Antifouling and easy-to-clean glazed material and application thereof

Abstract

The application discloses an antifouling and easy-to-clean glaze material and application. The antifouling and easy-to-clean glaze material comprises the following raw materials: 10-30 parts of sodium feldspar, 20-40 parts of potassium feldspar, 5-15 parts of washed soil, 1-5 parts of calcite, 5-15 parts of talc, 5-15 parts of dolomite, 1-10 parts of zinc oxide, 1-10 parts of clinker, 1-5 parts of aluminum oxide, 1-5 parts of quartz, 1-3 parts of strontium titanate, 0.1-1 part of an additive and 1-5 parts of modified graphene oxide. Compared with the prior art, the antifouling and easy-to-clean glaze material prepared by the application has the advantages of smooth surface, low roughness, easy cleaning, good wear resistance and the like.

Description

Technical Field

[0001] The present invention relates to the technical field of ceramic glazes, and in particular to an anti-fouling and easy-to-clean glaze material and its application. Background Art

[0002] Ceramic glaze is a liquid or slurry applied to ceramic surfaces. Its primary components are oxides and glass. During the firing process, it forms a hard, glossy coating, protecting the surface and enhancing its decorative effect and aesthetic appeal. Ceramic glazes come in a variety of types, including colorless and transparent glazes and colored glazes, and are widely used in tableware, kitchenware, and decorative items.

[0003] In recent years, with the development of science and technology and the improvement of health awareness, the use of places has become more and more extensive. Some require beauty, some require fineness, and some require high strength wear resistance and easy cleaning. However, the existing glazed tiles have poor easy-cleaning functionality, are difficult to clean, and are not very convenient to maintain. At the same time, they have poor wear resistance and a short life span due to easy wear. It is difficult to achieve a coordinated improvement in the ease of cleaning and wear resistance of the product, which further limits the product's use efficiency. Therefore, it is very necessary to provide an anti-fouling and easy-to-clean glaze material that is easy to clean and has good wear resistance.

[0004] CN116573859A discloses an antifouling protective glaze and a preparation method thereof, which improves the antifouling performance by: potassium feldspar, sodium feldspar, calcined talc, calcined soil, washed soil, zinc oxide, high-barium frit, high-calcium frit and calcined alumina. However, this invention mainly forms the glaze by material ratio, and the porosity that can be reduced is limited, and the antifouling effect may be improved to a low level. CN116023031A discloses a wear-resistant glazed tile glaze and a preparation method thereof, glazed tiles and their preparation method, comprising a raw material composition, a first frit and a second frit; the raw material composition comprises kaolin, calcined kaolin, quartz, dolomite, calcined talc, nepheline, zinc oxide, strontium carbonate and barium sulfate; and improves the wear resistance. However, this invention has the problems of low flatness and low antifouling performance. Summary of the Invention

[0005] In view of the above-mentioned defects of the prior art, the anti-fouling and easy-to-clean glaze material prepared by the present invention has the advantages of smooth surface, low roughness, easy cleaning and good wear resistance.

[0006] To achieve the above object, the present invention provides an anti-fouling and easy-to-clean glaze material, characterized in that it comprises the following raw material components, calculated by mass: 10-30 parts of albite, 20-40 parts of potassium feldspar, 5-15 parts of water-washed soil, 1-5 parts of calcite, 5-15 parts of talc, 5-15 parts of dolomite, 1-10 parts of zinc oxide, 1-10 parts of frit, 1-5 parts of aluminum oxide, and 1-5 parts of quartz;

[0007] Or, 10-30 parts of albite, 20-40 parts of potassium feldspar, 5-15 parts of water-washed soil, 1-5 parts of calcite, 5-15 parts of talc, 5-15 parts of dolomite, 1-10 parts of zinc oxide, 1-10 parts of frit, 1-5 parts of aluminum oxide, 1-5 parts of quartz, 1-3 parts of strontium titanate, 0.1-1 parts of additives, and 1-5 parts of modified graphene oxide;

[0008] The additive is selected from at least one of lanthanum oxide microspheres, silica microspheres, and hollow glass microspheres;

[0009] The modified graphene oxide is silicon dioxide-modified graphene oxide.

[0010] Preferably, the preparation method of the lanthanum oxide microspheres comprises the following steps, calculated by mass:

[0011] 0.1-1 parts of lanthanum nitrate, 0.01-0.1 parts of iridium nitrate, 1-3 parts of urea and 20-30 parts of water are mixed uniformly, and then 0.1-0.5 parts of melamine formaldehyde microspheres are added, and the mixture is stirred and mixed uniformly, followed by ultrasonic treatment to obtain a solution a; the solution a is reacted at 80-90°C and 700-1000 rpm for 2-4 hours; after cooling to room temperature, the precipitate is collected after centrifugation, washed, and dried to obtain a solid a; the solid a is heated to 800°C at a heating rate of 2°C / min and calcined at 800°C for 1-3 hours to obtain lanthanum oxide microspheres.

[0012] More preferably, the ultrasonic condition is 30-50 KHz for 20-40 min.

[0013] As a further illustration of the present invention, urea, a precipitant, reacts with lanthanum nitrate and iridium nitrate solutions to form a precursor. Melamine formaldehyde microspheres serve as a hard template to form a core-shell structure. The melamine formaldehyde microspheres decompose and volatilize during high-temperature calcination, leaving behind a porous microsphere structure. This improves the mechanical strength, wear resistance, and temperature resistance of the glaze material. The porous microsphere structure also exhibits excellent formaldehyde absorption.

[0014] Preferably, the preparation method of the modified graphene oxide comprises the following steps, calculated in parts by mass:

[0015] Step 1: Evenly mix 5-15 parts of nano-silica with 50-150 parts of a 70-80% ethanol aqueous solution, and then ultrasonically treat to obtain a mixed solution 1; evenly mix 1-5 parts of γ-aminopropyltriethoxysilane and 40-60 parts of anhydrous ethanol, add 5-15wt% acetic acid aqueous solution to adjust the pH to 3-4, and then stir and mix to obtain a mixed solution 2; add the mixed solution 2 to the mixed solution 1, and react at 70-90°C and 800-1000 rpm for 3-5 hours; after cooling to room temperature, centrifuge and collect the precipitate, wash, and dry to obtain modified silica;

[0016] Step 2: 5-15 parts of the modified silicon dioxide obtained in step 1 and 150-250 parts of N,N-dimethylacetamide are mixed uniformly, followed by ultrasonic treatment; 20-40 parts of graphene oxide are added, followed by ultrasonic treatment to obtain a mixed solution 3; the mixed solution 3 is reacted at 70-90° C. and 800-1000 rpm for 3-5 hours; the reaction is continued at 100-110° C. and 800-1000 rpm for 3-5 hours; after cooling to room temperature, the precipitate is collected by centrifugation, washed, and dried to obtain modified graphene oxide.

[0017] As a further illustration of the present invention, nano-SiO2 is modified using γ-aminopropyltriethoxysilane. In an N,N-dimethylacetamide solvent, the modified nano-SiO2 surface becomes positively charged, while the surface carboxyl groups of graphene oxide become negatively charged after ionization. This generates electrostatic attraction between the two, causing the nano-SiO2 to adsorb on the surface of the graphene oxide, filling the gaps between the graphene oxide sheets and forming a denser protective layer. Furthermore, the steric hindrance effect of the nano-SiO2 can improve the dispersion of graphene oxide in the glaze material. Under high-temperature firing conditions, the graphene oxide can also induce silicon dioxide to form a dense layer. This helps improve the mechanical strength, wear resistance, and temperature resistance of the glaze material.

[0018] Preferably, the chemical composition of the frit is: 49-52% SiO2, 15-18% Al2O3, 3.5-4% K2O, 2.5-3% Na2O, 8-9.5% CaO, 5-6% MgO, 4.5-5.5% ZnO, 0.3-0.5% B2O3, and the rest are unavoidable impurities.

[0019] The present invention also provides a method for preparing an antifouling and easy-to-clean glaze material, which is characterized by comprising the following steps:

[0020] Mixing sodium feldspar, potassium feldspar, washed soil, calcite, talc, dolomite, zinc oxide, frit, aluminum oxide, and quartz evenly, adding the mixture to a ball mill, performing a first ball milling, sieving, then adding water to adjust the slurry density, and performing a second ball milling to obtain an antifouling and easy-to-clean glaze material;

[0021] Alternatively, sodium feldspar, potassium feldspar, washed soil, calcite, talc, dolomite, zinc oxide, frit, aluminum oxide, quartz, strontium titanate, additives, and modified graphene oxide are uniformly mixed and added to a ball mill, ball-milled once, sieved, and then water is added to adjust the slurry density, and ball-milled a second time to obtain an anti-fouling and easy-to-clean glaze material.

[0022] Preferably, the first ball milling is performed at a ball milling speed of 150-250 rpm for 3-5 hours.

[0023] Preferably, the sieving is through a 300-400 mesh sieve.

[0024] Preferably, the slurry specific gravity is adjusted to 1.2-1.6 using water.

[0025] Preferably, the secondary ball milling is performed at a ball milling speed of 250-350 rpm for 25-30 h.

[0026] Beneficial effects of the present invention:

[0027] 1. Compared with existing technologies, the present invention utilizes the interactions between various substances in a reasonable proportion and optimizes the preparation process to produce a stain-resistant and easy-to-clean glaze material. After high-temperature calcination, the stain-resistant and easy-to-clean glaze material produced by the present invention forms a ceramic material with high oil resistance, excellent thermal shock resistance, and excellent wear resistance.

[0028] 2. Compared with the existing technology, the present invention adds lanthanum oxide microspheres, which is beneficial to improving the mechanical strength, wear resistance and temperature resistance of the glaze material; the porous microsphere structure formed has good formaldehyde absorption performance; modified graphene oxide is beneficial to improving the mechanical strength, wear resistance and temperature resistance of the glaze material. DETAILED DESCRIPTION

[0029] Parameters for specific chemical substances used, sources.

[0030] Graphene oxide: diameter: 0.5-10 μm, oxygen content: 35wt%;

[0031] Hollow glass microspheres, model: HL38, true density (g / cm³): 0.38, D50 (μm): 40, D90 (μm): 65, compressive strength: 5500 psi, floatation rate: ≥95%, moisture content: ≤3%, sourced from Zhengzhou Shenglait Hollow Microsphere New Materials Co., Ltd.

[0032] Silica microspheres: Product number: EMS-015-5, particle size: 150 nm, from Nanjing Caina Technology Co., Ltd.

[0033] Nano-silica: Model: TSP-H10T, Particle size: 20nm, Specific surface area: 200g / m 2 , from Jiangsu Tianxing New Materials Co., Ltd.;

[0034] Melamine formaldehyde microspheres: Name: UniMF melamine formaldehyde microspheres, state: dry powder, average particle size 6μm, sourced from Wuhan Huake Micro-Technology Co., Ltd.

[0035] Frit, commercially available; chemical composition is 50% SiO2, 17% Al2O3, 3.8% K2O, 2.8% Na2O, 9.2% CaO, 5.5% MgO, 5% ZnO, 0.4% B2O3, and the rest are inevitable impurities.

[0036] Example 1

[0037] A method for preparing an anti-fouling and easy-to-clean glaze material comprises the following steps, calculated by mass: 20 parts of albite, 30 parts of potassium feldspar, 10 parts of water-washed soil, 3 parts of calcite, 10 parts of talc, 12 parts of dolomite, 5 parts of zinc oxide, 5 parts of frit, 2 parts of aluminum oxide, and 3 parts of quartz are uniformly mixed, and the mixture is added into a ball mill, ball milled once at a ball mill speed of 200 rpm for 4 hours, passed through a 400-mesh sieve, and then water is added to adjust the slurry specific gravity to 1.4, and ball milled twice at a ball mill speed of 300 rpm for 28 hours to obtain the anti-fouling and easy-to-clean glaze material.

[0038] Example 2

[0039] A method for preparing an anti-fouling and easy-to-clean glaze material comprises the following steps, calculated by mass: 20 parts of albite, 30 parts of potassium feldspar, 10 parts of water-washed soil, 3 parts of calcite, 10 parts of talc, 12 parts of dolomite, 5 parts of zinc oxide, 5 parts of frit, 2 parts of aluminum oxide, 3 parts of quartz, 2 parts of strontium titanate, 0.5 parts of hollow glass microspheres, and 3 parts of modified graphene oxide are uniformly mixed, and then added into a ball mill, subjected to a primary ball milling at a ball milling speed of 200 rpm for 4 hours, passed through a 400-mesh sieve, and then water is added to adjust the slurry specific gravity to 1.4, and subjected to a secondary ball milling at a ball milling speed of 300 rpm for 28 hours to obtain the anti-fouling and easy-to-clean glaze material.

[0040] The preparation method of the modified graphene oxide comprises the following steps, calculated by mass:

[0041] Step 1: 10 parts of nano-silica were mixed with 100 parts of 75% ethanol aqueous solution, and ultrasonicated at 40KHz for 60 minutes to obtain a mixed solution 1; 3 parts of γ-aminopropyltriethoxysilane and 50 parts of anhydrous ethanol were mixed, 10wt% acetic acid aqueous solution was added to adjust the pH to 3, and then stirred at 800rpm for 60 minutes to obtain a mixed solution 2; the mixed solution 2 was added to the mixed solution 1, and the mixture was reacted at 80°C and 900rpm for 4 hours. After cooling to room temperature, the mixture was centrifuged at 3000rpm for 10 minutes, and the precipitate was collected. The precipitate was washed with anhydrous ethanol 4 times and dried at 50°C for 5 hours to obtain modified silica;

[0042] Step 2: After mixing 10 parts of the modified silica obtained in step 1 and 200 parts of N,N-dimethylacetamide, 30 parts of graphene oxide were added after ultrasonication at 40 kHz for 30 min, followed by ultrasonication at 40 kHz for 30 min to obtain a mixed solution 3. The mixed solution 3 was reacted at 80°C and 900 rpm for 4 h, and then at 105°C and 900 rpm for 4 h. After cooling to room temperature, the mixture was centrifuged at 3000 rpm for 10 min, and the precipitate was collected. The precipitate was washed four times with anhydrous ethanol and dried at 50°C for 5 h to obtain modified graphene oxide.

[0043] Example 3

[0044] A method for preparing an anti-fouling and easy-to-clean glaze material comprises the following steps, calculated by mass: 20 parts of albite, 30 parts of potassium feldspar, 10 parts of water-washed soil, 3 parts of calcite, 10 parts of talc, 12 parts of dolomite, 5 parts of zinc oxide, 5 parts of frit, 2 parts of aluminum oxide, 3 parts of quartz, 2 parts of strontium titanate, 0.5 part of silicon dioxide microspheres, and 3 parts of modified graphene oxide are uniformly mixed, and then added into a ball mill, subjected to a primary ball milling at a ball milling speed of 200 rpm for 4 hours, passed through a 400-mesh sieve, and then water is added to adjust the slurry specific gravity to 1.4, and subjected to a secondary ball milling at a ball milling speed of 300 rpm for 28 hours to obtain the anti-fouling and easy-to-clean glaze material.

[0045] The preparation method of the modified graphene oxide is consistent with that of Example 2.

[0046] Example 4

[0047] A method for preparing an anti-fouling and easy-to-clean glaze material comprises the following steps, calculated by mass: 20 parts of albite, 30 parts of potassium feldspar, 10 parts of water-washed soil, 3 parts of calcite, 10 parts of talc, 12 parts of dolomite, 5 parts of zinc oxide, 5 parts of frit, 2 parts of aluminum oxide, 3 parts of quartz, 2 parts of strontium titanate, 0.5 parts of lanthanum oxide microspheres, and 3 parts of modified graphene oxide are uniformly mixed, and then added into a ball mill, subjected to a primary ball milling at a ball milling speed of 200 rpm for 4 hours, passed through a 400-mesh sieve, and then water is added to adjust the slurry specific gravity to 1.4, and subjected to a secondary ball milling at a ball milling speed of 300 rpm for 28 hours to obtain the anti-fouling and easy-to-clean glaze material.

[0048] The preparation method of the modified graphene oxide is consistent with that of Example 2.

[0049] The preparation method of the lanthanum oxide microspheres comprises the following steps, calculated by weight:

[0050] 0.5 parts of lanthanum nitrate, 0.05 parts of iridium nitrate, 2 parts of urea and 25 parts of water were mixed evenly, and then 0.3 parts of melamine formaldehyde microspheres were added, stirred at 800 rpm for 30 minutes, and ultrasonicated at 40 kHz for 30 minutes to obtain solution a. Solution a was reacted at 85°C and 800 rpm for 3 hours. After cooling to room temperature, it was centrifuged at 3000 rpm for 10 minutes, and the precipitate was collected. The precipitate was washed four times with anhydrous ethanol and dried at 50°C for 5 hours to obtain solid a. Solid a was heated to 800°C at a heating rate of 2°C / min and calcined at 800°C for 2 hours to obtain lanthanum oxide microspheres.

[0051] Comparative Example 1

[0052] A method for preparing an anti-fouling and easy-to-clean glaze material comprises the following steps, calculated by mass: 20 parts of albite, 30 parts of potassium feldspar, 10 parts of water-washed soil, 3 parts of calcite, 10 parts of talc, 12 parts of dolomite, 5 parts of zinc oxide, 5 parts of frit, 2 parts of aluminum oxide, 3 parts of quartz, 2 parts of strontium titanate, 0.5 parts of lanthanum oxide microspheres, and 3 parts of modified graphene oxide are uniformly mixed, and then added into a ball mill, subjected to a primary ball milling at a ball milling speed of 200 rpm for 4 hours, passed through a 400-mesh sieve, and then water is added to adjust the slurry specific gravity to 1.4, and subjected to a secondary ball milling at a ball milling speed of 300 rpm for 28 hours to obtain the anti-fouling and easy-to-clean glaze material.

[0053] The preparation method of the modified graphene oxide is consistent with that of Example 2.

[0054] The preparation method of the lanthanum oxide microspheres comprises the following steps, calculated by weight:

[0055] 0.5 parts of lanthanum nitrate, 2 parts of urea and 25 parts of water were mixed evenly, and then 0.3 parts of melamine formaldehyde microspheres were added, stirred at 800 rpm for 30 minutes, and ultrasonicated at 40 kHz for 30 minutes to obtain solution a. Solution a was reacted at 85°C and 800 rpm for 3 hours. After cooling to room temperature, it was centrifuged at 3000 rpm for 10 minutes, and the precipitate was collected. The precipitate was washed four times with anhydrous ethanol and dried at 50°C for 5 hours to obtain solid a. Solid a was calcined at 800°C for 2 hours at a heating rate of 2°C / min to obtain lanthanum oxide microspheres.

[0056] Comparative Example 2

[0057] A method for preparing an anti-fouling and easy-to-clean glaze material comprises the following steps, calculated by mass: uniformly mixing 20 parts of albite, 30 parts of potassium feldspar, 10 parts of water-washed soil, 3 parts of calcite, 10 parts of talc, 12 parts of dolomite, 5 parts of zinc oxide, 5 parts of frit, 2 parts of aluminum oxide, 3 parts of quartz, 2 parts of strontium titanate, 0.5 part of lanthanum oxide, and 3 parts of modified graphene oxide; adding the mixture to a ball mill; performing a primary ball milling at a ball milling speed of 200 rpm for 4 hours; passing the mixture through a 400-mesh sieve; then adding water to adjust the slurry specific gravity to 1.4; and performing a secondary ball milling at a ball milling speed of 300 rpm for 28 hours to obtain the anti-fouling and easy-to-clean glaze material.

[0058] The preparation method of the modified graphene oxide is consistent with that of Example 2.

[0059] The preparation method of lanthanum oxide comprises the following steps, calculated by mass:

[0060] 0.5 parts of lanthanum nitrate, 2 parts of urea and 25 parts of water were mixed evenly, stirred at 800 rpm for 30 minutes, and ultrasonicated at 40 kHz for 30 minutes to obtain solution a. Solution a was reacted at 85°C and 800 rpm for 3 hours. After cooling to room temperature, it was centrifuged at 3000 rpm for 10 minutes, and the precipitate was collected. The precipitate was washed four times with anhydrous ethanol and dried at 50°C for 5 hours to obtain solid a. Solid a was calcined at 800°C for 2 hours at a heating rate of 2°C / min to obtain lanthanum oxide.

[0061] Comparative Example 3

[0062] A method for preparing an anti-fouling and easy-to-clean glaze material comprises the following steps, calculated by mass: uniformly mixing 20 parts of sodium feldspar, 30 parts of potassium feldspar, 10 parts of water-washed soil, 3 parts of calcite, 10 parts of talc, 12 parts of dolomite, 5 parts of zinc oxide, 5 parts of frit, 2 parts of aluminum oxide, 3 parts of quartz, 2 parts of strontium titanate, and 0.5 parts of lanthanum oxide microspheres; adding the mixture into a ball mill; performing a primary ball milling at a ball milling speed of 200 rpm for 4 hours; passing the mixture through a 400-mesh sieve; then adding water to adjust the slurry specific gravity to 1.4; and performing a secondary ball milling at a ball milling speed of 300 rpm for 28 hours to obtain the anti-fouling and easy-to-clean glaze material.

[0063] The preparation method of the lanthanum oxide microspheres is consistent with that of Example 4.

[0064] Comparative Example 4

[0065] A method for preparing an anti-fouling and easy-to-clean glaze material comprises the following steps, calculated by mass: 20 parts of albite, 30 parts of potassium feldspar, 10 parts of water-washed soil, 3 parts of calcite, 10 parts of talc, 12 parts of dolomite, 5 parts of zinc oxide, 5 parts of frit, 2 parts of aluminum oxide, 3 parts of quartz, 2 parts of strontium titanate, and 3 parts of modified graphene oxide are uniformly mixed, and then added into a ball mill, ball-milled once at a ball mill speed of 200 rpm for 4 hours, passed through a 400-mesh sieve, and then water is added to adjust the slurry specific gravity to 1.4, and ball-milled twice at a ball mill speed of 300 rpm for 28 hours to obtain the anti-fouling and easy-to-clean glaze material.

[0066] The preparation method of the lanthanum oxide microspheres is consistent with that of Example 4.

[0067] Test Example 1

[0068] Wear resistance and thermal shock resistance testing

[0069] The anti-fouling and easy-cleaning glaze materials prepared in Examples 1-4 of the present invention and Comparative Examples 1-4 were respectively and evenly dipped onto the surface of the blank by a dipping method, with a glaze layer having a thickness of 1 mm. The blank was then air-dried to obtain a glazed daily-use ceramic body. The glazed daily-use ceramic body was placed in a kiln and fired at a heating rate of 20°C / min to 1250±10°C for 8 hours. The body was kept warm and then naturally cooled to obtain a finished anti-fouling and easy-clean ceramic body.

[0070] The green body is a conventional commercially available ceramic body.

[0071] The anti-fouling, easy-to-clean ceramics obtained in Examples 1-4 and Comparative Examples 1-4 were tested for wear resistance according to GB / T 1768-2006 Paints and varnishes - Determination of abrasion resistance - Rotating rubber grinding wheel method. The mass loss (mg) of the sample was measured after 500 rotations. Thermal shock resistance was also tested according to GB / T 3298-2022 Test method for thermal shock resistance of household ceramics. During the test, the test samples were heated to 400°C and then immersed in 20°C water three times. The samples were observed for cracking. Eight samples were used in each test example, and none showed any cracks or damage. The performance results are shown in Table 1.

[0072] Table 1 Test results

[0073]

[0074] Comparison of Examples 1-4 with Comparative Examples 1-4 reveals that Example 4 exhibits the lowest mass loss of 0.06 mg and the best wear resistance. This is likely due to the simultaneous addition of modified graphene oxide and lanthanum oxide microspheres in Example 4, which exhibit excellent mechanical properties and can enhance wear resistance in glaze materials.

[0075] Comparison of Examples 1-4 and Comparative Examples 1-4 reveals that Example 4 and Comparative Examples 1-2 exhibit superior thermal shock resistance. This may be due to the addition of lanthanum oxide microspheres. The stable crystal structure formed during high-temperature calcination may impart enhanced thermal stability to the glaze material, and their hollow structure can reduce the impact of temperature changes on the glaze. While the silica microspheres added in Example 3 also possess a hollow structure, their heat resistance may be inferior to that of lanthanum oxide microspheres. The hollow glass microspheres added in Example 2 also exhibit inferior heat resistance to silica and lanthanum oxide microspheres.

[0076] Test Example 2

[0077] Formaldehyde removal rate test

[0078] The anti-fouling and easy-cleaning glaze materials prepared in Examples 1-4 of the present invention and Comparative Examples 1-4 were respectively and evenly dipped onto the surface of the blank by a dipping method, with a glaze layer having a thickness of 1 mm. The blank was then air-dried to obtain a glazed daily-use ceramic body. The glazed daily-use ceramic body was placed in a kiln and fired at a heating rate of 20°C / min to 1250±10°C for 8 hours. The body was kept warm and then naturally cooled to obtain a finished anti-fouling and easy-clean ceramic body.

[0079] The green body is a conventional commercially available ceramic body.

[0080] The anti-fouling and easy-to-clean ceramics obtained in Examples 1-4 and Comparative Examples 1-4 were tested for formaldehyde removal rates according to the standard of "QB / T2761-2024 Method for Determination of Purification Effect of Indoor Air Purification Products". A fan was built into the experimental chamber to allow air to flow. The experiment was conducted under sunlight for 6 hours. The test results are shown in Table 2.

[0081] Table 2 Formaldehyde removal rate test results

[0082]

[0083] A comparison of Examples 1-4 and Comparative Examples 1-4 shows that Example 4 has the highest formaldehyde removal rate, reaching 84.1%. This may be because the lanthanum oxide microspheres added to Example 4 contain iridium nitrate and strontium titanate, which can generate strong oxidative free radicals under ultraviolet light to degrade formaldehyde molecules; the lanthanum oxide microspheres can broaden the light response range to the visible light region, enhancing the degradation effect of strontium titanate on formaldehyde; and the interaction between the molecular orbitals and internal oxygen vacancies within the iridium atoms causes the directional movement of electrons, which, together with the lanthanum oxide, can further enhance the degradation of formaldehyde molecules.

Claims

1. A stain-resistant and easy-to-clean glaze material, characterized in that: The following raw materials are included by mass: 10-30 parts of albite, 20-40 parts of potassium feldspar, 5-15 parts of water-washed soil, 1-5 parts of calcite, 5-15 parts of talc, 5-15 parts of dolomite, 1-10 parts of zinc oxide, 1-10 parts of frit, 1-5 parts of aluminum oxide, 1-5 parts of quartz, 1-3 parts of strontium titanate, 0.1-1 parts of additives, and 1-5 parts of modified graphene oxide; The additive is lanthanum oxide microspheres; the modified graphene oxide is silicon dioxide-modified graphene oxide; The preparation method of the lanthanum oxide microspheres comprises the following steps, calculated by weight: 0.1-1 parts of lanthanum nitrate, 0.01-0.1 parts of iridium nitrate, 1-3 parts of urea, and 20-30 parts of water are mixed uniformly, and then 0.1-0.5 parts of melamine formaldehyde microspheres are added, the mixture is stirred and mixed uniformly, and then ultrasonically treated to obtain a solution a; the solution a is reacted at 80-90°C and 700-1000 rpm for 2-4 hours; after cooling to room temperature, the precipitate is collected after centrifugation, washed, and dried to obtain a solid a; the solid a is heated to 800°C at a heating rate of 2°C / min and calcined at 800°C for 1-3 hours to obtain lanthanum oxide microspheres; The preparation method of the modified graphene oxide comprises the following steps, calculated by mass: Step 1: Evenly mix 5-15 parts of nano-silica with 50-150 parts of a 70-80% ethanol aqueous solution, and then ultrasonically treat to obtain a mixed solution 1; evenly mix 1-5 parts of γ-aminopropyltriethoxysilane and 40-60 parts of anhydrous ethanol, add 5-15wt% acetic acid aqueous solution to adjust the pH to 3-4, and then stir and mix to obtain a mixed solution 2; add the mixed solution 2 to the mixed solution 1, and react at 70-90°C and 800-1000 rpm for 3-5 hours; after cooling to room temperature, centrifuge and collect the precipitate, wash, and dry to obtain modified silica; Step 2: Evenly mix 5-15 parts of the modified silica obtained in step 1 and 150-250 parts of N,N-dimethylacetamide, and then perform ultrasonic treatment; 20-40 parts of graphene oxide are added, followed by ultrasonic treatment to obtain a mixed solution 3; the mixed solution 3 is reacted at 70-90° C. and 800-1000 rpm for 3-5 hours; the reaction is continued at 100-110° C. and 800-1000 rpm for 3-5 hours; after cooling to room temperature, the precipitate is collected by centrifugation, washed, and dried to obtain modified graphene oxide.

2. The antifouling and easy-to-clean glaze material according to claim 1, characterized in that: The chemical composition of the frit is: 49-52% SiO2, 15-18% Al2O3, 3.5-4% K2O, 2.5-3% Na2O, 8-9.5% CaO, 5-6% MgO, 4.5-5.5% ZnO, 0.3-0.5% B2O3, and the rest are inevitable impurities.

3. The method for preparing the antifouling and easy-to-clean glaze material according to any one of claims 1 to 2, characterized in that: The following steps are involved: Sodium feldspar, potassium feldspar, washed soil, calcite, talc, dolomite, zinc oxide, frit, aluminum oxide, quartz, strontium titanate, additives, and modified graphene oxide are uniformly mixed and added into a ball mill, ball-milled once, sieved, and then water is added to adjust the slurry density, and ball-milled a second time to obtain an anti-fouling and easy-to-clean glaze material; the additive is lanthanum oxide microspheres.

4. The method for preparing the antifouling and easy-to-clean glaze material according to claim 3, wherein: The first ball milling is performed at a ball milling speed of 150-250 rpm for 3-5 hours.

5. The method for preparing the antifouling and easy-to-clean glaze material according to claim 3, characterized in that: The sieving is through a 300-400 mesh sieve.

6. The method for preparing the antifouling and easy-to-clean glaze material according to claim 3, wherein: The water adjusts the slurry specific gravity to 1.2-1.

6.

7. The method for preparing the antifouling and easy-to-clean glaze material according to claim 3, characterized in that: The secondary ball milling is performed at a ball milling speed of 250-350 rpm for 25-30 hours.

8. Use of the antifouling and easy-to-clean glaze material according to any one of claims 1 to 2 in the fields of construction and decoration.

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