Ceramic glaze and preparation method and application thereof

Abstract

This invention discloses a ceramic glaze, its preparation method, and its application. By weight, it comprises the following components: 20-35 parts silica, 10-25 parts composite metal oxide, 20-30 parts talc, 10-30 parts anorthite, 1-4 parts borax, 5-15 parts zirconium silicate, 0.1-2 parts dispersant, and 30-70 parts water. The composite metal oxide contains zinc oxide, lanthanum-containing copper titanium dioxide, and carbon nanotubes. The lanthanum-containing copper titanium dioxide is prepared from tetrabutyl titanate, lanthanum salt, and copper salt via a sol-gel method. The molar ratio of titanium in the tetrabutyl titanate, lanthanum in the lanthanum salt, and copper in the copper salt is Ti:La:Cu = 1:(0.05-0.3):(0.1-0.5). The dispersant contains sodium polynaphthalene sulfonate and Tween. Tiles prepared using this ceramic glaze exhibit high antibacterial properties and high compressive strength.

Description

Technical Field

[0001] This invention relates to the field of ceramic technology, and more specifically, to a ceramic glaze, its preparation method, and its application. Background Technology

[0002] Ceramic tiles are a type of ceramic product widely used in building and decoration. They typically consist of a body and a glaze layer. The body is the main part of the tile, also known as the tile blank or unglazed tile. The glaze layer is a layer of vitreous material covering the surface of the tile body, and the raw material for the glaze layer is glaze pigment. Ceramic tiles come in various types, sizes, colors, and patterns to meet different decorative and functional needs. They are widely used for floor and wall decoration in homes, offices, shopping malls, hotels, hospitals, and other places, and are also commonly used for paving outdoor plazas, sidewalks, and garden landscapes.

[0003] Antibacterial ceramic tiles are a type of ceramic tile that can inhibit and kill bacteria, meaning they possess antibacterial properties. The antibacterial function of these tiles comes from antibacterial agents contained in their glaze. When the tile comes into contact with bacteria, these agents activate, inhibiting and killing bacteria. High compressive strength means antibacterial tiles are more durable and can withstand greater pressure and weight, reducing the risk of cracking during use. This is crucial for ensuring personal safety and extending the tile's lifespan. Furthermore, high compressive strength ensures that the antibacterial glaze layer remains undamaged even under continuous pressure and abrasion, maintaining stability over long-term use and preserving the antibacterial effect.

[0004] Therefore, developing a ceramic glaze that can improve the antibacterial effect and compressive strength of ceramic tiles has significant economic value. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of the prior art and to provide a ceramic glaze, its preparation method, and its application.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0007] In a first aspect, the present invention provides a ceramic glaze, comprising the following components by weight:

[0008] 20-35 parts silica, 10-25 parts composite metal oxides, 20-30 parts talc, 10-30 parts anorthite, 1-4 parts borax, 5-15 parts zirconium silicate, 0.1-2 parts dispersant, 30-70 parts water;

[0009] The composite metal oxide contains zinc oxide, lanthanum-containing copper titanium dioxide, and carbon nanotubes. The lanthanum-containing copper titanium dioxide is prepared by a sol-gel method using tetrabutyl titanate, lanthanum salt, and copper salt. The molar ratio of titanium in tetrabutyl titanate, lanthanum in lanthanum salt, and copper in copper salt is Ti:La:Cu = 1:(0.05-0.3):(0.1-0.5).

[0010] The dispersant contains sodium polynaphthalene sulfonate (CAS No.: 9084-06-4) and Tween.

[0011] The ceramic glaze of this invention can improve the antibacterial effect and compressive strength of ceramic tiles.

[0012] Specifically, the present invention utilizes the sol-gel method to prepare lanthanum-copper titanium dioxide by using a specific molar ratio of tetrabutyl titanate, lanthanum salt, and copper salt. This allows the antibacterial lanthanum oxide and copper oxide to be uniformly dispersed in the titanium dioxide system and tightly connected to each other, thus fusing the lanthanum oxide, copper oxide, and titanium dioxide to form a structurally stable solid, thereby improving the antibacterial effect and compressive strength of the ceramic.

[0013] This invention utilizes zinc oxide and carbon nanotubes to synergistically enhance the function of lanthanum-containing copper titanium dioxide, thereby improving the antibacterial effect and compressive strength of ceramic tiles.

[0014] The dispersants sodium polynaphthalene sulfonate (CAS No.: 9084-06-4) and Tween of the present invention can promote the dispersibility of composite metal oxides, especially lanthanum copper titanium dioxide, in ceramic glazes, thereby stabilizing the properties of ceramic glazes and helping components such as lanthanum copper titanium dioxide to better adhere to the surface of the ceramic tile body, thus improving the antibacterial effect and compressive strength of the ceramic tile.

[0015] Preferably, the molar ratio of titanium in the tetrabutyl titanate, lanthanum in the lanthanum salt, and copper in the copper salt is Ti:La:Cu = 1:(0.1-0.2):(0.2-0.4).

[0016] More preferably, the molar ratio of titanium in the tetrabutyl titanate, lanthanum in the lanthanum salt, and copper in the copper salt is Ti:La:Cu = 1:0.15:0.3.

[0017] Preferably, the weight ratio of zinc oxide, lanthanum-containing copper titanium dioxide, and carbon nanotubes is 1:(1-5):(0.1-0.5).

[0018] More preferably, the weight ratio of zinc oxide, lanthanum-containing copper titanium dioxide, and carbon nanotubes is 1:(1-5):0.3.

[0019] More preferably, the weight ratio of zinc oxide, lanthanum-containing copper titanium dioxide, and carbon nanotubes is 1:(2-4):0.3, specifically 1:3:0.3.

[0020] Preferably, the composite metal oxide is present in 15-20 parts by weight.

[0021] Preferably, the weight ratio of the sodium polynaphthalene sulfonate (CAS No.: 9084-06-4) to Tween is 1:(0.5-5).

[0022] More preferably, the weight ratio of the sodium polynaphthalene sulfonate (CAS No.: 9084-06-4) to Tween is 1:(1-4).

[0023] Further, the weight ratio of the sodium polynaphthalene sulfonate (CAS No.: 9084-06-4) to Tween is 1:3.

[0024] Preferably, the carbon nanotube is at least one of single-walled carbon nanotube, double-walled carbon nanotube, and multi-walled carbon nanotube.

[0025] Preferably, the lanthanum salt is at least one of lanthanum chloride and lanthanum nitrate.

[0026] Preferably, the copper salt is at least one of copper chloride, copper nitrate, and copper sulfate.

[0027] Preferably, the Tween is at least one of Tween-20, Tween-40, Tween-60, and Tween-80.

[0028] In this invention, lanthanum-containing copper titanium dioxide is prepared by the sol-gel method. Therefore, the preparation method of the lanthanum-containing copper titanium dioxide includes the following steps:

[0029] S1. Mix tetrabutyl titanate and ethanol to obtain solution A;

[0030] S2. Mix lanthanum salt, copper salt and solvent, adjust pH to 2-3 to obtain solution B;

[0031] S3. Mix solution B and solution A, react them, and calcine to obtain lanthanum-containing copper titanium dioxide.

[0032] More preferably, in step S1, the weight ratio of tetrabutyl titanate to ethanol is 1:(1-100).

[0033] More preferably, the weight ratio of tetrabutyl titanate to solvent is 1:(1-60).

[0034] More preferably, in step S2, the solvent is at least one of water and ethanol.

[0035] More preferably, the weight ratio of water to ethanol is 1:(1-10).

[0036] More preferably, in step S2, the pH adjuster is acetic acid.

[0037] More preferably, in step S3, the mixed solution B and solution A refer to adding solution B dropwise into solution A.

[0038] More preferably, in step S3, the reaction time is 0.5-12 hours.

[0039] More preferably, in step S3, the calcination temperature is 500-800℃.

[0040] More preferably, in step S3, the calcination time is 0.5-8 hours.

[0041] More preferably, in step S3, drying is also included before calcination.

[0042] More preferably, the drying temperature is 50-70°C and the time is 2-24 hours.

[0043] More preferably, in step S3, after calcination, grinding is also included.

[0044] Secondly, the present invention provides a method for preparing ceramic glaze, comprising: mixing the components to obtain ceramic glaze.

[0045] Thirdly, the present invention provides an application of ceramic glaze in ceramic tiles.

[0046] Fourthly, the present invention provides a ceramic tile, comprising a body and a glaze layer, wherein the raw material of the glaze layer contains ceramic glaze.

[0047] Preferably, the raw materials for the blank contain kaolin, silicon nitride, limestone, quartz, and talc.

[0048] More preferably, the raw material of the billet contains the following components in parts by weight:

[0049] 20-40 parts kaolin, 15-25 parts silicon nitride, 10-20 parts limestone, 5-15 parts quartz, 3-8 parts talc.

[0050] Fifthly, the present invention provides a method for preparing ceramic tiles, comprising the following steps:

[0051] A1. Mix the raw materials of the billet, press them into shape, and obtain the green billet;

[0052] A2. Apply and / or spray ceramic glaze onto the green body, sinter, and obtain ceramic tile.

[0053] Preferably, step A1 specifically involves: wet ball milling the raw material of the billet into a slurry, drying it, pressing it into shape, and obtaining the green billet.

[0054] Preferably, the sintering temperature is 1100-1500℃ and the time is 1-24h.

[0055] Preferably, drying is also included before sintering.

[0056] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0057] The ceramic glaze of this invention can improve the antibacterial effect and compressive strength of ceramic tiles.

[0058] Specifically, the present invention utilizes the sol-gel method to prepare lanthanum-copper titanium dioxide by using a specific molar ratio of tetrabutyl titanate, lanthanum salt, and copper salt. This allows the antibacterial lanthanum oxide and copper oxide to be uniformly dispersed in the titanium dioxide system and tightly connected to each other, thus fusing the lanthanum oxide, copper oxide, and titanium dioxide to form a structurally stable solid, thereby improving the antibacterial effect and compressive strength of the ceramic.

[0059] This invention utilizes zinc oxide and carbon nanotubes to synergistically enhance the function of lanthanum-containing copper titanium dioxide, thereby improving the antibacterial effect and compressive strength of ceramic tiles.

[0060] The dispersants sodium polynaphthalene sulfonate (CAS No.: 9084-06-4) and Tween of the present invention can promote the dispersibility of composite metal oxides, especially lanthanum copper titanium dioxide, in ceramic glazes, thereby stabilizing the properties of ceramic glazes and helping components such as lanthanum copper titanium dioxide to better adhere to the surface of the ceramic tile body, thus improving the antibacterial effect and compressive strength of the ceramic tile. Attached Figure Description

[0061] Figure 1 The figures show actual images of the tiles used in Application Example 1 and Comparative Application Example 1. In the figures, Figure A is an actual image of the tiles used in Application Example 1, and Figure B is an actual image of the tiles used in Comparative Application Example 1. Detailed Implementation

[0062] To better illustrate the purpose, technical solution, and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments.

[0063] The experimental methods in the following examples, comparative examples, application examples and comparative application examples, unless otherwise specified, are generally performed under conventional conditions in the art or under conditions recommended by the manufacturer; the raw materials and reagents used, unless otherwise specified, are all commercially available from the conventional market.

[0064] The use of reagents in the various embodiments, comparative examples, application examples, and comparative application examples of this invention is as follows:

[0065] Single-walled carbon nanotubes, C434649, Shanghai Aladdin;

[0066] Double-walled carbon nanotubes, C493449, Shanghai Aladdin;

[0067] Multi-walled carbon nanotubes, C313046, Shanghai Aladdin.

[0068] Example 1

[0069] This embodiment provides a ceramic glaze, which, by weight, comprises the following components:

[0070] 30 parts silica, 18 parts composite metal oxide, 25 parts talc, 20 parts anorthite, 3 parts borax, 9 parts zirconium silicate, 1 part dispersant, 50 parts water;

[0071] The composite metal oxide contains zinc oxide, lanthanum-containing copper titanium dioxide, and double-walled carbon nanotubes in a weight ratio of 1:3:0.3.

[0072] The dispersant contains sodium polynaphthalene sulfonate and Tween 40 in a weight ratio of 1:3.

[0073] The method for preparing the lanthanum-containing copper titanium dioxide includes the following steps:

[0074] S1. Mix tetrabutyl titanate and anhydrous ethanol in a weight ratio of 1:7 to obtain solution A;

[0075] S2. Mix lanthanum salt (lanthanum chloride), copper salt (copper chloride) and solvent (water and anhydrous ethanol in a weight ratio of 1:4), adjust the pH to 2.5 with glacial acetic acid to obtain solution B;

[0076] S3. At 2500 r / min, solution B was added dropwise to solution A, and the reaction was carried out for 3 h. The solution was dried at 70 °C, calcined at 700 °C for 2 h, and ground to obtain lanthanum-containing copper titanium dioxide.

[0077] The weight ratio of the tetrabutyl titanate to the solvent (water and anhydrous ethanol in a weight ratio of 1:4) is 1:2.

[0078] The molar ratio of titanium in the tetrabutyl titanate, lanthanum in the lanthanum salt (lanthanum chloride), and copper in the copper salt (copper chloride) is Ti:La:Cu = 1:0.15:0.3;

[0079] The above-mentioned method for preparing ceramic glaze includes: mixing the components to obtain the ceramic glaze.

[0080] Examples 1-9 and Comparative Examples 1-4

[0081] Examples 1-9 and Comparative Examples 1-4 provide different ceramic glazes. The difference between them and Example 1 lies in the molar ratio (Ti:La:Cu) of titanium in tetrabutyl titanate, lanthanum in lanthanum salt, and copper in copper salt. All other aspects are the same as in Example 1, as shown in the table below:

[0082] Table 1. Molar ratios of titanium, lanthanum in lanthanum salts, and copper in copper salts in tetrabutyl titanate of Examples 1-9 and Comparative Examples 1-4

[0083]

[0084] Comparative Example 5

[0085] This comparative example provides a ceramic glaze that differs from Example 1 in that it uses titanium dioxide, lanthanum oxide (La2O3), and copper oxide (CuO) in a molar ratio of 1:0.075:0.3 instead of lanthanum-containing copper titanium dioxide. In this case, the molar ratio of titanium, lanthanum, and copper in this comparative example is Ti:La:Cu = 1:0.15:0.3, which is consistent with Example 1.

[0086] Examples 10-13 and Comparative Examples 6-8

[0087] Examples 10-13 and Comparative Examples 6-8 provide different ceramic glazes, differing from Example 1 in the weight ratio of zinc oxide, lanthanum-containing copper titanium dioxide, and double-walled carbon nanotubes. All other aspects are identical to Example 1, as detailed in the table below:

[0088] Table 2. Weight ratios of zinc oxide, lanthanum-containing copper titanium dioxide, and double-walled carbon nanotubes in Examples 1, 10-13, and Comparative Examples 6-8.

[0089] The weight ratio of zinc oxide, lanthanum-containing copper titanium dioxide, and double-walled carbon nanotubes Example 1 1:3:0.3 Example 10 1:2:0.3 Example 11 1:4:0.3 Example 12 1:1:0.3 Example 13 1:5:0.3 Comparative Example 6 1:0:0.3 Comparative Example 7 0:3:0.3 Comparative Example 8 1:3:0

[0090] Examples 14-15

[0091] Examples 14-15 provide different ceramic glazes, which differ from Example 1 in that they use different types of carbon nanotubes; otherwise, they are the same as Example 1, as shown in the table below:

[0092] Table 3. Types of carbon nanotubes in Examples 1, 14-15

[0093] Types of carbon nanotubes Example 1 Double-walled carbon nanotubes Example 14 Single-walled carbon nanotubes Example 15 Multi-walled carbon nanotubes

[0094] Examples 16-19

[0095] Examples 16-19 provide different ceramic glazes, which differ from Example 1 in the weight percentage of the composite metal oxide; otherwise, they are identical to Example 1, as shown in the table below:

[0096] Table 4. Weight parts of composite metal oxides in Examples 1 and 16-19

[0097] Parts by weight of composite metal oxides Example 1 18 Example 16 15 Example 17 20 Example 18 10 Example 19 25

[0098] Examples 20-23 and Comparative Examples 9-10

[0099] Examples 20-23 and Comparative Examples 9-10 provide different ceramic glazes, differing from Example 1 in the weight ratio of sodium polynaphthalene sulfonate and Tween 40; otherwise, they are identical to Example 1, as shown in the table below:

[0100] Table 5. Weight ratio of sodium polynaphthalene sulfonate and Tween 40 in Examples 1, 20-23 and Comparative Examples 9-10

[0101] The weight ratio of sodium polynaphthalene sulfonate and Tween 40 Example 1 1:3 Example 20 1:1 Example 21 1:4 Example 22 1:0.5 Example 23 1:5 Comparative Example 9 1:0 Comparative Example 10 0:1

[0102] Comparative Example 11

[0103] This comparative example provides a ceramic glaze, which differs from Example 1 in that sodium carboxymethyl cellulose is used instead of sodium polynaphthalene sulfonate, while the other two aspects are consistent with Example 1.

[0104] Examples 24-26

[0105] Examples 24-26 provide different ceramic glazes, which differ from Example 1 in that they use different types of Tween; otherwise, they are the same as Example 1, as shown in the table below:

[0106] Table 6. Types of Tween in Examples 1, 24-26

[0107] Types of Twain Example 1 Twain 40 Example 24 Twain 20 Example 25 Twain 60 Example 26 Twain 80

[0108] Examples 27-28 and Comparative Examples 12-13

[0109] Examples 27-28 and Comparative Examples 12-13 provide different ceramic glazes, differing from Example 1 in the weight percentage of the dispersant; otherwise, they are identical to Example 1, as shown in the table below:

[0110] Table 7. Parts by weight of dispersants in Examples 1, 27-28 and Comparative Examples 12-13

[0111] Dispersant weight parts / parts Example 1 1 Example 27 0.1 Example 28 2 Comparative Example 12 10 Comparative Example 13 0

[0112] Example 29

[0113] This embodiment provides a ceramic glaze, which, by weight, comprises the following components:

[0114] 20 parts silica, 10 parts composite metal oxide, 20 parts talc, 10 parts anorthite, 1 part borax, 5 parts zirconium silicate, 0.1 part dispersant, 30 parts water;

[0115] The composite metal oxide contains zinc oxide, lanthanum-containing copper titanium dioxide, and double-walled carbon nanotubes in a weight ratio of 1:3:0.3.

[0116] The dispersant contains sodium polynaphthalene sulfonate and Tween 40 in a weight ratio of 1:3.

[0117] The method for preparing the lanthanum-containing copper titanium dioxide includes the following steps:

[0118] S1. Mix tetrabutyl titanate and anhydrous ethanol in a weight ratio of 1:7 to obtain solution A;

[0119] S2. Mix lanthanum salt (lanthanum chloride), copper salt (copper chloride) and solvent (water and anhydrous ethanol in a weight ratio of 1:4), adjust the pH to 2.5 with glacial acetic acid to obtain solution B;

[0120] S3. At 2500 r / min, solution B was added dropwise to solution A, and the reaction was carried out for 3 h. The solution was dried at 70 °C, calcined at 700 °C for 2 h, and ground to obtain lanthanum-containing copper titanium dioxide.

[0121] The weight ratio of the tetrabutyl titanate to the solvent (water and anhydrous ethanol in a weight ratio of 1:4) is 1:2.

[0122] The molar ratio of titanium in the tetrabutyl titanate, lanthanum in the lanthanum salt (lanthanum chloride), and copper in the copper salt (copper chloride) is Ti:La:Cu = 1:0.15:0.3;

[0123] The above-mentioned method for preparing ceramic glaze includes: mixing the components to obtain the ceramic glaze.

[0124] Example 30

[0125] This embodiment provides a ceramic glaze, which, by weight, comprises the following components:

[0126] 35 parts silica, 25 parts composite metal oxide, 30 parts talc, 30 parts anorthite, 4 parts borax, 15 parts zirconium silicate, 2 parts dispersant, 70 parts water;

[0127] The composite metal oxide contains zinc oxide, lanthanum-containing copper titanium dioxide, and double-walled carbon nanotubes in a weight ratio of 1:3:0.3.

[0128] The dispersant contains sodium polynaphthalene sulfonate and Tween 40 in a weight ratio of 1:3.

[0129] The method for preparing the lanthanum-containing copper titanium dioxide includes the following steps:

[0130] S1. Mix tetrabutyl titanate and anhydrous ethanol in a weight ratio of 1:7 to obtain solution A;

[0131] S2. Mix lanthanum salt (lanthanum chloride), copper salt (copper chloride) and solvent (water and anhydrous ethanol in a weight ratio of 1:4), adjust the pH to 2.5 with glacial acetic acid to obtain solution B;

[0132] S3. At 2500 r / min, solution B was added dropwise to solution A, and the reaction was carried out for 3 h. The solution was dried at 70 °C, calcined at 700 °C for 2 h, and ground to obtain lanthanum-containing copper titanium dioxide.

[0133] The weight ratio of the tetrabutyl titanate to the solvent (water and anhydrous ethanol in a weight ratio of 1:4) is 1:2.

[0134] The molar ratio of titanium in the tetrabutyl titanate, lanthanum in the lanthanum salt (lanthanum chloride), and copper in the copper salt (copper chloride) is Ti:La:Cu = 1:0.15:0.3;

[0135] The above-mentioned method for preparing ceramic glaze includes: mixing the components to obtain the ceramic glaze.

[0136] Application Example 1

[0137] This application example provides a ceramic tile, comprising a body and a glaze layer, wherein the raw material of the glaze layer contains the ceramic glaze prepared in Example 1, and the raw material of the body contains the following components in parts by weight:

[0138] 30 parts kaolin, 20 parts silicon nitride, 15 parts limestone, 10 parts quartz, 5 parts talc;

[0139] The above-mentioned method for preparing ceramic tiles includes the following steps:

[0140] A1. The raw material of the billet is wet ball-milled into a slurry, dried, and pressed into shape to obtain the green billet;

[0141] A2. Spray ceramic glaze onto the green body, dry, and sinter at 1200℃ for 7 hours to obtain ceramic tiles;

[0142] Each square centimeter of the green body contains 2.5g of ceramic glaze.

[0143] Application Example 2-30

[0144] Application Examples 2-30 provide different ceramic tiles, which differ from Application Example 1 in that the ceramic glaze prepared in Examples 2-30 is used instead of the ceramic glaze in Example 1, while the rest are the same as Application Example 1.

[0145] Comparative Application Example 1

[0146] This comparative application example provides a ceramic tile, comprising a body and a glaze layer, wherein the raw material of the glaze layer contains the ceramic glaze prepared in Comparative Example 1, and the raw material of the body contains the following components in parts by weight:

[0147] 30 parts kaolin, 20 parts silicon nitride, 15 parts limestone, 10 parts quartz, 5 parts talc;

[0148] The above-mentioned method for preparing ceramic tiles includes the following steps:

[0149] A1. The raw material of the billet is wet ball-milled into a slurry, dried, and pressed into shape to obtain the green billet;

[0150] A2. Spray ceramic glaze onto the green body, dry, and sinter at 1200℃ for 7 hours to obtain ceramic tiles;

[0151] Each square centimeter of the green body contains 2.5g of ceramic glaze.

[0152] Compare and contrast with example 2-13

[0153] Comparative Application Examples 2-13 provide different ceramic tiles. The difference between Comparative Application Examples 2-13 and Application Example 1 is that the ceramic glaze prepared in Comparative Examples 2-13 is used instead of the ceramic glaze in Example 1. Otherwise, they are the same as Application Example 1.

[0154] Comparative Application Example 14

[0155] This comparative application example provides a ceramic tile, comprising a body and a glaze layer, wherein the raw material of the glaze layer contains ceramic glaze, and the raw material of the body contains the following components in parts by weight:

[0156] 30 parts kaolin, 20 parts silicon nitride, 15 parts limestone, 10 parts quartz, 5 parts talc;

[0157] The ceramic glaze, by weight, comprises the following components:

[0158] 30 parts silica, 0 parts composite metal oxide, 25 parts talc, 20 parts anorthite, 3 parts borax, 9 parts zirconium silicate, 1 part dispersant, 50 parts water;

[0159] The dispersant contains sodium polynaphthalene sulfonate and Tween 40 in a weight ratio of 1:3.

[0160] The above-mentioned method for preparing ceramic glaze includes: mixing the components to obtain the ceramic glaze.

[0161] The above-mentioned method for preparing ceramic tiles includes the following steps:

[0162] A1. The raw material of the billet is wet ball-milled into a slurry, dried, and pressed into shape to obtain the green billet;

[0163] A2. Spray ceramic glaze onto the green body, dry, and sinter at 1200℃ for 7 hours to obtain ceramic tiles;

[0164] Each square centimeter of the green body contains 2.5g of ceramic glaze.

[0165] Performance testing

[0166] Performance tests were conducted on the tiles in each application example and the comparative application example, as detailed below:

[0167] 1. Antibacterial effect test:

[0168] According to Appendix A, "Test Methods for Antibacterial Properties," of standard JC / T 897-2014 "Antibacterial Properties of Antibacterial Ceramic Products," antibacterial tests were conducted on the ceramic tiles in each application example and the comparative application example. *Escherichia coli* was used as the test bacteria, and the concentration of the test bacterial solution was 2.0 × 10⁻⁶. 4 With CFU / mL and a volume of 0.3mL, the ceramic tile of Application Example 14 without the addition of composite metal oxides was used as a blank control sample. The antibacterial rate (%) of each application example and the control application example ceramic tile was recorded and calculated.

[0169] The higher the antibacterial rate, the better the antibacterial effect of the tile;

[0170] 2. Compressive strength test:

[0171] The compressive strength of ceramic tiles in each application example and comparative application example was tested according to the standard GB / T 4740-1999 "Test Method for Compressive Strength of Ceramic Materials". The sample shape used was circular, and the compressive strength (MPa) of ceramic tiles in each application example and comparative application example was recorded.

[0172] The experimental results are shown in the table below:

[0173] Table 8. Performance test results of tiles in various application examples and comparative application examples.

[0174]

[0175]

[0176]

[0177] Figure 1 The figures show actual images of the tiles used in Application Example 1 and Comparative Application Example 1. In the figures, Figure A is an actual image of the tiles used in Application Example 1, and Figure B is an actual image of the tiles used in Comparative Application Example 1.

[0178] As shown in Table 8, the ceramic glaze of the present invention can improve the antibacterial effect and compressive strength of ceramic tiles.

[0179] Specifically, the present invention utilizes the sol-gel method to prepare lanthanum-copper titanium dioxide by using a specific molar ratio of tetrabutyl titanate, lanthanum salt, and copper salt. This allows the antibacterial lanthanum oxide and copper oxide to be uniformly dispersed in the titanium dioxide system and tightly connected to each other, thus fusing the lanthanum oxide, copper oxide, and titanium dioxide to form a structurally stable solid, thereby improving the antibacterial effect and compressive strength of the ceramic.

[0180] This invention utilizes zinc oxide and carbon nanotubes to synergistically enhance the function of lanthanum-containing copper titanium dioxide, thereby improving the antibacterial effect and compressive strength of ceramic tiles.

[0181] The dispersants sodium polynaphthalene sulfonate (CAS No.: 9084-06-4) and Tween of the present invention can promote the dispersibility of composite metal oxides, especially lanthanum copper titanium dioxide, in ceramic glazes, thereby stabilizing the properties of ceramic glazes and helping components such as lanthanum copper titanium dioxide to better adhere to the surface of the ceramic tile body, thus improving the antibacterial effect and compressive strength of the ceramic tile.

[0182] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A ceramic glaze, characterized in that, Calculated by weight, it includes the following components: 20-35 parts silica, 10-25 parts composite metal oxides, 20-30 parts talc, 10-30 parts anorthite, 1-4 parts borax, 5-15 parts zirconium silicate, 0.1-2 parts dispersant, 30-70 parts water; The composite metal oxide contains zinc oxide, lanthanum-containing copper titanium dioxide, and carbon nanotubes. The lanthanum-containing copper titanium dioxide is prepared by a sol-gel method using tetrabutyl titanate, lanthanum salt, and copper salt. The molar ratio of titanium in tetrabutyl titanate, lanthanum in lanthanum salt, and copper in copper salt is Ti:La:Cu = 1:(0.05-0.3):(0.1-0.5). The dispersant contains sodium polynaphthalene sulfonate and Tween.

2. The ceramic glaze as described in claim 1, characterized in that, Includes at least one of the following (1)-(3): (1) The molar ratio of titanium in the tetrabutyl titanate, lanthanum in the lanthanum salt, and copper in the copper salt is Ti:La:Cu=1:(0.1-0.2):(0.2-0.4); (2) The weight ratio of zinc oxide, lanthanum-containing copper titanium dioxide, and carbon nanotubes is 1:(1-5):(0.1-0.5); (3) The weight ratio of sodium polynaphthalene sulfonate to Tween is 1:(0.5-5).

3. The ceramic glaze as described in claim 2, characterized in that, Includes at least one of the following (1)-(2): (1) The weight ratio of zinc oxide, lanthanum-containing copper titanium dioxide, and carbon nanotubes is 1:(1-5):0.3; (2) The weight ratio of the sodium polynaphthalene sulfonate salt to Tween is 1:(1-4).

4. The ceramic glaze as described in claim 3, characterized in that, The weight ratio of zinc oxide, lanthanum-containing copper titanium dioxide, and carbon nanotubes is 1:(2-4):0.

3.

5. The ceramic glaze as described in claim 1, characterized in that, Includes at least one of the following (1)-(5): (1) The composite metal oxide is 15-20 parts by weight; (2) The carbon nanotubes are at least one of single-walled carbon nanotubes, double-walled carbon nanotubes, and multi-walled carbon nanotubes; (3) The Tween is at least one of Tween 20, Tween 40, Tween 60, and Tween 80; (4) The lanthanum salt is at least one of lanthanum chloride and lanthanum nitrate; (5) The copper salt is at least one of copper chloride, copper nitrate, and copper sulfate.

6. The ceramic glaze as described in claim 1, characterized in that, The method for preparing the lanthanum-containing copper titanium dioxide includes the following steps: S1. Mix tetrabutyl titanate and ethanol to obtain solution A; S2. Mix lanthanum salt, copper salt and solvent, adjust pH to 2-3 to obtain solution B; S3. Mix solution B and solution A, react them, and calcine to obtain lanthanum-containing copper titanium dioxide.

7. A method for preparing the ceramic glaze according to any one of claims 1-6, characterized in that, include: By mixing the components, the ceramic glaze is obtained.

8. The application of any one of the ceramic glazes described in claims 1-6 in ceramic tiles.

9. A type of ceramic tile, characterized in that, It includes a body and a glaze layer, wherein the raw material of the glaze layer contains any of the ceramic glazes described in claims 1-6.

10. A method for preparing the ceramic tile according to claim 9, characterized in that, Includes the following steps: A1. Mix the raw materials of the billet, press them into shape, and obtain the green billet; A2. Apply and / or spray ceramic glaze onto the green body, sinter, and obtain ceramic tile.

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