Highly transparent anti-fouling full polishing glaze and polishing glaze tile using the same

Abstract

The application relates to the technical field of ceramic glazes, and discloses a high-transparency anti-fouling full-polishing glaze and polishing glaze bricks using the same, the high-transparency anti-fouling full-polishing glaze comprises the following raw materials in parts by mass: 25-30 parts of tea crystal feldspar, 5-10 parts of zinc oxide, 10-15 parts of barium carbonate, 2-5 parts of composite silicon carbide nanowires, 8-12 parts of calcined talc, 8-10 parts of kaolin, 8-10 parts of corundum, 23-27 parts of glass frit, and 1-3 parts of zirconium silicate. The composite silicon carbide nanowires contain modified silicon carbide nanowires and magnesium-aluminum spinel powder. During the firing process, the modified silicon carbide nanowires can be uniformly filled into the full-polishing glaze layer through the magnesium-aluminum spinel powder, so that the compactness, mechanical properties and gloss of the glaze layer are improved. In addition, the modified silicon carbide nanowires can be filled into the pores and defects introduced by the magnesium-aluminum spinel powder in the glaze layer, so that the gloss, anti-fouling performance and mechanical properties of the full-polishing glaze layer are improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of ceramic glaze, in particular to a high-transparency anti-fouling full-polishing glaze and polished glaze brick using the same. BACKGROUND

[0002] Full-polishing glaze is a special formula glaze that can be polished on the glaze surface, which is the last glaze applied to the brick body, generally transparent face glaze or transparent convex glaze, and the glaze surface is as smooth as polished brick, while the glaze pattern is as rich as antique brick, with thick and heavy or gorgeous colors; transparent full-polishing glaze can improve the surface properties of ceramic products, without covering the underlying face glaze and each layer of glaze, giving the brick body products the characteristics of smoothness, brightness and non-water absorption, and also improving the strength, thermal stability and chemical stability of the brick body products.

[0003] After the components of the full-polishing glaze are mixed and ball milled in water, a full-polishing glaze slurry is formed, which is applied to the brick body, and after drying, firing and polishing, the polished glaze brick has excellent anti-fouling performance and gloss, but the full-polishing glaze is prone to produce a large number of bubbles during firing, resulting in poor anti-fouling ability and loss of gloss of the formed glaze layer, and the expansion coefficient of the glaze layer of the full-polishing glaze glaze brick is smaller than that of the ceramic brick body, so the internal stress of the glaze layer is large, which causes deformation during firing, thereby causing the phenomenon of missing polishing or local exposure during polishing. SUMMARY

[0004] The present application provides a high-transparency anti-fouling full-polishing glaze and polished glaze brick using the same, which solves the problem of deformation of the full-polishing glaze during firing, leading to missing polishing or local exposure during polishing.

[0005] The technical scheme of the present application is as follows:

[0006] A high-transparency anti-fouling full-polishing glaze, comprising the following raw materials by mass: 25-30 parts of tea crystal feldspar, 5-10 parts of zinc oxide, 10-15 parts of barium carbonate, 2-5 parts of composite silicon carbide nanowire, 8-12 parts of calcined talc, 8-10 parts of kaolin, 8-10 parts of corundum, 23-27 parts of glass frit, and 1-3 parts of zirconium silicate.

[0007] A preparation method of a high-transparency anti-fouling full-polishing glaze, comprising the following preparation steps:

[0008] The tea crystal feldspar, zinc oxide, barium carbonate, composite silicon carbide nanowire, calcined talc, kaolin, corundum, glass frit and zirconium silicate are mixed uniformly, crushed and passed through a 350-400 mesh sieve to obtain the high-transparency anti-fouling full-polishing glaze.

[0009] Further, the composite silicon carbide nanowire is prepared by the following steps:

[0010] A1. The silicon carbide nanowires are added to nitric acid solution and sulfuric acid solution, etched, taken out, washed, dried, and acid-etched silicon carbide nanowires are obtained;

[0011] A2. The zirconium oxychloride octahydrate and the acid-etched silicon carbide nanowires are added to deionized water, stirred uniformly, and ammonia, glycine and potassium chloride are added. After the reaction is completed, the hydrothermal reaction is carried out at 170-190°C for 20-22h, cooled to room temperature, filtered, washed, and dried to obtain modified silicon carbide nanowires;

[0012] A3. The modified silicon carbide nanowires, magnesium aluminum spinel powder and hydroxypropyl methyl cellulose are added to ethanol, stirred uniformly, heated to 80-90°C, and continue to stir until the solvent is volatilized. After cooling to room temperature, the composite silicon carbide nanowires are obtained.

[0013] Further, in the above A1 reaction process, after the silicon carbide nanowires are acid-etched by nitric acid and sulfuric acid, the surface impurities and oxide layers can be removed, and the nitric acid and sulfuric acid as oxidizing agents can oxidize the Si-C covalent bond on the surface of the silicon carbide nanowires, thereby forming a large number of Si-O bonds on the surface of the silicon carbide nanowires, improving the surface activity, and being conducive to the synthesis of nano zirconium oxide on the surface of the silicon carbide nanowires.

[0014] Further, in the above A2 reaction process, the acid-etched silicon carbide nanowires contain a large number of hydrophilic groups of hydroxyl groups on the surface, which can combine with zirconium ions in the zirconium oxychloride octahydrate, so that the zirconium oxychloride octahydrate is adsorbed to the surface of the acid-etched silicon carbide nanowires. Ammonia as a precipitating agent and glycine and potassium chloride as an aid can react with the zirconium oxychloride octahydrate to generate zirconium hydroxide deposited on the surface of the acid-etched silicon carbide nanowires. Continue to react, and the zirconium hydroxide is decomposed by heat to synthesize nano zirconium oxide with a particle size of 30-40nm on the surface of the acid-etched silicon carbide nanowires, and obtain modified silicon carbide nanowires.

[0015] Further, in the above A3 reaction process, the magnesium aluminum spinel powder is loaded on the surface of the modified silicon carbide nanowires through the binder, so that the magnesium aluminum spinel powder is uniformly coated on the surface of the modified silicon carbide nanowires, and the composite silicon carbide nanowires are obtained.

[0016] Further, in step A1, the mass ratio of silicon carbide nanowires, nitric acid solution and sulfuric acid solution is (5-6):(25-35):(25-35).

[0017] Further, in step A2, the mass ratio of zirconium oxychloride octahydrate, acid-etched silicon carbide nanowires, deionized water, ammonia, glycine and potassium chloride is (0.4-0.6):(1.4-1.6):(90-110):(1.5-2.5):(0.3-0.5):(0.7-0.9).

[0018] Further, in step A3, the mass ratio of modified silicon carbide nanowires, magnesium aluminum spinel powder, hydroxypropyl methyl cellulose and ethanol is (2.4-2.6):(1-1.2):(0.2-0.4):(38-42).

[0019] Further, the silicon carbide nanowires have a diameter of 0.1-0.6 µm and a length of 50-100 µm, and are purchased from Changsha Saite New Material Co., Ltd.

[0020] Further, the magnesium aluminum spinel powder has a particle size of 1-5 µm, and is a product of a premium grade, and is purchased from Hubei Langbo Wan Biological Medicine Co., Ltd.

[0021] A preparation method of glaze-throwing bricks, which are prepared by using the high-transparency anti-fouling full-glaze provided above, comprises the following preparation steps:

[0022] S1. Mixing high-transparency anti-fouling full-glaze, sodium carboxymethyl cellulose, sodium tripolyphosphate and water to perform ball milling to obtain full-glaze slurry;

[0023] S2. Applying bottom glaze, printing glaze and surface glaze on the brick body in sequence to form a glaze-throwing brick body, applying the full-glaze slurry to the glaze-throwing brick body by glazing, and performing drying, firing and polishing to obtain the glaze-throwing brick.

[0024] Further, in step S1, the mass ratio of high-transparency anti-fouling full-glaze, sodium carboxymethyl cellulose, sodium tripolyphosphate and water is (70-75):(0.1-0.2):(0.2-0.3):(30-35).

[0025] Further, in step S1, the ball milling is performed in a ball mill, the grinding balls are zirconium balls with a diameter of 8-10 mm, the ball-to-material ratio is (2-3):1, and the ball milling time is 18-22 h.

[0026] Further, in step S2, the glazing specific gravity is 1.5-1.6, and the glazing amount can be 500-550 g / m 2 .

[0027] Further, in step S2, the drying temperature is 80-110 ℃, and the drying time is 20-30 min.

[0028] Further, in step S2, the firing temperature is 1200-1220 ℃, and the firing time is 60-80 min.

[0029] Further, in step S2, the polishing is performed by using diamond particles with a particle size of 800-1000 mesh, the polishing time is 4-6 min, and the polishing pressure is 0.03-0.1 MP.

[0030] The present application has the following beneficial effects:

[0031] (1) In the technical scheme of the present application, the silicon carbide nanowires are etched by nitric acid and sulfuric acid to form a large number of hydrophilic groups, i.e. silicon hydroxyl groups, on the surface of the silicon carbide nanowires, thereby improving the dispersibility of the silicon carbide nanowires and facilitating the synthesis of a large number of nano zirconium oxide on the surface of the silicon carbide nanowires. The nano zirconium oxide is synthesized on the surface of the acid-etched silicon carbide nanowires to obtain modified silicon carbide nanowires. On the one hand, the acid-etched silicon carbide nanowires serve as carriers for the nano zirconium oxide, thereby improving the dispersibility of the nano zirconium oxide in the full polishing glaze slurry. During the coating process of the full polishing glaze slurry, the nano zirconium oxide pins the grain boundaries and inhibits the growth of the crystal grains, thereby improving the compactness of the full polishing glaze layer. The compact glaze layer structure can reduce the adhesion of stains and bacteria, thereby improving the stain resistance, glossiness of the polished glaze tile. On the other hand, the silicon carbide nanowires have an excellent aspect ratio and form a network skeleton in the full polishing glaze layer. The silicon carbide nanowires and the nano zirconium oxide can fill the gaps in the full polishing glaze layer, thereby significantly improving the scratch resistance of the glaze layer and reducing the wear during daily use. In addition, the silicon carbide nanowires and the nano zirconium oxide have excellent thermal stability, which can relieve the thermal stress of the glaze layer when the temperature changes. The expansion coefficient of the glaze layer is smaller than that of the ceramic tile body, and the internal stress of the glaze layer is large, which causes the deformation of the glaze layer during the firing process. The stain resistance, glossiness and mechanical properties of the glaze layer are improved.

[0032] (2) In the technical scheme of the present application, the magnesium aluminum spinel powder is uniformly coated on the surface of the modified silicon carbide nanowires to obtain composite silicon carbide nanowires. On the one hand, the magnesium aluminum spinel powder has high hardness, high melting point, excellent chemical stability and thermal stability, and its thermal expansion coefficient matches that of the ceramic tile body. The difference between the expansion coefficients of the glaze layer and the ceramic tile body is small, and the internal stress of the glaze layer is small, which avoids the deformation of the glaze layer during the firing process. On the other hand, the magnesium aluminum spinel powder can provide a large amount of aluminum oxide component during the firing process of the full polishing glaze. The aluminum oxide component can form four-coordination by capturing free oxygen in the full polishing glaze and enter the silicon-oxygen network structure of the full polishing glaze, which is helpful for the formation of the glaze layer network structure and improves the chemical stability, hardness and elasticity.

[0033] The coating of the magnesium aluminum spinel powder on the surface of the modified silicon carbide nanowires can improve the dispersibility of the fine magnesium aluminum spinel powder in the full polishing glaze. During the firing process, the modified silicon carbide nanowires can be uniformly filled into the full polishing glaze layer through the magnesium aluminum spinel powder, thereby improving the compactness, mechanical properties and glossiness of the glaze layer. In addition, the nano zirconium oxide on the surface of the modified silicon carbide nanowires can fill the pore defects introduced by the magnesium aluminum spinel powder in the glaze layer, thereby avoiding the introduction of pores by the magnesium aluminum spinel powder in the full polishing glaze layer, which can cause a decrease in the glossiness, stain resistance and mechanical properties of the full polishing glaze layer. DETAILED DESCRIPTION

[0034] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments of the present application. Based on the embodiments of the present application, all other embodiments obtained by a person of ordinary skill in the art without creative work fall within the protection scope of the present application.

[0035] The raw materials used in the embodiments of the present application are shown as follows, and all the reagents used are analytical grade.

[0036] The tea crystal feldspar and the glass frit are purchased from Foshan Sanjing Stone Ceramic Glaze Co., Ltd., and the glass frit is barium-free frit, and the chemical composition is: SiO2: 67%, Al2O3: 5.0%, CaO: 20.5%, MgO: 2.3%, K2O: 2.8%, ZnO: 2.3%, and Na2O: 0.8%.

[0037] The glaze throwing brick base has a thickness of 12 mm and is purchased from Zibo Shuncheng Building Ceramic Co., Ltd.

[0038] The silicon carbide nanowire has a diameter of 0.5 µm and a length of 70 µm, and is purchased from Changsha Saite New Material Co., Ltd.

[0039] The magnesium aluminate spinel powder has a particle size of 2 µm, and the product grade is premium grade, and is purchased from Hubei Langbo Wan Biomedical Co., Ltd.

[0040] Embodiment 1

[0041] A high-transparency anti-fouling full-polishing glaze comprises the following raw materials in mass parts: tea crystal feldspar 25 parts, zinc oxide 5 parts, barium carbonate 10 parts, composite silicon carbide nanowire 2 parts, calcined talc 8 parts, kaolin 8 parts, corundum 8 parts, glass frit 23 parts, and zirconium silicate 1 part.

[0042] A preparation method of a high-transparency anti-fouling full-polishing glaze comprises the following preparation steps:

[0043] The tea crystal feldspar, zinc oxide, barium carbonate, composite silicon carbide nanowire, calcined talc, kaolin, corundum, glass frit, and zirconium silicate are uniformly mixed, crushed through a 350-mesh sieve, and a high-transparency anti-fouling full-polishing glaze is obtained.

[0044] A preparation method of a glaze throwing brick comprises the following preparation steps:

[0045] S1. The high-transparency anti-fouling full-polishing glaze, sodium carboxymethyl cellulose, sodium tripolyphosphate, and water are mixed and ball milled, the ball milling is performed in a ball mill, the grinding balls are zirconium balls with a diameter of 8 mm, the ball-to-material ratio is 2:1, and the ball milling time is 18 h, to obtain a full-polishing glaze slurry; the mass ratio of the high-transparency anti-fouling full-polishing glaze, sodium carboxymethyl cellulose, sodium tripolyphosphate, and water is 70:0.1:0.2:30.

[0046] S2. The full polishing glaze slurry is applied to the polishing glaze brick body by spraying, and the spraying density is 1.5, and the spraying amount can be 500g / m 2 The full polishing glaze slurry is applied to the polishing glaze brick body by spraying, and the spraying density is 1.5, and the spraying amount can be 500g / m

[0047] The composite silicon carbide nanowire is prepared by the following steps:

[0048] A1. The silicon carbide nanowire is added to a nitric acid solution with a concentration of 0.5M and a sulfuric acid solution with a concentration of 0.5M, etched for 1min, taken out, washed with deionized water until the pH of the washing liquid is neutral, dried in a 70℃ oven for 10min, and the acid-etched silicon carbide nanowire is obtained; the mass ratio of silicon carbide nanowire, nitric acid solution and sulfuric acid solution is 5:25:25;

[0049] A2. The zirconium oxychloride octahydrate and the acid-etched silicon carbide nanowire are added to deionized water, stirred uniformly, and then ammonia water, glycine and potassium chloride are added, stirred at 85℃ for 10min, placed in a reaction kettle, and hydrothermal reaction is carried out at 170℃ for 20h, cooled to room temperature, filtered, washed with deionized water for 3 times, and dried in an 80℃ oven for 3h to obtain the modified silicon carbide nanowire; the mass ratio of zirconium oxychloride octahydrate, acid-etched silicon carbide nanowire, deionized water, ammonia water, glycine and potassium chloride is 0.4:1.4:90:1.5:0.3:0.7.

[0050] A3. The modified silicon carbide nanowire, magnesium aluminate spinel powder and hydroxypropyl methyl cellulose are added to ethanol, stirred uniformly, heated to 85℃, and then continue to stir until the solvent volatilizes, and then cooled to room temperature to obtain the composite silicon carbide nanowire; the mass ratio of modified silicon carbide nanowire, magnesium aluminate spinel powder, hydroxypropyl methyl cellulose and ethanol is 2.4:1:0.2:38.

[0051] Example 2

[0052] A high-transparency and anti-fouling full polishing glaze, comprising the following raw materials in parts by mass: tea crystal feldspar 28 parts, zinc oxide 8 parts, barium carbonate 13 parts, composite silicon carbide nanowire 3 parts, calcined talc 10 parts, kaolin 9 parts, corundum 9 parts, glass clinker 25 parts, zirconium silicate 2 parts;

[0053] A preparation method of a high-transparency and anti-fouling full polishing glaze, comprising the following preparation steps:

[0054] The tea crystal feldspar, zinc oxide, barium carbonate, composite silicon carbide nanowire, calcined talc, kaolin, corundum, glass clinker and zirconium silicate are uniformly mixed and crushed through a 380 mesh sieve to obtain the high-transparency and anti-fouling full polishing glaze.

[0055] A preparation method of a glaze throwing brick, comprising the following preparation steps:

[0056] S1. Mix high-transparency anti-fouling full polishing glaze, sodium carboxymethyl cellulose, sodium tripolyphosphate and water for ball milling, the ball milling is performed in a ball mill, the grinding balls are zirconium balls with a diameter of 9 mm, the ball-to-material ratio is 2.5:1, the ball milling time is 20 h, and a full polishing glaze slurry is obtained; the mass ratio of the high-transparency anti-fouling full polishing glaze, sodium carboxymethyl cellulose, sodium tripolyphosphate and water is 73:0.15:0.25:33;

[0057] S2. The glaze throwing brick is prepared by controlling the glaze throwing brick to have a glaze throwing ratio of 1.55 and a glaze throwing amount of 530 g / m 2 The full polishing glaze slurry is applied to the glaze throwing brick substrate in a glaze throwing manner, dried at 100 DEG C for 25 min, fired at 1210 DEG C for 70 min, polished with diamond particles with a particle size of 1000 mesh for 5 min at a polishing pressure of 0.05 MPa, and a glaze throwing brick is obtained.

[0058] The composite silicon carbide nanowire is prepared by the following steps:

[0059] A1. The silicon carbide nanowire is added to a 0.5M nitric acid solution and a 0.5M sulfuric acid solution, etched for 1 min, taken out, washed with deionized water until the pH of the washing liquid is neutral, and dried in a 70 DEG C oven for 10 min to obtain acid-etched silicon carbide nanowire; the mass ratio of the silicon carbide nanowire, the nitric acid solution and the sulfuric acid solution is 5.5:30:30;

[0060] A2. The zirconium oxychloride octahydrate and the acid-etched silicon carbide nanowire are added to deionized water, stirred uniformly, and then the ammonia water, glycine and potassium chloride are added, stirred at 85 DEG C for 10 min, placed in a reaction kettle, and subjected to hydrothermal reaction at 180 DEG C for 21 h, cooled to room temperature, filtered, washed with deionized water for 3 times, and dried in an 80 DEG C oven for 3 h to obtain modified silicon carbide nanowire; the mass ratio of the zirconium oxychloride octahydrate, the acid-etched silicon carbide nanowire, the deionized water, the ammonia water, the glycine and the potassium chloride is 0.5:1.5:100:2:0.4:0.8.

[0061] A3. The modified silicon carbide nanowire, the magnesium aluminum spinel powder and the hydroxypropyl methyl cellulose are added to ethanol, stirred uniformly, heated to 85 DEG C, and continuously stirred until the solvent is volatilized, and then cooled to room temperature to obtain the composite silicon carbide nanowire; the mass ratio of the modified silicon carbide nanowire, the magnesium aluminum spinel powder, the hydroxypropyl methyl cellulose and the ethanol is 2.5:1.1:0.3:40.

[0062] Example 3

[0063] A high-transparency anti-fouling full polishing glaze, comprising the following raw materials in parts by mass: tea crystal feldspar 30 parts, zinc oxide 10 parts, barium carbonate 15 parts, composite silicon carbide nanowires 5 parts, calcined talc 12 parts, kaolin 10 parts, corundum 10 parts, glass clinker 27 parts, and zirconium silicate 3 parts;

[0064] A preparation method of a high-transparency anti-fouling full polishing glaze, comprising the following preparation steps:

[0065] The tea crystal feldspar, zinc oxide, barium carbonate, composite silicon carbide nanowires, calcined talc, kaolin, corundum, glass clinker, and zirconium silicate are mixed uniformly, crushed through a 400-mesh sieve, and a high-transparency anti-fouling full polishing glaze is obtained.

[0066] A preparation method of a polishing glaze brick, comprising the following preparation steps:

[0067] S1. The high-transparency anti-fouling full polishing glaze, sodium carboxymethyl cellulose, sodium tripolyphosphate, and water are mixed and ball milled, the ball milling is performed in a ball mill, the grinding balls are zirconium balls with a diameter of 10 mm, the ball-to-material ratio is 3:1, the ball milling time is 22 h, and a full polishing glaze slurry is obtained; the mass ratio of the high-transparency anti-fouling full polishing glaze, sodium carboxymethyl cellulose, sodium tripolyphosphate, and water is 75:0.2:0.3:35;

[0068] S2. The full polishing glaze slurry is controlled to have a glazing specific gravity of 1.6, and the glazing amount can be 550 g / m 2 The full polishing glaze slurry is applied to the polishing glaze brick substrate in a glazing manner, dried at 110°C for 30 min, fired at 1220°C for 80 min, polished with diamond particles with a particle size of 1000 mesh for 5 min at a polishing pressure of 0.05 MPa, and a polishing glaze brick is obtained.

[0069] The composite silicon carbide nanowires are prepared by the following steps:

[0070] A1. The silicon carbide nanowires are added to a 0.5M nitric acid solution and a 0.5M sulfuric acid solution, etched for 1 min, taken out, washed with deionized water until the washing liquid has a neutral pH, and dried in a 70°C oven for 10 min to obtain acid-etched silicon carbide nanowires; the mass ratio of the silicon carbide nanowires, the nitric acid solution, and the sulfuric acid solution is 6:35:35;

[0071] A2. The zirconium oxychloride octahydrate and the acid-etched silicon carbide nanowires are added to deionized water, stirred uniformly, and then the ammonia water, glycine, and potassium chloride are added, stirred at 85°C for 10 min, placed in a reaction kettle, and subjected to hydrothermal reaction at 190°C for 22 h, cooled to room temperature, filtered, washed with deionized water three times, and dried in an 80°C oven for 3 h to obtain modified silicon carbide nanowires; the mass ratio of the zirconium oxychloride octahydrate, the acid-etched silicon carbide nanowires, the deionized water, the ammonia water, the glycine, and the potassium chloride is 0.6:1.6:110:2.5:0.5:0.9.

[0072] A3. The modified silicon carbide nanowire, magnesium aluminum spinel powder and hydroxypropyl methyl cellulose are added into ethanol, stirred uniformly, heated to 85℃, continue to stir until the solvent volatilizes, cooled to room temperature, to obtain a composite silicon carbide nanowire; the mass ratio of the modified silicon carbide nanowire, magnesium aluminum spinel powder, hydroxypropyl methyl cellulose and ethanol is 2.6:1.2:0.4:42.

[0073] Comparative Example 1

[0074] A high-transparency anti-fouling full-polishing glaze, comprising the following raw materials in parts by mass: tea crystal feldspar 30 parts, zinc oxide 10 parts, barium carbonate 15 parts, composite silicon carbide nanowire 5 parts, calcined talc 12 parts, kaolin 10 parts, corundum 10 parts, glass clinker 27 parts, zirconium silicate 3 parts.

[0075] A preparation method of a high-transparency anti-fouling full-polishing glaze, comprising the following preparation steps:

[0076] The tea crystal feldspar, zinc oxide, barium carbonate, composite silicon carbide nanowire, calcined talc, kaolin, corundum, glass clinker and zirconium silicate are uniformly mixed and crushed through a 400-mesh sieve to obtain a high-transparency anti-fouling full-polishing glaze.

[0077] A preparation method of a polished glaze brick, comprising the following preparation steps:

[0078] S1. The high-transparency anti-fouling full-polishing glaze, sodium carboxymethyl cellulose, sodium tripolyphosphate and water are mixed and ball milled, the ball milling is carried out in a ball mill, the grinding balls are zirconium balls with a diameter of 10 mm, the ball-to-material ratio is 3:1, and the ball milling time is 22 h to obtain a full-polishing glaze slurry; the mass ratio of the high-transparency anti-fouling full-polishing glaze, sodium carboxymethyl cellulose, sodium tripolyphosphate and water is 75:0.2:0.3:35;

[0079] S2. The full-polishing glaze slurry is controlled to have a glazing specific gravity of 1.6, and the glazing amount can be 550 g / m 2 The full-polishing glaze slurry is applied to the polished glaze brick substrate in a glazing manner, dried at 110℃ for 30 min, fired at 1220℃ for 80 min, and then polished for 5 min using diamond particles with a particle size of 1000 mesh at a polishing pressure of 0.05 MPa to obtain a polished glaze brick.

[0080] The composite silicon carbide nanowire is prepared by the following steps:

[0081] A1. Add zirconium oxychloride octahydrate and silicon carbide nanowires into deionized water, stir uniformly, add ammonia water, glycine and potassium chloride, stir at 85℃ for 10 min, place in a reaction kettle, hydrothermal reaction at 190℃ for 22h, cool to room temperature, filter, deionized water washing 3 times, drying in an oven at 80℃ for 3h, to obtain modified silicon carbide nanowires; the mass ratio of zirconium oxychloride octahydrate, silicon carbide nanowires, deionized water, ammonia water, glycine and potassium chloride is 0.6:1.6:110:2.5:0.5:0.9.

[0082] A2. Add modified silicon carbide nanowires, magnesium aluminum spinel powder and hydroxypropyl methyl cellulose into ethanol, stir uniformly, heat to 85℃, continue to stir until the solvent volatilizes, cool to room temperature, to obtain composite silicon carbide nanowires; the mass ratio of modified silicon carbide nanowires, magnesium aluminum spinel powder, hydroxypropyl methyl cellulose and ethanol is 2.6:1.2:0.4:42.

[0083] Comparative example 2

[0084] A high-transparency anti-fouling full-polishing glaze, comprising the following mass parts of raw materials: tea crystal feldspar 30 parts, zinc oxide 10 parts, barium carbonate 15 parts, composite silicon carbide nanowires 5 parts, calcined talc 12 parts, kaolin 10 parts, corundum 10 parts, glass clinker 27 parts, zirconium silicate 3 parts.

[0085] A preparation method of a high-transparency anti-fouling full-polishing glaze, comprising the following preparation steps:

[0086] Mixing tea crystal feldspar, zinc oxide, barium carbonate, composite silicon carbide nanowires, calcined talc, kaolin, corundum, glass clinker and zirconium silicate uniformly, crushing through a 400 mesh sieve to obtain a high-transparency anti-fouling full-polishing glaze.

[0087] A preparation method of a polishing glaze brick, comprising the following preparation steps:

[0088] S1. Mix high-transparency anti-fouling full-polishing glaze, sodium carboxymethyl cellulose, sodium tripolyphosphate and water for ball milling, the ball milling is carried out in a ball mill, the grinding ball is a zirconium ball with a diameter of 10mm, the ball-to-material ratio is 3:1, and the ball milling time is 22h to obtain a full-polishing glaze slurry; the mass ratio of high-transparency anti-fouling full-polishing glaze, sodium carboxymethyl cellulose, sodium tripolyphosphate and water is 75:0.2:0.3:35;

[0089] S2. Control the glaze spraying specific gravity of the full-polishing glaze slurry to be 1.6, and the glaze spraying amount can be 550g / m 2 The full-polishing glaze slurry is applied to the polishing glaze brick substrate in a glaze spraying manner, dried at 110℃ for 30min, fired at 1220℃ for 80min, and then polished with diamond particles with a particle size of 1000 mesh for 5min at a polishing pressure of 0.05MPa to obtain a polishing glaze brick.

[0090] The composite silicon carbide nanowire is prepared by the following steps:

[0091] A1. The silicon carbide nanowire is added to a nitric acid solution with a concentration of 0.5M and a sulfuric acid solution with a concentration of 0.5M, etched for 1 min, taken out, washed with deionized water until the pH of the washing liquid is neutral, and dried in a 70℃ oven for 10 min to obtain acid-etched silicon carbide nanowire; the mass ratio of silicon carbide nanowire, nitric acid solution and sulfuric acid solution is 6:35:35;

[0092] A2. The acid-etched silicon carbide nanowire, magnesium aluminum spinel powder and hydroxypropyl methyl cellulose are added to ethanol, stirred uniformly, heated to 85℃, and continuously stirred until the solvent volatilizes, and cooled to room temperature to obtain composite silicon carbide nanowire; the mass ratio of acid-etched silicon carbide nanowire, magnesium aluminum spinel powder, hydroxypropyl methyl cellulose and ethanol is 2.6:1.2:0.4:42.

[0093] Comparative Example 3

[0094] A high-transparency anti-fouling full-polishing glaze, comprising the following raw materials in parts by mass: tea crystal feldspar 30 parts, zinc oxide 10 parts, barium carbonate 15 parts, composite nano zirconium oxide 5 parts, calcined talc 12 parts, kaolin 10 parts, corundum 10 parts, glass clinker 27 parts, and zirconium silicate 3 parts.

[0095] A preparation method of a high-transparency anti-fouling full-polishing glaze, comprising the following preparation steps:

[0096] The tea crystal feldspar, zinc oxide, barium carbonate, composite nano zirconium oxide, calcined talc, kaolin, corundum, glass clinker and zirconium silicate are uniformly mixed and crushed through a 400-mesh sieve to obtain the high-transparency anti-fouling full-polishing glaze.

[0097] A preparation method of a polishing glaze brick, comprising the following preparation steps:

[0098] S1. The high-transparency anti-fouling full-polishing glaze, sodium carboxymethyl cellulose, sodium tripolyphosphate and water are mixed and ball milled, the ball milling is performed in a ball mill, the grinding balls are zirconium balls with a diameter of 10 mm, the ball-to-material ratio is 3:1, and the ball milling time is 22 h to obtain a full-polishing glaze slurry; the mass ratio of the high-transparency anti-fouling full-polishing glaze, sodium carboxymethyl cellulose, sodium tripolyphosphate and water is 75:0.2:0.3:35;

[0099] S2. The full-polishing glaze slurry is controlled to have a glazing specific gravity of 1.6, and the glazing amount can be 550 g / m 2 The full-polishing glaze slurry is applied to the polishing glaze brick substrate in a glazing manner, dried at 110℃ for 30 min, fired at 1220℃ for 80 min, polished with diamond particles with a particle size of 1000 mesh for 5 min at a polishing pressure of 0.05 MPa to obtain the polishing glaze brick.

[0100] The composite nano zirconium oxide is prepared by the following steps:

[0101] A1. Add zirconium oxychloride octahydrate into deionized water, stir uniformly, add ammonia water, glycine and potassium chloride, stir at 85°C for 10 min, place in a reaction kettle, conduct hydrothermal reaction at 190°C for 22h, cool to room temperature, filter, wash with deionized water for 3 times, dry in an oven at 80°C for 3h, to obtain nano zirconium oxide; the mass ratio of zirconium oxychloride octahydrate, acid-etched silicon carbide nanowire, deionized water, ammonia water, glycine and potassium chloride is 0.6:1.6:110:2.5:0.5:0.9.

[0102] A2. Add nano zirconium oxide, magnesium aluminate spinel powder and hydroxypropyl methyl cellulose into ethanol, stir uniformly, heat to 85°C, continue to stir until the solvent volatilizes, cool to room temperature, to obtain composite nano zirconium oxide; the mass ratio of nano zirconium oxide, magnesium aluminate spinel powder, hydroxypropyl methyl cellulose and ethanol is 2.6:1.2:0.4:42.

[0103] Comparative example 4

[0104] A high-transparency anti-fouling full-polishing glaze, comprising the following raw materials in parts by mass: tea crystal feldspar 30 parts, zinc oxide 10 parts, barium carbonate 15 parts, composite silicon carbide nanowire 5 parts, calcined talc 12 parts, kaolin 10 parts, corundum 10 parts, glass frit 27 parts, zirconium silicate 3 parts.

[0105] A preparation method of a high-transparency anti-fouling full-polishing glaze, comprising the following preparation steps:

[0106] Mixing tea crystal feldspar, zinc oxide, barium carbonate, composite silicon carbide nanowire, calcined talc, kaolin, corundum, glass frit and zirconium silicate uniformly, crushing through a 400-mesh sieve, to obtain a high-transparency anti-fouling full-polishing glaze.

[0107] A preparation method of a polishing glaze brick, comprising the following preparation steps:

[0108] S1. Mix high-transparency anti-fouling full-polishing glaze, sodium carboxymethyl cellulose, sodium tripolyphosphate and water for ball milling, the ball milling is carried out in a ball mill, the grinding ball is a zirconium ball with a diameter of 10mm, the ball-to-material ratio is 3:1, and the ball milling time is 22h, to obtain a full-polishing glaze slurry; the mass ratio of high-transparency anti-fouling full-polishing glaze, sodium carboxymethyl cellulose, sodium tripolyphosphate and water is 75:0.2:0.3:35;

[0109] S2. Control the glaze spraying specific gravity of the full-polishing glaze slurry to be 1.6, and the glaze spraying amount can be 550g / m 2The full polishing glaze paste is applied to the polishing glaze brick body by glazing, dried at 110 DEG C for 30 min, fired at 1220 DEG C for 80 min, polished by diamond particles with a particle size of 1000 mesh for 5 min under a polishing pressure of 0.05 MPa, and the full polishing glaze brick is obtained.

[0110] The composite silicon carbide nanowire is prepared by the following steps:

[0111] A1. The silicon carbide nanowire is added into a nitric acid solution with a concentration of 0.5 M and a sulfuric acid solution with a concentration of 0.5 M, etched for 1 min, taken out, washed with deionized water until the pH of the washing liquid is neutral, and dried in a 70 DEG C oven for 10 min to obtain the acid-etched silicon carbide nanowire; the mass ratio of the silicon carbide nanowire, the nitric acid solution and the sulfuric acid solution is 6:35:35;

[0112] A2. The acid-etched silicon carbide nanowire and zirconium oxychloride octahydrate are added into deionized water, stirred uniformly, and then ammonia water, glycine and potassium chloride are added, stirred at 85 DEG C for 10 min, placed in a reaction kettle, and subjected to hydrothermal reaction at 190 DEG C for 22 h, cooled to room temperature, filtered, washed with deionized water for 3 times, and dried in an 80 DEG C oven for 3 h to obtain the modified silicon carbide nanowire; the mass ratio of the zirconium oxychloride octahydrate, the acid-etched silicon carbide nanowire, the deionized water, the ammonia water, the glycine and the potassium chloride is 0.6:1.6:110:2.5:0.5:0.9.

[0113] A3. The modified silicon carbide nanowire and magnesium aluminate spinel powder are added into ethanol, stirred uniformly, heated to 85 DEG C, and continuously stirred until the solvent is volatilized, and then cooled to room temperature to obtain the composite silicon carbide nanowire; the mass ratio of the modified silicon carbide nanowire, the magnesium aluminate spinel powder and the ethanol is 2.6:1.2:42.

[0114] Comparative Example 5

[0115] A high-transparency and stain-resistant full polishing glaze comprises the following raw materials in parts by mass: tea crystal feldspar 30 parts, zinc oxide 10 parts, barium carbonate 15 parts, composite silicon carbide nanowire 5 parts, calcined talc 12 parts, kaolin 10 parts, corundum 10 parts, glass clinker 27 parts, and zirconium silicate 3 parts.

[0116] A preparation method of a high-transparency and stain-resistant full polishing glaze comprises the following preparation steps:

[0117] The tea crystal feldspar, the zinc oxide, the barium carbonate, the composite silicon carbide nanowire, the calcined talc, the kaolin, the corundum, the glass clinker and the zirconium silicate are uniformly mixed, and then crushed through a 400-mesh sieve to obtain the high-transparency and stain-resistant full polishing glaze.

[0118] A preparation method of a polishing glaze brick comprises the following preparation steps:

[0119] S1. Mix high-transparency anti-fouling full polishing glaze, sodium carboxymethyl cellulose, sodium tripolyphosphate and water to perform ball milling, the ball milling is performed in a ball mill, the grinding balls are zirconium balls with a diameter of 10 mm, the ball-to-material ratio is 3:1, and the ball milling time is 22 h to obtain a full polishing glaze slurry; the mass ratio of high-transparency anti-fouling full polishing glaze, sodium carboxymethyl cellulose, sodium tripolyphosphate and water is 75:0.2:0.3:35;

[0120] S2. The glazing ratio of the full polishing glaze slurry is controlled to be 1.6, and the glazing amount can be 550 g / m 2 The full polishing glaze slurry is applied to the polishing glaze brick substrate in a glazing manner, dried at 110℃ for 30 min, fired at 1220℃ for 80 min, and then polished for 5 min using diamond particles with a particle size of 1000 mesh at a polishing pressure of 0.05 MPa to obtain a polishing glaze brick.

[0121] The composite silicon carbide nanowire is prepared by the following steps:

[0122] A1. The silicon carbide nanowire is added to a 0.5M nitric acid solution and a 0.5M sulfuric acid solution, etched for 1 min, then taken out, washed with deionized water until the pH of the washing liquid is neutral, and dried in a 70℃ oven for 10 min to obtain acid-etched silicon carbide nanowire; the mass ratio of silicon carbide nanowire, nitric acid solution and sulfuric acid solution is 6:35:35;

[0123] A2. Zirconium oxychloride octahydrate and acid-etched silicon carbide nanowire are added to deionized water, stirred uniformly, and then ammonia water, glycine and potassium chloride are added, stirred at 85℃ for 10 min, placed in a reaction kettle, and subjected to hydrothermal reaction at 190℃ for 22 h, cooled to room temperature, filtered, washed with deionized water for 3 times, and dried in an 80℃ oven for 3 h to obtain modified silicon carbide nanowire; the mass ratio of zirconium oxychloride octahydrate, acid-etched silicon carbide nanowire, deionized water, ammonia water, glycine and potassium chloride is 0.6:1.6:110:2.5:0.5:0.9.

[0124] A3. The modified silicon carbide nanowire and hydroxypropyl methyl cellulose are added to ethanol, stirred uniformly, heated to 85℃, and then continuously stirred until the solvent evaporates, and cooled to room temperature to obtain composite silicon carbide nanowire; the mass ratio of modified silicon carbide nanowire, hydroxypropyl methyl cellulose and ethanol is 2.6:0.4:42.

[0125] The performance of the polishing glaze bricks prepared from the high-transparency anti-fouling full polishing glaze provided in Examples 1-3 and Comparative Examples 1-5 is detected.

[0126] Vickers hardness detection: diamond with a right tetrahedral pyramid and an included angle of 136 degrees is used as a pressure head, the load is 1000g, and the load time is 30s, and the Vickers hardness of the above-prepared polishing glaze bricks is tested.

[0127] Stain resistance test: The prepared polished glazed tiles were tested for stain resistance according to the GB / T3810.14-2016 standard.

[0128] Gloss test: The gloss of the prepared polished glazed tiles was tested according to the GB / T13891.14-2008 standard.

[0129] Wear resistance test: The wear resistance (g / 12000 turns) of the prepared polished glazed tiles was tested according to the GB / T3810.7-2016 standard.

[0130] As shown in Table 1.

[0131] Table 1 Performance test of the polished glazed tiles prepared from the high-transparency stain-resistant full polishing glaze of Examples 1-3 and Comparative Examples 1-5

[0132] Item Vickers Hardness / HV Stain Resistance Rating / Grade Gloss / ° Wear Loss (g / 12000 Rev) Example 1 586.3 5 97.6 0.07 Example 2 587.8 5 97.9 0.06 Example 3 585.7 5 97.2 0.07 Comparative Example 1 523.6 4 92.5 0.11 Comparative Example 2 513.9 3 90.1 0.15 Comparative Example 3 511.4 3 89.6 0.18 Comparative Example 4 505.1 3 89.7 0.17 Comparative Example 5 486.5 3 85.1 0.14

[0133] As can be seen from the data in Table 1, the polished glazed tiles prepared from the high-transparency stain-resistant full polishing glaze provided in Examples 1-3 have good stain resistance, gloss, and mechanical properties.

[0134] In Comparative Example 1, the acid-etched silicon carbide nanowires were replaced by the composite silicon carbide nanowires prepared from silicon carbide nanowires to prepare the full polishing glaze, and the stain resistance, mechanical properties, and gloss of the polished glazed tiles prepared therefrom were reduced, proving that the acid etching of the silicon carbide nanowires is beneficial to the synthesis of a large amount of nano-zirconium oxide on the surface of the silicon carbide nanowires, thereby inhibiting the grain growth and improving the density of the full polishing glaze layer. The dense glaze layer structure can reduce the adhesion of stains and bacteria, thereby improving the stain resistance and gloss of the polished glazed tiles.

[0135] In Comparative Example 2, the modified silicon carbide nanowires were replaced by the composite silicon carbide nanowires prepared from acid-etched silicon carbide nanowires to prepare the full polishing glaze, and the stain resistance, mechanical properties, and gloss of the polished glazed tiles prepared therefrom were reduced, proving that the synthesis of nano-zirconium oxide on the surface of the acid-etched silicon carbide nanowires pinning the grain boundaries, inhibits the grain growth, improves the density of the full polishing glaze layer, and fills the gaps in the full polishing glaze layer, significantly improving the scratch resistance of the glaze layer and reducing the wear during daily use. In addition, the composite silicon carbide nanowires have excellent thermal stability, which can relieve the thermal stress of the glaze layer during temperature changes.

[0136] In Comparative Example 3, the composite nano-zirconium oxide prepared from the acid-etched silicon carbide nanowires was not added to the full polishing glaze, and the stain resistance, mechanical properties, and gloss of the polished glazed tiles prepared therefrom were reduced, proving that the silicon carbide nanowires have an excellent aspect ratio and form a network skeleton in the full polishing glaze layer. In addition, the silicon carbide nanowires can significantly improve the scratch resistance of the glaze layer and reduce the wear during daily use.

[0137] The composite silicon carbide nanowires prepared without adding magnesium aluminate spinel powder to hydroxypropyl methyl cellulose are added to the full polishing glaze, and the prepared polishing glaze tiles have poor stain resistance, mechanical properties and gloss, which proves that the magnesium aluminate spinel powder can provide more alumina components, the alumina components can form four-coordination by taking free oxygen in the full polishing glaze, and enter the silicon-oxygen network structure of the full polishing glaze, which helps the formation of the glaze layer network structure, improves the chemical stability, hardness and elasticity, and can avoid the large difference between the expansion coefficient of the glaze layer and the ceramic tile body, the large internal stress of the glaze layer, the deformation of the glaze layer during firing, and the improvement of the stain resistance, gloss and mechanical properties of the glaze layer.

[0138] The composite silicon carbide nanowires prepared without adding magnesium aluminate spinel powder to hydroxypropyl methyl cellulose are added to the full polishing glaze, and the prepared polishing glaze tiles have poor stain resistance, mechanical properties and gloss, which proves that the magnesium aluminate spinel powder can provide more alumina components, the alumina components can form four-coordination by taking free oxygen in the full polishing glaze, and enter the silicon-oxygen network structure of the full polishing glaze, which helps the formation of the glaze layer network structure, improves the chemical stability, hardness and elasticity, and can avoid the large difference between the expansion coefficient of the glaze layer and the ceramic tile body, the large internal stress of the glaze layer, the deformation of the glaze layer during firing, and the improvement of the stain resistance, gloss and mechanical properties of the glaze layer.

[0139] In the description of the specification, the description of the terms "one embodiment", "example", "specific example" and the like means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are contained in at least one embodiment or example of the present application. In the specification, the illustrative description of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0140] The above is only an example and description of the present application, and those skilled in the art can make various modifications or supplements to the described specific embodiments or use similar ways to replace, as long as they do not deviate from the invention or exceed the scope defined by the present claims, which shall belong to the protection scope of the present application.

Claims

1. A high-transparency, stain-resistant, fully polished glaze, characterized in that, The raw materials include the following parts by weight: 25-30 parts of smoky feldspar, 5-10 parts of zinc oxide, 10-15 parts of barium carbonate, 2-5 parts of composite silicon carbide nanowires, 8-12 parts of calcined talc, 8-10 parts of kaolin, 8-10 parts of corundum, 23-27 parts of glass frit, and 1-3 parts of zirconium silicate. The composite silicon carbide nanowires are specifically prepared by the following steps: A1. Add silicon carbide nanowires to nitric acid solution and sulfuric acid solution, etch them, remove them, wash them, and dry them to obtain acid-etched silicon carbide nanowires; A2. Zirconium oxychloride octahydrate and acid-etched silicon carbide nanowires were added to deionized water and stirred until homogeneous. Ammonia, glycine and potassium chloride were added and stirred until the reaction was complete. The mixture was then subjected to a hydrothermal reaction at 170-190℃ for 20-22 hours. After cooling to room temperature, the mixture was filtered, washed and dried to obtain modified silicon carbide nanowires. A3. Add modified silicon carbide nanowires, magnesium aluminum spinel powder and hydroxypropyl methylcellulose to ethanol, stir evenly, heat to 80-90℃, continue stirring until the solvent evaporates, cool to room temperature, and obtain composite silicon carbide nanowires.

2. The high-transparency, stain-resistant, fully polished glaze according to claim 1, characterized in that, In step A1, the mass ratio of the silicon carbide nanowires, nitric acid solution, and sulfuric acid solution is (5-6):(25-35):(25-35).

3. The high-transparency, stain-resistant, fully polished glaze according to claim 1, characterized in that, In step A2, the mass ratio of zirconium oxychloride octahydrate, acid-etched silicon carbide nanowires, deionized water, ammonia, glycine, and potassium chloride is (0.4-0.6):(1.4-1.6):(90-110):(1.5-2.5):(0.3-0.5):(0.7-0.9).

4. The high-transparency, stain-resistant, fully polished glaze according to claim 1, characterized in that, In step A3, the mass ratio of the modified silicon carbide nanowires, magnesium aluminum spinel powder, hydroxypropyl methylcellulose and ethanol is (2.4-2.6):(1-1.2):(0.2-0.4):(38-42).

5. A method for preparing a high-transparency, stain-resistant, fully polished glaze as described in any one of claims 1-4, characterized in that, The preparation steps include the following: The smoky feldspar, zinc oxide, barium carbonate, composite silicon carbide nanowires, calcined talc, kaolin, corundum, glass frit, and zirconium silicate are mixed evenly and then pulverized through a 350-400 mesh sieve to obtain a high-transparency, stain-resistant, fully polished glaze.

6. A method for preparing glazed tiles, characterized in that, The high-transparency, stain-resistant, fully polished glaze according to any one of claims 1-4 is prepared by the following steps: S1. High-transparency, stain-resistant full-polished glaze, sodium carboxymethyl cellulose, sodium tripolyphosphate and water are mixed and ball-milled to obtain full-polished glaze slurry; S2. Apply the full-glaze slurry to the glazed tile substrate by glazing, and then dry, fire and polish to obtain the glazed tile.

7. The method for preparing a glazed tile according to claim 6, characterized in that, In step S1, the mass ratio of the high-permeability, anti-fouling polished glaze, sodium carboxymethyl cellulose, sodium tripolyphosphate, and water is (70-75):(0.1-0.2):(0.2-0.3):(30-35).

8. The method for preparing a glazed tile according to claim 6, characterized in that, In step S2, the specific gravity of the glaze is 1.5-1.6, and the amount of glaze applied is 500-550 g / m³. 2 .

9. The method for preparing a glazed tile according to claim 6, characterized in that, In step S2, the drying temperature is 80-110℃ and the drying time is 20-30 minutes. The firing temperature is 1200-1220℃, and the firing time is 60-80 minutes; The polishing is performed using diamond particles with a particle size of 800-1000 mesh, a polishing time of 4-6 minutes, and a polishing pressure of 0.03-0.1 MPa.