Antiskid and antifouling ceramic tile and production process thereof

Abstract

The invention relates to the technical field of architectural ceramics, and particularly discloses an anti-skid and anti-fouling ceramic tile and a production process thereof. The invention discloses an anti-slip and anti-fouling ceramic tile which comprises a green body and a cover glaze layer, the green body comprises the following raw materials: potassium feldspar, quartz sand, calcined kaolin and silicon carbide; the cover glaze layer is prepared from the following raw materials: potassium feldspar, calcined kaolin, quartz, nanorod-like aluminum oxide, talcum powder and graphene oxide. According to the obtained ceramic tile, the minimum oil stain residual amount per unit area is 0.30 g / m < 2 >, the stain resistance grade is 4-5 grade, the maximum anti-skid coefficient is 0.92, and the anti-skid and anti-fouling properties of the ceramic tile are improved.

Description

Technical Field

[0001] The present invention relates to the field of building ceramics, and more particularly to a non-slip and anti-fouling ceramic tile and a production process thereof. Background Art

[0002] With the rapid development of the building decoration industry, ceramic tiles have become a key decorative material, widely used for indoor and outdoor floor and wall decoration. However, the relatively smooth surface of ceramic tiles can easily cause pedestrians to slip in humid environments such as bathrooms and kitchens, posing a significant safety hazard. Furthermore, current ceramic tiles easily absorb stains such as oil, water, and dust, making them difficult to clean. This affects the aesthetics and lifespan of the tiles, making them difficult to meet people's demands for a high-quality living environment.

[0003] In the prior art, in order to improve the anti-slip properties of tiles, the surface roughness is increased. Although the anti-slip effect is achieved, the surface is very easy to harbor dirt and grime, and it is difficult to clean. Some tiles with certain anti-fouling properties have poor anti-slip properties. Therefore, there is an urgent need for a tile that is both anti-slip and anti-fouling. Summary of the Invention

[0004] In order to improve the anti-slip and anti-fouling properties of ceramic tiles, the present application provides an anti-slip and anti-fouling ceramic tile and a production process thereof.

[0005] In a first aspect, the present application provides a non-slip and anti-fouling ceramic tile, which adopts the following technical solution: A non-slip and anti-fouling ceramic tile comprises a body and a glaze layer; The green body comprises the following raw materials in parts by weight: 20-30 parts of potassium feldspar, 20-30 parts of quartz, 10-20 parts of calcined kaolin, and 2-5 parts of yttrium oxide; Based on the weight of the surface glaze layer, the surface glaze layer includes the following raw materials in parts by weight: 30-50 parts of potassium feldspar, 20-30 parts of quartz, 10-15 parts of calcined kaolin, 5-10 parts of nanorod-shaped aluminum oxide, 5-15 parts of talc powder, and 3-5 parts of graphene oxide.

[0006] By adopting this solution, the calcined kaolin in the green body imparts plasticity, facilitating tile molding. Potassium feldspar regulates the temperature and promotes sintering. The addition of quartz sand creates micropores and a concave-convex structure in the green body, increasing surface roughness and thus enhancing the tile's slip resistance. Silicon carbide forms sharp particles after sintering, significantly increasing surface friction and improving the tile's slip resistance.

[0007] The calcined kaolin in the glaze has excellent suspension properties, making the glaze more uniform and stable, preventing sedimentation and enhancing the glaze's adhesion to the body, thereby improving the glazing effect. Furthermore, the alumina in the calcined kaolin promotes the formation of mullite, increasing the hardness and wear resistance of the top glaze layer.

[0008] Talc powder can lower the melting temperature of glaze, promote the flow of glaze, fill the density of glaze surface, reduce the permeability of surface glaze layer, and improve the waterproof and anti-fouling properties of glaze layer.

[0009] Nanorod-shaped aluminum oxide has a unique rod-like structure. When added to the glaze, it creates a microscopic concave-convex structure, increasing the surface roughness of the tile, enhancing the friction between the tile surface and the sole of the shoe, and improving the tile's slip resistance. Furthermore, nanorod-shaped aluminum oxide is firmly embedded in the glaze layer, forming a stable anti-slip layer that is resistant to wear and damage. Furthermore, the addition of nanorod-shaped aluminum oxide imparts hydrophobic and oleophobic properties to the glaze, making the surface less susceptible to adsorption of liquids such as water and oil, thereby improving the tile's stain resistance.

[0010] The graphene oxide in the glaze is hydrophobic and has low surface energy, which reduces stain adhesion and improves the tile's stain resistance. Graphene oxide also has a unique two-dimensional layered structure that forms nanoscale wrinkles and textures, increasing the contact area between the tile and the shoe sole, creating a vacuum adsorption effect and enhancing wet anti-slip properties, thereby achieving an anti-slip effect.

[0011] The simultaneous addition of nanorod-shaped aluminum oxide and graphene oxide forms a double microstructure on the surface of the tile, effectively increasing the friction coefficient, making the surface denser, filling the tiny pores in the glaze layer, and further improving the anti-slip and anti-fouling properties of the tile.

[0012] Preferably, the green body comprises the following raw materials in parts by weight: 23-27 parts of potassium feldspar, 23-27 parts of quartz sand, 13-17 parts of calcined kaolin, and 3-4 parts of silicon carbide, based on the weight of the green body; Based on the weight of the surface glaze layer, the surface glaze layer includes the following raw materials in parts by weight: 35-45 parts of potassium feldspar, 12-14 parts of calcined kaolin, 23-28 parts of quartz, 7-9 parts of nanorod-shaped aluminum oxide, 8-13 parts of talc powder, and 3.5-4.5 parts of graphene oxide.

[0013] The base material of this application is composed of 23-27 parts potassium feldspar, 23-27 parts quartz sand, 13-17 parts calcined kaolin, and 3-4 parts silicon carbide. Within any value range, the performance of the tile is predictable, and all have high anti-slip and anti-fouling properties. The top glaze layer is composed of 35-45 parts potassium feldspar, 12-14 parts calcined kaolin, 23-28 parts quartz, 7-9 parts nanorod-shaped aluminum oxide, 8-13 parts talc, and 3.5-4.5 parts graphene oxide. Within any value range, the performance of the tile is predictable, and all have high anti-slip and anti-fouling properties.

[0014] Preferably, the weight ratio of the graphene oxide to the nanorod-shaped aluminum oxide is 1:(1-3).

[0015] By adopting the above scheme and adjusting the weight ratio of graphene oxide and nanorod-shaped aluminum oxide, the microstructure formed by graphene oxide and nanorod-shaped aluminum oxide on the surface of the tile can be further optimized, the friction coefficient can be increased, and the anti-slip and anti-fouling properties of the tile can be improved.

[0016] As a preference, the nanorod-shaped aluminum oxide is prepared by modification, specifically: Add the silane coupling agent to anhydrous ethanol at a ratio of 1:20, adjust the pH to 3-4, and stir for 1-2 hours to obtain a silane coupling agent solution; The nanorod-shaped aluminum oxide is surface cleaned and dried at 300-500°C for heat treatment, added to a silane coupling agent solution and heated to 60-80°C, a composite dispersant is added, stirred for 2-3 hours, added to xylene, mixed, heated to 110-120°C for reaction for 3-5 hours, filtered, washed, and vacuum-dried to obtain modified nanorod-shaped aluminum oxide; The silane coupling agent accounts for 1-3% of the mass of the nanorod-shaped aluminum oxide; and the composite dispersant comprises polyvinyl pyrrolidone and sodium polyacrylate.

[0017] By adopting the above scheme, the nanorod-shaped alumina is dried and heat-treated at 300-500°C, which not only removes surface moisture to facilitate subsequent modification, but also increases the number and activity of surface hydroxyl groups, which is more conducive to the coating of the nanorod-shaped alumina by the silane coupling agent. Finally, vacuum drying is performed to prevent the modified nanorod-shaped alumina from agglomerating under high-temperature drying conditions.

[0018] The addition of polyvinyl pyrrolidone (PVP) can adsorb onto the surface of nanorod-shaped alumina to form a steric hindrance layer, improving the dispersion stability of the nanorod-shaped alumina in the silane coupling agent. Polyvinyl pyrrolidone also increases the reactivity of the silane coupling agent, allowing it to anchor more tightly to the surface of the nanorod-shaped alumina, forming a dense and ordered modified layer. Furthermore, the addition of polyvinyl pyrrolidone can inhibit structural collapse or deformation during high temperature or chemical treatments, maintaining the integrity of the rod-shaped structure and further improving the anti-slip and anti-fouling properties of the tiles.

[0019] The added sodium polyacrylate and polyvinyl pyrrolidone have a composite effect. Sodium polyacrylate enhances the repulsive force between particles through electrostatic repulsion. The two form a dual stabilization mechanism, which significantly improves the dispersion uniformity of nanorod-shaped alumina. It can also avoid local excessive cross-linking, forming a dense and uniform modified layer, and further improving the anti-slip and anti-fouling properties of tiles.

[0020] Preferably, the mass ratio of the sodium polyacrylate to polyvinyl pyrrolidone is 1:(1-2).

[0021] By adopting the above scheme, the mass ratio of sodium polyacrylate and polyvinyl pyrrolidone is adjusted to further improve the dispersion uniformity of nanorod-shaped aluminum oxide, avoid local excessive cross-linking, form a dense and uniform modified layer, and further improve the anti-slip and anti-fouling properties of tiles.

[0022] Preferably, the glaze layer further comprises 2-4 parts by weight of sodium silicate and 1-2 parts by weight of sodium tripolyphosphate.

[0023] By adopting this solution, sodium silicate promotes the uniform distribution of various raw materials in the glaze, forming a uniform microscopic concave-convex structure after firing, maintaining glaze stability, reducing caking and sagging during glazing, lowering glaze viscosity, improving fluidity, and making the glaze surface more uniform, reducing defects such as pinholes and ripples in the glaze. Furthermore, sodium tripolyphosphate reduces stain penetration, improves the tile's stain resistance, ensures the stability of the surface roughness after firing, and enhances the tile's slip resistance.

[0024] Preferably, the weight ratio of the sodium silicate to sodium tripolyphosphate is 1:(2-3).

[0025] By adopting the above scheme and adjusting the weight ratio of sodium silicate and sodium tripolyphosphate, the anti-slip and anti-fouling properties of the tiles can be further improved.

[0026] In a second aspect, the present application provides a production process for any of the above-mentioned anti-slip and anti-fouling tiles, which is specifically achieved through the following technical solutions: A production process for anti-slip and anti-fouling ceramic tiles comprises the following steps: grinding raw materials of a green body, passing through a 100-300 mesh sieve, pressing into shape, maintaining the temperature at 600°C for 10 hours, heating to 1000°C for 1 hour, further heating to 1400°C for firing for 3 hours, cooling, edge grinding, and polishing to obtain a green body; Mix all the raw materials of glaze, add water and ball grind to 325 mesh, sieve, and control the specific gravity of glaze slurry to 1.4-1.6g / cm 3 , rotary glaze is applied on the surface of the blank with a thickness of 0.1-0.3mm, dried at 80-120℃ for 10-20min, fired at 1050-1100℃ for 1-1.5h, cooled and polished to obtain anti-slip and anti-fouling tiles.

[0027] In summary, this application includes at least one of the following beneficial technical effects: 1. This application controls the types and dosage of raw materials for the tile body and glaze layer to make the oil residue per unit area of ​​the tile 0.40-0.42g / m 2 The anti-slip coefficient is 0.80-0.82, which improves the anti-slip and anti-fouling properties of the tiles.

[0028] 2. This application modifies the nanorod-shaped aluminum oxide in the glaze layer raw materials and controls the mass ratio of sodium polyacrylate and polyvinyl pyrrolidone to make the oil residue per unit area of ​​the tile 0.35-0.37g / m 2 The anti-slip coefficient is 0.86-0.88, which improves the anti-slip and anti-fouling properties of the tiles.

[0029] 3. This application adds sodium silicate and sodium tripolyphosphate to the original raw materials of the glaze layer and controls the ratio of the two to make the oil residue per unit area of ​​the tile 0.30-0.31g / m 2 The anti-slip coefficient is 0.90-0.92, which improves the anti-slip and anti-fouling properties of the tiles. DETAILED DESCRIPTION

[0030] The present application is further described in detail below with reference to specific examples. The following raw materials in this application are all commercially available products, and are intended to fully disclose the raw materials of this application. They should not be understood as limiting the sources of the raw materials. Specifically: calcined kaolin, particle size 325 mesh; quartz sand, particle size 100 mesh; potassium feldspar, particle size 200 mesh; silicon carbide, particle size 40nm; nanorod-shaped alumina, effective substance content 98.5%, particle size 80nm; talc; graphene oxide, particle size 400 mesh; silane coupling agent, model KH560; xylene, effective substance content 99%; polyvinyl pyrrolidone, effective substance content 99%; sodium polyacrylate, effective substance content 99%; sodium silicate, effective substance content 40%; sodium tripolyphosphate, effective substance content 96%.

[0031] The following is an example of the preparation of modified nanorod-shaped aluminum oxide: Preparation Example 1 The modified nanorod-shaped aluminum oxide of Example 1 was prepared by adding 20 g of a silane coupling agent to 400 mL of anhydrous ethanol, adjusting the pH to 3, and stirring for 1.5 h to obtain a silane coupling agent solution; The surface of 1 kg of nanorod-shaped alumina was cleaned and dried at 400°C for heat treatment, then added to a silane coupling agent solution and heated to 70°C. 40 g of a composite dispersant (26.7 g of sodium polyacrylate and 13.3 g of polyvinyl pyrrolidone) was added and stirred for 2.5 h. The mixture was added to 30 L of xylene and mixed. The mixture was heated to 110°C for reaction for 4 h. The mixture was filtered, washed, and vacuum dried to obtain modified nanorod-shaped alumina.

[0032] Preparation Example 2-5 The modified nanorod-shaped alumina in Preparation Examples 2-5 has exactly the same raw material types and preparation methods as Preparation Example 1, except that the dosages of polyvinyl pyrrolidone and sodium polyacrylate are different, specifically 20g and 20g, 16g and 24g, 13.3g and 26.7, and 11.4g and 28.6g. The remaining steps are the same as Preparation Example 1.

[0033] Example 1 The anti-slip and anti-fouling ceramic tile of Example 1 is prepared by the following steps: According to the dosage of each raw material in Table 1, the raw materials of the green body were ground, passed through a 200-mesh sieve, pressed into shape, kept at 600°C for 10 hours, heated to 1000°C for 1 hour, and continued to heat to 1400°C for 3 hours. The green body was then cooled, edged, and polished to obtain the green body. According to the dosage of each raw material in Table 2, the raw materials of the glaze were mixed, ball-milled with water to 325 mesh, sieved, and the specific gravity of the glaze slurry was controlled at 1.5g / cm 3 , rotary glaze is applied on the surface of the blank with a thickness of 0.2mm, dried at 100℃ for 15min, fired at 1050℃ for 1.5h, cooled and polished to obtain anti-slip and anti-fouling tiles.

[0034] Examples 2-5 The anti-slip and anti-fouling tiles of Examples 2-5 are prepared in the same manner and using the same raw materials as in Example 1. The difference lies in the different amounts of the raw materials used. See Table 2 for details.

[0035] Table 2 Amount of each raw material in the green body of Examples 1-5 (unit: kg) raw material Examples 1-5 Potassium feldspar 25 quartz sand 25 Calcined kaolin 15 Silicon carbide 3 Table 2 Amount of each raw material of the glaze of Examples 1-5 (unit: kg) raw material Example 1 Example 2 Example 3 Example 4 Example 5 Potassium feldspar 40 40 40 40 40 Calcined kaolin 13 13 13 13 13 quartz 25 25 25 25 25 Nanorod-shaped aluminum oxide 5 10 7.5 9 10 talcum powder 10 10 10 10 10 graphene oxide 5 5 3 3 3 Examples 6-10 The production process of the anti-slip and anti-fouling tiles of Examples 6-10 is the same as that of Example 3, except that the nanorod-shaped alumina in the glaze is the modified nanorod-shaped alumina prepared in Preparation Examples 1-5, and the other raw material types and dosages are the same as those in Example 3.

[0036] Examples 11-15 The production process of the anti-slip and anti-fouling tiles of Examples 11-15 is the same as that of Example 8, except that sodium silicate and sodium polyphosphate are also added to the glaze, and the specific dosages are 2kg and 2kg, 2kg and 4kg, 1kg and 2.5kg, 1kg and 3kg, and 1kg and 4kg, respectively. The types and dosages of other raw materials are the same as those in Example 8.

[0037] Comparative Example 1 The production process of the anti-slip and anti-fouling ceramic tiles of Comparative Example 1 is exactly the same as that of Example 1, except that an equal amount of nanorod-shaped aluminum oxide in the surface glaze layer is replaced by graphene oxide, and the remaining raw materials and dosages are the same as those of Example 1.

[0038] Comparative Example 2 The production process of the anti-slip and anti-fouling ceramic tiles of Comparative Example 2 is exactly the same as that of Example 1, except that an equal amount of graphene oxide in the glaze layer is replaced by nanorod-shaped aluminum oxide, and the remaining raw materials and dosages are the same as those of Example 1.

[0039] Comparative Example 3 The production process of the anti-slip and anti-fouling ceramic tiles of Comparative Example 3 is exactly the same as that of Example 1, except that no talc powder is added to the glaze layer, and the remaining raw materials and dosages are the same as those of Example 1.

[0040] Performance testing The following testing standards or methods were used to test the performance of the tiles obtained in different Examples 1-15 and Comparative Examples 1-3. The test results are shown in Table 3.

[0041] Flexural strength: The flexural strength of tiles is tested in accordance with GB / T2542-2012 standard.

[0042] Water absorption rate: The water absorption rate of tiles is tested in accordance with GB / T3810-2016 standard.

[0043] Residual oil content per unit area: GB / T23764 "Test method for performance of photocatalytic self-cleaning materials" is used to detect the residual oil content per unit area of ​​tiles.

[0044] Stain resistance level: GB / T3810.14-2016 "Test methods for ceramic tiles - Part 14: Determination of stain resistance" is used to measure the stain resistance level of ceramic tiles.

[0045] Anti-slip coefficient: The anti-slip coefficient of tiles is tested in accordance with JC / T1050-2007 standard.

[0046] Table 3 Performance test results of different tiles The test results in Table 3 show that the tiles obtained in this application have a maximum flexural strength of 67.3 MPa and a minimum water absorption rate of 0.10%, which means they have high flexural strength and moisture resistance. The minimum oil residue per unit area of ​​the tiles obtained is 0.30 g / m 2 The stain resistance level is 4-5, and the anti-slip coefficient is up to 0.92, which improves the anti-slip and anti-fouling properties of the tiles.

[0047] Combined with the performance test data of the tiles of Examples 1-5, it was found that the oil residue per unit area of ​​the tiles of Examples 2-4 was 0.40-0.42 g / m 2 , lower than Example 1 and Example 5, and the anti-slip coefficient is 0.80-0.82, which is higher than Example 1 and Example 5. This shows that when the weight ratio of graphene oxide to nanorod-shaped aluminum oxide in the glaze layer raw materials is 1:(2-3), it is more suitable, which improves the anti-slip and anti-fouling properties of the tiles.

[0048] Combined with the performance test data of the tiles of Examples 6-10, it was found that the oil residue per unit area of ​​the tiles of Examples 7-9 was 0.35-0.37 g / m 2 , which is lower than that of Example 6 and Example 10, and the anti-slip coefficient is 0.86-0.88, which is higher than that of Example 6 and Example 10. This shows that when modifying the nanorod-shaped alumina in the surface glaze layer raw material, it is more appropriate to control the mass ratio of sodium polyacrylate and polyvinyl pyrrolidone to 1: (1-2), which improves the anti-slip and anti-fouling properties of the tiles.

[0049] Combined with the performance test data of the tiles of Examples 11-15, it was found that the oil residue per unit area of ​​the tiles of Examples 12-14 was 0.30-0.31 g / m 2 , which is lower than that of Example 11 and Example 15, and the anti-slip coefficient is 0.90-0.92, which is higher than that of Example 11 and Example 15. This shows that sodium silicate and sodium tripolyphosphate are added to the original raw materials of the glaze layer, and the weight ratio of sodium silicate to sodium tripolyphosphate is 1:(2-3), which is more appropriate, thereby improving the anti-slip and anti-fouling properties of the tiles.

[0050] Combining the performance test data of the tiles of Example 1 and Comparative Examples 1-3, it was found that adding nanorod-shaped aluminum oxide, talc powder, and graphene oxide to the raw materials of the tile glaze layer can improve the anti-slip and anti-fouling properties of the tiles to varying degrees.

[0051] This specific embodiment is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make non-creative modifications to the present embodiment as needed, but as long as they are within the scope of the claims of the present application, they are protected by the patent law.

Claims

1. A non-slip and anti-fouling tile, characterized in that: It includes a body and a glaze layer; The green body comprises the following raw materials in parts by weight: 20-30 parts of potassium feldspar, 20-30 parts of quartz sand, 10-20 parts of calcined kaolin, and 2-5 parts of silicon carbide. Based on the weight of the surface glaze layer, the surface glaze layer includes the following raw materials in parts by weight: 30-50 parts of potassium feldspar, 10-15 parts of calcined kaolin, 20-30 parts of quartz, 5-10 parts of nanorod-shaped aluminum oxide, 5-15 parts of talc powder, and 3-5 parts of graphene oxide.

2. The anti-slip and anti-fouling ceramic tile according to claim 1, characterized in that: The green body comprises the following raw materials in parts by weight: 23-27 parts of potassium feldspar, 23-27 parts of quartz sand, 13-17 parts of calcined kaolin, and 3-4 parts of silicon carbide. Based on the weight of the surface glaze layer, the surface glaze layer includes the following raw materials in parts by weight: 35-45 parts of potassium feldspar, 12-14 parts of calcined kaolin, 23-28 parts of quartz, 7-9 parts of nanorod-shaped aluminum oxide, 8-13 parts of talc powder, and 3.5-4.5 parts of graphene oxide.

3. The anti-slip and anti-fouling ceramic tile according to claim 1, characterized in that: The weight ratio of the graphene oxide to the nanorod-shaped aluminum oxide is 1:(2-3).

4. The anti-slip and anti-fouling ceramic tile according to claim 3, characterized in that: The nanorod-shaped aluminum oxide is prepared by modification, specifically: Add the silane coupling agent to anhydrous ethanol at a ratio of 1:20, adjust the pH to 3-4, and stir for 1-2 hours to obtain a silane coupling agent solution; The nanorod-shaped aluminum oxide is surface cleaned and dried at 300-500°C for heat treatment, added to a silane coupling agent solution and heated to 60-80°C, a composite dispersant is added, stirred for 2-3 hours, added to xylene, mixed, heated to 110-120°C for reaction for 3-5 hours, filtered, washed, and vacuum-dried to obtain modified nanorod-shaped aluminum oxide; The silane coupling agent accounts for 1-3% of the mass of the nanorod-shaped aluminum oxide; the composite dispersant accounts for 2-6% of the mass of the nanorod-shaped aluminum oxide, and the composite dispersant comprises polyvinyl pyrrolidone and sodium polyacrylate.

5. The anti-slip and anti-fouling ceramic tile according to claim 4, characterized in that: The mass ratio of the sodium polyacrylate to polyvinyl pyrrolidone is 1:(1-2).

6. The anti-slip and anti-fouling ceramic tile according to claim 1, characterized in that: The glaze layer further comprises 2-4 parts by weight of sodium silicate and 1-2 parts by weight of sodium tripolyphosphate.

7. The anti-slip and anti-fouling ceramic tile according to claim 6, characterized in that: The weight ratio of the sodium silicate to sodium tripolyphosphate is 1:(2-3).

8. A process for producing the anti-slip and anti-fouling ceramic tiles according to any one of claims 1 to 7, characterized in that: The method comprises the following steps: grinding the raw materials of the green body, passing through a 100-300 mesh sieve, pressing into shape, maintaining the temperature at 600°C for 10 hours, heating to 1000°C for 1 hour, further heating to 1400°C for firing for 3 hours, cooling, edge grinding, and polishing to obtain the green body; The raw materials of the glaze are mixed, ball-milled with water to 325 mesh, sieved, and the glaze slurry density is controlled at 1.4-1.6g / cm³. The glaze is applied on the surface of the body in a rotary manner to a thickness of 0.1-0.3mm. The glaze is dried at 80-120℃ for 10-20min, fired at 1050-1100℃ for 1-1.5h, cooled, and polished to obtain anti-slip and anti-fouling tiles.

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