Antibacterial ceramic glaze as well as preparation method and application thereof

Abstract

The invention discloses antibacterial ceramic glaze as well as a preparation method and application thereof, belongs to the technical field of ceramic glaze processing, and aims to solve the technical problem that the antibacterial property of ceramic glaze needs to be further improved in the prior art. The high-temperature-resistant glaze specifically comprises the following components in parts by weight: 40-60 parts of modified kaolin, 10-20 parts of modified calcite, 40-60 parts of feldspar powder, 5-10 parts of zinc oxide, 8-10 parts of borax, 20-30 parts of alumina and 20-30 parts of perlite. Silver ions and copper ions are used as antibacterial agents, complementation of the two antibacterial agents is achieved, the limitation of a single antibacterial agent is broken through when the two antibacterial agents are used in cooperation, common microorganisms such as bacteria, fungi and molds can be covered after cooperation, and the effects of rapid sterilization and long-acting bacteriostasis are achieved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of ceramic glaze processing, and particularly relates to an antibacterial ceramic glaze and a preparation method and application thereof. BACKGROUND

[0002] With the improvement of living standards, people's health consciousness is constantly enhanced, and in recent years, the frequent H1N1 influenza A, E. coli epidemic and other events make people realize that they need to fight against bacteria and other microorganisms for a long time, so the research on antibacterial materials gradually rises.

[0003] Since ceramic products are widely used in people's daily life, the application of antibacterial ceramics in the medical and health, construction, water treatment and other industries has attracted more and more attention, and with the strengthening of environmental protection consciousness and the improvement of biological technology, inorganic antibacterial agents are more and more favored by researchers due to their wide application range, good heat resistance, wide antibacterial spectrum, long-acting antibacterial, low toxicity and no drug resistance.

[0004] At present, most of the antibacterial ceramics are obtained by adding antibacterial agents on the surface or inside of the ceramic to inhibit or kill the bacteria contacting the functional ceramic material, but the traditional ceramic directly adds metal ion salt or oxide in the glaze, and in the high-temperature sintering process of the ceramic, the undecomposed metal ions may react with silicates or aluminates in the glaze to form stable copper silicate or copper aluminate, and the metal ions in these compounds are difficult to dissolve and lose antibacterial activity; if the antibacterial agent is directly introduced, the antibacterial components such as silver ions and copper ions are combined with the glaze matrix mainly through physical adsorption, and this combination depends on the van der Waals force between molecules, and the force is weak, and the free state exists in the glaze micropore or surface, when the ceramic contacts water and detergent, the free antibacterial agent is quickly dissolved out, and finally loses the sterilization capacity, which is difficult to meet the demand of people for multifunctional daily ceramics. SUMMARY

[0005] The present application aims to provide an antibacterial ceramic glaze and a preparation method and application thereof, which are used to solve the technical problem that the antibacterial performance of the ceramic glaze in the prior art needs to be further improved.

[0006] The purpose of the present application can be achieved by the following technical scheme: an antibacterial ceramic glaze comprises the following components in parts by weight: modified kaolin 40-60 parts, modified calcite 10-20 parts, feldspar powder 40-60 parts, zinc oxide 5-10 parts, borax 8-10 parts, alumina 20-30 parts, and perlite 20-30 parts.

[0007] The preparation method of the modified kaolin is as follows:

[0008] A1, the kaolin is dried, crushed, mixed with sodium hydroxide solution in a beaker, the temperature is raised to 50-70℃, and the reaction is carried out for 5-7h, and then the activated kaolin is obtained after post-processing;

[0009] A2, the activated kaolin and the ethanol aqueous solution are added into a three-necked flask and uniformly dispersed, nitric acid is added to adjust the pH to 3-5, the temperature is raised to 50-60℃ and stirred, the silver nitrate aqueous solution and the tetraethyl orthosilicate ethanol solution are added into the system, and the saturated ammonia water is added to adjust the pH to 8-10, the reaction is carried out for 8-10h, and then the modified kaolin is obtained after post-processing

[0010] The synthesis mechanism of the modified kaolin is as follows:

[0011] The sodium hydroxide as the alkali solution medium reacts with the silicate and aluminate in the kaolin, breaks the interlayer chemical bond, generates the soluble silicate and aluminate, and at the same time, generates micropores and defects on the surface of the kaolin particles; the ethanol aqueous solution as the dispersion medium can inhibit the premature hydrolysis of the tetraethyl orthosilicate, and then the weak alkalinity is adjusted to make the tetraethyl orthosilicate hydrolyze into silica sol, the silver ion is provided by the silver nitrate, under the weak alkaline condition, the silver ion combines with the hydroxyl in the silica sol, is wrapped in the silica gel network, avoids the silver ion from agglomerating, the high temperature makes the silica gel convert into the dense silica coating layer, stably loads the silver ion on the surface of the kaolin, and the modified kaolin is obtained.

[0012] Further, in step A1, the amount ratio of the kaolin to the sodium hydroxide aqueous solution is 1g:2-5mL; and the concentration of the sodium hydroxide aqueous solution is 2-5mol / L.

[0013] Further, in step A1, the post-processing step includes: centrifugal separation, the solid is placed in a muffle furnace at 800℃ and calcined for 5h, cooled to room temperature, washed with deionized water at 80℃ until neutral, filtered, and the filter cake is placed in a drying oven at 60℃ and dried to constant weight to obtain the activated kaolin.

[0014] Further, in step A2, the amount ratio of the activated kaolin, the ethanol aqueous solution, the silver nitrate aqueous solution and the tetraethyl orthosilicate ethanol solution is 10g:40-90mL:3mL:10mL; the ethanol aqueous solution is composed of ethanol and deionized water in a volume ratio of 1:1, the tetraethyl orthosilicate ethanol solution is composed of tetraethyl orthosilicate and anhydrous ethanol in an amount ratio of 1.5g:8.5mL; the concentration of the silver nitrate aqueous solution is 0.6mol / L, and the post-processing step includes: after the reaction is completed, the filter cake is washed with deionized water for 3-5 times, transferred to a drying oven at 100-120℃ and dried to constant weight, and placed in a muffle furnace at 300-500℃ and calcined for 1-2h to obtain the modified kaolin.

[0015] Further, the preparation method of the modified calcite is as follows:

[0016] B1, calcite powder and hydrochloric acid solution are added into a beaker, stirred at room temperature for 10-20 min, saturated ammonia water is added to adjust pH to neutral, centrifugal washing and drying are carried out, and pretreated calcite powder is obtained;

[0017] B2, the pretreated calcite powder is added into deionized water, ultrasonic dispersion is carried out for 20-30 min, a KH-550 solution is added, the temperature is increased to 60-80 DEG C, copper sulfate pentahydrate is added, a sodium hydroxide solution is added to adjust pH to 9-10, stirring is carried out for 30-40 min, post-treatment is carried out, and modified calcite is obtained.

[0018] The synthesis mechanism of the modified calcite is as follows:

[0019] Calcite reacts with hydrochloric acid, is partially dissolved to release carbon dioxide, forms a porous loose structure, and ammonia water neutralizes excess hydrochloric acid; a large number of holes are generated on the surface of residual calcium carbonate due to acid etching, activation is achieved, silanol is generated by hydrolysis of the silane coupling agent, and the silanol is condensed with the hydroxyl groups on the surface of the calcite to form a silicon-oxygen bond; under alkaline conditions, copper ions are coordinated with the amino groups of the silane coupling agent, are anchored on the silane molecular chain, form a composite structure, and the modified calcite is obtained.

[0020] Further, in step B1, the use amount ratio of the calcite powder and hydrochloric acid is 1g:5mL, and the concentration of the hydrochloric acid solution is 3wt%; in step B2, the use amount ratio of the calcite powder, deionized water, KH-550 solution and copper sulfate pentahydrate is 100g:500-800mL:5.8mL:4.8-6.8g; the KH-550 solution is composed of γ-aminopropyl triethoxysilane and ethanol at a volume ratio of 2.7:3.1; the post-treatment includes: after the reaction is completed, standing is carried out, the temperature is reduced to room temperature, centrifugal washing is carried out with deionized water until neutral, the filter cake is transferred to a 60-80 DEG C drying oven for drying until the weight is constant, and the modified calcite is obtained.

[0021] The application further provides a preparation method of the antibacterial ceramic glaze.

[0022] S1, 40-60 parts of modified antibacterial kaolin, 10-20 parts of modified calcite, 40-60 parts of feldspar powder, 5-10 parts of zinc oxide, 8-10 parts of borax, 20-30 parts of alumina, and 20-30 parts of perlite are added into a mixing machine and uniformly mixed, are calcined to a molten state in a high-temperature gradient furnace, are kept warm, and are water-quenched to obtain a glass material;

[0023] S2, the glass material is placed in a ball mill tank, the ball mill rotation speed is 300-400 rpm, ball milling is carried out for 5-6 h, the ball mill tank is passed through a 200-mesh screen, and deionized water is added to obtain the ceramic glaze.

[0024] Further, in step S1, the water quenching step comprises: uniformly pouring the heat-insulated molten glass into a cooling water tank through a high-temperature-resistant guide groove, solidifying for 5-15 min, transferring the glass frit to filter cloth, and drying in an oven at 80-100 DEG C for 2-4 h to obtain the glass frit; in step S2, the dosage ratio of the glass frit to deionized water is 10 g:5-7 mL, and the ball frit ratio is 2:1.

[0025] The application further provides application of the antibacterial ceramic glaze.

[0026] The application has the following advantages:

[0027] 1. In the preparation of the antibacterial ceramic glaze, the kaolin is modified, a silicon dioxide coating layer forms a physical barrier, allowing slow release of silver ions and isolation from external interference, ensuring that the silver ions always maintain bactericidal activity, the composite structure after high-temperature baking can withstand the sintering temperature of the ceramic glaze and will not cause the antibacterial components to lose effectiveness or turn yellow due to high-temperature decomposition; the activation treatment of the kaolin partially disintegrates the original layered structure to generate more reactive silico-aluminate phases, which cooperate with the subsequently introduced silicon dioxide to promote the formation of a glass phase during high-temperature melting of the glaze, fill the internal pores of the glaze layer, and improve the glaze surface density, while the stable silver-based particles loaded can be used as a reinforcing phase to combine with the glass phase, thereby improving the hardness and wear resistance of the glaze layer and reducing scratches during daily use.

[0028] 2. In the preparation of the antibacterial ceramic glaze, the calcite is modified, the calcite is etched with acid to make the specific surface area of the calcite larger, and the surface hydroxyl groups can form hydrogen bonds with the silicon dioxide or aluminum oxide in the glaze, thereby enhancing the interfacial bonding force; the silicon-oxygen chain of the silane coupling agent is resistant to high temperature, and the molecular cage formed locks the copper ions, thereby greatly improving the antibacterial property of the ceramic glaze at high temperature; the silane coupling agent is hydrolyzed to generate silicon hydroxyl groups, which react with the hydroxyl groups on the surface of the calcite to form covalent bonds, thereby fixing the silane on the surface of the substrate, the amino group acts as a ligand to form a coordination bond with the copper ions, thereby anchoring the copper ions on the silane molecules to form a stable silane-copper ion complex, forming a slow-release structure, improving the antibacterial efficiency of the material, and prolonging the antibacterial period; the copper ions loaded on the calcite form stable cuprate during high-temperature melting, which is chemically inert and can resist corrosion by acids and bases, the presence of the copper ions can inhibit microbial reproduction and avoid corrosion of the glaze layer by organic acids produced by biological metabolism, thereby significantly improving the corrosion resistance of the ceramic glaze.

[0029] 3. In the process of preparing antibacterial ceramic glaze, the present invention uses silver ions and copper ions as antibacterial agents. The two antibacterial agents complement each other and break through the limitations of a single antibacterial agent when used in combination. The combination can cover common microorganisms such as bacteria, fungi, and molds; silver ions quickly control the initial bacterial population, and copper ions subsequently enhance sterilization and inhibit regeneration, which significantly improves the antibacterial efficiency. The relay action of the two ions can reduce the dosage of a single ion and avoid glaze discoloration caused by high concentrations of metal ions; the silica shell structure of the modified kaolin wraps the silver ions, and the silane bridging structure of the modified calcite fixes the copper ions. At the same time, the porous structures of the two carriers form a reservoir effect, which significantly extends the antibacterial effectiveness period. DETAILED DESCRIPTION

[0030] The technical solutions of the present invention will be clearly and completely described below in conjunction with the embodiments. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0031] Example 1

[0032] This embodiment provides an antibacterial ceramic glaze and a preparation method thereof, comprising the following steps:

[0033] S1. Preparation of modified kaolin

[0034] Add 500 mL of ethanol and 500 mL of deionized water into a beaker and mix to obtain an ethanol-water solution;

[0035] Add 15 g of ethyl orthosilicate and 85 mL of anhydrous ethanol into a beaker and mix to obtain an ethyl orthosilicate ethanol solution for later use;

[0036] Weigh: 100g of kaolin, dry it, crush it, add it to 250mL of 2mol / L sodium hydroxide aqueous solution in a beaker and mix it evenly. Raise the temperature to 50℃ and react for 5h. After the reaction is complete, cool it to room temperature and filter it. Wash the filter cake with 70℃ deionized water until it is neutral, and then dry it in a 60℃ drying oven to constant weight to obtain activated kaolin.

[0037] Weigh: 100g activated kaolin and 500mL ethanol aqueous solution are added to a three-necked flask and dispersed evenly, nitric acid is added to adjust the pH to 3, the temperature is raised to 50°C and stirred, 30mL 0.6mol / L silver nitrate aqueous solution and 100mL ethyl orthosilicate ethanol solution are added to the system, saturated ammonia water is added to adjust the pH to 8, and the reaction is carried out for 8h. After the reaction is completed, filter, wash the filter cake 3 times with deionized water, transfer to a 100°C drying oven and dry to constant weight, place it in a 300°C muffle furnace and calcine for 1h to obtain modified kaolin.

[0038] S2. Preparation of modified calcite

[0039] Mix γ-aminopropyltriethoxysilane and ethanol in a volume ratio of 2.7:3.1 to obtain a KH-550 solution, which is set aside;

[0040] Weigh: 100 g of calcite powder and 500 mL of 3 wt% hydrochloric acid solution were added to a beaker, stirred at room temperature for 10 min, saturated ammonia was added to adjust the pH to neutral, centrifuged and washed three times with deionized water, and then transferred to a 60°C drying oven to dry to constant weight to obtain pretreated calcite powder;

[0041] Weigh: 100g pretreated calcite powder is added to 500mL deionized water, ultrasonically dispersed for 20min, 5.8mL KH-550 solution is added, the temperature is raised to 60°C, 4.8g copper sulfate pentahydrate is added, sodium hydroxide solution is added to adjust the pH to 9, and stirred for 30min. After the reaction is completed, it is allowed to stand, the temperature is lowered to room temperature, centrifuged, washed with deionized water, and transferred to a 60°C drying oven to dry to constant weight to obtain square modified calcite.

[0042] S3. Preparation of ceramic glaze

[0043] 40 parts of modified antibacterial kaolin, 10 parts of modified calcite, 40 parts of feldspar powder, 5 parts of zinc oxide, 8 parts of borax, 20 parts of alumina, and 20 parts of perlite were added to a mixer and mixed evenly. The mixture was placed in a high-temperature gradient furnace and calcined to a molten state. The mixture was kept warm, and the molten glass after the insulation was uniformly poured into a cooling water tank through a high-temperature resistant diversion trough and solidified for 5 minutes. The glass material was transferred to a filter cloth and placed in an 80°C oven to dry for 2 hours to obtain a glass material.

[0044] 100 g of glass material was placed in a ball mill jar at a ball mill speed of 300 rpm for 5 h, passed through a 200-mesh sieve, and 50 mL of deionized water was added to obtain a ceramic glaze.

[0045] Example 2

[0046] This embodiment provides an antibacterial ceramic glaze and a preparation method thereof, comprising the following steps:

[0047] S1. Preparation of modified kaolin

[0048] Add 500 mL of ethanol and 500 mL of deionized water into a beaker and mix to obtain an ethanol-water solution;

[0049] Add 15 g of ethyl orthosilicate and 85 mL of anhydrous ethanol into a beaker and mix to obtain an ethyl orthosilicate ethanol solution for later use;

[0050] Weighing: 100 g of kaolin is dried and pulverized, and then mixed with 250 mL of 3 mol / L sodium hydroxide aqueous solution in a beaker. The temperature is raised to 60°C, and the reaction is carried out for 6 h. After the reaction is completed, the temperature is cooled to room temperature, and then filtered. The filter cake is washed with deionized water at 80°C until it is neutral, and then dried in a 70°C drying oven until the weight is constant to obtain activated kaolin.

[0051] Weighing: 100 g of activated kaolin and 500 mL of ethanol aqueous solution are added to a three-necked flask and uniformly dispersed. Nitric acid is added to adjust the pH to 4, and the temperature is raised to 55°C and stirred. 30 mL of 0.6 mol / L silver nitrate aqueous solution and 100 mL of tetraethyl orthosilicate ethanol solution are added to the system, and saturated ammonia water is added to adjust the pH to 9. The reaction is carried out for 9 h, and after the reaction is completed, the filter cake is washed with deionized water for 4 times, and then transferred to a 110°C drying oven to dry until the weight is constant. It is calcined in a 400°C muffle furnace for 1.5 h to obtain modified kaolin.

[0052] S2, preparation of modified calcite

[0053] Mix 15 g of hydrochloric acid and 485 mL of deionized water to obtain a hydrochloric acid solution;

[0054] Mix γ-aminopropyl triethoxysilane and ethanol in a volume ratio of 2.7:3.1 to obtain a KH-550 solution, which is ready for use;

[0055] Weighing: 100 g of calcite powder and 500 mL of 3 wt% hydrochloric acid solution are added to a beaker, stirred at room temperature for 10-20 min, and then adjusted to neutral pH with saturated ammonia water. Centrifugal washing is carried out 4 times with deionized water, and then transferred to a 70°C drying oven to dry until the weight is constant to obtain pretreated calcite powder;

[0056] Weighing: 100 g of pretreated calcite powder is added to 500 mL of deionized water, and ultrasonic dispersion is carried out for 25 min. 5.8 mL of KH-550 solution is added, the temperature is raised to 70°C, 4.8 g of copper sulfate pentahydrate is added, and sodium hydroxide solution is added to adjust the pH to 10. Stirring is carried out for 35 min, and after the reaction is completed, the temperature is lowered to room temperature, centrifugal washing is carried out with deionized water, and then transferred to a 70°C drying oven to dry until the weight is constant to obtain modified calcite.

[0057] S3, preparation of ceramic glaze

[0058] Mix 50 parts of modified antibacterial kaolin, 14 parts of modified calcite, 50 parts of feldspar powder, 7 parts of zinc oxide, 9 parts of borax, 25 parts of alumina, and 25 parts of perlite in a mixer to mix uniformly. After calcination to a molten state in a high-temperature gradient furnace, the molten glass after heat preservation is uniformly poured into a cooling water tank at a constant speed, and solidified for 10 min. The glass material is transferred to filter cloth and dried in a 90°C oven for 3 h to obtain a glass material.

[0059] Put 100 g of glass frit into a ball mill tank, the ball mill rotates at 350 rpm, ball mill for 5.5 h, pass through a 200 mesh screen, add 60 mL of deionized water to obtain a ceramic glaze.

[0060] Example 3

[0061] The present embodiment provides an antibacterial ceramic glaze and a preparation method thereof, comprising the following steps:

[0062] S1, preparation of modified kaolin

[0063] Mix 500 mL of ethanol and 500 mL of deionized water in a beaker to obtain an ethanol aqueous solution;

[0064] Mix 15 g of tetraethyl orthosilicate and 85 mL of anhydrous ethanol in a beaker to obtain a tetraethyl orthosilicate ethanol solution, ready for use;

[0065] Weigh: 100 g of kaolin is dried and crushed, and 250 mL of 3 mol / L sodium hydroxide solution is added to the beaker and mixed uniformly, the temperature is raised to 70°C, and the reaction is carried out for 7 h. After the reaction is completed, cool to room temperature, filter, wash the filter cake with 90°C deionized water until it is neutral, and then place it in a 70°C drying oven to dry to constant weight to obtain activated kaolin;

[0066] Weigh: 100 g of activated kaolin and 500 mL of ethanol aqueous solution are added to a three-necked flask and dispersed uniformly, add nitric acid to adjust the pH to 5, increase the temperature to 60°C and stir, add 30 mL of 0.6 mol / L silver nitrate aqueous solution and 100 mL of tetraethyl orthosilicate ethanol solution to the system, adjust the pH to 10 with saturated ammonia water, and react for 10 h. After the reaction is completed, filter, wash the filter cake with deionized water 5 times, transfer to a 120°C drying oven and dry to constant weight, and place it in a 500°C muffle furnace and calcine for 2 h to obtain modified kaolin.

[0067] S2, preparation of modified calcite

[0068] Mix 15 g of hydrochloric acid and 485 mL of deionized water to obtain a hydrochloric acid solution;

[0069] Mix γ-aminopropyltriethoxysilane and ethanol at a volume ratio of 2.7:3.1 to obtain a KH-550 solution, ready for use;

[0070] Weigh: 100 g of calcite powder and 500 mL of 3 wt% hydrochloric acid solution are added to a beaker, stirred at room temperature for 20 min, adjusted to neutral pH with saturated ammonia water, washed with deionized water by centrifugation 5 times, then transferred to an 80°C drying oven and dried to constant weight to obtain pretreated calcite powder;

[0071] Weigh: 100g pretreated calcite powder is added to 500mL deionized water, ultrasonically dispersed for 30min, 5.8mL KH-550 solution is added, the temperature is raised to 80°C, 4.8g copper sulfate pentahydrate is added, sodium hydroxide solution is added to adjust the pH to 10, and stirred for 40min. After the reaction is completed, it is allowed to stand, the temperature is lowered to room temperature, centrifuged, washed with deionized water, and transferred to an 80°C drying oven to dry to constant weight to obtain square modified calcite.

[0072] S3. Preparation of ceramic glaze

[0073] 60 parts of modified antibacterial kaolin, 20 parts of modified calcite, 60 parts of feldspar powder, 10 parts of zinc oxide, 10 parts of borax, 30 parts of alumina, and 30 parts of perlite were added to a mixer and mixed evenly. The mixture was placed in a high-temperature gradient furnace and calcined to a molten state. The mixture was kept warm, and the molten glass after the insulation was uniformly poured into a cooling water tank through a high-temperature resistant diversion trough and solidified for 15 minutes. The glass material was transferred to a filter cloth and placed in an oven at 100°C for 4 hours to obtain a glass material.

[0074] 100 g of glass material was placed in a ball mill jar at a ball mill speed of 400 rpm for 6 h, passed through a 200-mesh sieve, and 70 mL of deionized water was added to obtain a ceramic glaze.

[0075] Comparative Example 1

[0076] The difference between this comparative example and Example 3 is that step S1 is omitted and the kaolin in step S1 is used instead of the modified kaolin.

[0077] Comparative Example 2

[0078] The difference between this comparative example and Example 3 is that in step S1, no ethyl orthosilicate solution is added.

[0079] Comparative Example 3

[0080] The difference between this comparative example and Example 3 is that step S2 is eliminated and the modified calcite is replaced by the calcite powder in step S2.

[0081] Comparative Example 4

[0082] The difference between this comparative example and Example 3 is that the copper sulfate pentahydrate in step S2 is replaced by copper oxide.

[0083] Performance testing:

[0084] Preparation of ceramic glaze: align the body with the axis of the rotating table, fix it with a vacuum chuck, ensure that it does not shake during rotation, pour the prepared ceramic glaze into the glaze machine storage tank, open the valve to fill the glaze pipe with ceramic glaze, discharge the air in the pipe, first start the rotating table, wait for the speed to stabilize, then open the glaze nozzle valve, let the ceramic glaze flow down in the form of a column or a fan, cover the center to the edge of the body, after closing the glaze nozzle valve, keep the body rotating for 13 seconds, use the centrifugal force to make the glaze layer flow evenly, remove the excess ceramic glaze, place the glazed body in a well-ventilated area to dry naturally until the glaze surface has no flowability, then place the body in the kiln smoothly for firing, and obtain the ceramic glaze.

[0085] The antibacterial properties and antibacterial durability of the ceramic glaze prepared in Examples 1-3 and Comparative Examples 1-4 were determined according to the standard JC / T 897-2014 "Antibacterial properties of antibacterial ceramic products", wherein the tested bacteria were Staphylococcus aureus and Escherichia coli;

[0086] The wear resistance of the ceramic glaze prepared in Examples 1-3 and Comparative Examples 1-4 was determined according to the standard GB / T 3810.7-2016 "Ceramic tiles - Test methods - Part 7: Determination of the surface abrasion resistance of glazed tiles".

[0087] The acid corrosion resistance of the ceramic glaze prepared in Examples 1-3 and Comparative Examples 1-4 was determined according to the standard JC / T 2138-2012 "Test method for acid and alkali corrosion resistance of fine ceramics", wherein the test mass change was the change in mass per unit area, and the corrosion solution was a 3.0 mol / L sulfuric acid solution soaked for 72 h;

[0088] The Vickers hardness of the ceramic glaze prepared in Examples 1-3 and Comparative Examples 1-4 was determined according to the standard GB / T 16534-2009 "Test method for hardness of fine ceramics at room temperature", and the specific test results are shown in Table 1 below:

[0089] Table 1 - Performance test data table of the sample

[0090]

[0091] Data analysis:

[0092] Analyzing the data in Table 1 above, during the preparation of the antibacterial ceramic glaze, the kaolin and calcite were modified, the Staphylococcus aureus antibacterial property of the ceramic glaze reached 99.8%, the Escherichia coli antibacterial property reached 99.8%, the Staphylococcus aureus antibacterial durability reached 99.5%, the Escherichia coli antibacterial durability reached 99.5%, the wear resistance grade was 5, the Vickers hardness reached 8.2 GPa, and the unit mass change of corrosion resistance was 0.3 x 10 - 3 g·m -2The embodiments are all superior to the comparative examples, indicating that the application uses silver ions and copper ions as antibacterial agents, the two antibacterial agents complement each other, and when used together, the limitations of a single antibacterial agent are broken through, and after cooperation, common microorganisms such as bacteria, fungi, and molds can be covered, and the effect of rapid sterilization and long-acting bacteriostasis is achieved.

[0093] Compared with the comparative example 1 and the embodiment, the kaolinite is modified to solve the contradiction between the antibacterial efficiency and the long-acting property of the traditional antibacterial agent, and the coating layer of the silicon dioxide is combined to protect the bactericidal activity of the silver ions and further improve the wear resistance and hardness of the glaze layer.

[0094] Compared with the comparative example 2 and the embodiment, the addition of the tetraethyl orthosilicate forms a silicon dioxide coating layer to form a physical barrier, slowly releases the silver ions, and isolates external interference, so that the silver ions always maintain the bactericidal activity.

[0095] Compared with the comparative example 3 and the embodiment, the calcite is modified, the high-temperature resistance of the silane coupling agent and the antibacterial property of the copper ions are mutually matched, and the antibacterial property and the corrosion resistance of the ceramic glaze are significantly improved.

[0096] Compared with the comparative example 4 and the embodiment, if the copper oxide is replaced, the release rate and the concentration of the copper ions will be significantly reduced, the antibacterial efficiency of the ceramic glaze will be obviously decreased, and the inhibition effect on the rapidly reproducing bacteria will be weakened. If the same antibacterial efficiency needs to be maintained, the addition amount of the copper oxide needs to be greatly increased, and at the same time, the problems of deepened color, rough surface, and the like will be caused.

[0097] The preferred embodiments of the application disclosed above are only used to help explain the application. The preferred embodiments do not describe all the details, and the application is not limited to the specific embodiments. Obviously, many modifications and changes can be made according to the content of the specification. The embodiments are selected and described in the specification in order to better explain the principles and practical applications of the application, so that those skilled in the art can well understand and utilize the application. The application is limited by the claims and their entire scope and equivalents.

Claims

1. An antibacterial ceramic glaze, characterized in that: The invention comprises the following components in parts by weight: 40-60 parts of modified kaolin, 10-20 parts of modified calcite, 40-60 parts of feldspar powder, 5-10 parts of zinc oxide, 8-10 parts of borax, 20-30 parts of alumina and 20-30 parts of perlite; The preparation method of the modified kaolin is: A1. Dry and crush kaolin, add it to a beaker with sodium hydroxide aqueous solution and mix evenly. Raise the temperature to 50-70°C, react for 5-7 hours, and post-treat to obtain activated kaolin. A2. Add activated kaolin and ethanol aqueous solution into a three-necked flask and disperse evenly. Add nitric acid to adjust the pH to 3-5. Raise the temperature to 50-60°C and stir. Add silver nitrate aqueous solution and ethyl orthosilicate ethanol solution to the system. Add saturated ammonia water to adjust the pH to 8-10. React for 8-10 hours and post-treat to obtain modified kaolin.

2. The antibacterial ceramic glaze according to claim 1, characterized in that: In step A1, the usage ratio of kaolin and sodium hydroxide aqueous solution is 1 g:2-5 mL; the concentration of sodium hydroxide aqueous solution is 2-5 mol / L.

3. The antibacterial ceramic glaze according to claim 1, characterized in that: In step A1, the post-treatment step includes: centrifugal separation, taking the solid and placing it in a muffle furnace at 800°C for 5 hours, cooling it to room temperature, washing it with deionized water at 80°C until it is neutral, filtering it, and drying the filter cake in a drying oven at 60°C to constant weight to obtain activated kaolin.

4. The antibacterial ceramic glaze according to claim 1, characterized in that: In step A2, the activated kaolin, ethanol aqueous solution, silver nitrate aqueous solution and tetraethyl orthosilicate ethanol solution are used in a ratio of 10 g:40-90 mL:3 mL:10 mL; the ethanol aqueous solution is composed of ethanol and deionized water in a volume ratio of 1:1, and the tetraethyl orthosilicate ethanol solution is composed of tetraethyl orthosilicate and anhydrous ethanol in a ratio of 1.5 g:8.5 mL; the concentration of the silver nitrate aqueous solution is 0.6 mol / L, and the post-processing step includes: after the reaction is completed, filtering, washing the filter cake with deionized water 3-5 times, transferring to a 100-120°C drying oven to dry to constant weight, and placing it in a 300-500°C muffle furnace for calcination for 1-2 hours to obtain modified kaolin.

5. The antibacterial ceramic glaze according to claim 1, characterized in that: The preparation method of the modified calcite is: B1, add calcite powder and hydrochloric acid solution into a beaker, stir at room temperature for 10-20 minutes, add saturated ammonia water to adjust the pH to neutral, centrifuge, wash and dry to obtain pretreated calcite powder; B2. Add the pretreated calcite powder to deionized water, ultrasonically disperse for 20-30 minutes, add KH-550 solution, increase the temperature to 60-80°C, add copper sulfate pentahydrate, add sodium hydroxide solution to adjust the pH to 9-10, stir for 30-40 minutes, and post-treat to obtain modified calcite.

6. The antibacterial ceramic glaze according to claim 5, characterized in that: In step B1, the amount ratio of the calcite powder and the hydrochloric acid solution is 1g:5mL, and the concentration of the hydrochloric acid solution is 3wt%; in step B2, the amount ratio of the calcite powder, deionized water, KH-550 solution and copper sulfate pentahydrate is 100g:500-800mL:5.8mL:4.8-6.8g; the KH-550 solution is composed of γ-aminopropyltriethoxysilane and ethanol in a volume ratio of 2.7:3.1; post-treatment includes: after the reaction is completed, standing, cooling the temperature to room temperature, centrifuging, washing with deionized water until neutral, and transferring the filter cake to a 60-80°C drying oven to dry to constant weight to obtain square modified calcite.

7. A method for preparing an antibacterial ceramic glaze, using the antibacterial ceramic glaze according to any one of claims 1 to 6, characterized in that: The steps include: S1, add 40-60 parts of modified antibacterial kaolin, 10-20 parts of modified calcite, 40-60 parts of feldspar powder, 5-10 parts of zinc oxide, 8-10 parts of borax, 20-30 parts of bauxite, and 20-30 parts of perlite into a mixer and mix them evenly, place them in a high-temperature gradient furnace and calcine them to a molten state, keep them warm, and water quench them to obtain glass frit; S2. Place the glass material in a ball mill at a speed of 300-400 rpm for 5-6 hours, pass through a 200-mesh sieve, and add deionized water to obtain a ceramic glaze.

8. The method for preparing an antibacterial ceramic glaze according to claim 7, characterized in that: In step S1, the water quenching step includes: pouring the insulated molten glass into a cooling water tank at a uniform speed through a high-temperature resistant guide trough, solidifying for 5-15 minutes, transferring the glass frit to a filter cloth, and placing it in an 80-100°C oven to dry for 2-4 hours to obtain glass frit; in step S2, the ratio of the glass frit to deionized water is 10g:5-7mL, and the ball-to-material ratio is 2:

1.

9. An application of an antibacterial ceramic glaze, characterized in that: The antibacterial ceramic glaze according to any one of claims 1 to 6 is applied to sanitary ware.

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