High-gloss antibacterial ceramic color glaze and preparation method thereof

Abstract

This invention discloses a high-gloss antibacterial ceramic glaze and its preparation method, relating to the field of ceramic glaze technology. By weight, its raw material composition includes: 75-85 parts of base glaze, 8-10 parts of antibacterial system, 6-10 parts of nucleating agent, 3-8 parts of colorant, 1.5-3 parts of auxiliary agent, 0.2-1.5 parts of functional additive, and 0.5-1.5 parts of nano-glossing agent. The functional additive is a compound of graphene quantum dots, quaternary ammonium salt modified montmorillonite, and rare earth carbonates in a weight ratio of (0.02-0.08):(0.1-0.3):(0.1-1). This ceramic glaze achieves a balance of high gloss, efficient and long-lasting antibacterial effect, and excellent glaze quality.

Description

Technical Field

[0001] This invention relates to the field of ceramic glaze technology, and in particular to a high-gloss antibacterial ceramic color glaze and its preparation method. Background Technology

[0002] With the improvement of people's living standards and the enhancement of health awareness, ceramic products not only need to have an aesthetically pleasing decorative effect, but also need to have long-lasting antibacterial functions. This is especially true for daily-use ceramics that come into frequent contact with the human body and building and sanitary ceramics used in public places, where antibacterial performance has become one of the core requirements. As the surface protective and decorative layer of ceramic products, the performance of ceramic glaze directly determines the appearance, texture, and functionality of ceramic products. Therefore, the development of ceramic colored glazes that combine high-gloss decorative properties with highly effective antibacterial properties is of great practical significance.

[0003] Currently, traditional antibacterial ceramic glazes are mainly divided into three categories: silver-based, copper-based, and zinc-based. Among them, silver-based antibacterial agents have excellent antibacterial effects, but they have drawbacks such as high cost, easy oxidation and discoloration, and impact on the gloss and color purity of the glaze, making them unsuitable for the preparation of high-gloss colored glazes. Zinc-based antibacterial agents have high safety and moderate cost, but their antibacterial efficiency is low, and they are prone to reacting with glaze components during high-temperature firing, leading to defects such as pinholes and loss of gloss on the glaze surface. Copper-based antibacterial agents are inexpensive and have stable antibacterial effects, but they also have the problem of easy color development at high temperatures, resulting in impurities and a grainy texture on the glaze surface, which in turn reduces the gloss of the glaze and cannot meet the decorative requirements of high-gloss colored glazes.

[0004] In addition, many antibacterial ceramic glazes on the market suffer from insufficient antibacterial durability. After repeated washing, wiping, or long-term use, the antibacterial agent easily detaches and is lost from the glaze, leading to a significant decrease in antibacterial performance and failing to achieve a long-lasting antibacterial effect. Some antibacterial glazes, in pursuit of superior antibacterial performance, excessively add antibacterial agents, increasing production costs and compromising the stability of the glaze, resulting in cracking, peeling, and other quality problems that affect the lifespan of ceramic products. Furthermore, the color formulation of existing antibacterial glazes often relies on a single colorant, resulting in limited color variety and low saturation. These colors are also prone to fading and discoloration during high-temperature firing, failing to meet consumers' diverse and high-quality decorative needs for ceramic products. Moreover, some antibacterial glazes use antibacterial agents that pose a risk of excessive heavy metal leaching, especially when used in food contact ceramic products, which could potentially harm human health and contradict the industry's trend towards environmentally friendly and safe development.

[0005] Therefore, developing a ceramic colored glaze that can balance high gloss, efficient and long-lasting antibacterial properties, excellent glaze quality, safety and environmental protection, and controllable cost has become an urgent need in the industry. Summary of the Invention

[0006] To address the shortcomings of existing technologies, such as poor compatibility between antibacterial agents and glazes, difficulty in achieving both glaze gloss and antibacterial performance, low color purity, complex preparation processes, and unstable antibacterial effects, this invention provides a high-gloss antibacterial ceramic glaze and its preparation method. By optimizing the glaze formula, screening suitable antibacterial systems and process parameters, the invention achieves a synergistic effect of "high gloss, efficient antibacterial, and excellent glaze quality".

[0007] To achieve the above objectives, the present invention provides a high-gloss antibacterial ceramic glaze, which, by weight, comprises the following raw materials: 75-85 parts of base glaze, 8-10 parts of antibacterial system, 6-10 parts of nucleating agent, 3-8 parts of colorant, 1.5-3 parts of auxiliary agent, 0.2-1.5 parts of functional additive, and 0.5-1.5 parts of nano-glossing agent; wherein the functional additive is a compound of graphene quantum dots, quaternary ammonium salt modified montmorillonite, and rare earth carbonate in a weight ratio of (0.02-0.08):(0.1-0.3):(0.1-1).

[0008] Preferably, the base glaze is made of the following components by weight: 25-35 parts potassium feldspar, 20-25 parts quartz sand, 8-12 parts dolomite, 3-5 parts barium carbonate, 3-5 parts zinc oxide, 2-4 parts zirconium oxide, 1-2 parts boron oxide, 1-2 parts bismuth oxide, 1-2 parts borax, 0.8-1.3 parts lithium carbonate, and 1-3 parts zinc borate.

[0009] Preferably, the antibacterial system is a mixture of silver-zinc composite antibacterial agent, nano copper oxide, and rare earth oxide in a mass ratio of (3-5):1:(0.3-0.5).

[0010] Preferably, the silver-zinc composite antibacterial agent is the silver-zinc composite antibacterial agent Micro-KF136; the average particle size of the nano-copper oxide is 10-70 nm; and the rare earth oxide is at least one of cerium oxide, lanthanum oxide, and neodymium oxide.

[0011] Preferably, the nucleating agent is a compound of calcined bovine bone powder and zirconium silicate in a mass ratio of (2-3):(1-2).

[0012] Preferably, the calcined bovine bone powder is made by calcining bovine bones at 800-900℃ for 4-6 hours and then pulverizing them to 800-1000 mesh.

[0013] Preferably, the colorant is a compound of iron oxide, chromium oxide and manganese oxide in a mass ratio of (6-10):(4-7):(3-6).

[0014] Preferably, the auxiliary agent is a mixture of dispersant, defoamer and coupling agent in a mass ratio of (1-2):(0.8-1.2):(0.5-0.8).

[0015] Preferably, the dispersant is a compound of sodium carboxymethyl cellulose and sodium tripolyphosphate in a mass ratio of (2-3):1; the sodium carboxymethyl cellulose has a viscosity of 200-400 mPa·s and a DS of 0.5-0.7.

[0016] Preferably, the defoamer is an organosilicon defoamer BYK-024.

[0017] Preferably, the coupling agent is at least one of silane coupling agent KH550, silane coupling agent KH560, and silane coupling agent KH570.

[0018] Preferably, the graphene quantum dots have a particle size of 5-15 nm; the quaternary ammonium salt modified montmorillonite is DK3 polymer-grade organic clay.

[0019] Preferably, the rare earth carbonate is at least one of lanthanum carbonate and cerium carbonate.

[0020] Preferably, the nano-brightening agent is nano-silica with an average particle size of 20-80 nm.

[0021] Another object of the present invention is to provide a method for preparing the high-gloss antibacterial ceramic colored glaze, comprising the following steps: Step S1: Mix the raw material components evenly according to the weight parts to obtain the mixed raw material, add deionized water, ball mill for 4-6 hours, and pass through a 325 mesh sieve to obtain a high-gloss antibacterial ceramic color glaze slurry. Step S2: Apply glaze to the ceramic bisque that has been dried at 110-130℃ for 2-3 hours using a spray glazing method. The spray glazing pressure is 0.3-0.5MPa, the spray glazing distance is 20-30cm, and the glaze thickness is 0.3-0.8mm. After glazing, place the ceramic bisque in an oven and dry it at 120-140℃ for 3-4 hours. Then transfer it to a roller kiln for firing. After firing, a ceramic product with a high-gloss antibacterial colored glaze is obtained.

[0022] Preferably, the mass ratio of the mixed raw materials to deionized water is 1:1.5.

[0023] Preferably, the firing process is as follows: In the heating stage, the temperature is raised from room temperature to 600℃ at a rate of 100-120℃ / h; in the holding stage, the temperature is held at 600℃ for 30-40 minutes to fully remove residual moisture and volatile substances from the bisque and glaze; then the temperature is raised to 1200-1280℃ at a rate of 80-100℃ / h to ensure the glaze is fully melted and vitrified; in the high-temperature holding stage, the temperature is held at 1200-1280℃ for 60-90 minutes to promote the nucleating agent's effect, refine the glaze grains, and improve the density and gloss of the glaze surface; in the cooling stage, the temperature is lowered from the high temperature to room temperature at a rate of 50-80℃ / h to avoid excessively rapid cooling that could cause glaze cracking, ensuring a smooth and even glaze surface with stable color.

[0024] Due to the application of the above technical solution, the present invention has the following beneficial effects: (1) It combines high gloss, high efficiency antibacterial and stable color, solving the bottleneck of existing technologies that are difficult to achieve all three: This invention promotes the full vitrification of the glaze at high temperature by reasonably matching the nano-glossing agent (nano-silica) and nucleating agent, and synergistically combining the components such as borax and lithium carbonate in the base glaze. The glaze has high gloss, far exceeding that of existing antibacterial ceramic glazes. The antibacterial system uses the silver-zinc composite antibacterial agent Micro-KF136, nano-copper oxide and rare earth oxide compound, and synergistically combines the graphene quantum dots and quaternary ammonium salt modified montmorillonite in the functional additives to achieve multiple antibacterial synergy. It has a high antibacterial rate against Escherichia coli and Staphylococcus aureus and excellent antibacterial durability. The colorant uses iron oxide, chromium oxide and manganese oxide compound, combined with the refining effect of the nucleating agent, so that the color is uniform and full, without impurities and no graininess, and can achieve stable color development to meet different decorative needs.

[0025] (2) The antibacterial agent has excellent compatibility with the glaze and the antibacterial effect is long-lasting and stable: The antibacterial system uses the silver-zinc composite antibacterial agent Micro-KF136, combined with nano copper oxide and rare earth oxides, which has good compatibility and avoids the problem of agglomeration and layering of single antibacterial agents; the graphene quantum dots in the functional additives have small particle size and good dispersibility, which can synergistically enhance the antibacterial system and improve the antibacterial efficiency and durability; the quaternary ammonium salt modified montmorillonite (DK3 polymer-grade organic clay) can enhance the binding force between the antibacterial agent and the glaze matrix, reduce the antibacterial agent shedding, and its layered structure can physically adsorb bacteria, further enhancing the antibacterial effect; the rare earth carbonate and rare earth oxides work together to enhance the thermal stability of the antibacterial system, ensuring that the antibacterial effect does not decay after high-temperature firing, and achieving long-lasting antibacterial effect.

[0026] (3) The preparation process is simple and suitable for large-scale industrial production: The present invention optimizes the raw material ratio and preparation process. No complicated modification and pretreatment procedures are required. Only mixing, ball milling and sieving are needed to prepare the glaze slurry. The operation is simple and easy to control. The firing temperature is controlled at 1200-1280℃, which is lower than the existing high-gloss antibacterial glaze (which is usually 1300-1350℃). Energy consumption is reduced by 8%-12%. The ratio of mixed raw materials to deionized water is optimized, the ball milling time is reasonable, the product qualification rate is high, the production cost is significantly reduced, and it is suitable for large-scale industrial production.

[0027] (4) High safety and wide applicability: The raw materials used in this invention are all environmentally friendly materials that are non-toxic and free from heavy metal pollution. The dispersants, defoamers and coupling agents in the auxiliary agents are all food contact grade compatible products. The dosage of components such as borax and lithium carbonate is reasonable. The rare earth carbonates in the functional additives further reduce the risk of heavy metal leaching, improve product safety, and also improve gloss. It is suitable for various ceramic blanks and can be widely used in daily ceramics, building ceramics, sanitary ceramics and other fields. It is compatible with various glazing methods such as spray glazing, pour glazing and dip glazing. The nano-glossing agent (nano-silica) can form a dense surface barrier to achieve self-cleaning and anti-fouling function, further expanding the applicable scenarios of the product.

[0028] (5) Comprehensive improvement of glaze performance: Nucleating agent (calcined bovine bone powder and zirconium silicate compound) can refine glaze grains, reduce glaze porosity, and improve glaze density and hardness; Nano-brightening agent (nano-silica) works synergistically with basic glaze components to improve glaze gloss and transparency; Quaternary ammonium salt modified montmorillonite can enhance the bonding force between glaze and green body, and reduce glaze peeling and cracking defects; Dispersant in auxiliary agents ensures uniform dispersion of each component, defoamer effectively avoids glaze pinhole defects, coupling agent improves the compatibility of each component, and the synergistic effect of each component significantly improves glaze quality, wear resistance, corrosion resistance and color stability are significantly improved, and product service life is extended. Detailed Implementation

[0029] The following description is intended to disclose the invention and enable those skilled in the art to implement it. The preferred embodiments described below are merely examples, and other obvious variations will occur to those skilled in the art. Example 1

[0030] A high-gloss antibacterial ceramic glaze, by weight, comprises the following raw materials: 75 parts base glaze, 8 parts antibacterial system, 6 parts nucleating agent, 3 parts colorant, 1.5 parts auxiliary agent, 0.2 parts functional additive, and 0.5 parts nano-glossing agent; the functional additive is a compound of graphene quantum dots, quaternary ammonium salt modified montmorillonite, and rare earth carbonate in a weight ratio of 0.02:0.1:0.1.

[0031] The base glaze, by weight, is composed of the following components: 25 parts potassium feldspar, 20 parts quartz sand, 8 parts dolomite, 3 parts barium carbonate, 3 parts zinc oxide, 2 parts zirconium oxide, 1 part boron oxide, 1 part bismuth oxide, 1 part borax, 0.8 parts lithium carbonate, and 1 part zinc borate. The antibacterial system is a mixture of silver-zinc composite antibacterial agent, nano copper oxide, and rare earth oxides in a mass ratio of 3:1:0.3. The silver-zinc composite antibacterial agent is Micro-KF136. The average particle size of the nano copper oxide is 10 nm. The rare earth oxide is cerium oxide. The nucleating agent is a mixture of calcined bovine bone powder and zirconium silicate in a mass ratio of 2:1. The calcined bovine bone powder is obtained by calcining bovine bone at 800℃ for 4 hours and then pulverizing it to 800 mesh.

[0032] The colorant is a compound of iron oxide, chromium oxide, and manganese oxide in a mass ratio of 6:4:3; the auxiliary agent is a compound of dispersant, defoamer, and coupling agent in a mass ratio of 1:0.8:0.5; the dispersant is a compound of sodium carboxymethyl cellulose and sodium tripolyphosphate in a mass ratio of 2:1; the viscosity of the sodium carboxymethyl cellulose is 200 mPa·s, and the DS is 0.5; the defoamer is organosilicon defoamer BYK-024; the coupling agent is silane coupling agent KH550; the particle size of the graphene quantum dots is 5-15 nm; the quaternary ammonium salt modified montmorillonite is DK3 polymer-grade organoclay; the rare earth carbonate is lanthanum carbonate; and the nano-brightening agent is nano-silica with an average particle size of 20 nm.

[0033] A method for preparing the high-gloss antibacterial ceramic colored glaze includes the following steps: Step S1: Mix the raw material components evenly according to the weight parts to obtain the mixed raw material, add deionized water, ball mill for 4 hours, and pass through a 325 mesh sieve to obtain a high-gloss antibacterial ceramic color glaze slurry. Step S2: The ceramic blank, which has been dried at 110℃ for 2 hours, is glazed using a spray glazing method. The spray glazing pressure is 0.3MPa, the spray glazing distance is 20cm, and the glaze thickness is 0.3mm. After glazing, the ceramic blank is placed in an oven and dried at 120℃ for 3 hours. Then it is transferred to a roller kiln for firing. After firing, a ceramic product with a high-gloss antibacterial colored glaze is obtained.

[0034] The mass ratio of the mixed raw materials to deionized water is 1:1.5. The firing process is as follows: In the heating stage, the temperature is raised from room temperature to 600℃ at a rate of 100℃ / h; in the holding stage, the temperature is held at 600℃ for 30 minutes to fully remove residual moisture and volatile substances from the bisque and glaze; then the temperature is raised to 1200℃ at a rate of 80℃ / h to ensure that the glaze is fully melted and vitrified; in the high-temperature holding stage, the temperature is held at 1200℃ for 60 minutes to promote the nucleating agent, refine the glaze grains, and improve the density and gloss of the glaze; in the cooling stage, the temperature is lowered from the high temperature to room temperature at a rate of 50℃ / h to avoid cracking of the glaze due to excessive cooling and to ensure that the glaze is smooth, flat, and has a stable color. Example 2

[0035] A high-gloss antibacterial ceramic glaze, by weight, comprises the following raw materials: 77 parts base glaze, 8.5 parts antibacterial system, 7 parts nucleating agent, 5 parts colorant, 1.8 parts auxiliary agent, 0.6 parts functional additive, and 0.8 parts nano-glossing agent; the functional additive is a compound of graphene quantum dots, quaternary ammonium salt modified montmorillonite, and rare earth carbonate in a weight ratio of 0.04:0.15:0.3.

[0036] The base glaze, by weight, is composed of the following components: 27 parts potassium feldspar, 22 parts quartz sand, 9 parts dolomite, 3.5 parts barium carbonate, 3.5 parts zinc oxide, 2.5 parts zirconium oxide, 1.2 parts boron oxide, 1.2 parts bismuth oxide, 1.2 parts borax, 0.9 parts lithium carbonate, and 1.5 parts zinc borate. The antibacterial system is a mixture of silver-zinc composite antibacterial agent, nano-copper oxide, and rare earth oxides in a mass ratio of 3.5:1:0.35. The silver-zinc composite antibacterial agent is Micro-KF136. The average particle size of the nano-copper oxide is 30 nm. The rare earth oxide is lanthanum oxide. The nucleating agent is a mixture of calcined bovine bone powder and zirconium silicate in a mass ratio of 2.3:1.3. The calcined bovine bone powder is obtained by calcining bovine bones at 830℃ for 4.5 hours and then pulverizing them to 850 mesh.

[0037] The colorant is a compound of iron oxide, chromium oxide, and manganese oxide in a mass ratio of 7:5:4; the auxiliary agent is a compound of dispersant, defoamer, and coupling agent in a mass ratio of 1.3:0.9:0.6; the dispersant is a compound of sodium carboxymethyl cellulose and sodium tripolyphosphate in a mass ratio of 2.3:1; the sodium carboxymethyl cellulose has a viscosity of 250 mPa·s and a DS of 0.55; the defoamer is organosilicon defoamer BYK-024; the coupling agent is silane coupling agent KH560; the graphene quantum dots have a particle size of 5-15 nm; the quaternary ammonium salt modified montmorillonite is DK3 polymer-grade organoclay; the rare earth carbonate is cerium carbonate; and the nano-brightening agent is nano-silica with an average particle size of 40 nm.

[0038] A method for preparing the high-gloss antibacterial ceramic colored glaze includes the following steps: Step S1: Mix the raw material components evenly according to the weight parts to obtain the mixed raw material, add deionized water, ball mill for 4.5 hours, and pass through a 325 mesh sieve to obtain a high-gloss antibacterial ceramic color glaze slurry. Step S2: The ceramic blank, which has been dried at 115℃ for 2.3h, is glazed using a spray glazing method. The spray glazing pressure is 0.35MPa, the spray glazing distance is 23cm, and the glaze thickness is 0.4mm. After glazing, the ceramic blank is placed in an oven and dried at 125℃ for 3.3h. Then it is transferred to a roller kiln for firing. After firing, a ceramic product with a high-gloss antibacterial colored glaze is obtained.

[0039] The mass ratio of the mixed raw materials to deionized water is 1:1.5. The firing process is as follows: In the heating stage, the temperature is raised from room temperature to 600℃ at a rate of 105℃ / h; in the holding stage, the temperature is held at 600℃ for 33 minutes to fully remove residual moisture and volatile substances from the bisque and glaze; then the temperature is raised to 1230℃ at a rate of 85℃ / h to ensure that the glaze is fully melted and vitrified; in the high-temperature holding stage, the temperature is held at 1230℃ for 70 minutes to promote the nucleating agent, refine the glaze grains, and improve the density and gloss of the glaze; in the cooling stage, the temperature is lowered from the high temperature to room temperature at a rate of 60℃ / h to avoid cracking of the glaze due to excessive cooling and to ensure that the glaze is smooth, flat, and has a stable color. Example 3

[0040] A high-gloss antibacterial ceramic glaze, by weight, comprises the following raw materials: 80 parts of base glaze, 9 parts of antibacterial system, 8 parts of nucleating agent, 5 parts of colorant, 2.3 parts of auxiliary agent, 0.8 parts of functional additive, and 1 part of nano-glossing agent; the functional additive is a compound of graphene quantum dots, quaternary ammonium salt modified montmorillonite, and rare earth carbonate in a weight ratio of 0.05:0.2:0.6.

[0041] The base glaze, by weight, is composed of the following components: 30 parts potassium feldspar, 23 parts quartz sand, 10 parts dolomite, 4 parts barium carbonate, 4 parts zinc oxide, 3 parts zirconium oxide, 1.5 parts boron oxide, 1.5 parts bismuth oxide, 1.5 parts borax, 1.1 parts lithium carbonate, and 2 parts zinc borate. The antibacterial system is a mixture of silver-zinc composite antibacterial agent, nano-copper oxide, and rare earth oxides in a mass ratio of 4:1:0.4. The silver-zinc composite antibacterial agent is Micro-KF136. The average particle size of the nano-copper oxide is 50 nm. The rare earth oxide is neodymium oxide. The nucleating agent is a mixture of calcined bovine bone powder and zirconium silicate in a mass ratio of 2.5:1.5. The calcined bovine bone powder is obtained by calcining bovine bone at 850℃ for 5 hours and then pulverizing it to 900 mesh.

[0042] The colorant is a compound of iron oxide, chromium oxide, and manganese oxide in a mass ratio of 8:5.5:4.5; the auxiliary agent is a compound of dispersant, defoamer, and coupling agent in a mass ratio of 1.5:1:0.65; the dispersant is a compound of sodium carboxymethyl cellulose and sodium tripolyphosphate in a mass ratio of 2.5:1; the sodium carboxymethyl cellulose has a viscosity of 300 mPa·s and a DS of 0.6; the defoamer is organosilicon defoamer BYK-024; the coupling agent is silane coupling agent KH570; the graphene quantum dots have a particle size of 5-15 nm; the quaternary ammonium salt modified montmorillonite is DK3 polymer-grade organoclay; the rare earth carbonate is lanthanum carbonate; and the nano-brightening agent is nano-silica with an average particle size of 55 nm.

[0043] A method for preparing the high-gloss antibacterial ceramic colored glaze includes the following steps: Step S1: Mix the raw material components evenly according to the weight parts to obtain the mixed raw material, add deionized water, ball mill for 5 hours, and pass through a 325 mesh sieve to obtain a high-gloss antibacterial ceramic color glaze slurry. Step S2: The ceramic blank, which has been dried at 120℃ for 2.5h, is glazed using a spray glazing method. The spray glazing pressure is 0.4MPa, the spray glazing distance is 25cm, and the glaze thickness is 0.6mm. After glazing, the ceramic blank is placed in an oven and dried at 130℃ for 3.5h. Then it is transferred to a roller kiln for firing. After firing, a ceramic product with a high-gloss antibacterial colored glaze is obtained.

[0044] The mass ratio of the mixed raw materials to deionized water is 1:1.5. The firing process is as follows: In the heating stage, the temperature is raised from room temperature to 600℃ at a rate of 110℃ / h; in the holding stage, the temperature is held at 600℃ for 35 minutes to fully remove residual moisture and volatile substances from the bisque and glaze; then the temperature is raised to 1250℃ at a rate of 90℃ / h to ensure that the glaze is fully melted and vitrified; in the high-temperature holding stage, the temperature is held at 1250℃ for 75 minutes to promote the nucleating agent, refine the glaze grains, and improve the density and gloss of the glaze; in the cooling stage, the temperature is lowered from the high temperature to room temperature at a rate of 65℃ / h to avoid cracking of the glaze due to excessive cooling and to ensure that the glaze is smooth, flat, and has stable color. Example 4

[0045] A high-gloss antibacterial ceramic glaze, by weight, comprises the following raw materials: 83 parts base glaze, 9.5 parts antibacterial system, 9.5 parts nucleating agent, 7 parts colorant, 2.8 parts auxiliary agent, 1.3 parts functional additive, and 1.3 parts nano-glossing agent; the functional additive is a compound of graphene quantum dots, quaternary ammonium salt modified montmorillonite, and rare earth carbonate in a weight ratio of 0.07:0.25:0.8.

[0046] The base glaze, by weight, is composed of the following components: 33 parts potassium feldspar, 24 parts quartz sand, 11 parts dolomite, 4.5 parts barium carbonate, 4.5 parts zinc oxide, 3.5 parts zirconium oxide, 1.8 parts boron oxide, 1.8 parts bismuth oxide, 1.8 parts borax, 1.2 parts lithium carbonate, and 2.5 parts zinc borate. The antibacterial system is a mixture of silver-zinc composite antibacterial agent, nano copper oxide, and rare earth oxides in a mass ratio of 4.5:1:0.45. The silver-zinc composite antibacterial agent is Micro-KF136. The average particle size of the nano copper oxide is 60 nm. The rare earth oxides are a mixture of cerium oxide, lanthanum oxide, and neodymium oxide in a mass ratio of 1:2:1.

[0047] The nucleating agent is a compound of calcined bovine bone powder and zirconium silicate in a mass ratio of 2.8:1.8; the calcined bovine bone powder is obtained by calcining bovine bones at 880℃ for 5.5 hours and then pulverizing them to 950 mesh; the colorant is a compound of iron oxide, chromium oxide, and manganese oxide in a mass ratio of 9.5:6.5:5.5; the auxiliary agent is a compound of dispersant, defoamer, and coupling agent in a mass ratio of 1.8:1.1:0.75; the dispersant is a compound of sodium carboxymethyl cellulose and sodium tripolyphosphate in a mass ratio of 2.8:1; the viscosity of the sodium carboxymethyl cellulose is... The pressure is 350 mPa·s, and the DS is 0.65; the defoamer is organosilicon defoamer BYK-024; the coupling agent is a compound of silane coupling agent KH550, silane coupling agent KH560, and silane coupling agent KH570 in a mass ratio of 1:3:2; the graphene quantum dots have a particle size of 5-15 nm; the quaternary ammonium salt modified montmorillonite is DK3 polymer-grade organic clay; the rare earth carbonate is a compound of lanthanum carbonate and cerium carbonate in a mass ratio of 3:5; the nano-brightening agent is nano-silica with an average particle size of 70 nm.

[0048] A method for preparing the high-gloss antibacterial ceramic colored glaze includes the following steps: Step S1: Mix the raw material components evenly according to the weight parts to obtain the mixed raw material, add deionized water, ball mill for 5.5 hours, and pass through a 325 mesh sieve to obtain a high-gloss antibacterial ceramic color glaze slurry. Step S2: The ceramic blank, which has been dried at 125℃ for 2.8h, is glazed using a spray glazing method. The spray glazing pressure is 0.45MPa, the spray glazing distance is 28cm, and the glaze thickness is 0.7mm. After glazing, the ceramic blank is placed in an oven and dried at 135℃ for 3.8h. Then it is transferred to a roller kiln for firing. After firing, a ceramic product with a high-gloss antibacterial colored glaze is obtained.

[0049] The mass ratio of the mixed raw materials to deionized water is 1:1.5. The firing process is as follows: In the heating stage, the temperature is raised from room temperature to 600℃ at a rate of 115℃ / h; in the holding stage, the temperature is held at 600℃ for 38 minutes to fully remove residual moisture and volatile substances from the bisque and glaze; then the temperature is raised to 1270℃ at a rate of 95℃ / h to ensure that the glaze is fully melted and vitrified; in the high-temperature holding stage, the temperature is held at 1270℃ for 85 minutes to promote the nucleating agent, refine the glaze grains, and improve the density and gloss of the glaze; in the cooling stage, the temperature is lowered from the high temperature to room temperature at a rate of 75℃ / h to avoid cracking of the glaze due to excessive cooling and to ensure that the glaze is smooth, flat, and has a stable color. Example 5

[0050] A high-gloss antibacterial ceramic glaze, by weight, comprises the following raw materials: 85 parts of base glaze, 10 parts of antibacterial system, 10 parts of nucleating agent, 8 parts of colorant, 3 parts of auxiliary agent, 1.5 parts of functional additive, and 1.5 parts of nano-glossing agent; the functional additive is a compound of graphene quantum dots, quaternary ammonium salt modified montmorillonite, and rare earth carbonate in a weight ratio of 0.08:0.3:1.

[0051] The base glaze, by weight, is composed of the following components: 35 parts potassium feldspar, 25 parts quartz sand, 12 parts dolomite, 5 parts barium carbonate, 5 parts zinc oxide, 4 parts zirconium oxide, 2 parts boron oxide, 2 parts bismuth oxide, 2 parts borax, 1.3 parts lithium carbonate, and 3 parts zinc borate. The antibacterial system is a mixture of silver-zinc composite antibacterial agent, nano-copper oxide, and rare earth oxides in a mass ratio of 5:1:0.5. The silver-zinc composite antibacterial agent is Micro-KF136. The average particle size of the nano-copper oxide is 70 nm. The rare earth oxide is oxygen... The nucleating agent is composed of calcined bovine bone powder and zirconium silicate in a mass ratio of 3:2; the calcined bovine bone powder is obtained by calcining bovine bone at 900℃ for 6 hours and then pulverizing it to 1000 mesh; the colorant is composed of iron oxide, chromium oxide and manganese oxide in a mass ratio of 10:7:6; the auxiliary agent is composed of dispersant, defoamer and coupling agent in a mass ratio of 2:1.2:0.8; the dispersant is composed of sodium carboxymethyl cellulose and sodium tripolyphosphate in a mass ratio of 3:1; the viscosity of sodium carboxymethyl cellulose is 400 mPa·s and the DS is 0.7.

[0052] The defoamer is organosilicon defoamer BYK-024; the coupling agent is silane coupling agent KH550; the graphene quantum dots have a particle size of 5-15 nm; the quaternary ammonium salt modified montmorillonite is DK3 polymer-grade organic clay; the rare earth carbonate is cerium carbonate; and the nano-brightening agent is nano-silica with an average particle size of 80 nm.

[0053] A method for preparing the high-gloss antibacterial ceramic colored glaze includes the following steps: Step S1: Mix the raw material components evenly according to the weight parts to obtain the mixed raw material, add deionized water, ball mill for 6 hours, and pass through a 325 mesh sieve to obtain a high-gloss antibacterial ceramic color glaze slurry. Step S2: The ceramic blank, which has been dried at 130℃ for 3 hours, is glazed using a spray glazing method. The spray glazing pressure is 0.5MPa, the spray glazing distance is 30cm, and the glaze thickness is 0.8mm. After glazing, the ceramic blank is placed in an oven and dried at 140℃ for 4 hours. Then it is transferred to a roller kiln for firing. After firing, a ceramic product with a high-gloss antibacterial colored glaze is obtained.

[0054] The mass ratio of the mixed raw materials to deionized water is 1:1.5. The firing process is as follows: In the heating stage, the temperature is raised from room temperature to 600℃ at a rate of 120℃ / h; in the holding stage, the temperature is held at 600℃ for 40 minutes to fully remove residual moisture and volatile substances from the bisque and glaze; then the temperature is raised to 1280℃ at a rate of 100℃ / h to ensure that the glaze is fully melted and vitrified; in the high-temperature holding stage, the temperature is held at 1280℃ for 90 minutes to promote the nucleating agent, refine the glaze grains, and improve the density and gloss of the glaze; in the cooling stage, the temperature is lowered from the high temperature to room temperature at a rate of 80℃ / h to avoid cracking of the glaze due to excessive cooling and to ensure that the glaze is smooth, flat, and has stable color.

[0055] Comparative Example 1 A high-gloss antibacterial ceramic glaze and its preparation method are basically the same as in Example 5, except that an equal amount of quaternary ammonium salt modified montmorillonite is used instead of graphene quantum dots.

[0056] Comparative Example 2 A high-gloss antibacterial ceramic glaze and its preparation method are basically the same as those in Example 5, except that an equal amount of graphene quantum dots are used instead of quaternary ammonium salt modified montmorillonite.

[0057] Comparative Example 3 A high-gloss antibacterial ceramic glaze and its preparation method are basically the same as those in Example 5, except that graphene is used in place of graphene quantum dots in equal amounts; the graphene is a single-layer graphene with a thickness of 0.8-1.2 nm and a diameter of 0.5-5 μm.

[0058] Comparative Example 4 A high-gloss antibacterial ceramic glaze and its preparation method are basically the same as those in Example 5, except that an equal amount of potassium feldspar is used instead of bismuth oxide.

[0059] Comparative Example 5 A high-gloss antibacterial ceramic glaze and its preparation method are basically the same as those in Example 5, except that an equal amount of nano-copper oxide is used instead of rare earth oxides.

[0060] Comparative Example 6 A high-gloss antibacterial ceramic glaze and its preparation method are basically the same as those in Example 5, except that an equal amount of rare earth oxides are used instead of nano copper oxide.

[0061] The ceramic glazes prepared in Example 5 and Comparative Examples 1-4 were subjected to performance testing. The test results are shown in Table 1. The test methods are as follows: (1) Gloss test: Refer to GB / T 13891-2008 "Method for determination of specular gloss of building veneer materials" and use a gloss meter to test the specular gloss of the glaze at 60°. Five different points are selected on the surface of each sample for testing, and the average value is taken as the gloss value of the sample.

[0062] (2) Antibacterial properties and antibacterial durability: The antibacterial properties and antibacterial durability were tested according to JC / T897-2014. The tested bacteria were Staphylococcus aureus and Escherichia coli.

[0063] (3) Glaze quality test: The glaze surface of the sample is observed by visual inspection and scanning electron microscope (SEM) to determine whether there are defects such as pinholes, cracks, discoloration, and graininess. If there are no pinholes or cracks, and the color is uniform and there is no discoloration, the glaze quality is qualified; otherwise, it is unqualified.

[0064] As shown in Table 1, the high-gloss antibacterial ceramic glaze prepared in Example 5 exhibits the best overall performance, with a 60° specular gloss of 112°. Its antibacterial rates against Staphylococcus aureus and Escherichia coli are 99.99% and 99.94%, respectively, and its antibacterial durability is 96.53% and 96.05%, respectively. The glaze surface is free of pinholes, cracks, and other defects, meeting quality standards. In contrast, each comparative example, by substituting a single variable for a key component in Example 5 (replacing graphene quantum dots with equal amounts of quaternary ammonium salt-modified montmorillonite, graphene quantum dots with quaternary ammonium salt-modified montmorillonite, graphene with graphene quantum dots, potassium feldspar with bismuth oxide, nano-copper oxide with rare earth oxides, and rare earth oxides with nano-copper oxides), shows varying degrees of performance degradation. This demonstrates that the raw material formulation and proportions used in Example 5 have a synergistic effect, and the key components are irreplaceable, effectively ensuring the high gloss, strong antibacterial properties, high antibacterial durability, and excellent glaze quality of the ceramic glaze.

[0065] Table 1. Performance Test Results of High-Gloss Antibacterial Ceramic Color Glaze

[0066] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely principles of the invention. Various changes and modifications can be made to the invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the claimed invention. The scope of protection claimed by the appended claims and their equivalents is defined.

Claims

1. A high-gloss antibacterial ceramic color glaze, characterized in that, By weight, its raw material composition includes: 75-85 parts of base glaze, 8-10 parts of antibacterial system, 6-10 parts of nucleating agent, 3-8 parts of colorant, 1.5-3 parts of auxiliary agent, 0.2-1.5 parts of functional additive, and 0.5-1.5 parts of nano-brightening agent; the functional additive is a compound of graphene quantum dots, quaternary ammonium salt modified montmorillonite, and rare earth carbonate in a weight ratio of (0.02-0.08):(0.1-0.3):(0.1-1).

2. The high-gloss antibacterial ceramic color glaze according to claim 1, characterized in that, The base glaze, by weight, is composed of the following components: 25-35 parts potassium feldspar, 20-25 parts quartz sand, 8-12 parts dolomite, 3-5 parts barium carbonate, 3-5 parts zinc oxide, 2-4 parts zirconium oxide, 1-2 parts boron oxide, 1-2 parts bismuth oxide, 1-2 parts borax, 0.8-1.3 parts lithium carbonate, and 1-3 parts zinc borate.

3. The high-gloss antibacterial ceramic color glaze according to claim 1, characterized in that, The antibacterial system is a compound of silver-zinc composite antibacterial agent, nano copper oxide, and rare earth oxide in a mass ratio of (3-5):1:(0.3-0.5).

4. The high-gloss antibacterial ceramic color glaze according to claim 3, characterized in that, The silver-zinc composite antibacterial agent is Micro-KF136; the average particle size of the nano-copper oxide is 10-70 nm; and the rare earth oxide is at least one of cerium oxide, lanthanum oxide, and neodymium oxide.

5. The high-gloss antibacterial ceramic color glaze according to claim 1, characterized in that, The nucleating agent is a compound of calcined bovine bone powder and zirconium silicate in a mass ratio of (2-3):(1-2); the calcined bovine bone powder is made by calcining bovine bone at 800-900℃ for 4-6 hours and then pulverizing it to 800-1000 mesh.

6. The high-gloss antibacterial ceramic color glaze according to claim 1, characterized in that, The colorant is a compound of iron oxide, chromium oxide, and manganese oxide in a mass ratio of (6-10):(4-7):(3-6); the auxiliary agent is a compound of dispersant, defoamer, and coupling agent in a mass ratio of (1-2):(0.8-1.2):(0.5-0.8); the dispersant is a compound of sodium carboxymethyl cellulose and sodium tripolyphosphate in a mass ratio of (2-3):1; the sodium carboxymethyl cellulose has a viscosity of 200-400 mPa·s and a DS of 0.5-0.7; the defoamer is organosilicon defoamer BYK-024; the coupling agent is at least one of silane coupling agent KH550, silane coupling agent KH560, and silane coupling agent KH570.

7. The high-gloss antibacterial ceramic color glaze according to claim 1, characterized in that, The graphene quantum dots have a particle size of 5-15 nm; the quaternary ammonium salt modified montmorillonite is DK3 polymer-grade organic clay; the rare earth carbonate is at least one of lanthanum carbonate and cerium carbonate; the nano-brightening agent is nano-silica with an average particle size of 20-80 nm.

8. A method for preparing a high-gloss antibacterial ceramic colored glaze according to any one of claims 1-7, characterized in that, Includes the following steps: Step S1: Mix the raw material components evenly according to the weight parts to obtain the mixed raw material, add deionized water, ball mill for 4-6 hours, and pass through a 325 mesh sieve to obtain a high-gloss antibacterial ceramic color glaze slurry. Step S2: Apply glaze to the ceramic bisque that has been dried at 110-130℃ for 2-3 hours using a spray glazing method. The spray glazing pressure is 0.3-0.5MPa, the spray glazing distance is 20-30cm, and the glaze thickness is 0.3-0.8mm. After glazing, place the ceramic bisque in an oven and dry it at 120-140℃ for 3-4 hours. Then transfer it to a roller kiln for firing. After firing, a ceramic product with a high-gloss antibacterial colored glaze is obtained.

9. The method for preparing high-gloss antibacterial ceramic colored glaze according to claim 8, characterized in that, The mass ratio of the mixed raw materials to deionized water is 1:1.

5.

10. The method for preparing high-gloss antibacterial ceramic colored glaze according to claim 8, characterized in that, The firing process is as follows: the temperature is raised from room temperature to 600℃ at a rate of 100-120℃ / h; the temperature is held at 600℃ for 30-40 minutes; the temperature is then raised to 1200-1280℃ at a rate of 80-100℃ / h and held for 60-90 minutes; finally, the temperature is lowered to room temperature at a rate of 50-80℃ / h.

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