High-strength toughened antibacterial ceramic material as well as preparation method and application thereof
The phenolic lignin reduction silver nitrate was prepared by enzymatic method and combined with acrylate copolymer and silane coupling agent, which solved the problem of easy cracking and insufficient antibacterial surface of sanitary ceramics, and achieved efficient antibacterial and anti-cracking effects.
Patent Information
- Application Number
- CN202510716747.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-05-30
- Publication Date
- 2025-08-15
AI Technical Summary
The glaze surface of existing sanitary ceramics is prone to cracks and bacterial breeding problems, and its antibacterial performance is insufficient, and the nanosilver has poor stability in the glaze, resulting in weakening of the antibacterial effect.
The phenolic lignin-reduced silver nitrate was prepared by combining tannin and ferulic acid enzyme method, combining acrylate copolymer and silane coupling agent to optimize the glaze structure, enhance the dispersion of nanosilver and the binding force of the glaze surface and the ceramic body.
It improves the crack resistance and antibacterial durability of the glaze surface, and the antibacterial rate is as high as 99.6%, which significantly improves the service life and hygiene status of sanitary ceramics.
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Figure CN120483675A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of sanitary ceramics, and in particular relates to a high-strength toughened antibacterial ceramic material and a preparation method and application thereof. Background Art
[0002] Sanitary ceramics refer to ceramic utensils used for hygiene and cleansing. As people's living standards improve, the demand for higher quality and functionality in sanitary ceramic products is growing. Bathrooms are characterized by high humidity, which can easily breed bacteria such as Escherichia coli and Staphylococcus aureus. These bacteria not only produce odor but can also pose a threat to human health, especially for those with weakened immune systems. Therefore, improving the antibacterial properties of sanitary ceramics can help inhibit bacterial growth, maintain a clean and hygienic bathroom environment, and promote healthy living. Furthermore, daily use, such as frequent use of hot water and seasonal changes, causes sanitary ceramics to undergo cycles of thermal expansion and contraction, resulting in thermal stress on the glaze, making it susceptible to cracking. The use of chemical cleaners can also corrode the glaze. Erosion and corrosion can weaken the glaze structure, reduce its strength, increase the risk of cracking, and reduce the product's aesthetics and lifespan. Therefore, enhancing the glaze's crack resistance is crucial.
[0003] Chinese patent CN105565667B discloses an easy-to-clean antibacterial functional sanitary ceramic and its preparation method. The product is prepared using ceramic glaze, inorganic antibacterial material, far-infrared radiation material and sepiolite mineral nanofibers. The product has good antibacterial properties, but in actual use, the inorganic antibacterial material is prone to agglomeration, resulting in a reduction in its effective specific surface area and the inability to fully exert its antibacterial properties. At the same time, the glaze formed is prone to internal stress, resulting in cracks during use, affecting the quality and performance of the glaze. Summary of the Invention
[0004] In response to the above problems, the present invention proposes a high-strength toughened antibacterial ceramic material and its preparation method and application, which effectively solves the anti-cracking and antibacterial problems of sanitary ceramics.
[0005] In order to achieve the above objectives, in a first aspect, the present invention provides a high-strength, toughened, antibacterial ceramic material.
[0006] A high-strength, toughened, and antibacterial ceramic material comprises a ceramic body and a glaze. The ceramic body comprises the following components in parts by weight: 10-30 parts of ball clay, 20-35 parts of kaolin, 5-15 parts of porcelain clay, 5-15 parts of quartz, 10-25 parts of calcined kaolin, 5-15 parts of wollastonite, and 2-5 parts of feldspar; the glaze comprises the following components in parts by weight: 3-5 parts of talc, 12-15 parts of calcite, 45-55 parts of feldspar, 7-10 parts of kaolin, 25-30 parts of quartz, 1-2 parts of zircon powder, 1.2-2.5 parts of wollastonite, 0.8-1.5 parts of zinc oxide, 1-2 parts of a silane coupling agent, 0.3-0.5 parts of an acrylate copolymer, and 3-5 parts of a carrier antibacterial agent.
[0007] Silver, one of the most popular antimicrobial agents, has broad antimicrobial properties and can effectively inhibit the growth of a variety of bacteria, such as Escherichia coli and Staphylococcus aureus. Nanosilver has a better antimicrobial effect, but adding nanosilver directly to sanitary ceramic glazes has poor stability. During the preparation and use of the ceramic glaze, nanosilver is prone to agglomeration, resulting in an increase in the nanosilver particle size and a possible gradual weakening of the antimicrobial effect. To address this issue, the applicant enzymatically prepared phenolic lignin with high reducing activity to reduce silver nitrate, resulting in nanosilver having superior stability and dispersion on the lignin, which can fully exert its antimicrobial properties and enhance its antimicrobial activity and durability. However, the addition of a carrier antimicrobial agent causes the carrier antimicrobial agent particles in the glaze to aggregate with each other, making the ceramic glaze prone to internal stress during firing and use, causing cracks and deglazing. In order to improve this situation, the applicant creatively added silane coupling agents and acrylate copolymers. Through the multiple active groups in the silane coupling agents and acrylate copolymers, the dispersion stability of the carrier antibacterial agent particles in the glaze was enhanced, and the particles interacted with the glaze. By improving the glaze structure, the bonding between the glaze and the ceramic body was enhanced, thereby improving its anti-cracking and deglazing performance.
[0008] Furthermore, the carrier antibacterial agent is prepared by the following steps: S1.1, dissolving lignin, tannic acid, and ferulic acid in an acetic acid-sodium acetate buffer solution, adding a horseradish peroxidase solution, stirring and reacting at 25-40°C for 6-8 hours, then maintaining at 60-80°C for 5-10 minutes, and then centrifuging the reaction solution at 3500-5000 r / min for 10-15 minutes, taking the precipitate, and drying to obtain modified lignin; S1.2, dissolving the modified lignin in water, adjusting the pH value to 8-8.5 with 1-1.2 mol / L sodium hydroxide solution, adding silver nitrate, and ultrasonicating at 60-70°C for 2-3 hours, and centrifuging at 1800-2200 r / min for purification to obtain the carrier antibacterial agent.
[0009] Furthermore, in S1.1, the usage ratio of lignin, tannic acid, ferulic acid, acetic acid-sodium acetate buffer solution, and horseradish peroxidase solution is (1-1.2) g: (0.5-0.8) g: (0.3-0.5) g: (100-120) mL: (10-15) mL.
[0010] Furthermore, in said S1.1, the pH value of the acetic acid-sodium acetate buffer solution is 4-6; in said S1.1, the horseradish peroxidase solution is an acetic acid-sodium acetate buffer solution containing a horseradish peroxidase activity concentration of 3-5 U / mL.
[0011] Furthermore, in S1.2, the usage ratio of modified lignin, water, and silver nitrate is (1-2) g: (80-120) mL: (0.8-1.5) g.
[0012] Through the above technical scheme, tannic acid and ferulic acid are used in combination with an enzymatic method to prepare phenolic lignin with high reducing activity to reduce silver nitrate, so that nanosilver has excellent stability and dispersibility on lignin, which can fully exert its antibacterial properties and enhance its antibacterial durability.
[0013] Furthermore, the acrylate copolymer is prepared by the following method: under a nitrogen environment, glycidyl methacrylate, 3-(trimethoxysilyl) methacrylate, and 2-hydroxyethyl methacrylate are dissolved in a solvent in proportion and mixed evenly, benzoyl peroxide is added, the mixture is stirred and heated to 70-80° C., the reaction is carried out for 5-8 hours, a polymerization inhibitor is added, and the reaction product is slowly poured into a precipitant to precipitate the polymer, which is then filtered and dried to obtain the acrylate copolymer.
[0014] Furthermore, the usage ratio of glycidyl methacrylate, 3-(trimethoxysilyl) methacrylate, 2-hydroxyethyl methacrylate, solvent, benzoyl peroxide, inhibitor, and precipitant is (2.1-2.8) g: (2.5-3.7) g: (1.3-2.0) g: (150-200) mL: (0.12-0.15) g: (0.1-0.2) g: (500-600) mL.
[0015] By preparing an acrylate copolymer with multiple active sites such as hydroxyl, silane, and epoxy groups, the long-chain structure of the acrylate copolymer can be entangled on the surface of the carrier antibacterial agent, effectively preventing the carrier antibacterial agent particles from aggregating with each other, making it evenly dispersed in the ceramic glaze. Its amphiphilic active groups can interact with the glaze system and the groups on the surface of the carrier antibacterial agent, further improving the dispersion stability of the carrier antibacterial agent and enhancing its antibacterial activity. In the initial stage of firing, the acrylate copolymer will undergo a cross-linking and curing reaction to form a three-dimensional network structure, further stabilizing the glaze system. This stable state can make the glaze crystals formed more uniform in size during firing, refine the glaze crystals, optimize the glaze structure, and improve its crack resistance.
[0016] Furthermore, the silane coupling agent is γ-aminopropyltriethoxysilane or N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane.
[0017] Through the above technical solution, on the one hand, the addition of the aminosilane coupling agent is conducive to reducing the surface energy of the carrier antibacterial agent, reducing the attraction between the carrier antibacterial agent particles, and better connecting the carrier antibacterial agent to the glaze matrix, thereby improving the dispersibility and binding stability of the phenolized lignin silver in the glaze surface; on the other hand, the amino group in the aminosilane coupling agent chemically reacts with the active groups such as the epoxy group in the acrylate copolymer, and its alkoxy group hydrolyzes in water to form a silanol group, which undergoes a condensation reaction with the hydroxyl groups on the surface of the ceramic glaze and the ceramic body to form a stable silicon-oxygen bond, adjusts the thermal expansion coefficient, and synergizes with the acrylate copolymer to further enhance the bonding force between the glaze surface and the ceramic body, so that the glaze surface and the ceramic body are more densely bonded after firing, reducing the occurrence of deglazing.
[0018] In a second aspect, the present invention provides a method for preparing a high-strength, toughened, and antibacterial ceramic material, comprising the following steps: S2.1, placing the raw materials of a ceramic body into a ball mill, adding 40-50 wt% of water, and grinding for 9-15 hours to obtain a slurry; adjusting the slurry concentration to 360-380 g / 200 mL, sieving, aging for 5-7 days, vacuum degassing, and then slip casting, drying, and repairing to obtain a ceramic body; S2.2, adding talc, calcite, feldspar, kaolin, quartz, zircon powder, wollastonite, and zinc oxide to a ball mill, adding water and zirconium oxide balls, ball milling for 10-12 hours, and passing through a 200-mesh sieve to obtain a mixed powder; S2.3, dissolve the acrylate copolymer in a 50-70wt% ethanol aqueous solution; suspend the carrier antibacterial agent in water, use 2-4W / cm² ultrasonic sonication for 10-12 minutes, then add the silane coupling agent, the treated acrylate copolymer and the carrier antibacterial agent to the mixed powder, continue grinding for 2-3 hours, add the electrolyte sodium tripolyphosphate, and adjust the viscosity to 18-25s to obtain a glaze; S2.4, completely immerse the ceramic body in the glaze slurry, stay for 3-8 seconds, and then take it out to allow a layer of glaze slurry to evenly adhere to the surface of the body to obtain a glaze blank; S2.5, dry the glaze blank, glaze-fire, and obtain a high-strength toughened antibacterial ceramic material.
[0019] Furthermore, in S2.5, the drying temperature is 80-120°C, the time is 1-3h, and the glaze firing procedure is to heat up to 500-600°C at 3-5°C / min, heat up to 900-1000°C at 5-10°C / min, heat up to 1200-1300°C at 8-12°C / min, keep warm for 30-60min, and cool to room temperature at 4-6°C / min, thereby obtaining a high-strength, toughened, and antibacterial ceramic material.
[0020] In a third aspect, the present invention provides an application of a high-strength and toughened antibacterial ceramic material, wherein the high-strength and toughened antibacterial ceramic material is used for sanitary ceramics.
[0021] Compared with the prior art, the present invention has the following beneficial effects: The invention adopts tannic acid and ferulic acid combined with an enzyme method to prepare phenolic lignin with high reducing activity to reduce silver nitrate, so that nano silver has excellent stability and dispersibility on lignin, enabling it to fully exert its antibacterial property and enhance its antibacterial durability.
[0022] The invention optimizes the glaze structure, improves the bonding force between the glaze and the ceramic body, and enhances the anti-cracking performance of the ceramic glaze by adding a specific amount of acrylate copolymer and silane coupling agent into the glaze. BRIEF DESCRIPTION OF THE DRAWINGS
[0023] Figure 1This is a graph showing the antibacterial effect of the high-strength and toughened antibacterial ceramic material prepared in Example 1 on Staphylococcus aureus, where C is the control group diluted 100 times, and the others are the experimental groups diluted 100 times; Figure 2 This is a diagram showing the antibacterial effect of the high-strength and toughened antibacterial ceramic material prepared in Example 1 on Escherichia coli, where C is the control group diluted 100 times, and the others are the experimental groups diluted 100 times. DETAILED DESCRIPTION
[0024] The following will provide a clear and complete description of the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. All other embodiments obtained by ordinary technicians in this field based on the embodiments of the present invention without making any creative efforts shall fall within the scope of protection of the present invention.
[0025] Example 1 A high-strength, toughened, and antibacterial ceramic material comprises a ceramic body and a glaze. The ceramic body comprises the following components in parts by weight: 10 parts of ball clay, 20 parts of kaolin, 5 parts of porcelain clay, 5 parts of quartz, 10 parts of calcined kaolin, 5 parts of wollastonite, and 2 parts of feldspar; the glaze comprises the following components in parts by weight: 3 parts of talc, 12 parts of calcite, 45 parts of feldspar, 7 parts of kaolin, 25 parts of quartz, 1 part of zircon powder, 1.2 parts of wollastonite, 0.8 parts of zinc oxide, 1 part of silane coupling agent, 0.3 parts of acrylate copolymer, and 3 parts of a carrier antibacterial agent.
[0026] The silane coupling agent is N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane.
[0027] The carrier antibacterial agent is prepared by the following steps: S1.1, dissolve 1 g of lignin, 0.5 g of tannic acid, and 0.3 g of ferulic acid in 100 mL of acetic acid-sodium acetate buffer solution with a pH of 4, add 10 mL of horseradish peroxidase solution, stir and react at 25°C for 6 hours, then maintain at 60°C for 5 minutes, then centrifuge the reaction solution at 3500 r / min for 10 minutes, take the precipitate, and dry to obtain modified lignin; the horseradish peroxidase solution is an acetic acid-sodium acetate buffer solution containing a horseradish peroxidase activity concentration of 3 U / mL.
[0028] S1.2. Dissolve 1 g of modified lignin in 80 mL of water, adjust the pH to 8 with 1 mol / L sodium hydroxide solution, add 0.8 g of silver nitrate, and ultrasonicate at 60°C for 2 h. Purify by centrifugation at 1800 rpm to obtain a carrier antibacterial agent.
[0029] The acrylate copolymer is prepared by the following method: under a nitrogen environment, 2.1 g of glycidyl methacrylate, 2.5 g of 3-(trimethoxysilyl) methacrylate, and 1.3 g of 2-hydroxyethyl methacrylate are dissolved in 150 mL of ethyl acetate as a solvent and mixed evenly; 0.12 g of benzoyl peroxide is added, the mixture is stirred and heated to 70° C., reacted for 5 hours, 0.1 g of hydroquinone as a polymerization inhibitor is added, and the reaction product is then slowly poured into 500 mL of methanol as a precipitant to precipitate the polymer, which is then filtered and dried to obtain the acrylate copolymer.
[0030] The method for preparing the high-strength and toughened antibacterial ceramic material comprises the following steps: S2.1, placing all raw materials for the ceramic body into a ball mill, adding 40 wt% water, and grinding for 15 h to obtain a slurry; adjusting the slurry concentration to 360 g / 200 mL, passing through a 350-mesh sieve, aging for 5 days, vacuum degassing, and then slip casting, drying, and repairing to obtain a ceramic body; S2.2, add talc, calcite, feldspar, kaolin, quartz, zircon powder wollastonite, and zinc oxide into a ball mill, add 25 parts of zirconium oxide balls, ball mill for 10 hours, and pass through a 200 mesh sieve to obtain a mixed powder; S2.3, dissolve the acrylate copolymer in 10 mL of 50 wt% ethanol aqueous solution; suspend the carrier antimicrobial agent in 10 mL of water and sonicate using 2 W / cm² ultrasound for 10 minutes. Then, add the silane coupling agent, the treated acrylate copolymer, and the carrier antimicrobial agent to the mixed powder, continue grinding for 2 hours, add the electrolyte sodium tripolyphosphate, and adjust the viscosity to 18 seconds to obtain the glaze; S2.4, completely immerse the ceramic body in the glaze slurry, wait for 3 seconds, then remove it and allow a layer of glaze slurry to evenly adhere to the surface of the body to obtain a glaze body; S2.5, drying the glaze blank and firing the glaze to obtain a high-strength, toughened, antibacterial ceramic material.
[0031] In S2.5, the drying temperature is 80℃, the time is 3h, and the glaze firing procedure is to heat up to 500℃ at 3℃ / min, heat up to 900℃ at 5℃ / min, heat up to 1200℃ at 8℃ / min, keep warm for 30min, and cool to room temperature at 4℃ / min to obtain a high-strength, toughened and antibacterial ceramic material.
[0032] Example 2 A high-strength, toughened, and antibacterial ceramic material comprises a ceramic body and a glaze. The ceramic body comprises the following components in parts by weight: 20 parts of ball clay, 28 parts of kaolin, 10 parts of porcelain clay, 10 parts of quartz, 18 parts of calcined kaolin, 10 parts of wollastonite, and 3 parts of feldspar; the glaze comprises the following components in parts by weight: 4 parts of talc, 14 parts of calcite, 50 parts of feldspar, 8 parts of kaolin, 28 parts of quartz, 1.5 parts of zircon powder, 1.8 parts of wollastonite, 1.2 parts of zinc oxide, 1.2 parts of a silane coupling agent, 0.4 parts of an acrylate copolymer, and 4 parts of a carrier antibacterial agent.
[0033] The silane coupling agent is N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane.
[0034] The carrier antibacterial agent is prepared by the following steps: S1.1, dissolve 1.1 g of lignin, 0.7 g of tannic acid, and 0.4 g of ferulic acid in 110 mL of an acetic acid-sodium acetate buffer solution with a pH of 5, add 12 mL of a horseradish peroxidase solution, stir and react at 32°C for 7 h, then maintain at 70°C for 8 min, and then centrifuge the reaction solution at 4200 rpm for 12 min. The precipitate is collected and dried to obtain modified lignin; the horseradish peroxidase solution is an acetic acid-sodium acetate buffer solution containing a horseradish peroxidase activity concentration of 4 U / mL.
[0035] S1.2, dissolve 1.5 g of modified lignin in 100 mL of water, adjust the pH to 8.2 with 1.1 mol / L sodium hydroxide solution, add 1.2 g of silver nitrate, and ultrasonicate at 65°C for 2.5 h. Purify by centrifugation at 2000 rpm to obtain a carrier antibacterial agent.
[0036] The acrylate copolymer is prepared by the following method: under a nitrogen environment, 2.5 g of glycidyl methacrylate, 3.2 g of 3-(trimethoxysilyl) methacrylate, and 1.7 g of 2-hydroxyethyl methacrylate are dissolved in 180 mL of ethyl acetate as a solvent and mixed evenly; 0.14 g of benzoyl peroxide is added, the mixture is stirred and heated to 75° C., and the reaction is carried out for 7 hours; 0.15 g of hydroquinone as a polymerization inhibitor is added, and the reaction product is then slowly poured into 550 mL of methanol as a precipitant to precipitate the polymer, which is then filtered and dried to obtain the acrylate copolymer.
[0037] The method for preparing the high-strength and toughened antibacterial ceramic material comprises the following steps: S2.1, placing all raw materials for the ceramic body into a ball mill, adding 45 wt% water, and grinding for 12 h to obtain a slurry; adjusting the slurry concentration to 370 g / 200 mL, passing through a 350-mesh sieve, aging for 6 days, vacuum degassing, and then slip casting, drying, and repairing to obtain a ceramic body; S2.2, add talc, calcite, feldspar, kaolin, quartz, zircon powder wollastonite, and zinc oxide into a ball mill, add 28 parts of zirconium oxide balls, ball mill for 11 hours, and pass through a 200 mesh sieve to obtain a mixed powder; S2.3, dissolve the acrylate copolymer in 16 mL of a 60 wt% ethanol aqueous solution; suspend the carrier antimicrobial agent in 13 mL of water and sonicate using 3 W / cm² ultrasound for 11 minutes. Then, add the silane coupling agent, the treated acrylate copolymer, and the carrier antimicrobial agent to the mixed powder, continue grinding for 2.5 hours, add the electrolyte sodium tripolyphosphate, and adjust the viscosity to 20 seconds to obtain the glaze; S2.4, completely immerse the ceramic body in the glaze slurry, wait for 5 seconds, then remove it and allow a layer of glaze slurry to evenly adhere to the surface of the body to obtain a glaze body; S2.5, drying the glaze blank and firing the glaze to obtain a high-strength, toughened, antibacterial ceramic material.
[0038] In S2.5, the drying temperature is 100°C, the time is 2h, and the glaze firing procedure is to heat up to 550°C at 4°C / min, heat up to 950°C at 8°C / min, heat up to 1250°C at 10°C / min, keep warm for 45min, and cool to room temperature at 5°C / min to obtain a high-strength, toughened, and antibacterial ceramic material.
[0039] Example 3 A high-strength, toughened, and antibacterial ceramic material comprises a ceramic body and a glaze. The ceramic body comprises the following components in parts by weight: 30 parts of ball clay, 35 parts of kaolin, 15 parts of porcelain clay, 15 parts of quartz, 25 parts of calcined kaolin, 15 parts of wollastonite, and 5 parts of feldspar; the glaze comprises the following components in parts by weight: 5 parts of talc, 15 parts of calcite, 55 parts of feldspar, 10 parts of kaolin, 30 parts of quartz, 2 parts of zircon powder, 2.5 parts of wollastonite, 1.5 parts of zinc oxide, 2 parts of silane coupling agent, 0.5 part of acrylate copolymer, and 5 parts of carrier antibacterial agent.
[0040] The silane coupling agent is γ-aminopropyltriethoxysilane.
[0041] The carrier antibacterial agent is prepared by the following steps: S1.1, dissolve 1.2 g of lignin, 0.8 g of tannic acid, and 0.5 g of ferulic acid in 120 mL of acetic acid-sodium acetate buffer solution with a pH of 6, add 15 mL of horseradish peroxidase solution, stir and react at 40°C for 8 hours, then maintain at 80°C for 10 minutes, then centrifuge the reaction solution at 5000 rpm for 15 minutes, collect the precipitate, and dry it to obtain modified lignin; the horseradish peroxidase solution is an acetic acid-sodium acetate buffer solution containing a horseradish peroxidase activity concentration of 5 U / mL.
[0042] S1.2. Dissolve 2 g of modified lignin in 120 mL of water, adjust the pH to 8.5 with 1.2 mol / L sodium hydroxide solution, add 1.5 g of silver nitrate, and ultrasonicate at 70°C for 3 h. Purify by centrifugation at 2200 rpm to obtain a carrier antibacterial agent.
[0043] The acrylate copolymer is prepared by the following method: under a nitrogen environment, 2.8 g of glycidyl methacrylate, 3.7 g of 3-(trimethoxysilyl) methacrylate, and 2.0 g of 2-hydroxyethyl methacrylate are dissolved in 200 mL of ethyl acetate as a solvent and mixed evenly; 0.15 g of benzoyl peroxide is added, the mixture is stirred and heated to 80° C., and the reaction is carried out for 8 hours; 0.2 g of hydroquinone as a polymerization inhibitor is added, and the reaction product is slowly poured into 600 mL of methanol as a precipitant to precipitate the polymer; the polymer is filtered and dried to obtain the acrylate copolymer.
[0044] The method for preparing the high-strength and toughened antibacterial ceramic material comprises the following steps: S2.1, placing all raw materials for the ceramic body into a ball mill, adding 50wt% water, and grinding for 15h to obtain a slurry; adjusting the slurry concentration to 380g / 200mL, passing through a 350-mesh sieve, aging for 7d, vacuum degassing, and then slip casting, drying, and repairing to obtain a ceramic body; S2.2, add talc, calcite, feldspar, kaolin, quartz, zircon powder wollastonite, and zinc oxide into a ball mill, add 30 parts of zirconium oxide balls, ball mill for 12 hours, and pass through a 200 mesh sieve to obtain a mixed powder; S2.3, dissolve the acrylate copolymer in 27 mL of 70 wt% ethanol aqueous solution; suspend the carrier antimicrobial agent in 17 mL of water and sonicate using 4 W / cm² ultrasound for 12 minutes. Then, add the silane coupling agent, the treated acrylate copolymer, and the carrier antimicrobial agent to the mixed powder, continue grinding for 3 hours, add the electrolyte sodium tripolyphosphate, and adjust the viscosity to 25 seconds to obtain the glaze; S2.4, completely immerse the ceramic body in the glaze slurry, wait for 8 seconds, then remove it and allow a layer of glaze slurry to evenly adhere to the surface of the body to obtain a glaze body; S2.5, drying the glaze blank and firing the glaze to obtain a high-strength, toughened, antibacterial ceramic material.
[0045] In S2.5, the drying temperature is 120℃, the time is 3h, and the glaze firing procedure is to increase the temperature to 600℃ at 5℃ / min, increase the temperature to 1000℃ at 12℃ / min, increase the temperature to 1300℃ at 10℃ / min, keep warm for 60min, and cool to room temperature at 6℃ / min to obtain a high-strength, toughened and antibacterial ceramic material.
[0046] Comparative Example 1 The same as Example 1, except that nanosilver is added in the preparation method of the high-strength toughened antibacterial ceramic material, and the molar amount of nanosilver is the same as that of silver nitrate.
[0047] Comparative Example 2 The same as Example 1, except that the modified lignin was replaced with an equal amount of lignin.
[0048] Comparative Example 3 The same as Example 1, except that no acrylate copolymer is added in the preparation method of the high-strength toughened antibacterial ceramic material.
[0049] Comparative Example 4 The same as Example 1, except that no silane coupling agent is added in the preparation method of the high-strength toughened antibacterial ceramic material.
[0050] Performance testing (a) Antibacterial Performance Test: The antibacterial rate of the high-strength, toughened, antibacterial ceramic materials prepared in Examples 1 to 3 and Comparative Examples 1 to 4 was tested using the method in Appendix C of the national standard GB / T 21510-2008; the bacterial strains used were Staphylococcus aureus ATCC 6538 and Escherichia coli ATCC 25922.
[0051] (b) Crack resistance test: The crack resistance of the high-strength and toughened antibacterial ceramic materials prepared in Examples 1 to 3 and Comparative Examples 1 to 4 was tested using the method of the national standard GB / T6952-2015 "Sanitary Ceramics".
[0052] The results are shown in Table 1.
[0053] Table 1. Performance test As can be seen from Table 1, the high-strength, toughened, antibacterial ceramic materials prepared in Examples 1-3 of the present application exhibit high antibacterial and crack resistance, achieving an antibacterial rate of 99.6% against Staphylococcus aureus and 99.4% against Escherichia coli. Combined with Comparative Examples 1-4, it can be seen that the nanosilver loading significantly influences its antibacterial properties, while the silane coupling agent and acrylate copolymer significantly influence its crack resistance.
[0054] Antibacterial durability test: The high-strength toughened antibacterial ceramic material prepared in Example 1 was selected as the experimental group for a 6-month antibacterial test against two bacterial strains, and the ordinary ceramic was placed for 6 months as the control group. The test method was the same as above, and the results were as follows: Figure 1 and Figure 2 shown.
[0055] from Figure 1It can be seen that after 6 months of storage, the high-strength toughened antibacterial ceramic material prepared in this application still has excellent antibacterial properties against Staphylococcus aureus; Figure 2 It is also shown that the high-strength toughened antibacterial ceramic material prepared in this application still has super antibacterial ability against Escherichia coli.
[0056] Although the present invention has been described in detail with reference to the aforementioned embodiments, it is still possible for those skilled in the art to modify the technical solutions described in the aforementioned embodiments, or to make equivalent substitutions for some of the technical features therein. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.
Claims
1. A high-strength, toughened, antibacterial ceramic material comprising a ceramic body and a glaze, characterized in that: The ceramic body comprises the following components in parts by weight: 10-30 parts of ball clay, 20-35 parts of kaolin, 5-15 parts of porcelain clay, 5-15 parts of quartz, 10-25 parts of calcined kaolin, 5-15 parts of wollastonite, and 2-5 parts of feldspar; the glaze comprises the following components in parts by weight: 3-5 parts of talc, 12-15 parts of calcite, 45-55 parts of feldspar, 7-10 parts of kaolin, 25-30 parts of quartz, 1-2 parts of zircon powder, 1.2-2.5 parts of wollastonite, 0.8-1.5 parts of zinc oxide, 1-2 parts of silane coupling agent, 0.3-0.5 parts of acrylate copolymer, and 3-5 parts of carrier antibacterial agent.
2. The high-strength, toughened, antibacterial ceramic material according to claim 1, characterized in that: The carrier antibacterial agent is prepared by the following steps: S1.1, dissolving lignin, tannic acid, and ferulic acid in an acetic acid-sodium acetate buffer solution, adding a horseradish peroxidase solution, stirring and reacting at 25-40° C. for 6-8 hours, then maintaining at 60-80° C. for 5-10 minutes, and then centrifuging the reaction solution at 3500-5000 rpm for 10-15 minutes, collecting the precipitate, and drying to obtain modified lignin; S1.2, dissolving the modified lignin in water, adjusting the pH to 8-8.5 with 1-1.2 mol / L sodium hydroxide solution, adding silver nitrate, and ultrasonicating at 60-70°C for 2-3 hours, and centrifuging at 1800-2200 rpm to purify the carrier antibacterial agent.
3. The high-strength and toughened antibacterial ceramic material according to claim 2, characterized in that: In the S1.1, the dosage ratio of lignin, tannic acid, ferulic acid, acetic acid-sodium acetate buffer solution, and horseradish peroxidase solution is (1-1.2) g: (0.5-0.8) g: (0.3-0.5) g: (100-120) mL: (10-15) mL; in the S1.1, the pH value of the acetic acid-sodium acetate buffer solution is 4-6; in the S1.1, the horseradish peroxidase solution is an acetic acid-sodium acetate buffer solution containing a horseradish peroxidase activity concentration of 3-5 U / mL.
4. The high-strength, toughened, antibacterial ceramic material according to claim 3, characterized in that: In S1.2, the usage ratio of modified lignin, water, and silver nitrate is (1-2) g: (80-120) mL: (0.8-1.5) g.
5. The high-strength and toughened antibacterial ceramic material according to claim 4, characterized in that: The acrylate copolymer is prepared by the following method: under a nitrogen environment, glycidyl methacrylate, 3-(trimethoxysilyl) methacrylate, and 2-hydroxyethyl methacrylate are dissolved in a solvent in proportion and mixed evenly, benzoyl peroxide is added, the mixture is stirred and heated to 70-80° C., reacted for 5-8 hours, a polymerization inhibitor is added, the reaction product is slowly poured into a precipitant to precipitate a polymer, filtered, and dried to obtain the acrylate copolymer.
6. The high-strength and toughened antibacterial ceramic material according to claim 5, characterized in that: The usage ratio of the glycidyl methacrylate, 3-(trimethoxysilyl) methacrylate, 2-hydroxyethyl methacrylate, solvent, benzoyl peroxide, polymerization inhibitor, and precipitant is (2.1-2.8) g: (2.5-3.7) g: (1.3-2.0) g: (150-200) mL: (0.12-0.15) g: (0.1-0.2) g: (500-600) mL.
7. The high-strength and toughened antibacterial ceramic material according to claim 1, characterized in that: The silane coupling agent is γ-aminopropyltriethoxysilane or N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane.
8. A method for preparing a high-strength and toughened antibacterial ceramic material according to any one of claims 1 to 7, characterized in that: The following steps are involved: S2.1, put the raw materials of the ceramic body into a ball mill, add 40-50wt% of water, grind for 9-15h to obtain a slurry; adjust the slurry concentration to 360-380g / 200mL, sieve, age for 5-7d, vacuum degas, then slip cast, dry, and repair to obtain a ceramic body; S2.2, add talc, calcite, feldspar, kaolin, quartz, zircon powder wollastonite, and zinc oxide into a ball mill, add water and zirconium oxide balls, ball mill for 10-12h, and pass through a 200 mesh sieve to obtain a mixed powder; S2.3, acrylate copolymer is mixed with 50-7 0wt% ethanol aqueous solution is dissolved; the carrier antibacterial agent is suspended in water, and ultrasonicated with 2-4W / cm² for 10-12 minutes, and then the silane coupling agent, the treated acrylate copolymer and the carrier antibacterial agent are added to the mixed powder, and the grinding is continued for 2-3 hours, and the electrolyte sodium tripolyphosphate is added and the viscosity is adjusted to 18-25s to obtain a glaze; S2.4, the ceramic body is completely immersed in the glaze slurry, and after staying for 3-8 seconds, it is taken out to make a layer of glaze slurry evenly adhere to the surface of the body to obtain a glaze blank; S2.5, the glaze blank is dried and glaze fired to obtain a high-strength toughened antibacterial ceramic material.
9. The method for preparing a high-strength and toughened antibacterial ceramic material according to claim 8, characterized in that: In S2.5, the drying temperature is 80-120°C, the time is 1-3h, and the glaze firing procedure is to increase the temperature to 500-600°C at 3-5°C / min, increase the temperature to 900-1000°C at 5-10°C / min, increase the temperature to 1200-1300°C at 8-12°C / min, keep warm for 30-60min, and cool to room temperature at 4-6°C / min to obtain a high-strength, toughened, and antibacterial ceramic material.
10. Use of a high-strength and toughened antibacterial ceramic material according to any one of claims 1 to 7, characterized in that: Used in sanitary ceramics.
Citation Information
Patent Citations
An easy-to-clean antibacterial sanitary ceramic and its preparation method
CN105565667B