A wear-resistant antibacterial ceramic glaze and a preparation method thereof

Abstract

The application discloses a kind of wear-resistant antibacterial ceramic glaze and preparation method thereof, belong to ceramic glaze technical field.The glaze includes base glaze, fluxing agent, yttrium stabilized nanometer zirconium oxide and rare earth doped zirconium pyrophosphate silver-loaded antibacterial agent.The yttrium stabilized nanometer zirconium oxide particle size is 50-200nm, Y2O3 doping amount is 2-5mol%, tetragonal phase content is ≥90%;The chemical general formula of the rare earth doped zirconium pyrophosphate silver-loaded antibacterial agent is Zr 1‑X RE X P2O7:Ag, RE is Y 3+ And / or La 3+ , 0.01≤x≤0.10, Ag content is 3-6wt%.By controlling glaze layer and yttrium stabilized nanometer zirconium oxide thermal expansion matching, compressive stress field is formed after firing and cooling, and phase change toughening is induced, so as to improve the wear resistance and hardness of glaze surface;Rare earth doped zirconium pyrophosphate framework is stable at high temperature, and crystal lattice defects form efficient anchoring to Ag + Realize long-acting antibacterial.

Description

Technical Field

[0001] This invention belongs to the field of ceramic glaze technology, specifically relating to a wear-resistant and antibacterial ceramic glaze and its preparation method. Background Technology

[0002] Ceramic glaze is a key functional coating on the surface of ceramic bodies, and its performance directly determines the service life and hygiene safety level of ceramic products. With the increasing demands for performance in various application fields, glazes not only need high density and low water absorption for easy cleaning, but also high wear resistance to withstand long-term mechanical friction, and long-lasting antibacterial properties to inhibit microbial growth in humid environments. However, achieving these properties is constrained by high-temperature firing processes, which can easily lead to the failure of functional components, making it difficult to achieve multiple properties such as wear resistance and antibacterial properties simultaneously, thus hindering the development of high-performance antibacterial ceramic products.

[0003] In existing technologies, it is difficult to synergistically optimize wear resistance and antibacterial properties, and the suitable firing temperature for most functional glazes is below 1200℃. The specific reasons are as follows: Existing antibacterial glazes mostly employ antibacterial components such as silver-loaded zeolite, nano-zinc oxide, and hydroxyapatite, dispersing them within the glassy network structure of the glaze layer. Antibacterial properties are achieved through the slow release of silver and zinc ions. However, these materials suffer from the following problems during firing in an oxidizing atmosphere above 1200℃: Firstly, the crystal lattice framework of the zeolite and hydroxyapatite carriers melts or undergoes a phase transition at high temperatures, causing the collapse of the silver ion loading sites. Secondly, silver ions migrate and volatilize in large quantities from the carrier pores, or agglomerate into micron-sized elemental silver particles in the molten glaze layer, losing their antibacterial ability. Simultaneously, the antibacterial components settle or float in the high-temperature melt of the glaze due to density differences, making it difficult to form a uniform antibacterial layer on the glaze surface. These problems result in a significant decrease in the antibacterial rate and a marked reduction in the bacteriostatic rate after firing, failing to meet the requirements for long-lasting antibacterial effects.

[0004] Wear-resistant glazes typically form a dense glaze layer by adding high-hardness particles such as alumina and mullite as reinforcing phases or by optimizing the firing process. However, relying solely on physical filling can easily lead to stress concentration and an increase in microcracks on the glaze surface, which not only reduces the strength of the glaze layer but may also damage the integrity of the glaze surface, indirectly affecting the durability of its antibacterial function. Furthermore, organic additives or photocatalysts such as TiO2 introduced to enhance antibacterial effects are difficult to function in the absence of ultraviolet light, and organic additives are prone to carbonization at high temperatures, resulting in defects such as pinholes and bubble ruptures on the glaze surface. These microscopic defects can easily become hiding places for bacteria, and even if the initial antibacterial performance is good, the effect will significantly decrease after long-term use.

[0005] In summary, most existing technologies focus only on optimizing a single performance characteristic, making it difficult to simultaneously achieve excellent wear resistance and antibacterial properties under high-temperature conditions. Therefore, developing a novel glaze that can withstand high-temperature firing and possesses both excellent wear resistance and antibacterial properties is of significant practical importance. Summary of the Invention

[0006] In view of the shortcomings of existing ceramic glazes, such as poor wear resistance, unstable antibacterial effect and poor process compatibility, this invention provides a wear-resistant and antibacterial ceramic glaze, its preparation method and application.

[0007] In a first aspect, a formulation for a wear-resistant and antibacterial ceramic glaze is provided, comprising a base glaze, a flux, a wear-resistant and toughening phase, a high-temperature stable antibacterial phase, and a process aid; wherein the wear-resistant and toughening phase is yttrium-stabilized nano-zirconia; and the high-temperature stable antibacterial phase is a rare-earth-doped zirconium pyrophosphate silver-loaded antibacterial agent.

[0008] Furthermore, the ceramic glaze is made from the following raw materials in parts by weight: 40-60 parts of base glaze components, 8-15 parts of flux, 3-8 parts of wear-resistant and toughening phase, 4-10 parts of high-temperature stable antibacterial phase, and 0.1-1 parts of process aids.

[0009] Furthermore, the basic glaze components are selected from at least three of potassium feldspar, sodium feldspar, quartz, calcium carbonate, and calcined kaolin. The basic glaze components mainly serve to form the glaze skeleton and ensure the smoothness and density of the glaze surface. Among them, potassium feldspar and sodium feldspar provide the alkali metal oxides required by the glaze and reduce the melting temperature of the glaze; quartz improves the hardness and wear resistance of the glaze surface; calcium carbonate improves the gloss of the glaze surface; and calcined kaolin enhances the suspension and stability of the glaze and reduces glaze surface defects.

[0010] Furthermore, the flux is selected from at least one of lead-free high-boron frit and lithium carbonate. The flux promotes uniform spreading of the glaze on the ceramic body surface by lowering the melting temperature and viscosity of the glaze, reducing defects such as pinholes and cracks during firing, and its lead-free design meets environmental protection requirements. The lead-free high-boron frit improves the gloss and chemical stability of the glaze, while lithium carbonate lowers the melting temperature and enhances the glaze's fluidity.

[0011] Furthermore, the process aid is sodium carboxymethyl cellulose; its main function is to enhance the viscosity and suspension of the glaze slurry, prevent the precipitation of glaze components, ensure the uniformity of glazing, and at the same time improve the drying speed of the glaze surface and reduce cracking during the drying process.

[0012] Furthermore, the yttrium-stabilized zirconium oxide nanoparticles have a particle size of 50-200 nm, a Y₂O₃ doping amount of 2-5 mol%, and a specific surface area of ​​20-50 m². 2 / g, tetragonal phase content ≥90%; Yttrium-stabilized nano-zirconia, as a wear-resistant and toughening phase, has its nano-sized particles uniformly dispersed in the glaze, forming a dense composite structure with the glaze, significantly improving the hardness and wear resistance of the glaze surface. At the same time, tetragonal zirconia undergoes phase transformation and toughening under stress, reducing the generation and propagation of glaze cracks, and improving the toughness and impact resistance of the glaze layer.

[0013] Furthermore, the general chemical formula of the rare earth-doped zirconium pyrophosphate silver-loaded antibacterial agent is Zr. 1-X RE X P2O7:Ag, where RE is Y 3+ and / or La 3+ The antibacterial agent has a content of 3-6 wt% Ag, with a concentration of 0.01 ≤ x ≤ 0.10. It uses zirconium pyrophosphate as a carrier, and rare earth doping modification improves the high-temperature stability of the carrier and the dispersibility of the antibacterial agent. Loading silver ions achieves high-efficiency antibacterial activity, and the zirconium pyrophosphate carrier effectively immobilizes silver ions, preventing rapid precipitation during use and achieving long-lasting antibacterial effects. Simultaneously, the doping of rare earth elements further enhances the high-temperature resistance of the antibacterial agent, ensuring that it does not decompose or fail during high-temperature sintering, and maintaining stable antibacterial effects.

[0014] Furthermore, the average particle size of the rare earth-doped zirconium pyrophosphate silver-loaded antibacterial agent is <2μm; the smaller particle size allows the antibacterial agent to be uniformly dispersed in the glaze, avoiding agglomeration and ensuring uniform antibacterial performance throughout the glaze surface, while not affecting the smoothness and gloss of the glaze surface.

[0015] Secondly, a method for preparing a rare-earth-doped zirconium pyrophosphate silver-loaded antibacterial agent is provided, comprising the following steps: S1. Dissolve zirconium source, rare earth source, phosphorus source and silver source in water according to stoichiometric ratio, add complexing agent, adjust pH to 9-10 with ammonia water, stir and age for 2-4 h to form coprecipitate; zirconium source can be zirconium oxychloride, zirconium nitrate, etc., rare earth source can be yttrium nitrate, lanthanum nitrate, etc., phosphorus source can be ammonium dihydrogen phosphate, phosphoric acid, etc., and silver source can be silver nitrate; the complexing agent can prevent precipitation of each ion and ensure precipitation uniformity.

[0016] S2. Centrifuge and wash the precipitate until no impurity ions are present. Confirm this by testing the conductivity or ion concentration of the washing solution. Dry at 70-90℃. Drying removes moisture from the precipitate, preparing it for subsequent calcination. Too high a drying temperature can cause the precipitate to clump, while too low a temperature will result in incomplete drying.

[0017] S3. Calcine at 850-950℃ for 2.5-3.5 h in air atmosphere, grind and sieve to obtain composite powder, namely rare earth doped zirconium pyrophosphate silver-loaded antibacterial agent; calcination causes precipitation crystallization to form a stable zirconium pyrophosphate crystal structure, while achieving uniform loading of silver ions; grinding and sieving control the particle size of the antibacterial agent to ensure that it meets the requirements for use.

[0018] Furthermore, the complexing agent is citric acid or disodium ethylenediaminetetraacetate, and the amount of the complexing agent added is 5-10% of the total mass of the zirconium source, rare earth source, phosphorus source and silver source. These two complexing agents have good complexing effect, effectively stabilize the metal ions in the solution, and completely decompose during calcination without leaving any impurities or affecting the performance of the antibacterial agent.

[0019] Thirdly, a method for preparing wear-resistant and antibacterial ceramic glaze is provided, including the following steps: S1. Weigh the base glaze, yttrium-stabilized nano-zirconia powder, rare earth-doped zirconium pyrophosphate silver-loaded antibacterial agent, and flux according to the specified ratio. Mix them and add a deionized aqueous solution containing sodium carboxymethyl cellulose. Ball mill for 8-12 hours and pass through a 250-mesh sieve to obtain a glaze slurry. Then adjust the specific gravity of the glaze slurry to 1.70-1.75 g / cm³. 3 Ball milling ensures thorough and uniform mixing of all raw materials, refines particles, and guarantees the uniformity and stability of the glaze slurry. Passing through a 250-mesh sieve removes unground impurities and agglomerated particles to avoid affecting the glaze quality. Adjusting the glaze slurry specific gravity ensures uniform glaze thickness and improves the smoothness of the glaze surface.

[0020] S2. Apply the glaze slurry to the surface of the ceramic body. The glazing method can be spraying, pouring, etc. The dried ceramic body surface is fired in an air atmosphere at 1270-1290℃ for 15-25 minutes. After cooling, the finished product is obtained. Firing in an air atmosphere at 1270-1290℃ allows the glaze to fully melt and crystallize, forming a dense glaze layer. At the same time, it ensures the stability of the performance of yttrium-stabilized nano-zirconia and rare earth-doped zirconium pyrophosphate silver-loaded antibacterial agent. The heat preservation process reduces the stress on the glaze surface and avoids cracks after cooling.

[0021] Furthermore, the amount of deionized water used in step S1 is 60%-70% of the total weight of the base glaze, flux, wear-resistant toughening phase, and high-temperature stable antibacterial phase. At this amount, the solid components can be fully dispersed to form a stable glaze slurry, which not only meets the fluidity required for ball milling and avoids particle agglomeration and glaze surface defects, but also controls the viscosity of the glaze slurry, ensures uniform glazing, and guarantees the bonding strength between the glaze layer and the body.

[0022] Fourthly, the present invention provides the application of the wear-resistant and antibacterial ceramic glaze according to the first aspect or the preparation method according to the third aspect in the preparation of ceramic products. The beneficial effects of the present invention are: 1. This invention uses yttrium-stabilized nano-zirconia as a wear-resistant and toughening phase. Its nano-sized particles are uniformly dispersed in the glaze. Combined with the toughening effect of tetragonal phase transformation, it significantly improves the hardness and wear resistance of the glaze surface. It is not easy to produce scratches after long-term use, thus extending the service life of the product.

[0023] 2. This invention uses rare earth-doped zirconium pyrophosphate silver-loaded antibacterial agent as a high-temperature stable antibacterial phase. The zirconium pyrophosphate carrier has good high-temperature stability, ensuring that the antibacterial agent does not decompose during the calcination process. Rare earth doping improves the dispersibility of the antibacterial agent, and silver ion loading achieves efficient antibacterial effect. Moreover, the silver ions are firmly fixed and not easy to precipitate, achieving long-lasting antibacterial effect and high safety.

[0024] 3. The glaze formula of this invention is reasonable, and the flux is made of lead-free material, which is environmentally friendly and pollution-free. After firing, the glaze surface is dense, smooth and glossy, without defects such as pinholes and cracks, and the product qualification rate is high.

[0025] 4. The ceramic glaze produced by this invention is suitable for the preparation of various ceramic sanitary ware, meeting people's multiple needs for sanitary ware to be wear-resistant, antibacterial, environmentally friendly, and aesthetically pleasing, and has broad application prospects. Detailed Implementation

[0026] To further illustrate the technical means and effects of the present invention in achieving its intended purpose, the following detailed description of the specific implementation methods, structures, features and effects of the present invention, in conjunction with embodiments, is provided below.

[0027] The raw materials used in the following examples are from: Potassium feldspar, sodium feldspar, quartz, calcium carbonate, calcined kaolin: commercially available industrial-grade raw materials; Lead-free high-boron frit: Commercially available frit specifically for sanitary ceramics; Lithium carbonate: analytical grade; Sodium carboxymethyl cellulose: industrial grade, viscosity 800-1200 mPa·s; Yttrium-stabilized nano-zirconia: Particle size D 50 =68nm, Y2O3 doping content 5.2wt%, tetragonal phase content 92.7%, specific surface area 32.5m² 2 / g; Zirconium oxychloride (ZrOCl2·8H2O), lanthanum nitrate (La(NO3)3·6H2O), yttrium nitrate, silver nitrate (AgNO3), diammonium hydrogen phosphate ((NH4)2HPO4), citric acid, disodium ethylenediaminetetraacetate, and ammonia: all were of analytical grade. All the equipment used is commonly used in existing ceramic production. Example 1

[0028] 1. Preparation of rare earth-doped zirconium pyrophosphate silver-loaded antibacterial agent Zirconium oxychloride (ZrOCl2·8H2O), lanthanum nitrate (La(NO3)3·6H2O), and silver nitrate (AgNO3) were weighed according to a molar ratio of Zr:La:Ag = 0.95:0.05:0.03. Diammonium hydrogen phosphate ((NH4)2HPO4) was weighed according to a stoichiometric ratio, and the P:(Zr+La) molar ratio was controlled at 2:1. The zirconium source, rare earth source, phosphorus source, and silver source were dissolved in deionized water, and 8% of the total mass of citric acid was added as a complexing agent. The pH was adjusted to 9.5 with ammonia water, and the mixture was stirred and aged for 3 hours to form a white coprecipitate. The precipitate was separated by centrifugation, washed three times with deionized water until no chloride ions were detected, and dried at 80℃ for 12 hours. The dried product was placed in a muffle furnace and heated to 900℃ at a rate of 5℃ / min under air atmosphere, held at that temperature for 3 hours, and then cooled with the furnace. The calcined product was ground in a planetary ball mill for 2 hours and then passed through a 400-mesh sieve to obtain Zr with an average particle size of 1.6 μm. 0.95 La 0.05 The P2O7:Ag composite powder, as determined by ICP-OES, has an Ag content of 4.2 wt%.

[0029] 2. Preparation of wear-resistant and antibacterial ceramic glaze Weigh the raw materials by weight as follows: 13 parts potassium feldspar, 11 parts sodium feldspar, 10 parts quartz, 4 parts calcium carbonate, 4 parts calcined kaolin, 10 parts lead-free high-boron frit, 6 parts of the rare earth-doped zirconium pyrophosphate silver-loaded antibacterial agent prepared above, 5 parts yttrium-stabilized nano-zirconia, and 0.3 parts sodium carboxymethyl cellulose.

[0030] Potassium feldspar, sodium feldspar, quartz, calcium carbonate, calcined kaolin, and lead-free high-boron frit are mixed and added to a ball mill jar. Deionized water is added in a ratio of 1:2:0.6 for the dry powder of glaze raw materials: zirconia balls: deionized water, with 37.8 parts of deionized water accounting for 60% of the total weight of the dry powder. The mixture is ball-milled for 8 hours and passed through a 325-mesh sieve to obtain the basic glaze slurry.

[0031] The rare-earth-doped zirconium pyrophosphate silver-loaded antibacterial agent prepared in Example 1 and yttrium-stabilized nano-zirconia were added to the basic glaze slurry, along with sodium carboxymethyl cellulose. The mixture was then ball-milled for 3 hours, passed through a 250-mesh sieve, and the glaze slurry specific gravity was adjusted to 1.72 g / cm³. 3 Iron is removed by magnetic force to obtain the finished glaze.

[0032] 3. Glazing and firing The above-mentioned glaze is applied to the surface of the ceramic body by spraying, with the glaze thickness controlled at 0.5-0.6 mm, and dried at 80℃ for 2 hours. The dried body is then placed in a high-temperature kiln and heated to 1280℃ in an air atmosphere, held at that temperature for 20 minutes, and naturally cooled to room temperature to obtain a finished ceramic product with a wear-resistant and antibacterial glaze layer on the surface. Example 2

[0033] 1. Preparation of rare earth-doped zirconium pyrophosphate silver-loaded antibacterial agent Zirconium oxychloride (ZrOCl2·8H2O), yttrium nitrate (Y(NO3)3·6H2O), and silver nitrate (AgNO3) were weighed according to a molar ratio of Zr:La:Ag = 0.93:0.07:0.05. Diammonium hydrogen phosphate ((NH4)2HPO4) was weighed according to a stoichiometric ratio, and the P:(Zr+La) molar ratio was controlled at 2:1. The zirconium source, rare earth source, phosphorus source, and silver source were dissolved in deionized water, and 8% of the total mass of citric acid was added as a complexing agent. The pH was adjusted to 9.5 with ammonia water, and the mixture was stirred and aged for 3 hours to form a white coprecipitate. The precipitate was separated by centrifugation, washed three times with deionized water until no chloride ions were detected, and dried at 80℃ for 12 hours. The dried product was placed in a muffle furnace and heated to 900℃ at a rate of 5℃ / min under air atmosphere, held at that temperature for 3 hours, and then cooled with the furnace. The calcined product was ground in a planetary ball mill for 2 hours and then passed through a 400-mesh sieve to obtain Zr with an average particle size of 1.4 μm. 0.93 Y 0.07 The P2O7:Ag composite powder, as determined by ICP-OES, has an Ag content of 4.8 wt%.

[0034] 2. Preparation of wear-resistant and antibacterial ceramic glaze Weigh the raw materials by weight as follows: 14 parts potassium feldspar, 14 parts sodium feldspar, 12 parts quartz, 4 parts calcium carbonate, 6 parts calcined kaolin, 12 parts lead-free high-boron frit, 2 parts lithium carbonate, 5 parts of the rare earth-doped zirconium pyrophosphate silver-loaded antibacterial agent prepared above, 6 parts yttrium-stabilized nano-zirconia, and 0.4 parts sodium carboxymethyl cellulose.

[0035] Potassium feldspar, sodium feldspar, quartz, calcium carbonate, calcined kaolin, and lead-free high-boron frit are mixed and added to a ball mill jar. Deionized water is added in a ratio of 1:2:0.65 for the dry powder of glaze raw materials: zirconia balls: deionized water, with 48.8 parts of deionized water accounting for 65% of the total weight of the dry powder. The mixture is ball-milled for 8 hours and passed through a 325-mesh sieve to obtain the basic glaze slurry.

[0036] The rare-earth-doped zirconium pyrophosphate silver-loaded antibacterial agent prepared in Example 2 and yttrium-stabilized nano-zirconia were added to the basic glaze slurry, along with sodium carboxymethyl cellulose. The mixture was then ball-milled for 3 hours, passed through a 250-mesh sieve, and the glaze slurry specific gravity was adjusted to 1.70 g / cm³. 3 Iron is removed by magnetic force to obtain the finished glaze.

[0037] 3. Glazing and firing The above-mentioned glaze is applied to the surface of the ceramic body by spraying, with the glaze thickness controlled at 0.5-0.6 mm, and dried at 80℃ for 2 hours. The dried body is then placed in a high-temperature kiln and heated to 1280℃ in an oxidizing atmosphere, held for 15 minutes, and naturally cooled to room temperature to obtain a finished ceramic product with a wear-resistant and antibacterial glaze layer on the surface. Example 3

[0038] 1. Preparation of rare earth-doped zirconium pyrophosphate silver-loaded antibacterial agent Zirconium oxychloride (ZrOCl2·8H2O), lanthanum nitrate (La(NO3)3·6H2O), yttrium nitrate (Y(NO3)3·6H2O), and silver nitrate (AgNO3) were weighed according to the molar ratio Zr:La:Y:Ag = 0.9:0.05:0.05:0.04. Diammonium hydrogen phosphate ((NH4)2HPO4) was weighed according to the stoichiometric ratio, controlling the P:(Zr+La+Y) molar ratio to be 2:1. The zirconium source, rare earth source, phosphorus source, and silver source were dissolved in deionized water, and 6% by mass of disodium ethylenediaminetetraacetate was added as a complexing agent. The pH was adjusted to 9.0 with ammonia water, and the mixture was stirred and aged for 4 hours to form a white coprecipitate. The precipitate was separated by centrifugation, washed three times with deionized water until no chloride ions were detected, and tested with 1% AgNO3 solution to ensure no white precipitate was found. The precipitate was then dried at 90℃ for 10 hours. The dried product was placed in a muffle furnace and heated to 850°C at a rate of 5°C / min under air atmosphere, held at that temperature for 3.5 h, and then cooled with the furnace. The calcined product was then ground in a planetary ball mill for 2.5 h and passed through a 400-mesh sieve to obtain Zr with an average particle size of 1.8 μm. 0.9 La 0.05 Y 0.05 The P2O7:Ag composite powder, as determined by ICP-OES, has an Ag content of 5.1 wt%.

[0039] 2. Preparation of wear-resistant and antibacterial ceramic glaze The raw materials are weighed according to the following parts by weight: 19 parts potassium feldspar, 12 parts sodium feldspar, 15 parts quartz, 7 parts calcium carbonate, 5 parts calcined kaolin, 8 parts lead-free high-boron frit, 1 part lithium carbonate, 7 parts of the rare earth-doped zirconium pyrophosphate silver-loaded antibacterial agent prepared above, 4 parts yttrium-stabilized nano-zirconia, and 0.2 parts sodium carboxymethyl cellulose.

[0040] Potassium feldspar, sodium feldspar, quartz, calcium carbonate, calcined kaolin, and lead-free high-boron frit are mixed and added to a ball mill jar. Deionized water is added in a ratio of 1:2:0.7 of dry powder of glaze raw materials: zirconia balls: deionized water, with 54.6 parts of deionized water accounting for 70% of the total weight of dry powder. The mixture is ball-milled for 8 hours and passed through a 325-mesh sieve to obtain the basic glaze slurry.

[0041] The rare-earth-doped zirconium pyrophosphate silver-loaded antibacterial agent prepared in Example 3 and yttrium-stabilized nano-zirconia were added to the basic glaze slurry, along with sodium carboxymethyl cellulose. The mixture was then ball-milled for 3 hours, passed through a 250-mesh sieve, and the glaze slurry specific gravity was adjusted to 1.75 g / cm³. 3 Iron is removed by magnetic force to obtain the finished glaze.

[0042] 3. Glazing and firing The above-mentioned glaze is applied to the surface of the ceramic body by spraying, with the glaze thickness controlled at 0.5-0.6 mm, and dried at 80℃ for 2 hours. The dried body is then placed in a high-temperature kiln and heated to 1280℃ in an oxidizing atmosphere, held at that temperature for 25 minutes, and then naturally cooled to room temperature to obtain a finished ceramic product with a wear-resistant and antibacterial glaze layer on the surface. Example 4

[0043] 1. Preparation of rare earth-doped zirconium pyrophosphate silver-loaded antibacterial agent Zirconium oxychloride (ZrOCl2·8H2O), lanthanum nitrate (La(NO3)3·6H2O), and silver nitrate (AgNO3) were weighed according to a molar ratio of Zr:La:Ag = 0.95:0.05:0.03. Diammonium hydrogen phosphate ((NH4)2HPO4) was weighed according to a stoichiometric ratio, controlling the P:(Zr+La) molar ratio to be 2:1. The zirconium source, rare earth source, phosphorus source, and silver source were dissolved in deionized water, and 8% of the total mass of citric acid was added as a complexing agent. The pH was adjusted to 9.5 with ammonia water, and the mixture was stirred and aged for 3 hours to form a white coprecipitate. The precipitate was separated by centrifugation, washed three times with deionized water until no chloride ions were detected, and dried at 80℃ for 12 hours. The dried product was placed in a muffle furnace and heated to 900℃ at a rate of 5℃ / min under air atmosphere, held at that temperature for 3 hours, and then cooled with the furnace. The calcined product was ground in a planetary ball mill for 2 hours and then passed through a 400-mesh sieve to obtain Zr with an average particle size of 1.6 μm. 0.95 La 0.05 The P2O7:Ag composite powder, as determined by ICP-OES, has an Ag content of 4.2 wt%.

[0044] 2. Preparation of wear-resistant and antibacterial ceramic glaze Weigh the raw materials by weight as follows: 14 parts potassium feldspar, 11 parts sodium feldspar, 10 parts quartz, 5 parts calcium carbonate, 5 parts calcined kaolin, 10 parts lead-free high-boron frit, 6 parts of the rare earth-doped zirconium pyrophosphate silver-loaded antibacterial agent prepared above, 5 parts yttrium-stabilized nano-zirconia, and 0.3 parts sodium carboxymethyl cellulose.

[0045] Potassium feldspar, sodium feldspar, quartz, calcium carbonate, calcined kaolin, and lead-free high-boron frit are mixed and added to a ball mill jar. Deionized water is added in a ratio of 1:2:0.68 for the dry powder of glaze raw materials: zirconia balls: deionized water, with 40.9 parts of deionized water accounting for 62% of the total weight of the dry powder. The mixture is ball-milled for 8 hours and passed through a 325-mesh sieve to obtain the basic glaze slurry.

[0046] The rare-earth-doped zirconium pyrophosphate silver-loaded antibacterial agent prepared in Example 4 and yttrium-stabilized nano-zirconia were added to the basic glaze slurry, along with sodium carboxymethyl cellulose. The mixture was then ball-milled for 3 hours, passed through a 250-mesh sieve, and the glaze slurry specific gravity was adjusted to 1.72 g / cm³. 3 Iron is removed by magnetic force to obtain the finished glaze.

[0047] 3. Glazing and firing The above-mentioned glaze is applied to the surface of the ceramic body by spraying, with the glaze thickness controlled at 0.5-0.6 mm, and dried at 80℃ for 2 hours. The dried body is then placed in a high-temperature kiln and heated to 1270℃ in an air atmosphere, held at that temperature for 20 minutes, and then naturally cooled to room temperature to obtain a finished ceramic product with a wear-resistant and antibacterial glaze layer on the surface. Example 5

[0048] 1. Preparation of rare earth-doped zirconium pyrophosphate silver-loaded antibacterial agent Zirconium oxychloride (ZrOCl2·8H2O), lanthanum nitrate (La(NO3)3·6H2O), and silver nitrate (AgNO3) were weighed according to a molar ratio of Zr:La:Ag = 0.95:0.05:0.03. Diammonium hydrogen phosphate ((NH4)2HPO4) was weighed according to a stoichiometric ratio, controlling the P:(Zr+La) molar ratio to be 2:1. The zirconium source, rare earth source, phosphorus source, and silver source were dissolved in deionized water, and 8% of the total mass of citric acid was added as a complexing agent. The pH was adjusted to 9.5 with ammonia water, and the mixture was stirred and aged for 3 hours to form a white coprecipitate. The precipitate was separated by centrifugation, washed three times with deionized water until no chloride ions were detected, and dried at 80℃ for 12 hours. The dried product was placed in a muffle furnace and heated to 900℃ at a rate of 5℃ / min under air atmosphere, held at that temperature for 3 hours, and then cooled with the furnace. The calcined product was ground in a planetary ball mill for 2 hours and then passed through a 400-mesh sieve to obtain Zr with an average particle size of 1.6 μm. 0.95 La 0.05 The P2O7:Ag composite powder, as determined by ICP-OES, has an Ag content of 4.2 wt%.

[0049] 2. Preparation of wear-resistant and antibacterial ceramic glaze The raw materials are weighed according to the following parts by weight: 17 parts potassium feldspar, 14 parts sodium feldspar, 12 parts quartz, 6 parts calcium carbonate, 6 parts calcined kaolin, 10 parts lead-free high-boron frit, 6 parts of the rare earth-doped zirconium pyrophosphate silver-loaded antibacterial agent prepared above, 5 parts yttrium-stabilized nano-zirconia, and 0.3 parts sodium carboxymethyl cellulose.

[0050] Potassium feldspar, sodium feldspar, quartz, calcium carbonate, calcined kaolin, and lead-free high-boron frit are mixed and added to a ball mill jar. Deionized water is added in a ratio of glaze raw material dry powder:zirconia balls:deionized water = 1:2:0.68, with 51.7 parts of deionized water accounting for 68% of the total weight of the dry powder. The mixture is ball-milled for 8 hours and then passed through a 325-mesh sieve to obtain the basic glaze slurry.

[0051] The rare-earth-doped zirconium pyrophosphate silver-loaded antibacterial agent prepared in Example 5 and yttrium-stabilized nano-zirconia were added to the basic glaze slurry, along with sodium carboxymethyl cellulose. The mixture was then ball-milled for 3 hours, passed through a 250-mesh sieve, and the glaze slurry specific gravity was adjusted to 1.72 g / cm³. 3 Iron is removed by magnetic force to obtain the finished glaze.

[0052] 3. Glazing and firing The above-mentioned glaze is applied to the surface of the ceramic body by spraying, with the glaze thickness controlled at 0.5-0.6 mm, and dried at 80℃ for 2 hours. The dried body is then placed in a high-temperature kiln and heated to 1290℃ in an air atmosphere, held at that temperature for 20 minutes, and naturally cooled to room temperature to obtain a finished ceramic product with a wear-resistant and antibacterial glaze layer on the surface.

[0053] Comparative Example 1 1. Preparation of conventional sanitary ceramic glazes Weigh the raw materials by weight as follows: 14 parts potassium feldspar, 11 parts sodium feldspar, 10 parts quartz, 4 parts calcium carbonate, 4 parts calcined kaolin, 10 parts lead-free high-boron frit, and 0.3 parts sodium carboxymethyl cellulose.

[0054] Mix the above raw materials and add them to a ball mill jar. Add deionized water at a ratio of glaze raw material dry powder: zirconia balls: deionized water = 1:2:0.65, with 34.5 parts of deionized water accounting for 65% of the total weight of the dry powder. Ball mill for 11 hours, pass through a 250-mesh sieve, and adjust the specific gravity of the glaze slurry to 1.72 g / cm³. 3 Iron is removed by magnetic force to obtain glaze.

[0055] 2. Glazing and firing The above-mentioned glaze is applied to the surface of the ceramic body by spraying, with the glaze thickness controlled at 0.5-0.6 mm, and dried at 80℃ for 2 hours. The dried body is then placed in a high-temperature kiln and heated to 1180℃ in an oxidizing atmosphere, held at that temperature for 20 minutes, and then naturally cooled to room temperature to obtain a finished ceramic product with a conventional glaze layer on the surface.

[0056] Comparative Example 2 1. Preparation of ceramic glaze with only yttrium-stabilized nano-zirconia The difference between this comparative example and Example 1 is that an equal amount of yttrium-stabilized nano-zirconia is added to the glaze formulation, but no rare earth-doped zirconium pyrophosphate silver-loaded antibacterial agent is added.

[0057] Weigh the raw materials by weight as follows: 13 parts potassium feldspar, 11 parts sodium feldspar, 10 parts quartz, 4 parts calcium carbonate, 4 parts calcined kaolin, 10 parts lead-free high-boron frit, 5 parts yttrium-stabilized nano-zirconia, and 0.3 parts sodium carboxymethyl cellulose.

[0058] Potassium feldspar, sodium feldspar, quartz, calcium carbonate, calcined kaolin, and lead-free high-boron frit are mixed and added to a ball mill jar. Deionized water is added in a ratio of 1:2:0.65 for the dry powder of glaze raw materials: zirconia balls: deionized water, with 37 parts of deionized water accounting for 65% of the total weight of the dry powder. The mixture is ball-milled for 8 hours and passed through a 325-mesh sieve to obtain the basic glaze slurry.

[0059] Yttrium-stabilized nano-zirconia was added to the base glaze slurry, along with sodium carboxymethyl cellulose. The mixture was then ball-milled for 3 hours, passed through a 250-mesh sieve, and the glaze slurry specific gravity was adjusted to 1.72 g / cm³. 3 Iron is removed by magnetic force to obtain the finished glaze.

[0060] 2. Glazing and firing The above-mentioned glaze is applied to the surface of the ceramic body by spraying, with the glaze thickness controlled at 0.5-0.6 mm, and dried at 80℃ for 2 hours. The dried body is then placed in a high-temperature kiln and heated to 1280℃ in an oxidizing atmosphere, held at that temperature for 20 minutes, and then naturally cooled to room temperature to obtain a ceramic finished product with a wear-resistant glaze layer on the surface.

[0061] Comparative Example 3 1. Preparation of ceramic glaze with only antibacterial agent added The difference between this comparative example and Example 1 is that an equal amount of rare earth-doped zirconium pyrophosphate silver-loaded antibacterial agent is added to the glaze formulation, but yttrium-stabilized nano-zirconia is not added.

[0062] The raw materials were weighed according to the following parts by weight: 13 parts potassium feldspar, 11 parts sodium feldspar, 10 parts quartz, 4 parts calcium carbonate, 4 parts calcined kaolin, 10 parts lead-free high-boron frit, 6 parts rare earth-doped zirconium pyrophosphate silver-loaded antibacterial agent prepared in Example 1, and 0.3 parts sodium carboxymethyl cellulose.

[0063] Potassium feldspar, sodium feldspar, quartz, calcium carbonate, calcined kaolin, and lead-free high-boron frit are mixed and added to a ball mill jar. Deionized water is added in a ratio of 1:2:0.65 (dry powder of glaze raw materials: zirconia balls: deionized water), with 37.7 parts of deionized water accounting for 65% of the total weight of the dry powder. The mixture is ball-milled for 8 hours and passed through a 325-mesh sieve to obtain the basic glaze slurry.

[0064] The rare-earth-doped zirconium pyrophosphate silver-loaded antibacterial agent prepared in Example 1 was added to the base glaze slurry, along with sodium carboxymethyl cellulose. The mixture was then ball-milled for 3 hours, passed through a 250-mesh sieve, and the glaze slurry specific gravity was adjusted to 1.72 g / cm³. 3 Iron is removed by magnetic force to obtain the finished glaze.

[0065] 2. Glazing and firing The above-mentioned glaze is applied to the surface of the ceramic body by spraying, with the glaze thickness controlled at 0.5-0.6 mm, and dried at 80℃ for 2 hours. The dried body is then placed in a high-temperature kiln and heated to 1280℃ in an oxidizing atmosphere, held at that temperature for 20 minutes, and then naturally cooled to room temperature to obtain a finished ceramic product with an antibacterial glaze layer on the surface.

[0066] Comparative Example 4 1. Preparation of silver-loaded zirconium pyrophosphate antibacterial agent without rare earth doping The difference between this comparative example and Example 1 is that no rare earth source is added during the preparation of the antibacterial agent, and undoped zirconium pyrophosphate is used as the silver ion carrier.

[0067] Zirconium oxychloride (ZrOCl2·8H2O) and silver nitrate (AgNO3) were weighed according to a molar ratio of Zr:Ag = 0.95:0.03, and diammonium hydrogen phosphate ((NH4)2HPO4) was weighed according to a stoichiometric ratio, controlling the P:Zr molar ratio to be 2:1. The zirconium, phosphorus, and silver sources were dissolved in deionized water, and 8% (by total mass) of citric acid was added as a complexing agent. The pH was adjusted to 9.5 with ammonia water, and the mixture was stirred and aged for 3 hours to form a white co-precipitate. The precipitate was centrifuged, washed three times with deionized water until no chloride ions were detected, and dried at 80℃ for 12 hours. The dried product was placed in a muffle furnace and heated to 900℃ at a rate of 5℃ / min under air atmosphere, held at that temperature for 3 hours, and then cooled with the furnace. The calcined product was ground in a planetary ball mill for 2 hours and passed through a 400-mesh sieve to obtain ZrP2O7:Ag composite powder with an average particle size of 1.7 μm. The Ag content was determined to be 4.0 wt% by ICP-OES.

[0068] 2. Preparation of wear-resistant and antibacterial ceramic glaze Weigh the raw materials by weight as follows: 13 parts potassium feldspar, 11 parts sodium feldspar, 10 parts quartz, 4 parts calcium carbonate, 4 parts calcined kaolin, 10 parts lead-free high-boron frit, 6 parts of the above-prepared undoped rare earth zirconium pyrophosphate silver-loaded antibacterial agent, 5 parts yttrium-stabilized nano-zirconia, and 0.3 parts sodium carboxymethyl cellulose.

[0069] Potassium feldspar, sodium feldspar, quartz, calcium carbonate, calcined kaolin, and lead-free high-boron frit are mixed and added to a ball mill jar. Deionized water is added in a ratio of 1:2:0.65 of dry powder of glaze raw materials: zirconia balls: deionized water, with 41 parts of deionized water accounting for 65% of the total weight of dry powder. The mixture is ball-milled for 8 hours and passed through a 325-mesh sieve to obtain the basic glaze slurry.

[0070] Undoped rare-earth zirconium pyrophosphate silver-loaded antibacterial agent and yttrium-stabilized nano-zirconia were added to the base glaze slurry, along with sodium carboxymethyl cellulose. The mixture was then ball-milled for 3 hours, passed through a 250-mesh sieve, and the glaze slurry specific gravity was adjusted to 1.72 g / cm³. 3 Iron is removed by magnetic force to obtain the finished glaze.

[0071] 3. Glazing and firing The above-mentioned glaze is applied to the surface of the ceramic body by spraying, with the glaze thickness controlled at 0.5-0.6 mm, and dried at 80℃ for 2 hours. The dried body is then placed in a high-temperature kiln and heated to 1280℃ in an oxidizing atmosphere, held at that temperature for 20 minutes, and then naturally cooled to room temperature to obtain a finished ceramic product with a wear-resistant and antibacterial glaze layer on the surface.

[0072] Performance testing The ceramic glaze samples prepared in Examples 1-5 and Comparative Examples 1-4 were subjected to the following performance tests, and the results are shown in Table 1.

[0073] 1. Wear resistance test The test was conducted according to GB / T 3810.7 "Test Methods for Ceramic Tiles - Part 7: Determination of Abrasion Resistance of Glazed Tiles". The test load was 750g, and the number of rotations when visible wear marks appeared on the glaze surface was recorded. The abrasion resistance level was determined with reference to the standard appendix.

[0074] 2. Antibacterial performance test The antibacterial properties and antibacterial durability of ceramic glazes were tested according to standard JC / T 897 "Antibacterial Properties of Antibacterial Ceramic Products". The tested bacteria were Staphylococcus aureus and Escherichia coli. To evaluate the antibacterial durability, the samples were soaked in deionized water for 30 days and then the antibacterial properties were tested again.

[0075] 3. Water absorption rate test The test was conducted according to the method specified in Appendix B of GB / T 6952-2015 "Sanitary Ceramics".

[0076] 4. Hardness test The Vickers hardness of ceramic glazes was determined according to standard GB / T 16534 "Test Method for Room Temperature Hardness of Fine Ceramics".

[0077] 5. High-temperature stability test of antibacterial agent The antibacterial agents used in Examples 1-5 and Comparative Example 4 were subjected to heat treatment: Examples 1-3 and Comparative Example 4 were kept at 1280℃ for 30 min, Example 4 was kept at 1270℃ for 30 min, and Example 5 was kept at 1290℃ for 30 min. The silver content before and after heat treatment was measured, and the silver retention rate was calculated.

[0078] The specific test results are shown in Table 1 below: Table 1 Performance test data of the samples In summary, this invention achieves a synergistic breakthrough in high wear resistance and long-lasting antibacterial properties of ceramic glaze surfaces under high-temperature glazing conditions through a functional compound design of rare-earth-doped zirconium pyrophosphate silver-loaded antibacterial agent and yttrium-stabilized nano-zirconia toughening phase. 1) Antibacterial properties: The glazes prepared in Examples 1-5 of this invention exhibit antibacterial rates ≥99.85% against Escherichia coli and Staphylococcus aureus, and antibacterial durability ≥99.79%, significantly exceeding the technical requirements of ≥90% antibacterial rate and ≥85% antibacterial durability specified in JC / T 897-2014 standard. Specifically, under firing conditions of 1280℃ (Examples 1-3), the antibacterial rate of the glaze surface can reach 99.85%-99.95%; even when fired at 1270℃ (Example 4) and 1290℃ (Example 5), the antibacterial rate can still be stably maintained at 99.87%-99.91%, fully demonstrating that the glazes of this invention achieve highly efficient and stable antibacterial effects within the firing temperature range of 1270-1290℃. Comparative Example 3 (without added yttrium-stabilized nano-zirconia) had a durable antibacterial rate of <83%, while Comparative Example 4 (antibacterial agent without rare earth doping) had a silver element retention rate of only 68.7% and a durable antibacterial rate of <72%. These results indicate that yttrium-stabilized nano-zirconia promotes densification of the glaze layer, and that rare earth doping has the effect of high-temperature anchoring of silver ions and ensuring the durability of antibacterial properties.

[0079] 2) Abrasion resistance: Under a load of 750g, the glaze surfaces in Examples 1-5 showed no visible marks after 14,500-15,000 revolutions of wear, achieving abrasion resistance grades of PEI 4 (Examples 1-4) and PEI 5 (Example 5), demonstrating high abrasion resistance. Regarding the effect of firing temperature, under firing conditions of 1280℃ (Examples 1-3), the glaze surface abrasion resistance reached 15,000 revolutions, with a Vickers hardness of 6.98-7.26 GPa. Comparative Example 2 (with only yttrium-stabilized nano-zirconia added) had a wear resistance of 9000 revolutions, Comparative Example 3 (with only antibacterial agent added) had a wear resistance of only 4500 revolutions, and Comparative Example 4 (with antibacterial agent without rare earth doping but with yttrium-stabilized nano-zirconia added) had a wear resistance of 4800 revolutions. The wear resistance of all three was inferior to that of Examples 1-5, which proves that there is a synergistic toughening effect between yttrium-stabilized nano-zirconia and rare earth-doped zirconium pyrophosphate loaded with silver antibacterial agent. The combination of the two significantly improves the wear resistance of the glaze.

[0080] 3) Glaze density: The water absorption rate of the glaze in Examples 1-5 is ≤0.25%. This result indicates that nano-yttrium stabilized nano-zirconia particles can effectively fill the micropores inside the glaze layer and increase the high-temperature viscosity of the glaze melt. Rare earth doped zirconium pyrophosphate silver-loaded antibacterial agent can achieve uniform dispersion. The two work together to promote the densification and sintering of the glaze layer, effectively reduce the porosity of the glaze layer, and thus endow the glaze with excellent easy-to-clean and stain-resistant properties, providing further assurance for the long-term antibacterial performance of the glaze.

[0081] In summary, Comparative Examples 1-4 verify the necessity and synergistic effect of each feature of the technical solution of the present invention from multiple dimensions, and the process is compatible with existing ceramic production lines, demonstrating good industrial applicability.

[0082] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some modifications or alterations to the above-disclosed technical content to create equivalent embodiments without departing from the scope of the present invention. Any simple modifications, equivalent changes and alterations made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the scope of the present invention.

Claims

1. A wear-resistant and antibacterial ceramic glaze, characterized in that: It includes a base glaze, flux, wear-resistant and toughening phase, high-temperature stable antibacterial phase, and process aids; the wear-resistant and toughening phase is yttrium-stabilized nano-zirconia; the high-temperature stable antibacterial phase is rare earth-doped zirconium pyrophosphate loaded with silver antibacterial agent.

2. The ceramic glaze according to claim 1, characterized in that, It is made from the following raw materials in parts by weight: 40-60 parts of base glaze components, 8-15 parts of flux, 3-8 parts of wear-resistant and toughening phase, 4-10 parts of high-temperature stable antibacterial phase, and 0.1-1 parts of process aids.

3. The ceramic glaze according to claim 1 or 2, characterized in that, The basic glaze components are selected from at least three of potassium feldspar, sodium feldspar, quartz, calcium carbonate, and calcined kaolin; the flux is selected from at least one of lead-free high-boron frit and lithium carbonate; and the process aid is sodium carboxymethyl cellulose.

4. The ceramic glaze according to claim 1, characterized in that, The yttrium-stabilized nano-zirconia has a particle size of 50-200 nm, a Y₂O₃ doping content of 2-5 mol%, and a specific surface area of ​​20-50 m². 2 / g, tetragonal phase content ≥90%.

5. The ceramic glaze according to claim 1, characterized in that, The general chemical formula of the rare earth-doped zirconium pyrophosphate silver-loaded antibacterial agent is Zr. 1-X RE X P2O7:Ag, where RE is Y 3+ and / or La 3+ , 0.01≤x≤0.10, Ag mass content is 3-6wt%.

6. The ceramic glaze according to claim 5, characterized in that, The preparation method of the rare earth-doped zirconium pyrophosphate silver-loaded antibacterial agent includes the following steps: S1. Dissolve zirconium source, rare earth source, phosphorus source and silver source in water according to stoichiometric ratio, add complexing agent, adjust pH to 9-10 with ammonia water, stir and age for 2-4 hours to form coprecipitate; S2. Centrifuge and wash the precipitate until no impurity ions are present, and dry it at 70-90℃; S3. Calcine at 850-950℃ in air for 2.5-3.5 hours, grind and sieve to obtain composite powder.

7. The ceramic glaze according to claim 6, characterized in that, The complexing agent is citric acid or disodium ethylenediaminetetraacetate, and the amount of the complexing agent added is 5-10% of the total mass of the zirconium source, rare earth source, phosphorus source and silver source.

8. The ceramic glaze according to claim 1, characterized in that, The average particle size of the rare earth-doped zirconium pyrophosphate silver-loaded antibacterial agent is <2 μm.

9. A method for preparing a wear-resistant and antibacterial ceramic glaze as described in any one of claims 1 to 8, characterized in that, Includes the following steps: S1. Weigh the base glaze, yttrium-stabilized nano-zirconia powder, rare earth-doped zirconium pyrophosphate silver-loaded antibacterial agent, and flux according to the formula. Mix them and add a deionized aqueous solution containing sodium carboxymethyl cellulose. Ball mill for 8-12 hours, pass through a 250-mesh sieve, and adjust the glaze slurry specific gravity to 1.70-1.75 g / cm³. 3 To obtain glaze slurry; S2. Apply the glaze slurry to the surface of the ceramic body, dry it, and then fire it in an air atmosphere at 1270-1290℃ for 15-25 minutes. After cooling, the finished product is obtained.

10. The method for preparing the wear-resistant and antibacterial ceramic glaze according to claim 9, characterized in that, The amount of deionized water used in step S1 is 60%-70% of the total weight of the base glaze, flux, wear-resistant toughening phase and high-temperature stable antibacterial phase.

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