 5℃ / min and held for 7 min; finally, it is cooled to room temperature. The wear-resistant ceramic tile is obtained.

[0051] The wear resistance of ceramic tiles prepared in Examples 1-3 and Comparative Examples 1 and 2 was tested according to the national standard GB / T 3810.7-2016: the wear condition of the tile surface after grinding at a specific number of grinding revolutions was observed and divided into 0-5 levels. Among them, the wear after 100 revolutions was level 0, the wear after 150 revolutions was level 1, the wear after 600 revolutions was level 2, the wear after 750 / 1200 / 1500 revolutions was level 3, the wear after 2100 / 6000 / 12000 revolutions was level 4, and the wear after more than 12000 revolutions was level 5.

[0052] The test results are shown in Table 1.

[0053] Table 1 As shown in Table 1, the abrasion resistance of the ceramic tile surfaces prepared in Examples 1-3 all reached level 3 at 1200 revolutions. However, the raw materials in Comparative Example 1 did not contain triethyl borate, and therefore could not form mullite microcrystals during high-temperature sintering at 1200℃, resulting in significantly reduced abrasion resistance. In Comparative Example 2, after adjusting the proportions of the raw materials, the alumina content was lower, leading to lower hardness of the mullite microcrystals, and the abrasion resistance level only reached level 3 at 750 revolutions.

[0054] It should be noted that, after testing, changing the formula of the base glaze while simultaneously ensuring that the Al2O3 content in the base glaze is < 24% does not affect the crystallization process of the silica-alumina-boron mullite described in this invention during high-temperature sintering. Therefore, this demonstrates that the silica-alumina-boron mullite described in this invention can be widely used in various glaze systems, as long as the aluminum content in the glaze is less than 24%.

[0055] Examples 4-6 This embodiment uses the same preparation process as Example 1, the only difference being that the addition ratio of silicon aluminum boron mullite is adjusted as shown in Table 2.

[0056] Examples 7-8 This embodiment uses the same preparation process as Example 2, the only difference being that the addition ratio of silicon aluminum boron mullite is adjusted as shown in Table 2.

[0057] Examples 9-10 This embodiment uses the same preparation process as Example 3, the only difference being that the addition ratio of silicon aluminum boron mullite is adjusted as shown in Table 2.

[0058] The wear resistance level of the ceramic tiles prepared in Examples 4 to 10 was tested, and the test results are shown in Table 2.

[0059] Table 2 As shown in Table 2, the wear resistance improved with the increase of the amount of silicon aluminum boron mullite. When the amount of addition reached 28%, the mullite microcrystals formed after sintering reached the threshold of uniform distribution, and the wear resistance level was improved to level 3 at 1500 revolutions. Further increasing the amount of silicon aluminum boron mullite added did not further improve the wear resistance level.

[0060] The surface of the ceramic tile glaze prepared in Example 5 was observed under a microscope, as shown in the image. Figure 1 and Figure 2 As shown. Black spots can be seen at low magnification. With higher magnification, it can be seen that the black spots are actually pores generated during the glaze venting process, rather than mullite grains. Therefore, it can be determined that the silicon aluminum boron mullite mixed in the glaze has formed microcrystalline crystals, existing as mullite microcrystal structures and being evenly distributed.

[0061] The 3D fitting images of the ceramic tile surface prepared in Example 5 before and after the wear resistance test are shown below. Figure 3 (Before the Level 3 1500 RPM abrasion resistance test) and Figure 4 (As shown after the Level 3 1500 RPM abrasion resistance test). The results before and after the test show slight and uniform wear on the tile surface (wear depth 1~3μm), without large pits or deep scratches. This indicates that the silicon-aluminum-boron mullite provided by this invention can achieve uniform distribution and effectively protect the tile surface. It should be noted that the aforementioned 1~3 micrometers is a slight wear depth, invisible to the naked eye. According to the national standard abrasion resistance rating, it meets the Level 3 1500 RPM abrasion resistance standard.

[0062] In summary, the silicon-aluminum-boron mullite described in this invention, when blended with the base glaze as a rigid filler and sintered at high temperature, forms on the surface of ceramic tiles, which can significantly improve the wear resistance of ceramic tiles, especially the wear resistance of dark-colored ceramic tiles.

[0063] The above description is merely a preferred embodiment of the present invention and does not limit the patent scope of the present invention. Any equivalent structural transformations made using the contents of the present invention under the inventive concept of the present invention, or direct / indirect applications in other related technical fields, are included within the patent protection scope of the present invention.

Claims

1. A method for preparing silica-alumina-boron mullite to improve the wear resistance of surface glaze, characterized in that, Includes the following steps: S1. Weigh out the silicon source, aluminum source and boron source according to the ratio, add them to the solvent, and stir at 40~60 ℃ for 12~20 h; filter and cool to room temperature, then age for at least 3 days. S2. The mixed solution obtained in step S1 is stirred and concentrated at 60~80 ℃, collected by drawing into fibers, dried at 60~80 ℃ for more than 2 hours, and then ground into powder. S3. The powder collected in step S2 is calcined. First, the temperature is raised to 160~170 ℃ and held for 1.5~2.5 h, then the temperature is raised to 680~700 ℃ and held for 2~4 h to obtain the silicon aluminum boron mullite.

2. The method for preparing silica-alumina-boron mullite for improving the wear resistance of surface glaze according to claim 1, characterized in that, The silicon source is at least one of tetraethoxysilane, methyltriethoxysilane, tetramethoxysilane, and trimethoxysilane; The aluminum source is at least one of aluminum acetate and aluminum dihydroxyaminoacetate; The boron source is at least one of low-viscosity polyethylene glycol borate and triethyl borate; The solvent includes ethanol and water, wherein the mass ratio of ethanol to water is 1:

1.

3. The method for preparing silica-alumina-boron mullite for improving the wear resistance of surface glaze according to claim 1, characterized in that, The molar ratio of silicon source: aluminum source: boron source is 0.32~0.43:0.82~1.00:0.23~0.

38.

4. The method for preparing silica-alumina-boron mullite for improving the wear resistance of surface glaze according to claim 1, characterized in that, In step S3, the heating rate is 1.5 ± 0.5 ℃ / min.

5. A silica-alumina-boron mullite for improving the wear resistance of surface glaze, characterized in that, The silicon-aluminum-boron mullite is prepared by the method for improving the wear resistance of surface glaze as described in any one of claims 1 to 4; the silicon-aluminum-boron mullite comprises the following components by mass percentage of oxides: SiO2 20-25%, Al2O3 60-70% and B2O3 10-18%.

6. A wear-resistant ceramic tile, characterized in that, From bottom to top, it includes: a body layer, a base glaze layer, a pattern layer, and a top glaze layer; the raw materials of the top glaze layer include a base glaze and the silica-alumina-boron mullite as described in claim 5; based on the total mass of the base glaze oxides as 100%, the Al2O3 content in the base glaze is < 24%.

7. The wear-resistant ceramic brick according to claim 6, characterized in that, The amount of silicon aluminum boron mullite added accounts for 20-30% of the total mass of the raw materials of the glaze layer.

8. A wear-resistant ceramic brick according to claim 6, characterized in that, The amount of silicon aluminum boron mullite added accounts for 28% of the total mass of the raw materials of the glaze layer.

9. A method for preparing wear-resistant ceramic bricks according to any one of claims 6 to 8, characterized in that, The process includes the following steps: pressing the green body, applying a base glaze to the green body layer, printing color ink, applying a top glaze, drying, and firing to obtain the wear-resistant ceramic tile.

10. The method for preparing wear-resistant ceramic bricks according to claim 9, characterized in that, The firing process is as follows: heat to 400-450 ℃ at a rate of 1-1.3 ℃ / min and hold for 20 min; then heat to 850-900 ℃ at a rate of 2.5-3 ℃ / min and hold for 30 min; then heat to 1250-1280 ℃ at a rate of 1-1.3 ℃ / min and hold for 20-30 min; then cool to 1200±10 ℃ at a rate of 1-1.3 ℃ / min and hold for 40-45 min; then cool to 700 ℃ at a rate of 5 ℃ / min and hold for 5-10 min; finally cool to room temperature.

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