Long-acting antibacterial and anti-slip ceramic tile material and preparation method thereof
By preparing stable antibacterial particles through the sol-gel method and setting up a multi-layer glaze structure, the problems of wear resistance and antibacterial durability of anti-slip ceramic tile materials were solved, achieving a high wet static friction coefficient and long-lasting antibacterial effect.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- LINYI KANGDU PORCELAIN CO LTD
- Filing Date
- 2026-04-28
- Publication Date
- 2026-06-19
Smart Images
Figure SMS_1
Abstract
Description
Technical Field
[0001] This invention relates to the field of protective ceramic tile processing technology, specifically to a long-lasting antibacterial antislip ceramic tile material and its preparation method. Background Technology
[0002] Ceramic tiles are widely used in residential, commercial buildings, hospitals, schools, public transportation areas, and sanitary spaces due to their advantages such as high strength, corrosion resistance, easy cleaning, and good decorative effect. With the continuous expansion of application scenarios, the market's functional requirements for ceramic tiles are no longer limited to traditional decorative and paving performance. Especially in wet and easily polluted environments such as kitchens, bathrooms, corridors, hospital wards, elderly care institutions, and public bath areas, the material not only needs to have good anti-slip properties, but also needs to have antibacterial properties and long-term stability.
[0003] Currently, anti-slip ceramic tiles typically improve the coefficient of friction by increasing surface roughness, creating anti-slip textures, or introducing hard particles into the glaze layer. Traditional methods involve introducing hard particles, such as silicon carbide, alumina, and corundum, into the glaze layer. Although these particles can partially protrude from the glaze surface during sintering to form a micro-uneven structure and improve the anti-slip coefficient, the thermal expansion coefficients of the hard particles and the glaze matrix differ significantly. After sintering and cooling, micro-cracks are easily generated at the interface. During wear-resistant use, the aggregate is prone to falling off, and the anti-slip performance rapidly declines over time. Meanwhile, traditional antibacterial tiles mainly use silver-based and zinc-based antibacterial agents, which achieve the bactericidal effect through the dissolution of antibacterial ions. The antibacterial agents are usually uniformly dispersed in the glaze layer. However, nano antibacterial agents have poor dispersibility in the glaze and are prone to agglomeration during high-temperature sintering, which greatly reduces the effective specific surface area and decreases the antibacterial efficiency. Moreover, the antibacterial agents lack chemical bonding with the glaze layer and are prone to falling off with the wear of the glaze layer during the wear process, resulting in poor antibacterial durability.
[0004] To address this technical deficiency, a solution is proposed. Summary of the Invention
[0005] The purpose of this invention is to provide a long-lasting antibacterial anti-slip ceramic tile material and its preparation method, in order to solve the technical problem that the wear resistance, antibacterial properties and antibacterial durability of existing anti-slip ceramic tile materials need to be further improved.
[0006] The objective of this invention can be achieved through the following technical solution: a long-lasting antibacterial and anti-slip ceramic tile material, comprising a ceramic tile substrate and a bottom glaze and a top glaze disposed on the surface of the ceramic tile substrate; The bottom glaze comprises the following components by weight: 65-75 parts of low melting point glass powder, 15-20 parts of spodumene micro powder, 5-8 parts of zinc oxide, and 3-5 parts of magnesium oxide. The surface glaze comprises the following components by weight: 65-75 parts of low melting point glass powder, 25-30 parts of spodumene micro powder, 30-40 parts of anti-slip aggregate, 15-25 parts of antibacterial particles, and 3-5 parts of aluminum dihydrogen phosphate.
[0007] Furthermore, the low-melting-point glass powder comprises the following components by weight: 45-55 parts SiO2, 15-20 parts B2O3, 10-15 parts ZnO, 35-8 parts Al2O, 5-8 parts Na2O, 3-5 parts K2O, and 2-4 parts CaO, with a softening point of 650-750℃ and a particle size of 5-15μm.
[0008] Furthermore, the anti-slip aggregate is composed of silicon carbide particles with a particle size of 20-50μm and alumina particles with a particle size of 10-30μm in a weight ratio of (1-2):1.
[0009] Furthermore, the antibacterial particles are obtained by the following steps: A1. Tetrabutyl tetrabutyl titanate, triethyl borate, silver nitrate, cerium nitrate, and anhydrous ethanol are mixed and stirred. At room temperature, ammonia is added to the reaction system to adjust the pH to 9-10. The mixture is stirred at room temperature for 20-24 hours to obtain silver-zinc co-doped silicate sol. A2. Spray granulation of silicate precursor sol to obtain precursor microspheres; A3. The precursor microspheres were calcined, quenched, and ground to obtain antibacterial particles with a particle size of 10-30 μm.
[0010] Furthermore, in step A1, the ratio of tetraethyl orthosilicate, tetrabutyl titanate, triethyl borate, silver nitrate, cerium nitrate, and anhydrous ethanol is 10-15g:5-7g:3-5g:0.8-1.2g:0.1-0.2g:70-80mL, and the concentration of ammonia is 6-8mol / L.
[0011] Further, in step A2, the spray granulation operation includes: allowing the silicate precursor sol to stand and degas before adding it to the feed tank of the spray dryer; using a two-fluid nozzle for atomization granulation; setting the inlet air temperature to 180-200℃, the outlet air temperature to 90-100℃, the atomizing gas pressure to 0.5-0.7MPa, the feed rate to 5-8mL / min; spray drying; and collecting the dried product to obtain the precursor microspheres.
[0012] Furthermore, in step A3, the calcination, quenching, and grinding operation includes: placing the precursor microspheres in a muffle furnace, heating the muffle furnace to 500-600℃ at a rate of 2-3℃ / min, holding for sintering for 2-3 hours, then heating to 800-900℃ at a rate of 5-7℃ / min, holding for sintering for 80-100 minutes, and while still hot, transferring them to cold water at 5-10℃ for water quenching, and grinding them to a particle size of 10-30μm to obtain antibacterial particles.
[0013] This invention also proposes a method for preparing a long-lasting antibacterial and antislip ceramic tile material, comprising the following steps: S1. Spray the bottom glaze slurry with a solid content of 40-50wt% onto the top of the ceramic tile substrate layer by layer, and dry each layer after spraying until the thickness reaches 50-60μm, forming a bottom glaze spray coating layer on the top of the ceramic tile substrate. S2. Spray a surface glaze with a solid content of 45-55wt% layer by layer onto the top of the bottom glaze coating layer. Dry each layer after spraying until the thickness reaches 70-80μm. A surface glaze coating layer is formed on top of the bottom glaze coating layer to obtain the anti-slip ceramic tile blank. S3. Place the anti-slip ceramic tile blank in a sintering furnace and sinter it by programmed temperature increase to obtain anti-slip ceramic tiles.
[0014] Furthermore, the preparation method of the ceramic tile matrix is as follows: clay, feldspar, and quartz are mixed in a weight ratio of (50-60):(20-30):(15-25), water is added, and the mixture is ball-milled to obtain a slurry. The slurry is then passed through an 80-mesh sieve and fed into a spray dryer for granulation. The inlet air temperature is set at 160-180℃, the outlet air temperature at 95-105℃, the atomizing gas pressure at 0.2-0.3MPa, and the feed rate at 10-15mL / min. The resulting powder is controlled. With a moisture content of 5-8%, the obtained powder is fed into a press mold, and the molding pressure is set to 20-25 MPa for dry pressing to obtain a ceramic tile substrate green body. The ceramic tile substrate green body is placed in a drying oven at 80-120℃ to dry, and then placed in a sintering furnace. The sintering furnace is heated to 650-750℃ at a rate of 3-5℃ / min, held for 15-25 min, and then heated to 980-1080℃ at a rate of 6-8℃ / min, held for 30-50 min, and then allowed to cool naturally to room temperature to obtain the ceramic tile substrate.
[0015] Furthermore, the programmed heating sintering operation includes: heating the sintering furnace to 700-750°C at a rate of 3-5°C / min, holding at that temperature for 15-20 min, then rapidly cooling it to 400-450°C at a rate of 8-12°C / min, then heating it again to 550-600°C at a rate of 2-3°C / min, holding it for 10-15 min, and then cooling it with the furnace.
[0016] The present invention has the following beneficial effects: 1. This invention introduces silver-containing active components and cerium-containing components into a silicate system using a sol-gel method, followed by spray drying, segmented calcination, water quenching, and grinding to obtain antibacterial particles. Segmented calcination improves the heat resistance stability of the antibacterial particles, making them less prone to deactivation during subsequent glazing. Water quenching and particle size control maintain high surface activity of the particles and facilitate uniform distribution in the surface glaze, thereby ensuring that antibacterial sites are fully exposed on the outermost surface of the tile and effectively contact bacteria. At the same time, the introduction of cerium components helps maintain the activity stability of the antibacterial system and slows down the decay of antibacterial performance. Through the synergistic effect of the stabilization preparation of antibacterial particles, surface directional distribution, and activity maintenance, the antibacterial rate of the material and its ability to retain antibacterial properties after washing are improved.
[0017] 2. This invention also provides a stable mechanical support and dimensional foundation for the functional glaze layer through the pre-sintered ceramic tile matrix, avoiding adverse effects on the antibacterial components during the high-temperature main firing process of the matrix. The bottom glaze spray layer set on the surface of the matrix utilizes low-melting-point glass powder, spodumene micro powder and metal oxide components to form a continuous glass phase, which improves the wettability, adhesion and thermal compatibility between the matrix and the surface functional glaze, thereby providing a reliable interface transition for the high-filler surface glaze. After adding aluminum dihydrogen phosphate to the surface glaze, it can promote the formation of a more stable inorganic bond structure during the re-firing process, enhance the interfacial fixation between antibacterial particles, anti-slip aggregate and glaze phase, and reduce the risk of particle detachment under wear and washing conditions. This makes the invention not only have good initial performance, but also maintain high antibacterial durability and excellent surface integrity under wear, washing and other usage conditions.
[0018] 3. This invention also forms a multi-scale micro-rough structure on the glaze surface by compounding silicon carbide particles and alumina particles in the surface glaze, which improves the mechanical interlocking of the surface under wet conditions, thereby increasing the wet static friction coefficient. At the same time, the two types of high-hardness aggregates can also serve as hard support points on the surface, improving the wear resistance of the glaze. By adopting specific re-firing anchoring, and then suppressing excessive surface flow by rapid cooling, followed by stress release and interface structure stabilization by secondary heating, the glaze is prevented from excessively leveling during firing and burying the rough structure. Thus, the anti-slip aggregate provides the surface rough structure, the double-layer glaze system provides particle support and interface transition, and the re-firing process effectively solidifies the above structure into a performance result that can be maintained for a long time. This allows the invention to maintain superior wear resistance and antibacterial durability even at a high level of wet anti-slip. Detailed Implementation
[0019] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.
[0020] Example 1: This example provides a method for preparing antibacterial particles, specifically including the following steps: Step 1: Preparation of silicate sol Weigh out 100g of tetraethyl orthosilicate, 50g of tetrabutyl titanate, 30g of triethyl borate, 8g of silver nitrate, 1g of cerium nitrate, and 700mL of anhydrous ethanol and add them to a reaction flask. Stir and add 6mol / L ammonia to the reaction flask at room temperature to adjust the pH to 9. Stir and react at room temperature for 20h to obtain silver-zinc co-doped silicate sol.
[0021] In the reaction, tetraethyl orthosilicate, tetrabutyl titanate, and triethyl borate undergo hydrolysis and condensation reactions under alkaline conditions provided by ammonia and moisture, gradually forming an inorganic sol system with a silicon-oxygen network as the main body and containing titanium-oxygen and boron-oxygen structures. The introduction of triethyl borate can participate in the formation of boron-oxygen structures on the one hand, and on the other hand, it helps to lower the softening temperature of the subsequent system and improve the compatibility with the glass phase of the glaze layer.
[0022] In silicate sols, silver nitrate and cerium nitrate are not simply mixed in as large particles, but rather enter the inorganic precursor system in an ionic or highly dispersed state during sol formation. This allows the antibacterial active components to be pre-dispersed and pre-immobilized in the silicate network during the sol stage. The active components are evenly distributed in the antibacterial particles, resulting in more continuous antibacterial active sites in the surface glaze, more stable surface antibacterial effect, and more effective inhibition of Staphylococcus aureus and Escherichia coli.
[0023] Step 2: Preparation of precursor microspheres After the silicate precursor sol was allowed to stand and degas, it was added to the liquid storage tank of a spray dryer. Atomization granulation was performed using a two-fluid nozzle. The inlet air temperature was set to 80℃, the outlet air temperature to 60℃, the atomizing gas pressure to 0.5MPa, and the feed rate to 5mL / min. The product was then collected after spray drying to obtain the precursor microspheres.
[0024] Step 3: Preparation of antibacterial particles Precursor microspheres were placed in a muffle furnace, heated to 500°C at a rate of 2°C / min, and sintered at that temperature for 2 hours. Then, the temperature was increased to 800°C at a rate of 5°C / min and sintered at that temperature for 80 minutes. While still hot, the microspheres were transferred to cold water at 5°C for water quenching and then ground to a particle size of 10-30 μm to obtain antibacterial particles.
[0025] In the reaction, the temperature is first raised to 500℃ at a low heating rate and held to remove residual organic groups, alcohol residues, some adsorbed water and nitrate decomposition products from the precursor, so that the system completes the initial inorganicization. Then, the temperature is raised to 800℃ and held to further densify and stabilize the inorganic framework, while the silver and cerium-related components are fixed in the silicate matrix in a more stable dispersion state.
[0026] After calcination, the original sol precursor transforms into inorganic particles with SiO2-TiO2-B2O3 as the matrix, while the silver and cerium components exist as highly dispersed active phases or oxidized dispersed phases within or on the surface of this matrix. This ensures that the antibacterial active components are no longer in a free or easily migrating state, but are stably embedded in the heat-resistant inorganic framework. After calcination, hot water quenching is performed to suppress further crystallization and coarsening at high temperatures, allowing the particle surface to retain more non-equilibrium structures or highly active structures.
[0027] Example 2: This example provides a method for preparing antibacterial particles, specifically including the following steps: Step 1: Preparation of silicate sol Weigh out 125g of tetrabutyl orthosilicate, 60g of tetrabutyl titanate, 40g of triethyl borate, 10g of silver nitrate, 1.5g of cerium nitrate, and 750mL of anhydrous ethanol and add them to a reaction flask. Stir and add 7mol / L ammonia to the reaction flask at room temperature to adjust the pH to 9.5. Stir and react at room temperature for 22h to obtain silver-zinc co-doped silicate sol.
[0028] Step 2: Preparation of precursor microspheres After the silicate precursor sol was allowed to stand and degas, it was added to the liquid storage tank of a spray dryer. Atomization granulation was performed using a two-fluid nozzle. The inlet air temperature was set to 85℃, the outlet air temperature to 65℃, the atomizing gas pressure to 0.6MPa, and the feed rate to 6.5mL / min. The product was then collected after spray drying to obtain the precursor microspheres.
[0029] Step 3: Preparation of antibacterial particles The precursor microspheres were placed in a muffle furnace, heated to 550°C at a rate of 2.5°C / min, and sintered at that temperature for 2.5 h. Then, the temperature was increased to 850°C at a rate of 6°C / min and sintered at that temperature for 90 min. While still hot, the microspheres were transferred to cold water at 7.5°C for water quenching and then ground to a particle size of 10-30 μm to obtain antibacterial particles.
[0030] Example 3: This example provides a method for preparing antibacterial particles, specifically including the following steps: Step 1: Preparation of silicate sol Weigh out 150g of tetraethyl orthosilicate, 70g of tetrabutyl titanate, 50g of triethyl borate, 12g of silver nitrate, 2g of cerium nitrate, and 800mL of anhydrous ethanol and add them to a reaction flask. Stir and add 8mol / L ammonia to the reaction flask at room temperature to adjust the pH to 10. Stir and react at room temperature for 24h to obtain silver-zinc co-doped silicate sol.
[0031] Step 2: Preparation of precursor microspheres After the silicate precursor sol was allowed to stand and degas, it was added to the liquid storage tank of a spray dryer. Atomization granulation was performed using a two-fluid nozzle. The inlet air temperature was set to 90℃, the outlet air temperature to 70℃, the atomizing gas pressure to 0.7MPa, and the feed rate to 8mL / min. The product was then collected after spray drying to obtain the precursor microspheres.
[0032] Step 3: Preparation of antibacterial particles Precursor microspheres were placed in a muffle furnace, heated to 600°C at a rate of 3°C / min, and sintered at that temperature for 3 hours. Then, the temperature was increased to 900°C at a rate of 7°C / min and sintered at that temperature for 100 minutes. While still hot, the microspheres were transferred to cold water at 10°C for water quenching and then ground to a particle size of 10-30 μm to obtain antibacterial particles.
[0033] Example 4: This example provides a method for preparing a long-lasting antibacterial and antislip ceramic tile material, including the following steps: Step I: Preparing the ceramic tile substrate Clay, feldspar, and quartz were mixed in a weight ratio of 50:20:15, and water was added for ball milling to obtain a slurry. The slurry was then passed through an 80-mesh sieve and fed into a spray dryer for granulation. The inlet air temperature was set at 160℃, the outlet air temperature at 95℃, the atomizing gas pressure at 0.2MPa, and the feed rate at 10mL / min. The spray drying was performed, and the moisture content of the resulting powder was controlled at 5%. The resulting powder was then fed into a press mold, and the molding pressure was set at 20MPa for dry pressing to obtain a green ceramic tile body. The green ceramic tile body was then dried in an 80℃ drying oven and then placed in a sintering furnace. The sintering furnace was heated to 650℃ at a rate of 3℃ / min and held for 15min. Then, the temperature was increased to 980℃ at a rate of 6℃ / min and held for 30min. The temperature was then allowed to cool naturally to room temperature to obtain the ceramic tile body.
[0034] Step II: Forming the Underlying Glaze Coating Weigh out the following components by weight: 45 parts SiO2, 15 parts B2O3, 10 parts ZnO, 5 parts Al2O3, 5 parts Na2O, 3 parts K2O, and 2 parts CaO. Add them to a melting furnace, heat and melt them, and keep them at that temperature for 20 minutes. Pour them into purified water at 5°C, and crush them to obtain low-melting-point glass powder with a particle size of 5-15 μm. Weigh out the following by weight: 65 parts of low melting point glass powder, 15 parts of spodumene micro powder, 5 parts of zinc oxide, and 3 parts of magnesium oxide. Add them to a ball mill and ball mill for 24 hours. Mix the ball-milled powder with purified water until uniform to obtain a bottom glaze slurry with a solid content of 40 wt%. The base glaze is sprayed layer by layer onto the top of the tile substrate. After each layer is sprayed, it is placed in a drying oven at 90°C for 70 seconds. The spraying is repeated until the thickness reaches 50μm, forming a base glaze coating layer on the top of the tile substrate.
[0035] The bottom glaze is formed by melting and water quenching low-melting-point glass powder, ball milling the glaze slurry, and spraying and drying. During the glaze firing process, zinc oxide partially dissolves to form a slow-release zinc ion reservoir. Spodumene regulates the coefficient of thermal expansion to create micro-compressive stress in the surface glaze. Water quenching amorphizes the glass powder, improving its adhesion to the substrate. This step mainly affects the antibacterial durability, ensuring antibacterial durability against Staphylococcus aureus and Escherichia coli after 500 washes. It also makes a minor contribution to the crack resistance and abrasion resistance of the glaze layer.
[0036] Step III: Preparing the Anti-slip Ceramic Tile Blank Silicon carbide particles with a particle size of 20-50μm and alumina particles with a particle size of 10-30μm are compounded at a weight ratio of 1:1 to obtain anti-slip aggregate. Weigh out the following by weight: 65 parts of low melting point glass powder, 25 parts of spodumene micro powder, 30 parts of anti-slip aggregate, 15 parts of antibacterial particles prepared in Example 1, and 3 parts of aluminum dihydrogen phosphate. Add them to a ball mill and ball mill for 24 hours. Mix the ball milled powder with purified water evenly to obtain a surface glaze slurry with a solid content of 45 wt%. The surface glaze is sprayed layer by layer on top of the bottom glaze coating. After each layer is sprayed, it is placed in a drying oven at 90℃ for 70 seconds. The spraying is repeated until the thickness reaches 70μm, forming a surface glaze coating on top of the bottom glaze coating, thus obtaining the anti-slip tile blank.
[0037] The surface glaze functional layer is formed by compounding anti-slip aggregates, preparing surface glaze slurry, adding antibacterial particles, adding aluminum dihydrogen phosphate, and spraying. Among them, silicon carbide and alumina are compounded to form a stable anti-slip skeleton, antibacterial particles provide silver ion bactericidal function and cerium ion valence state cycling function, and aluminum dihydrogen phosphate forms AlPO4 network phase during glaze firing and forms chemical bonds with the surface of antibacterial particles. This step directly determines the wet static friction coefficient, wear resistance and initial antibacterial rate, and is the direct bearing layer of the three core properties of anti-slip, antibacterial and wear resistance.
[0038] Step IV: Preparation of anti-slip ceramic tiles The anti-slip ceramic tile blank is placed in a sintering furnace, which is heated to 700°C at a rate of 3°C / min and held for 15 minutes. Then it is rapidly cooled to 400°C at a rate of 8°C / min, and then heated again to 550°C at a rate of 2°C / min and held for 10 minutes. The blank is then cooled with the furnace to obtain the anti-slip ceramic tile.
[0039] By employing a segmented heating and sintering process, including a first heating to 700℃ and holding for 15 minutes, rapid cooling to 400℃, a second heating to 550℃ and holding for 10 minutes, and subsequent furnace cooling, the sintering process achieves the following: the first heating fully melts the glass phase to ensure the densification of the glaze layer; rapid cooling inhibits excessive grain growth; the second heating utilizes density differences to achieve a gradient distribution of antibacterial particles on the surface and sedimentation of the lower layers of anti-slip aggregates; and furnace cooling forms micro-compressive stress on the surface. This step is crucial for the synergistic realization of all functions, thereby improving the material's wet static friction coefficient, wear resistance, initial antibacterial rate, and antibacterial durability after 500 washes.
[0040] Example 5: This example provides a method for preparing a long-lasting antibacterial and antislip ceramic tile material, including the following steps: Step I: Preparing the ceramic tile substrate Clay, feldspar, and quartz were mixed in a weight ratio of 55:25:20, and water was added for ball milling to obtain a slurry. The slurry was then passed through an 80-mesh sieve and fed into a spray dryer for granulation. The inlet air temperature was set at 170℃, the outlet air temperature at 100℃, the atomizing gas pressure at 0.25MPa, and the feed rate at 13mL / min. The spray drying was performed, and the moisture content of the resulting powder was controlled at 6.5%. The resulting powder was then fed into a press mold, and the molding pressure was set at 23MPa for dry pressing to obtain a green ceramic tile body. The green ceramic tile body was then dried in a 100℃ drying oven and then placed in a sintering furnace. The sintering furnace was heated to 700℃ at a rate of 4℃ / min and held for 20min. Then, the temperature was increased to 1030℃ at a rate of 7℃ / min and held for 40min. The temperature was then allowed to cool naturally to room temperature to obtain the ceramic tile body.
[0041] Step II: Forming the Underlying Glaze Coating Weigh out the following components by weight: 50 parts SiO2, 17 parts B2O3, 13 parts ZnO, 6.5 parts Al2O3, 6.5 parts Na2O, 4 parts K2O, and 3 parts CaO. Add them to a melting furnace, heat and melt them, and keep them at that temperature for 25 minutes. Pour them into purified water at 7.5℃, and crush them to obtain low-melting-point glass powder with a particle size of 5-15μm. Weigh out the following by weight: 70 parts of low melting point glass powder, 17 parts of spodumene micro powder, 6.5 parts of zinc oxide, and 4 parts of magnesium oxide. Add them to a ball mill and ball mill for 24 hours. Mix the ball-milled powder with purified water until uniform to obtain a bottom glaze slurry with a solid content of 45 wt%. The base glaze is sprayed layer by layer onto the top of the tile substrate. After each layer is sprayed, it is placed in a drying oven at 95°C for 60 seconds. The spraying is repeated until the thickness reaches 55μm, forming a base glaze coating layer on the top of the tile substrate.
[0042] Step III: Preparing the Anti-slip Ceramic Tile Blank Silicon carbide particles with a particle size of 20-50μm and alumina particles with a particle size of 10-30μm are compounded at a weight ratio of 1.5:1 to obtain anti-slip aggregate; Weigh out the following by weight: 70 parts of low melting point glass powder, 28 parts of spodumene micro powder, 35 parts of anti-slip aggregate, 20 parts of antibacterial particles prepared in Example 2, and 4 parts of aluminum dihydrogen phosphate. Add them to a ball mill and ball mill for 24 hours. Mix the ball milled powder with purified water evenly to obtain a surface glaze slurry with a solid content of 50 wt%. The surface glaze is sprayed layer by layer on top of the bottom glaze coating. After each layer is sprayed, it is placed in a drying oven at 95℃ for 60 seconds. The spraying is repeated until the thickness reaches 75μm, forming a surface glaze coating on top of the bottom glaze coating, thus obtaining the anti-slip tile blank.
[0043] Step IV: Preparation of anti-slip ceramic tiles The anti-slip ceramic tile blank is placed in a sintering furnace, which is heated to 725°C at a rate of 4°C / min and held for 17 minutes. Then it is rapidly cooled to 425°C at a rate of 10°C / min, and then heated again to 575°C at a rate of 2.5°C / min and held for 13 minutes. The blank is then cooled with the furnace to obtain the anti-slip ceramic tile.
[0044] Example 6: This example provides a method for preparing a long-lasting antibacterial and antislip ceramic tile material, including the following steps: Step I: Preparing the ceramic tile substrate Clay, feldspar, and quartz were mixed in a weight ratio of 60:30:25, and water was added for ball milling to obtain a slurry. The slurry was then passed through an 80-mesh sieve and fed into a spray dryer for granulation. The inlet air temperature was set at 180℃, the outlet air temperature at 105℃, the atomizing gas pressure at 0.3MPa, and the feed rate at 15mL / min. The spray drying was performed, and the moisture content of the resulting powder was controlled at 8%. The resulting powder was then fed into a press mold, and the molding pressure was set at 25MPa for dry pressing to obtain a green ceramic tile body. The green ceramic tile body was then dried in a drying oven at 120℃. After drying, it was placed in a sintering furnace, where the temperature was increased to 750℃ at a rate of 5℃ / min and held for 25 minutes. Then, the temperature was increased to 1080℃ at a rate of 8℃ / min and held for 50 minutes. The temperature was then allowed to cool naturally to room temperature to obtain the ceramic tile body.
[0045] Step II: Forming the Underlying Glaze Coating Weigh out the following components by weight: 55 parts SiO2, 20 parts B2O3, 15 parts ZnO, 8 parts Al2O3, 8 parts Na2O, 5 parts K2O, and 4 parts CaO. Add them to a melting furnace, heat and melt them, and keep them at that temperature for 30 minutes. Pour them into purified water at 10℃, crush them, and you will get low-melting-point glass powder with a particle size of 5-15μm. Weigh out the following by weight: 75 parts of low melting point glass powder, 20 parts of spodumene micro powder, 8 parts of zinc oxide, and 5 parts of magnesium oxide. Add them to a ball mill and ball mill for 24 hours. Mix the ball-milled powder with purified water until uniform to obtain a bottom glaze slurry with a solid content of 50 wt%. The base glaze is sprayed layer by layer onto the top of the tile substrate. After each layer is sprayed, it is placed in a drying oven at 100℃ for 50 seconds. The spraying is repeated until the thickness reaches 60μm, forming a base glaze coating layer on the top of the tile substrate.
[0046] Step III: Preparing the Anti-slip Ceramic Tile Blank Silicon carbide particles with a particle size of 20-50μm and alumina particles with a particle size of 10-30μm are compounded at a weight ratio of 2:1 to obtain anti-slip aggregate. Weigh out the following by weight: 75 parts of low melting point glass powder, 30 parts of spodumene micro powder, 40 parts of anti-slip aggregate, 25 parts of antibacterial particles prepared in Example 3, and 5 parts of aluminum dihydrogen phosphate. Add them to a ball mill and ball mill for 24 hours. Mix the ball milled powder with purified water evenly to obtain a surface glaze slurry with a solid content of 55 wt%. The surface glaze is sprayed layer by layer on top of the bottom glaze coating. After each layer is sprayed, it is placed in a drying oven at 100℃ for 50 seconds. The spraying is repeated until the thickness reaches 80μm, forming a surface glaze coating on top of the bottom glaze coating, thus obtaining the anti-slip tile blank.
[0047] Step IV: Preparation of anti-slip ceramic tiles The anti-slip ceramic tile blank is placed in a sintering furnace, which is heated to 750°C at a rate of 5°C / min and held for 20 minutes. Then it is rapidly cooled to 450°C at a rate of 12°C / min, and then heated again to 600°C at a rate of 3°C / min and held for 15 minutes. The blank is then cooled with the furnace to obtain the anti-slip ceramic tile.
[0048] Comparative Example 1: The difference between this comparative example and Example 6 is that, in the preparation of the antibacterial particles, step 3 is omitted, and the precursor microspheres prepared in step 2 are used instead of the antibacterial particles.
[0049] Comparative Example 2: The difference between this comparative example and Example 6 is that cerium nitrate was not added in step 1 during the preparation of the antibacterial particles used.
[0050] Comparative Example 3: The difference between this comparative example and Example 6 is that aluminum dihydrogen phosphate was not added in step III.
[0051] Comparative Example 4: The difference between this comparative example and Example 6 is that the bottom glaze in step II is replaced by the surface glaze in step III.
[0052] Performance testing: The antibacterial properties and antibacterial durability of the antislip ceramic tile samples prepared in Examples 4-6 and Comparative Examples 1-4 were determined in accordance with the standard JC / T 897-2014 "Antibacterial Properties of Antibacterial Ceramic Products". The tested bacteria were Staphylococcus aureus (AS1.89) and Escherichia coli (AS1.90). The wet static friction coefficient of the anti-slip ceramic tile samples prepared in Examples 4-6 and Comparative Examples 1-4 was determined in accordance with the standard GB / T 4100-2015 "Ceramic Tiles". The abrasion resistance of the anti-slip ceramic tile samples prepared in Examples 4-6 and Comparative Examples 1-4 was determined according to the standard GB / T 35153-2017 "Test Methods for Ceramic Tiles - Part 7: Determination of Abrasion Resistance of Glazed Tiles". The specific test data are shown in Table 1 below.
[0053] Table 1 - Performance Test Data of Samples
[0054] Data Analysis: Comparative analysis of the data in Table 1 shows that the wet static friction coefficient of the anti-slip ceramic tile prepared by this invention reaches 0.68-0.72, the wear resistance grade reaches level 5, the antibacterial performance against Staphylococcus aureus (AS1.89) reaches 97.1-97.6%, and the antibacterial performance against Escherichia coli (AS1.90) reaches 95.5-95.8%. After 500 washes with washing solution, the antibacterial durability against Staphylococcus aureus (AS1.89) reaches 94.8-95.4%, and the antibacterial durability against Escherichia coli (AS1.90) reaches 92.9-93.3%. All performance test data are superior to the comparative example, indicating that this invention, by setting a bottom glaze and a top glaze on the surface of the ceramic tile substrate... The glaze consists of a bottom glaze containing zinc oxide to form a slow-release zinc ion reservoir, and a top glaze containing anti-slip aggregate, antibacterial particles, and aluminum dihydrogen phosphate. The antibacterial particles are prepared by the sol-gel method and doped with silver and cerium. After calcination and water quenching, an amorphous layer is formed on the surface. During the glaze firing process, aluminum dihydrogen phosphate forms a network phase that chemically bonds with the surface of the antibacterial particles. The spatial gradient distribution of the antibacterial particles enriched on the surface and the anti-slip aggregate settled in the lower layer is achieved by utilizing the density difference. Through a multi-synergistic mechanism of slow-release zinc ions in the bottom glaze, rapid sterilization of silver ions in the top glaze, cyclic regeneration of cerium ions, and AlPO4 network fixation regulating dissolution, the wet static friction coefficient and wear resistance of the anti-slip ceramic tile material are improved, while the antibacterial performance and antibacterial durability of the ceramic tile material are also improved.
[0055] The preferred embodiments of the present invention disclosed above are merely illustrative of the invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the invention to specific implementations. Clearly, many modifications and variations can be made based on the content of this specification. This specification selects and specifically describes these embodiments to better explain the principles and practical applications of the invention, thereby enabling those skilled in the art to better understand and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims
1. A long-lasting antibacterial and antislip ceramic tile material, characterized in that, This includes the ceramic tile substrate and the base glaze and surface glaze applied to the surface of the ceramic tile substrate; The underlying glaze comprises the following components by weight: 65-75 parts of low melting point glass powder, 15-20 parts of spodumene micro powder, 5-8 parts of zinc oxide, and 3-5 parts of magnesium oxide. The surface glaze comprises the following components by weight: 65-75 parts of low melting point glass powder, 25-30 parts of spodumene micro powder, 30-40 parts of anti-slip aggregate, 15-25 parts of antibacterial particles, and 3-5 parts of aluminum dihydrogen phosphate.
2. The long-lasting antibacterial and anti-slip ceramic tile material according to claim 1, characterized in that, The low-melting-point glass powder comprises the following components by weight: 45-55 parts SiO2, 15-20 parts B2O3, 10-15 parts ZnO, 35-8 parts Al2O, 5-8 parts Na2O, 3-5 parts K2O, and 2-4 parts CaO, with a softening point of 650-750℃ and a particle size of 5-15μm.
3. The long-lasting antibacterial and antislip ceramic tile material according to claim 1, characterized in that, The anti-slip aggregate is composed of silicon carbide particles with a particle size of 20-50μm and alumina particles with a particle size of 10-30μm in a weight ratio of (1-2):
1.
4. The long-lasting antibacterial and anti-slip ceramic tile material according to claim 1, characterized in that, The antibacterial particles are obtained through the following steps: A1. Tetrabutyl tetrabutyl titanate, triethyl borate, silver nitrate, cerium nitrate, and anhydrous ethanol are mixed and stirred. At room temperature, ammonia is added to the reaction system to adjust the pH to 9-10. The mixture is stirred at room temperature for 20-24 hours to obtain silver-zinc co-doped silicate sol. A2. Spray granulation of silicate precursor sol to obtain precursor microspheres; A3. The precursor microspheres were calcined, quenched, and ground to obtain antibacterial particles with a particle size of 10-30 μm.
5. The long-lasting antibacterial and antislip ceramic tile material according to claim 4, characterized in that, In step A1, the ratio of tetraethyl orthosilicate, tetrabutyl titanate, triethyl borate, silver nitrate, cerium nitrate, and anhydrous ethanol is 10-15g:5-7g:3-5g:0.8-1.2g:0.1-0.2g:70-80mL, and the concentration of ammonia is 6-8mol / L.
6. The long-lasting antibacterial and antislip ceramic tile material according to claim 4, characterized in that, In step A2, the spray granulation operation includes: allowing the silicate precursor sol to stand and degas before adding it to the feed tank of the spray dryer; using a two-fluid nozzle for atomization granulation; setting the inlet air temperature to 180-200℃, the outlet air temperature to 90-100℃, the atomizing gas pressure to 0.5-0.7MPa, and the feed rate to 5-8mL / min; spray drying; and collecting the dried product to obtain the precursor microspheres.
7. The long-lasting antibacterial and antislip ceramic tile material according to claim 4, characterized in that, In step A3, the calcination, quenching, and grinding operation includes: placing the precursor microspheres in a muffle furnace, heating the muffle furnace to 500-600℃ at a rate of 2-3℃ / min, holding for sintering for 2-3 hours, then heating to 800-900℃ at a rate of 5-7℃ / min, holding for sintering for 80-100 minutes, and while still hot, transferring them to cold water at 5-10℃ for water quenching, and grinding them to a particle size of 10-30μm to obtain antibacterial particles.
8. A method for preparing a long-lasting antibacterial and anti-slip ceramic tile material according to any one of claims 1-7, characterized in that, Includes the following steps: S1. Spray the bottom glaze slurry with a solid content of 40-50wt% onto the top of the ceramic tile substrate layer by layer, and dry each layer after spraying until the thickness reaches 50-60μm, forming a bottom glaze spray coating layer on the top of the ceramic tile substrate. S2. Spray a surface glaze with a solid content of 45-55wt% layer by layer onto the top of the bottom glaze coating layer. Dry each layer after spraying until the thickness reaches 70-80μm. A surface glaze coating layer is formed on top of the bottom glaze coating layer to obtain the anti-slip ceramic tile blank. S3. Place the anti-slip ceramic tile blank in a sintering furnace and sinter it by programmed temperature increase to obtain anti-slip ceramic tiles.
9. The method for preparing a long-lasting antibacterial and anti-slip ceramic tile material according to claim 8, characterized in that, The method for preparing the ceramic tile matrix is as follows: clay, feldspar, and quartz are mixed in a weight ratio of (50-60):(20-30):(15-25), water is added, and the mixture is ball-milled to obtain a slurry. The slurry is then passed through an 80-mesh sieve and fed into a spray dryer for granulation. The inlet air temperature is set at 160-180℃, the outlet air temperature at 95-105℃, the atomizing gas pressure at 0.2-0.3MPa, and the feed rate at 10-15mL / min. The powder is then spray-dried, and the moisture content is controlled. The yield is 5-8%. The obtained powder is fed into the press mold, and the molding pressure is set to 20-25MPa. It is dry-pressed to obtain the ceramic tile substrate green body. The ceramic tile substrate green body is placed in a drying oven at 80-120℃ to dry. After drying, it is placed in a sintering furnace. The sintering furnace is heated to 650-750℃ at 3-5℃ / min and held for 15-25min. Then, it is heated to 980-1080℃ at 6-8℃ / min and held for 30-50min. It is then allowed to cool naturally to room temperature to obtain the ceramic tile substrate.
10. The method for preparing a long-lasting antibacterial and antislip ceramic tile material according to claim 8, characterized in that, The programmed heating sintering operation includes: heating the sintering furnace to 700-750℃ at a rate of 3-5℃ / min, holding at that temperature for 15-20min, then rapidly cooling it to 400-450℃ at a rate of 8-12℃ / min, then heating it again to 550-600℃ at a rate of 2-3℃ / min, holding it for 10-15min, and then cooling it with the furnace.