Antifouling easy-to-clean glaze material and application thereof

Abstract

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

Description

Technical Field

[0001] The present invention relates to the technical field of ceramic glazes, and particularly to a stain-resistant and easy-to-clean glaze material and its application. Background Art

[0002] Ceramic glaze is a liquid or paste-like substance coated on the surface of ceramics, and its main components include oxides and glass components. It can form a hard and shiny coating during the firing process, protecting the surface of the object and enhancing its decorative effect and aesthetic degree. There are various types of ceramic glazes, such as colorless transparent glaze, colored glaze, etc., which are widely used in the fields of tableware, kitchenware, decorations, etc.

[0003] In recent years, with the development of technology and the improvement of health awareness, the places of use have become more and more extensive. Some require aesthetics, some require fineness, and some require high-strength wear resistance and easy cleaning. However, the existing glazed tiles have poor easy-cleaning functionality, are not easy to clean, and are not very convenient to take care of. At the same time, they have poor wear resistance, are easily worn, and have a short service life. It is very difficult for products to achieve coordinated improvement in easy cleaning and wear resistance, further restricting the use efficiency of products. Therefore, it is necessary to provide a stain-resistant and easy-to-clean glaze material with good easy-cleaning and wear-resistant properties.

[0004] CN116573859A discloses a stain-resistant protective glaze and its preparation method. By: potassium feldspar, sodium feldspar, burnt talc, calcined clay, washed clay, zinc oxide, high-barium frit, high-calcium frit, and calcined alumina, the stain-resistant performance is improved. However, this invention mainly forms the glaze surface through material ratio, and the porosity that can be reduced is limited, and the stain-resistant effect may be improved to a relatively low level. CN116023031A discloses a wear-resistant glazed tile glaze, its preparation method, and a glazed tile and its preparation method, including a raw material composition, a first frit, and a second frit; the raw material composition includes kaolin, calcined kaolin, quartz, dolomite, burnt talc, nepheline, zinc oxide, strontium carbonate, and barium sulfate; the wear-resistant performance is improved. However, this invention has the problems of low flatness and low stain-resistant performance. Summary of the Invention

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

[0006] To achieve the above object, the present invention provides a stain-resistant and easy-to-clean glaze material, which is characterized in that it includes the following raw material components by mass parts: 10 - 30 parts of sodium feldspar, 20 - 40 parts of potassium feldspar, 5 - 15 parts of washed clay, 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 alumina, and 1 - 5 parts of quartz.

[0007] Or, 10 - 30 parts of albite, 20 - 40 parts of orthoclase, 5 - 15 parts of washed clay, 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 alumina, 1 - 5 parts of quartz, 1 - 3 parts of strontium titanate, 0.1 - 1 part of additive, 1 - 5 parts of modified graphene oxide;

[0008] The additive is selected from at least one of lanthanum oxide microspheres, silicon dioxide 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, by mass:

[0011] Mix 0.1 - 1 part of lanthanum nitrate, 0.01 - 0.1 part of iridium nitrate, 1 - 3 parts of urea, and 20 - 30 parts of water evenly, then add 0.1 - 0.5 part of melamine - formaldehyde microspheres, stir and mix evenly, and then perform ultrasonic treatment to obtain solution a; React solution a at 80 - 90 °C and 700 - 1000 rpm for 2 - 4 h; After cooling to room temperature, centrifuge to collect the precipitate, wash and dry to obtain solid a; Heat solid a to 800 °C at a heating rate of 2 °C / min and calcine at 800 °C for 1 - 3 h to obtain lanthanum oxide microspheres.

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

[0013] As a further illustration of the present invention, urea is used as a precipitating agent to react with lanthanum nitrate and iridium nitrate solutions to form a precursor, and melamine - formaldehyde microspheres are used as a hard template to form a core - shell structure. The melamine - formaldehyde microspheres decompose and volatilize during high - temperature calcination, leaving a porous microsphere structure. This is beneficial to improving the mechanical strength, wear resistance, and temperature resistance of the glaze material; The formation of a porous microsphere structure has good absorption performance for formaldehyde.

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

[0015] Step 1: Mix 5 - 15 parts of nano - silicon dioxide with 50 - 150 parts of 70 - 80% ethanol aqueous solution evenly and then perform ultrasonic treatment to obtain mixture 1; Mix 1 - 5 parts of γ - aminopropyltriethoxysilane and 40 - 60 parts of absolute ethanol evenly, add 5 - 15 wt% acetic acid aqueous solution to adjust the pH to 3 - 4, and then stir and mix evenly to obtain mixture 2; Add mixture 2 to mixture 1, and react at 70 - 90 °C and 800 - 1000 rpm for 3 - 5 h; After cooling to room temperature, centrifuge to collect the precipitate, wash and dry to obtain modified silicon dioxide;

[0016] Step 2: Mix 5 - 15 parts of the modified silica obtained in Step 1 with 150 - 250 parts of N,N - dimethylacetamide evenly and then perform ultrasonic treatment; add 20 - 40 parts of graphene oxide, and then perform ultrasonic treatment to obtain a mixed solution 3; react the mixed solution 3 at 70 - 90 °C and 800 - 1000 rpm for 3 - 5 h; continue to react at 100 - 110 °C and 800 - 1000 rpm for 3 - 5 h; after cooling to room temperature, centrifuge to collect the precipitate, wash, and dry to obtain modified graphene oxide.

[0017] As a further illustration of the present invention, γ - aminopropyltriethoxysilane is used to modify nano - SiO2. After modification in N,N - dimethylacetamide solvent, the surface of the nano - SiO2 is positively charged, and the surface carboxyl groups of graphene oxide are ionized to be negatively charged. Electrostatic attraction occurs between the two, and nano - SiO2 will adsorb on the surface of graphene oxide, filling the voids between the graphene oxide sheets to form a denser protective layer. In addition, the steric hindrance effect of nano - SiO2 can improve the dispersion effect of graphene oxide in the glaze material. Under high - temperature firing conditions, graphene oxide can also induce the formation of a dense layer of silica. This is beneficial to improving 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 inevitable impurities.

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

[0020] Mix albite, orthoclase, washed clay, calcite, talc, dolomite, zinc oxide, frit, alumina, and quartz evenly, then add them to a ball mill for primary ball milling, sieve, and then add water to adjust the slurry specific gravity for secondary ball milling to obtain the antifouling and easy - to - clean glaze material;

[0021] Or, mix albite, orthoclase, washed clay, calcite, talc, dolomite, zinc oxide, frit, alumina, quartz, strontium titanate, additive, and modified graphene oxide evenly, then add them to a ball mill for primary ball milling, sieve, and then add water to adjust the slurry specific gravity for secondary ball milling to obtain the antifouling and easy - to - clean glaze material.

[0022] Preferably, the primary ball milling is carried out at a ball milling speed of 150 - 250 rpm for 3 - 5 h.

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

[0024] Preferably, the proportion of the slurry is adjusted to 1.2 - 1.6 with water.

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

[0026] Advantages of the present invention:

[0027] 1. Compared with the prior art, through reasonable proportioning and utilization of the interaction between various substances, and optimization of the preparation process, the present invention obtains an anti - fouling and easy - to - clean glaze material. The anti - fouling and easy - to - clean glaze material prepared by the present invention can form a ceramic material with high - efficiency anti - oil effect, excellent thermal shock resistance and excellent wear resistance after high - temperature calcination.

[0028] 2. Compared with the prior art, 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 formation of a porous microsphere structure has good absorption performance for formaldehyde; modified graphene oxide is beneficial to improving the mechanical strength, wear resistance and temperature resistance of the glaze material. Specific embodiments

[0029] Use the parameters and sources of specific chemical substances.

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

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

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

[0033] Nano - silica: model: TSP - H10T, particle size: 20 nm, specific surface area: 200 g / m 2 , sourced from Jiangsu Tianxing New Materials Co., Ltd.

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

[0035] Frit, commercially available; the 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 preparation method of an anti-fouling and easy-to-clean glaze material, comprising the following steps, by mass: Mix 20 parts of albite, 30 parts of orthoclase, 10 parts of washed clay, 3 parts of calcite, 10 parts of talc, 12 parts of dolomite, 5 parts of zinc oxide, 5 parts of frit, 2 parts of alumina, and 3 parts of quartz evenly, then add them to a ball mill for primary ball milling. Ball mill at a speed of 200 rpm for 4 h, pass through a 400-mesh sieve, then add water to adjust the slurry specific gravity to 1.4, and perform secondary ball milling. Ball mill at a speed of 300 rpm for 28 h to obtain the anti-fouling and easy-to-clean glaze material.

[0038] Example 2

[0039] A preparation method of an anti-fouling and easy-to-clean glaze material, comprising the following steps, by mass: Mix 20 parts of albite, 30 parts of orthoclase, 10 parts of washed clay, 3 parts of calcite, 10 parts of talc, 12 parts of dolomite, 5 parts of zinc oxide, 5 parts of frit, 2 parts of alumina, 3 parts of quartz, 2 parts of strontium titanate, 0.5 part of hollow glass microspheres, and 3 parts of modified graphene oxide evenly, then add them to a ball mill for primary ball milling. Ball mill at a speed of 200 rpm for 4 h, pass through a 400-mesh sieve, then add water to adjust the slurry specific gravity to 1.4, and perform secondary ball milling. Ball mill at a speed of 300 rpm for 28 h to obtain the anti-fouling and easy-to-clean glaze material.

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

[0041] Step 1: Mix 10 parts of nano-silica with 100 parts of 75% ethanol aqueous solution evenly, and ultrasonicate for 60 min at 40 KHz to obtain mixture 1; Mix 3 parts of γ-aminopropyltriethoxysilane with 50 parts of absolute ethanol evenly, then add 10 wt% acetic acid aqueous solution to adjust the pH to 3, and then stir at 800 rpm for 60 min to obtain mixture 2; Add mixture 2 to mixture 1, react at 80 °C and 900 rpm for 4 h, cool to room temperature, then centrifuge at 3000 rpm for 10 min, collect the precipitate, wash the precipitate 4 times with absolute ethanol, and dry at 50 °C for 5 h to obtain modified silica;

[0042] Step 2: Mix 10 parts of the modified silica obtained in Step 1 with 200 parts of N,N-dimethylacetamide, ultrasonicate for 30 min at 40 KHz, add 30 parts of graphene oxide, then ultrasonicate for 30 min at 40 KHz to obtain Mixture 3. React Mixture 3 at 80 °C and 900 rpm for 4 h, then react at 105 °C and 900 rpm for 4 h. After cooling to room temperature, centrifuge at 3000 rpm for 10 min, collect the precipitate, wash the precipitate 4 times with absolute ethanol, and dry at 50 °C for 5 h to obtain modified graphene oxide.

[0043] Example 3

[0044] A preparation method of an anti-fouling and easy-to-clean glaze material includes the following steps, by mass: Mix 20 parts of albite, 30 parts of orthoclase, 10 parts of washed clay, 3 parts of calcite, 10 parts of talc, 12 parts of dolomite, 5 parts of zinc oxide, 5 parts of frit, 2 parts of alumina, 3 parts of quartz, 2 parts of strontium titanate, 0.5 part of silica microspheres, and 3 parts of modified graphene oxide evenly, then add them to a ball mill for primary ball milling at a ball milling speed of 200 rpm for 4 h, pass through a 400-mesh sieve, then add water to adjust the slurry specific gravity to 1.4, and perform secondary ball milling at a ball milling speed of 300 rpm for 28 h to obtain the anti-fouling and easy-to-clean glaze material.

[0045] The preparation method of the modified graphene oxide is the same as that in Example 2.

[0046] Example 4

[0047] A preparation method of an anti-fouling and easy-to-clean glaze material includes the following steps, by mass: Mix 20 parts of albite, 30 parts of orthoclase, 10 parts of washed clay, 3 parts of calcite, 10 parts of talc, 12 parts of dolomite, 5 parts of zinc oxide, 5 parts of frit, 2 parts of alumina, 3 parts of quartz, 2 parts of strontium titanate, 0.5 part of lanthanum oxide microspheres, and 3 parts of modified graphene oxide evenly, then add them to a ball mill for primary ball milling at a ball milling speed of 200 rpm for 4 h, pass through a 400-mesh sieve, then add water to adjust the slurry specific gravity to 1.4, and perform secondary ball milling at a ball milling speed of 300 rpm for 28 h to obtain the anti-fouling and easy-to-clean glaze material.

[0048] The preparation method of the modified graphene oxide is the same as that in Example 2.

[0049] The preparation method of the lanthanum oxide microspheres includes the following steps, by mass:

[0050] Mix 0.5 parts of lanthanum nitrate, 0.05 parts of iridium nitrate, 2 parts of urea and 25 parts of water evenly, then add 0.3 parts of melamine formaldehyde microspheres, stir at 800 rpm for 30 min, and ultrasonicate at 40 KHz for 30 min to obtain solution a. React solution a at 85 °C and 800 rpm for 3 h. After cooling to room temperature, centrifuge at 3000 rpm for 10 min, collect the precipitate, wash the precipitate 4 times with absolute ethanol, and dry at 50 °C for 5 h to obtain solid a. Heat solid a at a heating rate of 2 °C / min to 800 °C and calcine at 800 °C for 2 h to obtain lanthanum oxide microspheres.

[0051] Comparative Example 1

[0052] A preparation method of an antifouling and easy-to-clean glaze material comprises the following steps, by mass: Mix 20 parts of albite, 30 parts of orthoclase, 10 parts of washed clay, 3 parts of calcite, 10 parts of talc, 12 parts of dolomite, 5 parts of zinc oxide, 5 parts of frit, 2 parts of alumina, 3 parts of quartz, 2 parts of strontium titanate, 0.5 parts of lanthanum oxide microspheres, and 3 parts of modified graphene oxide evenly, then add them to a ball mill and perform primary ball milling at a ball milling speed of 200 rpm for 4 h, pass through a 400-mesh sieve, then add water to adjust the slurry specific gravity to 1.4, and perform secondary ball milling at a ball milling speed of 300 rpm for 28 h to obtain the antifouling and easy-to-clean glaze material.

[0053] The preparation method of the modified graphene oxide is the same as that in Example 2.

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

[0055] Mix 0.5 parts of lanthanum nitrate, 2 parts of urea and 25 parts of water evenly, then add 0.3 parts of melamine formaldehyde microspheres, stir at 800 rpm for 30 min, and ultrasonicate at 40 KHz for 30 min to obtain solution a. React solution a at 85 °C and 800 rpm for 3 h. After cooling to room temperature, centrifuge at 3000 rpm for 10 min, collect the precipitate, wash the precipitate 4 times with absolute ethanol, and dry at 50 °C for 5 h to obtain solid a. Heat solid a at a heating rate of 2 °C / min at 800 °C and calcine at 800 °C for 2 h to obtain lanthanum oxide microspheres.

[0056] Comparative Example 2

[0057] A preparation method of an antifouling and easy-to-clean glaze material, comprising the following steps, by mass parts: Mix 20 parts of albite, 30 parts of orthoclase, 10 parts of washed clay, 3 parts of calcite, 10 parts of talc, 12 parts of dolomite, 5 parts of zinc oxide, 5 parts of frit, 2 parts of alumina, 3 parts of quartz, 2 parts of strontium titanate, 0.5 part of lanthanum oxide, and 3 parts of modified graphene oxide evenly, then add them to a ball mill for primary ball milling. Ball mill at a speed of 200 rpm for 4 h, pass through a 400-mesh sieve, then add water to adjust the slurry specific gravity to 1.4, and perform secondary ball milling. Ball mill at a speed of 300 rpm for 28 h to obtain the antifouling and easy-to-clean glaze material.

[0058] The preparation method of the modified graphene oxide is the same as that in Example 2.

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

[0060] Mix 0.5 part of lanthanum nitrate, 2 parts of urea and 25 parts of water evenly, stir at 800 rpm for 30 min, and ultrasonicate at 40 KHz for 30 min to obtain solution a. React solution a at 85 °C and 800 rpm for 3 h. After cooling to room temperature, centrifuge at 3000 rpm for 10 min, collect the precipitate, wash the precipitate 4 times with absolute ethanol, and dry at 50 °C for 5 h to obtain solid a. Calcinate solid a at 800 °C for 2 h at a heating rate of 2 °C / min to obtain lanthanum oxide.

[0061] Comparative Example 3

[0062] A preparation method of an antifouling and easy-to-clean glaze material, comprising the following steps, by mass parts: Mix 20 parts of albite, 30 parts of orthoclase, 10 parts of washed clay, 3 parts of calcite, 10 parts of talc, 12 parts of dolomite, 5 parts of zinc oxide, 5 parts of frit, 2 parts of alumina, 3 parts of quartz, 2 parts of strontium titanate, 0.5 part of lanthanum oxide microspheres evenly, then add them to a ball mill for primary ball milling. Ball mill at a speed of 200 rpm for 4 h, pass through a 400-mesh sieve, then add water to adjust the slurry specific gravity to 1.4, and perform secondary ball milling. Ball mill at a speed of 300 rpm for 28 h to obtain the antifouling and easy-to-clean glaze material.

[0063] The preparation method of the lanthanum oxide microspheres is the same as that in Example 4.

[0064] Comparative Example 4

[0065] A preparation method of an anti-fouling and easy-to-clean glaze material comprises the following steps, by mass: mixing 20 parts of albite, 30 parts of orthoclase, 10 parts of washed clay, 3 parts of calcite, 10 parts of talc, 12 parts of dolomite, 5 parts of zinc oxide, 5 parts of frit, 2 parts of alumina, 3 parts of quartz, 2 parts of strontium titanate, and 3 parts of modified graphene oxide evenly, then adding them to a ball mill for primary ball milling at a ball milling speed of 200 rpm for 4 h, screening through a 400-mesh sieve, and then adding water to adjust the slurry specific gravity to 1.4 for secondary ball milling at a ball milling speed of 300 rpm for 28 h to obtain the anti-fouling and easy-to-clean glaze material.

[0066] The preparation method of the lanthanum oxide microspheres is the same as that in Example 4.

[0067] Test Example 1

[0068] Wear resistance and thermal shock resistance tests

[0069] The anti-fouling and easy-to-clean glaze materials prepared in Examples 1-4 and Comparative Examples 1-4 of the present invention are respectively and evenly dip-coated on the surface of the green body by the dip-glazing method, with the thickness of the glaze layer being 1 mm, and then air-dried to obtain the glazed daily-use ceramic body; the glazed daily-use ceramic body is placed in a kiln and fired at a heating rate of 20 °C / min to 1250 ± 10 °C for 8 h, and after heat preservation, it is naturally cooled to obtain the finished anti-fouling and easy-to-clean ceramic.

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

[0071] The anti-fouling and easy-to-clean ceramics obtained in Examples 1-4 and Comparative Examples 1-4 are subjected to wear resistance tests with reference to the "GB / T 1768-2006 Determination of abrasion resistance of paints and varnishes - Rotating rubber wheel method", and after rotating 500 revolutions, the mass loss (mg) of the test specimen is measured; the thermal shock resistance test is carried out according to the standard of "GB / T 3298-2022 Test method for thermal shock resistance of daily-use ceramic ware". During the test, the test sample is heated to 400 °C and then put into water at 20 °C three times repeatedly, and the crack situation is observed. Among them, the number of sample pieces set in each test example is 8 pieces, and the samples have no cracks and damages, and the performance measurement results are shown in Table 1.

[0072] Table 1 Test results

[0073]

[0074] It can be found from the comparison between Examples 1-4 and Comparative Examples 1-4 that the mass loss of Example 4 is the lowest at 0.06 mg, and the wear resistance is the best. The reason may be that in Example 4, both modified graphene oxide and lanthanum oxide microspheres are added, and the mechanical properties of modified graphene oxide and lanthanum oxide microspheres are good, which can increase the wear resistance in the glaze material.

[0075] By comparing Examples 1-4 and Comparative Examples 1-4, it can be found that Examples 4 and Comparative Examples 1-2 have good thermal shock resistance. The reason may be that lanthanum oxide microspheres are added. The stable crystal structure formed by lanthanum oxide microspheres during high-temperature calcination may endow the glaze material with better thermal stability, and its hollow structure can reduce the impact of temperature changes on the glaze. Although the silica microspheres added in Example 3 also have a hollow structure, their temperature resistance may be inferior to that of lanthanum oxide microspheres; the heat resistance of the hollow glass microspheres added in Example 2 is inferior to that of silica microspheres and lanthanum oxide microspheres.

[0076] Test Example 2

[0077] Formaldehyde removal rate detection

[0078] The antifouling and easy-to-clean glaze materials prepared in Examples 1-4 and Comparative Examples 1-4 of the present invention were uniformly dip-coated on the surface of the green body by the dip-coating method, and the thickness of the glaze layer was 1 mm, and then air-dried to obtain a glazed daily-use ceramic body; the glazed daily-use ceramic body was placed in a kiln and heated at a heating rate of 20 °C / min to 1250 ± 10 °C for firing, and the firing time was 8 h. After heat preservation, it was naturally cooled to obtain the finished antifouling and easy-to-clean ceramic.

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

[0080] The antifouling and easy-to-clean ceramics obtained in Examples 1-4 and Comparative Examples 1-4 were tested for formaldehyde removal rate according to the standard of "QB / T2761-2024 Determination Method for Purification Effect of Indoor Air Purification Products". A fan was installed in the test chamber to make the air flow, and the experiment was carried out under sunlight for 6 hours. The test results are shown in Table 2.

[0081] Table 2 Formaldehyde removal rate detection results

[0082]

[0083]

[0084] By comparing Examples 1-4 and Comparative Examples 1-4, it can be found that the formaldehyde removal rate of Example 4 is the highest, reaching 84.1%. The reason may be that iridium nitrate is added to the lanthanum oxide microspheres added in Example 4, and strontium titanate is also added. Strontium titanate can generate strong oxidizing free radicals under ultraviolet light to degrade formaldehyde molecules; lanthanum oxide microspheres can broaden the light response range to the visible light region and enhance the degradation effect of strontium titanate on formaldehyde; the interaction between the molecular orbitals inside iridium atoms and the internal oxygen vacancies causes the directional movement of electrons, and the combined action with lanthanum oxide can further enhance the effect of degrading formaldehyde molecules.

Claims

1. An anti-fouling and easy-to-clean glaze material, characterized in that, It includes the following raw material components by mass parts: 10 - 30 parts of albite, 20 - 40 parts of potassium feldspar, 5 - 15 parts of washed clay, 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 alumina, 1 - 5 parts of quartz; Or, 10 - 30 parts of albite, 20 - 40 parts of potassium feldspar, 5 - 15 parts of washed clay, 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 alumina, 1 - 5 parts of quartz, 1 - 3 parts of strontium titanate, 0.1 - 1 part of additive, 1 - 5 parts of modified graphene oxide; The additive is selected from at least one of lanthanum oxide microspheres, silica microspheres, and hollow glass microspheres; The modified graphene oxide is silica - modified graphene oxide.

2. The antifouling and easy-to-clean glazed material according to claim 1, characterized in that, The preparation method of the lanthanum oxide microspheres includes the following steps, by mass parts: Mix 0.1 - 1 part of lanthanum nitrate, 0.01 - 0.1 part of iridium nitrate, 1 - 3 parts of urea, and 20 - 30 parts of water evenly, then add 0.1 - 0.5 part of melamine - formaldehyde microspheres, stir and mix evenly, and then perform ultrasonic treatment to obtain solution a; React solution a at 80 - 90 °C and 700 - 1000 rpm for 2 - 4 h; After cooling to room temperature, centrifuge and collect the precipitate, wash and dry to obtain solid a; Heat solid a to 800 °C at a heating rate of 2 °C / min and calcine at 800 °C for 1 - 3 h to obtain lanthanum oxide microspheres.

3. The anti-fouling and easy-to-clean glaze material according to claim 1, characterized in that, The preparation method of the modified graphene oxide includes the following steps, by mass parts: Step 1: Mix 5 - 15 parts of nano - silica with 50 - 150 parts of 70 - 80% ethanol aqueous solution evenly and perform ultrasonic treatment to obtain mixture 1; Mix 1 - 5 parts of γ - aminopropyltriethoxysilane and 40 - 60 parts of absolute ethanol evenly, then add 5 - 15 wt% acetic acid aqueous solution to adjust the pH to 3 - 4, and then stir and mix evenly to obtain mixture 2; Add mixture 2 to mixture 1, and react at 70 - 90 °C and 800 - 1000 rpm for 3 - 5 h; After cooling to room temperature, centrifuge to collect the precipitate, wash and dry to obtain modified silica; Step 2: Mix 5 - 15 parts of the modified silica obtained in Step 1 with 150 - 250 parts of N,N - dimethylacetamide evenly and perform ultrasonic treatment; Add 20 - 40 parts of graphene oxide, then perform ultrasonic treatment to obtain mixture 3; React mixture 3 at 70 - 90 °C and 800 - 1000 rpm for 3 - 5 h; Continue to react at 100 - 110 °C and 800 - 1000 rpm for 3 - 5 h; After cooling to room temperature, centrifuge to collect the precipitate, wash and dry to obtain modified graphene oxide.

4. 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.

5. The preparation method of the antifouling and easy-to-clean glaze material according to any one of claims 1-4, characterized in that, It includes the following steps: Mix albite, orthoclase, washed clay, calcite, talc, dolomite, zinc oxide, frit, alumina, and quartz evenly, then add them to a ball mill for primary ball milling, sieve them, and then add water to adjust the slurry specific gravity for secondary ball milling to obtain a stain-resistant and easy-to-clean glaze material; Alternatively, mix albite, orthoclase, washed clay, calcite, talc, dolomite, zinc oxide, frit, alumina, quartz, strontium titanate, additives, and modified graphene oxide evenly, then add them to a ball mill for primary ball milling, sieve them, and then add water to adjust the slurry specific gravity for secondary ball milling to obtain a stain-resistant and easy-to-clean glaze material.

6. The preparation method of the antifouling and easy-to-clean glaze material according to claim 5, characterized in that, The primary ball milling is carried out at a ball milling speed of 150 - 250 rpm for 3 - 5 h.

7. The preparation method of the antifouling and easy-to-clean glaze material according to claim 5, characterized in that, The sieving is through a 300 - 400 mesh sieve.

8. The preparation method of the antifouling and easy-to-clean glaze material according to claim 5, characterized in that, Adjust the slurry specific gravity to 1.2 - 1.6 with water.

9. The preparation method of the antifouling and easy-to-clean glaze material according to claim 5, wherein, The secondary ball milling is carried out at a ball milling speed of 250 - 350 rpm for 25 - 30 h.

10. Application of the stain-resistant and easy-to-clean glaze material according to any one of claims 1 - 4 in the fields of architecture and decoration.

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