Super-easy-to-clean gold silk velvet ceramic tile and preparation method thereof

Abstract

The application discloses super-easy-to-clean gold-silk-velvet ceramic tiles and a preparation method thereof. The super-easy-to-clean gold-silk-velvet ceramic tile comprises, from bottom to top, a body, a bottom glaze layer and a surface glaze layer. The body raw material comprises, by weight, potassium-sodium stone powder, potassium sand, water-milled sodium sand, stone powder, transparent grey stone, magnesia stone powder, kaolin, ball clay, white clay, and bentonite. The bottom glaze layer raw material comprises potassium feldspar, sodium feldspar, calcined kaolin, quartz, zirconium silicate, diopside, boron-free calcium-magnesium series frit powder, and calcined alumina. The surface glaze layer raw material comprises potassium feldspar, sodium feldspar, calcined kaolin, quartz, dolomite, zinc oxide, barium carbonate, strontium carbonate, and calcium phosphate. The three-layer structure and the bottom glaze multiphase stain-proof design are adopted, the zirconium silicate and the diopside in the bottom glaze layer are compounded to form an effective stain-proof barrier, the stain-proof and easy-to-clean ability of the ceramic tile is greatly improved, the ceramic tile has a silky delicate touch, all performance indexes are balanced and excellent, and the ceramic tile has good industrial application value.

Description

Technical Field

[0001] This invention relates to the field of ceramic tile preparation technology, specifically to an ultra-easy-clean gold velvet ceramic tile and its preparation method. Background Technology

[0002] Velvet ceramic tiles are matte tiles that combine biomimetic technology with practicality. Building upon ordinary soft-light tiles, they feature innovative upgrades through multi-layered composite glazing, combined with finely sculpted textures and dry-granule processing, further enhancing the surface's smoothness and creating a low-reflection matte effect. This results in a silky smooth touch and a slightly frosted texture, achieving a visual effect of "soft light without glare, and a velvety sheen." Light creates soft variations in brightness and shadow within the textures, and when paired with a low-saturation milky white color scheme, it creates a warm and spacious feel. It is especially suitable for small apartments with continuous flooring or for spaces with a natural wood, minimalist, or light French style. It is a high-end renovation choice that balances aesthetic appeal, practicality, and long-term durability, and has become one of the preferred products in the high-end renovation market in recent years.

[0003] However, velvet ceramic tiles still face numerous technical challenges in practical applications. Early velvet products, due to immature manufacturing processes, were prone to defects such as roller marks, water ripples, and rounded corners. Furthermore, the velvet texture relies on the diffuse reflection of light by the microcrystalline structure in the glaze; this microstructure inevitably creates surface pores and unevenness, providing channels for stains to penetrate. During use, they easily absorb dirt, allowing liquid contaminants to seep into the tile body, forming stains that are difficult to remove. Even with repeated cleaning, traces may remain, especially in high-pollution environments such as hospital corridors and restaurant kitchens, resulting in extremely high cleaning and maintenance costs. Although years of technological iteration have significantly improved the surface smoothness and tactile feel of velvet ceramic tiles, stain resistance remains a key weakness hindering its further development.

[0004] To address the aforementioned technical problems, Chinese patent CN118373676A, "A Velvet-Textured Anti-Stain Ceramic Tile," discloses a velvet-textured anti-stain ceramic tile comprising, from bottom to top, a body layer, a lower glaze layer, an upper glaze layer, and a velvet glaze layer. It attempts to impart anti-stain and anti-mildew functions to the velvet ceramic tile by directly adding organosilicon anti-stain agents and organomercury anti-mildew agents to the glaze. However, this solution requires a firing temperature as high as 1400-1450℃, at which temperature the added organosilicon anti-stain agents have already decomposed and volatilized, losing their anti-stain function during firing and failing to retain an effective anti-stain effect in the finished product. Secondly, the anti-mildew agent used in this solution is phenylmercuric oleate, an organomercury compound, which is highly toxic, and its use in ceramic products seriously violates environmental and safety regulations. These defects make it difficult for this technical solution to achieve its claimed anti-stain and anti-mildew effects, and it also fails to meet the requirements of industrial production and environmental safety.

[0005] Therefore, there is an urgent need in this field for an ultra-easy-clean velvet ceramic tile and its preparation method that can simultaneously achieve the texture of velvet, durable stain resistance, non-toxicity and environmental friendliness, and good industrial feasibility. Summary of the Invention

[0006] The purpose of this invention is to provide an ultra-easy-clean gold velvet ceramic tile and its preparation method, so as to solve the problems mentioned in the background art.

[0007] To achieve the above objectives, the present invention provides the following technical solution: A super easy-to-clean gold velvet ceramic tile, which consists of a body, a base glaze layer and a top glaze layer from bottom to top; By weight, the raw materials for the green body include: 12-16 parts of potassium sodium stone powder, 8-12 parts of potassium sand, 12-16 parts of water-milled sodium sand, 6-10 parts of stone powder, 3-5 parts of siliceous limestone, 2-4 parts of magnesia powder, 10-14 parts of kaolin, 8-12 parts of ball clay, 5-8 parts of white clay, and 1-2 parts of bentonite; The raw materials for the base glaze layer include: 28-32 parts potassium feldspar, 20-25 parts sodium feldspar, 11-12 parts calcined kaolin, 12-16 parts quartz, 8-10 parts zirconium silicate, 10-13 parts diopside, 1-3 parts boron-free calcium-magnesium frit powder, and 2-3 parts calcined alumina. The raw materials for the surface glaze layer include: 32-38 parts potassium feldspar, 10-16 parts sodium feldspar, 8-12 parts calcined kaolin, 8-12 parts quartz, 8-12 parts dolomite, 7-10 parts zinc oxide, 2-2.5 parts barium carbonate, 1.5-2 parts strontium carbonate, and 1.5-3 parts calcium phosphate.

[0008] Preferably, in the base glaze material, the weight ratio of diopside to zirconium silicate is (1.1-1.6):1.

[0009] Preferably, in the glaze material, the weight ratio of calcium phosphate to strontium carbonate is (1-1.5):1.

[0010] Preferably, the boron-free calcium-magnesium frit powder has the following chemical composition: 50-55% SiO2, 10-15% CaO, 3-5% MgO, 8-12% Al2O3, ≤0.1% B2O3 content, and a softening point of 1050-1100℃.

[0011] In addition, the present invention also provides a method for preparing an ultra-easy-clean gold velvet ceramic tile.

[0012] A method for preparing ultra-easy-clean velvet ceramic tiles according to any one of the above claims includes the following steps: S1. Weigh each component according to the required ratio, prepare the green body, and dry it until the moisture content is <0.5% for later use; S2. Apply a base glaze to the blank obtained in S1 using the glazing method to form a base glaze layer; S3. Apply a top glaze to the base glaze layer obtained in S2 using the glazing method to form a top glaze layer; S4. Firing: Set the firing temperature to 1190-1200℃, hold for 20-40 minutes, and during the cooling phase, reduce the temperature from the highest temperature to 1050℃ at a rate of 10-12℃ / minute; then slowly reduce the temperature to 950℃ at a rate of 2-4℃ / minute, and force air cooling below 950℃. S5. After being removed from the kiln, the edges are ground, inspected, and packaged to obtain the super easy-clean gold velvet ceramic tile.

[0013] Preferably, water, sodium carboxymethyl cellulose, and sodium tripolyphosphate are added as additives during the preparation of the base glaze described in S2.

[0014] More preferably, the mass ratio of the base glaze material, water, sodium carboxymethyl cellulose, and sodium tripolyphosphate is 100:(38-42):(0.10-0.15):(0.30-0.40).

[0015] Preferably, the amount of base glaze applied in S2 is 280-320 g / m³. 2 .

[0016] Preferably, the amount of glaze applied in S3 is 250-350 g / m³. 2 .

[0017] Preferably, during the firing process described in S4, a slight positive pressure of 5-10 Pa is maintained during the 1190-1200℃ and 1050-950℃ stages.

[0018] Compared with the prior art, the beneficial effects of the present invention are: The super easy-clean velvet ceramic tile of this invention adopts a three-layer structure and a multi-phase anti-fouling design in the base glaze. In the body, potassium sodium stone powder, potassium sand, and water-milled sodium sand form a composite flux system, widening the firing temperature window of the body. Diospyrite and magnesia powder, as calcium-magnesium mineralizers, synergistically regulate the thermal expansion behavior of the body, allowing the body to achieve a thermal expansion coefficient matching the base glaze layer while being fully vitrified. In the base glaze layer, the combination of zirconium silicate and diopside produces a "crystal phase gradation filling effect"—zirconia silicate decomposes at high temperatures to form short columnar zircon crystal phases in situ, forming the main framework of the anti-fouling layer. Diopside recrystallizes in situ during firing to form granular diopside crystal phases, filling the gaps between zircon grains, reducing the porosity of the base glaze layer to an extremely low level, effectively blocking the penetration channels of liquid pollutants and significantly improving the tile's anti-fouling and easy-to-clean properties. The cleaning ability is enhanced by the pre-melting of boron-free calcium-magnesium frit powder to form localized low-viscosity micro-regions, providing preferential escape channels for gases discharged from the green body to avoid pinhole defects. Its boron-free design ensures that it does not interfere with the formation of zircon crystal phase. Phosphate ions released from the decomposition of calcium phosphate in the glaze layer form phosphorus-rich micro-regions in the glass phase, providing preferential nucleation sites for the precipitation of zinc siliceous minerals. Zinc oxide reacts with silicon oxide in the glass phase during the cooling process to precipitate zinc siliceous mineral crystal phases in situ, providing diffuse reflection light sources. Strontium oxide released after the decomposition of strontium carbonate enters the zinc siliceous mineral lattice, causing lattice distortion to inhibit excessive grain growth. At the same time, it acts as a network modifier to reduce the crystallization activation energy and promote uniform nucleation of grains at lower temperatures. The three factors work together to control the size of zinc siliceous mineral grains, resulting in a soft luster of 30-35 GU on the glaze surface and a velvety delicate touch. Detailed Implementation

[0019] To better illustrate the objectives, technical solutions, and advantages of the present invention, the present invention is further described through the following embodiments. Obviously, the following embodiments are only some embodiments of the present invention, and not all embodiments; these embodiments do not imply any limitation on the present invention. Those skilled in the art should understand that these embodiments are only used to illustrate the technical effects of the present invention, and not to limit the scope of protection of the present invention.

[0020] Experimental methods in the following examples, unless otherwise specified, are generally performed under standard conditions or as recommended by the manufacturer. These examples are primarily intended to provide a better understanding of the analytical methods of this invention and do not exhaustively cover all possible procedures.

[0021] All raw materials used in the examples are commercially available; unless otherwise specified, the reagents, methods and equipment used in this invention are conventional reagents, methods and equipment in this technical field. Example 1

[0022] A method for preparing ultra-easy-clean gold velvet ceramic tiles includes the following steps: S1. Weigh each component according to the required ratio. The raw materials for the green body include: 15 parts potassium sodium stone powder, 10 parts potassium sand, 14 parts water-milled sodium sand, 8 parts stone powder, 4 parts siliceous stone, 3 parts magnesia powder, 12 parts kaolin, 10 parts ball clay, 6 parts white clay, and 2 parts bentonite. After weighing according to the ratio, put them into a ball mill to prepare the green body. Ball mill until the residue on a 250-mesh sieve is ≤0.5%. Spray granulation is used to make powder. The powder is aged in a sealed chamber for 24 hours. It is then pressed into shape using a hydraulic press and dried until the moisture content is <0.5%. It is ready for use. S2. The base glaze material includes: 30 parts potassium feldspar, 22 parts sodium feldspar, 11 parts calcined kaolin, 13 parts quartz, 9 parts zirconium silicate, 12 parts diopside, 2 parts boron-free calcium-magnesium frit powder, and 2 parts calcined alumina. After weighing according to the proportions, it is put into a ball mill. Water, sodium carboxymethyl cellulose, and sodium tripolyphosphate are added. The mass ratio of the base glaze material, water, sodium carboxymethyl cellulose, and sodium tripolyphosphate is 100:40:0.12:0.3. The mixture is ball-milled until the residue on a 325-mesh sieve is ≤0.05%, and the median particle size D50 is ≤4μm. The thixotropic index (TI value = viscosity ratio at 6r / min to 60r / min) of the glaze slurry is tested, and the TI value is controlled between 1.2 and 1.5. The base glaze is applied to the green body obtained in S1 using a glazing method, with a glaze application rate of 300g / m³. 2 This forms the base glaze layer; S3. The raw materials for the top glaze layer include: 36 parts potassium feldspar, 13 parts sodium feldspar, 10 parts calcined kaolin, 10 parts quartz, 10 parts dolomite, 8 parts zinc oxide, 2.2 parts barium carbonate, 2 parts strontium carbonate, and 2.4 parts calcium phosphate. The mixture is ball-milled until the residue on a 325-mesh sieve is ≤0.1%. The top glaze is applied to the base glaze layer obtained in S2 using a glazing method, with a glaze application rate of 300 g / m². 2 This forms a surface glaze layer; S4. Firing: The firing temperature is set at 1195℃, held for 30 minutes, and then cooled from the highest temperature to 1050℃ at a rate of 10℃ / min during the cooling phase; then cooled slowly to 950℃ at a rate of 4℃ / min. Forced air cooling is used below 950℃, with a fan frequency of 32Hz. During the firing process, a slight positive pressure of 10Pa is maintained during the 1195℃ and 1050-950℃ stages. S5. After being removed from the kiln, the edges are ground, inspected, and packaged to obtain the super easy-clean gold velvet ceramic tile. Example 2

[0023] A method for preparing ultra-easy-clean gold velvet ceramic tiles includes the following steps: S1. Weigh each component according to the required ratio. The raw materials for the green body include: 12 parts potassium sodium stone powder, 8 parts potassium sand, 12 parts water-milled sodium sand, 6 parts stone powder, 4 parts siliceous stone, 2 parts magnesia powder, 10 parts kaolin, 8 parts ball clay, 5 parts white clay, and 2 parts bentonite. After weighing according to the ratio, put them into a ball mill to prepare the green body. Ball mill until the residue on a 250-mesh sieve is ≤0.5%. Spray granulation is used to make powder. The powder is aged in a sealed chamber for 24 hours. It is then pressed into shape using a hydraulic press and dried until the moisture content is <0.5%. It is ready for use. S2. The base glaze material includes: 30 parts potassium feldspar, 20 parts sodium feldspar, 11 parts calcined kaolin, 13 parts quartz, 9 parts zirconium silicate, 10 parts diopside, 2 parts boron-free calcium-magnesium frit powder, and 2 parts calcined alumina. After weighing according to the proportions, it is put into a ball mill, along with water, sodium carboxymethyl cellulose, and sodium tripolyphosphate. The mass ratio of the base glaze material, water, sodium carboxymethyl cellulose, and sodium tripolyphosphate is 100:40:0.12:0.4. The mixture is ball-milled until the residue on a 325-mesh sieve is ≤0.05%, and the median particle size D50 is ≤4μm. The thixotropic index (TI value = viscosity ratio at 6r / min to 60r / min) of the glaze slurry is tested, and the TI value is controlled between 1.2 and 1.5. The base glaze is applied to the green body obtained in S1 using a glazing method, with a glaze application rate of 300g / m³. 2 This forms the base glaze layer; S3. The raw materials for the top glaze layer include: 32 parts potassium feldspar, 10 parts sodium feldspar, 8 parts calcined kaolin, 10 parts quartz, 10 parts dolomite, 8 parts zinc oxide, 2 parts barium carbonate, 1.6 parts strontium carbonate, and 2 parts calcium phosphate. The mixture is ball-milled until the residue on a 325-mesh sieve is ≤0.1%. The top glaze is applied to the base glaze layer obtained in S2 using a glazing method, with a glaze application rate of 300 g / m². 2 This forms a surface glaze layer; S4. Firing: The firing temperature is set at 1190℃, held for 30 minutes, and then cooled from the highest temperature to 1050℃ at a rate of 10℃ / min during the cooling phase; then cooled slowly to 950℃ at a rate of 3℃ / min. Forced air cooling is used below 950℃, with a fan frequency of 32Hz. During the firing process, a slight positive pressure of 8Pa is maintained during the 1190℃ and 1050-950℃ stages. S5. After being removed from the kiln, the edges are ground, inspected, and packaged to obtain the super easy-clean gold velvet ceramic tile. Example 3

[0024] A method for preparing ultra-easy-clean gold velvet ceramic tiles includes the following steps: S1. Weigh each component according to the required ratio. The raw materials for the green body include: 15 parts potassium sodium stone powder, 10 parts potassium sand, 16 parts water-milled sodium sand, 10 parts stone powder, 4 parts siliceous stone, 3 parts magnesia powder, 14 parts kaolin, 12 parts ball clay, 8 parts white clay, and 2 parts bentonite. After weighing according to the ratio, put them into a ball mill to prepare the green body. Ball mill until the residue on a 250-mesh sieve is ≤0.5%. Spray granulation is used to make powder. The powder is aged in a sealed chamber for 24 hours. It is then pressed into shape using a hydraulic press and dried until the moisture content is <0.5%. It is ready for use. S2. The base glaze material includes: 30 parts potassium feldspar, 24 parts sodium feldspar, 12 parts calcined kaolin, 15 parts quartz, 9 parts zirconium silicate, 12 parts diopside, 2 parts boron-free calcium-magnesium frit powder, and 3 parts calcined alumina. After weighing according to the proportions, it is put into a ball mill. Water, sodium carboxymethyl cellulose, and sodium tripolyphosphate are added. The mass ratio of the base glaze material, water, sodium carboxymethyl cellulose, and sodium tripolyphosphate is 100:40:0.12:0.3. The mixture is ball-milled until the residue on a 325-mesh sieve is ≤0.05%, and the median particle size D50 is ≤4μm. The thixotropic index (TI value = viscosity ratio at 6 r / min to 60 r / min) of the glaze slurry is tested, and the TI value is controlled between 1.2 and 1.5. The base glaze is applied to the green body obtained in S1 using a glazing method, with a glaze application rate of 300 g / m³. 2 This forms the base glaze layer; S3. The raw materials for the top glaze layer include: 36 parts potassium feldspar, 16 parts sodium feldspar, 10 parts calcined kaolin, 10 parts quartz, 12 parts dolomite, 10 parts zinc oxide, 2.5 parts barium carbonate, 2 parts strontium carbonate, and 3 parts calcium phosphate. The mixture is ball-milled until the residue on a 325-mesh sieve is ≤0.1%. The top glaze is applied to the base glaze layer obtained in S2 using a glazing method, with a glaze application rate of 300 g / m². 2 This forms a surface glaze layer; S4. Firing: The firing temperature is set at 1200℃, held for 30 minutes, and during the cooling phase, the temperature is reduced from the highest temperature to 1050℃ at a rate of 10℃ / min; then, it is slowly reduced to 950℃ at a rate of 2℃ / min. Below 950℃, forced air cooling is used with a fan frequency of 32Hz. During the firing process, a slight positive pressure of 10Pa is maintained during the 1200℃ stage and the 1050-950℃ stage. S5. After being removed from the kiln, the edges are ground, inspected, and packaged to obtain the super easy-clean gold velvet ceramic tile.

[0025] Comparative Example 1 A method for preparing gold velvet ceramic tiles includes the following steps: S1. Weigh each component according to the required ratio. The raw materials for the green body include: 15 parts potassium sodium stone powder, 10 parts potassium sand, 14 parts water-milled sodium sand, 8 parts stone powder, 4 parts siliceous stone, 3 parts magnesia powder, 12 parts kaolin, 10 parts ball clay, 6 parts white clay, and 2 parts bentonite. After weighing according to the ratio, put them into a ball mill to prepare the green body. Ball mill until the residue on a 250-mesh sieve is ≤0.5%. Spray granulation is used to make powder. The powder is aged in a sealed chamber for 24 hours. It is then pressed into shape using a hydraulic press and dried until the moisture content is <0.5%. It is ready for use. S2. The base glaze material includes: 30 parts potassium feldspar, 22 parts sodium feldspar, 11 parts calcined kaolin, 13 parts quartz, 9 parts zirconium silicate, 2 parts boron-free calcium-magnesium frit powder, and 2 parts calcined alumina. After weighing according to the proportions, it is put into a ball mill, along with water, sodium carboxymethyl cellulose, and sodium tripolyphosphate. The mass ratio of the base glaze material, water, sodium carboxymethyl cellulose, and sodium tripolyphosphate is 100:40:0.12:0.3. The mixture is ball-milled until the residue on a 325-mesh sieve is ≤0.05%, and the median particle size D50 is ≤4μm. The thixotropic index (TI value = viscosity ratio at 6r / min to 60r / min) of the glaze slurry is tested, and the TI value is controlled between 1.2 and 1.5. The base glaze is applied to the green body obtained in S1 using a glazing method, with a glaze application rate of 300g / m³. 2 This forms the base glaze layer; S3. The raw materials for the top glaze layer include: 36 parts potassium feldspar, 13 parts sodium feldspar, 10 parts calcined kaolin, 10 parts quartz, 10 parts dolomite, 8 parts zinc oxide, 2.2 parts barium carbonate, 2 parts strontium carbonate, and 2.4 parts calcium phosphate. The mixture is ball-milled until the residue on a 325-mesh sieve is ≤0.1%. The top glaze is applied to the base glaze layer obtained in S2 using a glazing method, with a glaze application rate of 300 g / m². 2 This forms a surface glaze layer; S4. Firing: The firing temperature is set at 1195℃, held for 30 minutes, and then cooled from the highest temperature to 1050℃ at a rate of 10℃ / min during the cooling phase; then cooled slowly to 950℃ at a rate of 4℃ / min. Forced air cooling is used below 950℃, with a fan frequency of 32Hz. During the firing process, a slight positive pressure of 10Pa is maintained during the 1195℃ and 1050-950℃ stages. S5. After being removed from the kiln, the edges are ground, inspected, and packaged to obtain the gold velvet ceramic tile.

[0026] The main difference between this comparative example and Example 1 is that diopside is not added in step S2.

[0027] Comparative Example 2 A method for preparing gold velvet ceramic tiles includes the following steps: S1. Weigh each component according to the required ratio. The raw materials for the green body include: 15 parts potassium sodium stone powder, 10 parts potassium sand, 14 parts water-milled sodium sand, 8 parts stone powder, 4 parts siliceous stone, 3 parts magnesia powder, 12 parts kaolin, 10 parts ball clay, 6 parts white clay, and 2 parts bentonite. After weighing according to the ratio, put them into a ball mill to prepare the green body. Ball mill until the residue on a 250-mesh sieve is ≤0.5%. Spray granulation is used to make powder. The powder is aged in a sealed chamber for 24 hours. It is then pressed into shape using a hydraulic press and dried until the moisture content is <0.5%. It is ready for use. S2. The base glaze material includes: 30 parts potassium feldspar, 22 parts sodium feldspar, 11 parts calcined kaolin, 13 parts quartz, 12 parts diopside, 2 parts boron-free calcium-magnesium frit powder, and 2 parts calcined alumina. After weighing according to the proportions, it is put into a ball mill, along with water, sodium carboxymethyl cellulose, and sodium tripolyphosphate. The mass ratio of the base glaze material, water, sodium carboxymethyl cellulose, and sodium tripolyphosphate is 100:40:0.12:0.3. The mixture is ball-milled until the residue on a 325-mesh sieve is ≤0.05%, and the median particle size D50 is ≤4μm. The thixotropic index (TI value = viscosity ratio at 6r / min to 60r / min) of the glaze slurry is tested, and the TI value is controlled between 1.2 and 1.5. The base glaze is applied to the green body obtained in S1 using a glazing method, with a glaze application rate of 300g / m³. 2 This forms the base glaze layer; S3. The raw materials for the top glaze layer include: 36 parts potassium feldspar, 13 parts sodium feldspar, 10 parts calcined kaolin, 10 parts quartz, 10 parts dolomite, 8 parts zinc oxide, 2.2 parts barium carbonate, 2 parts strontium carbonate, and 2.4 parts calcium phosphate. The mixture is ball-milled until the residue on a 325-mesh sieve is ≤0.1%. The top glaze is applied to the base glaze layer obtained in S2 using a glazing method, with a glaze application rate of 300 g / m². 2 This forms a surface glaze layer; S4. Firing: The firing temperature is set at 1195℃, held for 30 minutes, and then cooled from the highest temperature to 1050℃ at a rate of 10℃ / min during the cooling phase; then cooled slowly to 950℃ at a rate of 4℃ / min. Forced air cooling is used below 950℃, with a fan frequency of 32Hz. During the firing process, a slight positive pressure of 10Pa is maintained during the 1195℃ and 1050-950℃ stages. S5. After being removed from the kiln, the edges are ground, inspected, and packaged to obtain the gold velvet ceramic tile.

[0028] The main difference between this comparative example and Example 1 is that zirconium silicate is not added in step S2.

[0029] Comparative Example 3 A method for preparing gold velvet ceramic tiles includes the following steps: S1. Weigh each component according to the required ratio. The raw materials for the green body include: 15 parts potassium sodium stone powder, 10 parts potassium sand, 14 parts water-milled sodium sand, 8 parts stone powder, 4 parts siliceous stone, 3 parts magnesia powder, 12 parts kaolin, 10 parts ball clay, 6 parts white clay, and 2 parts bentonite. After weighing according to the ratio, put them into a ball mill to prepare the green body. Ball mill until the residue on a 250-mesh sieve is ≤0.5%. Spray granulation is used to make powder. The powder is aged in a sealed chamber for 24 hours. It is then pressed into shape using a hydraulic press and dried until the moisture content is <0.5%. It is ready for use. S2. The base glaze material includes: 30 parts potassium feldspar, 22 parts sodium feldspar, 11 parts calcined kaolin, 13 parts quartz, 9 parts zirconium silicate, 12 parts diopside, 2 parts boron-free calcium-magnesium frit powder, and 2 parts calcined alumina. After weighing according to the proportions, it is put into a ball mill. Water, sodium carboxymethyl cellulose, and sodium tripolyphosphate are added. The mass ratio of the base glaze material, water, sodium carboxymethyl cellulose, and sodium tripolyphosphate is 100:40:0.12:0.3. The mixture is ball-milled until the residue on a 325-mesh sieve is ≤0.05%, and the median particle size D50 is ≤4μm. The thixotropic index (TI value = viscosity ratio at 6r / min to 60r / min) of the glaze slurry is tested, and the TI value is controlled between 1.2 and 1.5. The base glaze is applied to the green body obtained in S1 using a glazing method, with a glaze application rate of 300g / m³. 2 This forms the base glaze layer; S3. The raw materials for the top glaze layer include: 36 parts potassium feldspar, 13 parts sodium feldspar, 10 parts calcined kaolin, 10 parts quartz, 10 parts dolomite, 8 parts zinc oxide, 2.2 parts barium carbonate, and 2.4 parts calcium phosphate. The mixture is ball-milled until the residue on a 325-mesh sieve is ≤0.1%. The top glaze is applied to the base glaze layer obtained in S2 using a glazing method, with a glaze application rate of 300 g / m². 2 This forms a surface glaze layer; S4. Firing: The firing temperature is set at 1195℃, held for 30 minutes, and then cooled from the highest temperature to 1050℃ at a rate of 10℃ / min during the cooling phase; then cooled slowly to 950℃ at a rate of 4℃ / min. Forced air cooling is used below 950℃, with a fan frequency of 32Hz. During the firing process, a slight positive pressure of 10Pa is maintained during the 1195℃ and 1050-950℃ stages. S5. After being removed from the kiln, the edges are ground, inspected, and packaged to obtain the gold velvet ceramic tile.

[0030] The main difference between this comparative example and Example 1 is that strontium carbonate is not added in step S3.

[0031] Comparative Example 4 A method for preparing gold velvet ceramic tiles includes the following steps: S1. Weigh each component according to the required ratio. The raw materials for the green body include: 15 parts potassium sodium stone powder, 10 parts potassium sand, 14 parts water-milled sodium sand, 8 parts stone powder, 4 parts siliceous stone, 3 parts magnesia powder, 12 parts kaolin, 10 parts ball clay, 6 parts white clay, and 2 parts bentonite. After weighing according to the ratio, put them into a ball mill to prepare the green body. Ball mill until the residue on a 250-mesh sieve is ≤0.5%. Spray granulation is used to make powder. The powder is aged in a sealed chamber for 24 hours. It is then pressed into shape using a hydraulic press and dried until the moisture content is <0.5%. It is ready for use. S2. The base glaze material includes: 30 parts potassium feldspar, 22 parts sodium feldspar, 11 parts calcined kaolin, 13 parts quartz, 9 parts zirconium silicate, 12 parts diopside, 2 parts boron-free calcium-magnesium frit powder, and 2 parts calcined alumina. After weighing according to the proportions, it is put into a ball mill. Water, sodium carboxymethyl cellulose, and sodium tripolyphosphate are added. The mass ratio of the base glaze material, water, sodium carboxymethyl cellulose, and sodium tripolyphosphate is 100:40:0.12:0.3. The mixture is ball-milled until the residue on a 325-mesh sieve is ≤0.05%, and the median particle size D50 is ≤4μm. The thixotropic index (TI value = viscosity ratio at 6r / min to 60r / min) of the glaze slurry is tested, and the TI value is controlled between 1.2 and 1.5. The base glaze is applied to the green body obtained in S1 using a glazing method, with a glaze application rate of 300g / m³. 2 This forms the base glaze layer; S3. The raw materials for the top glaze layer include: 36 parts potassium feldspar, 13 parts sodium feldspar, 10 parts calcined kaolin, 10 parts quartz, 10 parts dolomite, 8 parts zinc oxide, 2.2 parts barium carbonate, 2 parts strontium carbonate, and 2.4 parts calcium phosphate. The mixture is ball-milled until the residue on a 325-mesh sieve is ≤0.1%. The top glaze is applied to the base glaze layer obtained in S2 using a glazing method, with a glaze application rate of 300 g / m². 2 This forms a surface glaze layer; S4. Firing: The firing temperature is set at 1195℃, held for 30 minutes, and during the cooling phase, the temperature is reduced from the highest temperature to 950℃ at a rate of 10℃ / minute. Below 950℃, forced air cooling is used with a fan frequency of 32Hz. During the firing process, a slight positive pressure of 10Pa is maintained between 1195℃ and 950℃. S5. After being removed from the kiln, the edges are ground, inspected, and packaged to obtain the gold velvet ceramic tile.

[0032] The main difference between this comparative example and Example 1 is that step S4 uses a two-stage cooling process.

[0033] Performance tests were conducted on Examples 1-3 and Comparative Examples 1-4, and the specific test methods are as follows: (1) Gloss measurement Gloss determination was performed in accordance with GB / T 13891-2008 "Method for Determination of Specular Gloss of Building Facing Materials". A gloss meter with 60° geometry (WGG-60 type) was used. Before testing, the sample was calibrated with a standard gloss plate. The surface of the ceramic tile sample to be tested was cleaned and placed on a flat table. The gloss meter was placed in close contact with the sample surface. Five measurement points were selected evenly distributed on the surface of each sample. The arithmetic mean of the measurements was taken as the gloss value of the sample. The result was expressed in gloss units (GU).

[0034] (2) Test of easy-to-clean performance The easy-to-clean performance was determined according to GB / T 31859-2015 "Test Method for Easy-to-Cleanliness of Daily-Use Porcelain". The sample was cut into 50mm × 50mm pieces, cleaned, and dried in an oven at 110℃ until constant weight (the difference between two consecutive weighings should not exceed 0.1%). The pieces were then cooled to room temperature in a desiccator and weighed, and the initial mass m0 was recorded. Salad oil was evenly applied to the surface of the sample according to the standard. After standing for 10 minutes, the sample was placed on a sample holder at a 45° angle to the horizontal plane and rinsed with distilled water at 25℃ at a flow rate of 50mL / s for 1 minute. It was then dried again until constant weight, and the mass m1 after rinsing was recorded. The residual oil content per unit area was calculated using the formula A = (m1 - m0) × 10. 6 / S is calculated, where S is the working area of ​​the test piece, and the result is expressed in g / m². 2 express.

[0035] (3) Antifouling test The stain resistance test was conducted according to GB / T 3810.14-2016 "Test Methods for Ceramic Tiles - Part 14: Determination of Stain Resistance". The wetting method was used. Four standard contaminants—olive oil, tomato sauce, coffee (20 g / L), and black tea (20 g / L)—were dropped onto the sample surface, with droplets approximately 10 mm in diameter, covering two locations for each contaminant. After standing at room temperature for 24 hours, the sample was first rinsed with water, then cleaned with the specified cleaning agent. After cleaning, residual stains were observed at a distance of approximately 300 mm from the sample surface. The stain level was assessed according to the standard: Level 5 indicates no visible stain residue, Level 4 indicates slight stain (visible only at certain angles), Level 3 indicates obvious stain, Level 2 indicates moderate stain, and Level 1 indicates severe stain.

[0036] (4) Abrasion resistance test Abrasion resistance was determined according to GB / T 3810.7-2016 "Test Methods for Ceramic Tiles Part 7: Determination of Abrasion Resistance of Glazed Tiles". A glazed tile surface abrasion resistance tester was used, with steel balls and silicon carbide as the abrasive media, to grind the sample surface at a specified number of revolutions. After the test, the sample was cleaned, and the glaze wear was observed at a distance of approximately 300 mm from the sample surface. Abrasion resistance grades were assigned according to the standard: Grade 5 was the highest abrasion resistance grade (no visible wear at the specified number of revolutions), Grade 4 was a relatively high abrasion resistance grade, and Grade 3 was a medium abrasion resistance grade. The grade corresponding to the number of revolutions at which visible wear appeared was used as the evaluation result.

[0037] (5) Water absorption rate determination Water absorption rate was determined according to GB / T 3810.3-2016 "Test Methods for Ceramic Tiles Part 3: Determination of Water Absorption, Apparent Porosity, Apparent Relative Density and Bulk Density". The vacuum method was used for testing. The sample was dried in an oven at 110℃ until constant weight (the difference between two consecutive weighings should not exceed 0.1%), and the dry weight m1 was recorded. The dried sample was placed in a vacuum device, and a vacuum was drawn until the pressure was below 10 kPa. After maintaining this pressure for 30 minutes, distilled water was injected, and the sample was soaked for another 15 minutes. The pressure was then restored to normal, and the sample was soaked in water for another 15 minutes. The sample was removed, and the surface moisture was wiped off with a damp cloth. The saturated wet weight m2 was then measured. The water absorption rate was calculated using the formula W = (m2 - m1) / m1 × 100%, and the result was expressed as a percentage.

[0038] (6) Chemical resistance test Chemical resistance was determined according to GB / T 3810.13-2016 "Test Methods for Ceramic Tiles - Part 13: Determination of Chemical Resistance". Low-concentration acid solution (3% hydrochloric acid solution) and low-concentration alkali solution (20g / L potassium hydroxide solution) were respectively added dropwise to the sample surface. The sample was covered with a watch glass and allowed to stand at room temperature for 24 hours. Afterward, the sample was rinsed with water and cleaned with the specified cleaning agent. Surface changes were observed at a distance of approximately 300mm from the sample surface. The chemical resistance grade was assessed according to the standard: GLA grade: no visible change (no change in surface gloss and color); GLB grade: slight visible change; GLC grade: significant visible change. (7) Determination of destructive strength The breaking strength was determined in accordance with GB / T 3810.4-2016 "Test Methods for Ceramic Tiles - Part 4: Determination of Modulus of Rupture and Breaking Strength". The three-point bending method was used. The specimen was placed on two supports with a support distance of 200 mm. A load was applied to the middle of the specimen at a certain rate, and the maximum load value at which the specimen broke was recorded, expressed in Newtons (N).

[0039] The specific test results of Examples 1-3 and Comparative Examples 1-4 are shown in the table below: Table 1. Specific test results of Examples 1-3 and Comparative Examples 1-4 As shown in Table 1, the residual oil content per unit area of ​​the super easy-clean gold velvet ceramic tiles prepared in Examples 1-3 of this invention is no higher than 0.10 g / m². 2 All exhibit stable anti-fouling performance reaching level 4, excellent cleaning performance, wear resistance reaching level 4, water absorption rate ≤0.10%, breaking strength ≥1800N, chemical corrosion resistance reaching GLA level, stable and excellent mechanical and chemical properties, no visible defects such as pinholes and microcracks on the glaze surface, delicate and smooth surface feel, and gloss between 30-35GU, which is within the typical gloss range of velvet textured ceramic tiles. All performance indicators are balanced and excellent, and it has good industrial application value.

[0040] In contrast, the base glaze of Comparative Example 1 did not contain diopside, lacking the filling and gradation effect of the diopside crystalline phase. It relied solely on the single crystalline phase of zircon for stain prevention, resulting in increased microscopic porosity. Some pores connected to the glaze surface, leading to a residual oil content of 0.48 g / m² per unit area. 2 The anti-fouling performance dropped to level 3, the abrasion resistance dropped to level 3, the water absorption rate increased to 0.12%, and the gloss increased to 38GU (too bright), indicating poor performance. Comparative Example 2's base glaze did not contain zirconium silicate and relied solely on the diopside single-phase anti-fouling agent, lacking the support of the zircon main framework phase. The base glaze density was severely insufficient, and the residual oil content was 0.65g / m³. 2 The stain resistance dropped to level 2, the worst among all examples and comparative examples; the abrasion resistance dropped to level 3; and the water absorption rate increased to 0.15%, resulting in poor overall performance. Comparative example 3 did not add strontium carbonate to its glaze, lacking the control of strontium carbonate on the size of the zinc siliceous mineral grains. This led to excessive growth of the zinc siliceous mineral grains, reducing the gloss to 24 GU (matte) and making the velvety texture rough, unsuitable for use as a velvety textured tile. Comparative example 4 used a two-stage cooling process without a slow crystallization stage at 1050-950℃, preventing the zinc siliceous mineral grains from growing sufficiently. This resulted in a gloss increase to 42 GU (glossy), strong reflectivity, and a weakened velvety texture, also making it unsuitable for use as a velvety textured tile.

[0041] In summary, the super easy-clean velvet ceramic tile of this invention, which adopts a three-layer structure and a multi-phase anti-fouling design in the base glaze, forms an effective anti-fouling barrier through the combination of zirconium silicate and diopside in the base glaze layer, greatly improving the tile's anti-fouling and easy-to-clean ability, and presenting a velvety delicate touch. Its various performance indicators are balanced and excellent, and it has good industrial application value.

[0042] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A super easy-to-clean gold velvet ceramic tile, characterized in that, The super easy-clean gold velvet ceramic tile comprises, from bottom to top, a body, a base glaze layer, and a top glaze layer; By weight, the raw materials for the green body include: 12-16 parts of potassium sodium stone powder, 8-12 parts of potassium sand, 12-16 parts of water-milled sodium sand, 6-10 parts of stone powder, 3-5 parts of siliceous limestone, 2-4 parts of magnesia powder, 10-14 parts of kaolin, 8-12 parts of ball clay, 5-8 parts of white clay, and 1-2 parts of bentonite; The raw materials for the base glaze layer include: 28-32 parts potassium feldspar, 20-25 parts sodium feldspar, 11-12 parts calcined kaolin, 12-16 parts quartz, 8-10 parts zirconium silicate, 10-13 parts diopside, 1-3 parts boron-free calcium-magnesium frit powder, and 2-3 parts calcined alumina. The raw materials for the surface glaze layer include: 32-38 parts potassium feldspar, 10-16 parts sodium feldspar, 8-12 parts calcined kaolin, 8-12 parts quartz, 8-12 parts dolomite, 7-10 parts zinc oxide, 2-2.5 parts barium carbonate, 1.5-2 parts strontium carbonate, and 1.5-3 parts calcium phosphate.

2. The super easy-clean gold velvet ceramic tile according to claim 1, characterized in that: In the raw material of the base glaze layer, the weight ratio of diopside to zirconium silicate is (1.1-1.6):

1.

3. The super easy-clean gold velvet ceramic tile according to claim 1, characterized in that: In the raw material of the glaze layer, the weight ratio of calcium phosphate to strontium carbonate is (1-1.5):

1.

4. The super easy-clean gold velvet ceramic tile according to claim 1, characterized in that: The boron-free calcium-magnesium frit powder has the following chemical composition: SiO2 50-55%, CaO 10-15%, MgO 3-5%, Al2O3 8-12%, B2O3 content ≤0.1%, and softening point of 1050-1100℃.

5. A method for preparing an ultra-easy-clean gold velvet ceramic tile according to any one of claims 1-4, characterized in that, Includes the following steps: S1. Weigh each component according to the required ratio, prepare the green body, and dry it until the moisture content is <0.5% for later use; S2. Apply a base glaze to the blank obtained in S1 using the glazing method to form a base glaze layer; S3. Apply a top glaze to the base glaze layer obtained in S2 using the glazing method to form a top glaze layer; S4. Firing: Set the firing temperature to 1190-1200℃, hold for 20-40 minutes, and during the cooling phase, reduce the temperature from the highest temperature to 1050℃ at a rate of 10-12℃ / minute; then slowly reduce the temperature to 950℃ at a rate of 2-4℃ / minute, and force air cooling below 950℃. S5. After being removed from the kiln, the edges are ground, inspected, and packaged to obtain the super easy-clean gold velvet ceramic tile.

6. The method for preparing an ultra-easy-clean gold velvet ceramic tile according to claim 5, characterized in that: Water, sodium carboxymethyl cellulose, and sodium tripolyphosphate are added as additives during the preparation of the base glaze described in S2.

7. The method for preparing an ultra-easy-clean gold velvet ceramic tile according to claim 6, characterized in that: The mass ratio of the base glaze raw material, water, sodium carboxymethyl cellulose, and sodium tripolyphosphate is 100:(38-42):(0.10-0.15):(0.30-0.40).

8. The method for preparing an ultra-easy-clean gold velvet ceramic tile according to claim 5, characterized in that: The base glaze application rate for S2 is 280-320g / m². 2 .

9. The method for preparing an ultra-easy-clean gold velvet ceramic tile according to claim 5, characterized in that: The surface glaze application rate for S3 is 250-350g / m². 2 .

10. The method for preparing an ultra-easy-clean gold velvet ceramic tile according to claim 5, characterized in that: During the firing process described in S4, a slight positive pressure of 5-10 Pa is maintained during the 1190-1200℃ and 1050-950℃ stages.

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