Bacteriostatic biological composite ceramic and preparation method thereof

Abstract

The invention relates to antibacterial biological composite ceramic and a preparation method thereof, and belongs to the technical field of ceramic preparation. A modified antibacterial material is added into the biological composite ceramic material, so that the prepared composite ceramic has a better antibacterial effect, thymol and sodium alginate in the modified antibacterial material have natural antibacterial performance, growth of various bacteria can be effectively inhibited, and the antibacterial ability of the material is remarkably improved; sodium tripolyphosphate has good solubility and complexing property in water, so that thymol can be more uniformly dispersed in the solution, and aggregation and precipitation of thymol are prevented; in the preparation process, the sodium alginate and the thymol can permeate into the porous structure of the added hydroxyapatite to form a stable compound, and the structure not only contributes to slow release of antibacterial components, but also can increase the contact area between the antibacterial components and microorganisms; the beewax added into the antibacterial material also has good antibacterial performance, so that the antibacterial performance of the composite material can be further improved.

Description

Technical Field

[0001] The invention belongs to the technical field of ceramic preparation, and relates to an antibacterial biological composite ceramic and a preparation method thereof. Background Art

[0002] In the medical and biomedical fields, bioceramics are widely used in orthopedic implants, dental restoration materials and artificial joints. Biocomposite ceramic materials have good compatibility in the body, do not cause rejection reactions, and are conducive to combining with biological tissues. By compounding different materials, the mechanical properties of the material, such as strength and toughness, can be significantly improved to meet the needs of different biomedical applications. In addition, biocomposite ceramic materials can maintain stable chemical properties in the body and will not degrade or denature due to environmental changes.

[0003] With the continuous development of science and technology, the research on biocomposite ceramic materials is also deepening. In order to better meet the requirements of different fields, the present invention provides an antibacterial biocomposite ceramic and a preparation method thereof. Summary of the invention

[0004] The object of the present invention is to provide an antibacterial biocomposite ceramic and a preparation method thereof, which has the characteristics of good antibacterial effect and long service life.

[0005] The purpose of the present invention can be achieved by the following technical solutions:

[0006] An antibacterial biological composite ceramic, the composite ceramic formula is as follows, by mass percentage, polyvinyl alcohol 20-30%, nano alumina 30-40%, zirconium oxide 10-15%, nano titanium dioxide 10-20%, zinc oxide 5-10%, modified antibacterial material 4-7%, nano silver particles 3-5%, dispersant 1-2%,

[0007] Wherein, the preparation method of the modified antibacterial material is as follows:

[0008] S1: dissolving sodium tripolyphosphate in deionized water to obtain a sodium tripolyphosphate solution with a mass fraction of 20-30%, dispersing thymol in the sodium tripolyphosphate solution, with the mass ratio of thymol to sodium tripolyphosphate being 1:2, adding 1wt% Tween-80, and ultrasonicating for 0.5h to obtain a solid-liquid mixture A;

[0009] S2: Sodium alginate is dissolved in deionized water to prepare a sodium alginate solution with a mass fraction of 20%, the sodium alginate solution and the solid-liquid mixture A are mixed in a volume ratio of 1:1, stirred at a speed of 200 r / min for 1 h, and then ultrasonicated for 0.5 h to obtain a solid-liquid mixture B;

[0010] S3: freeze-dry the solid-liquid mixture B in liquid nitrogen for 10 minutes, and then use a freeze dryer to vacuum dry the mixture at a temperature of -70°C, and grind the freeze-dried solid to obtain a mixture C;

[0011] S4: Mix the mixture C and hydroxyapatite in a mass ratio of 1:(0.5-2), add 1wt% beeswax, put into a ball mill and grind at a speed of 400r / min for 0.5h to obtain the modified antibacterial material.

[0012] Furthermore, the dispersant is polyethylene glycol, and its number average molecular weight is 2000-5000.

[0013] Furthermore, the particle size of the modified antibacterial material obtained by grinding in S4 is 150 mesh.

[0014] A method for preparing an antibacterial biological composite ceramic, the specific process of the preparation method of the composite ceramic is as follows:

[0015] S41: according to the formula ratio, nano-alumina, zirconium oxide, nano-titanium dioxide and zinc oxide are put into a ball mill for grinding, the speed of the ball mill is 300r / min, and the grinding time is 0.5h;

[0016] S42: sintering the ground mixture in a muffle furnace at 300° C. for 3 h, and cooling to room temperature after sintering to obtain a mixture D;

[0017] S43: Heat polyvinyl alcohol from room temperature to 200°C in a blender, and stir at a speed of 200 r / min for 1 hour, then put mixture D, nanosilver particles, modified antibacterial material, and dispersant into the blender, and continue stirring at a speed of 300 r / min for 2 hours. While stirring, introduce ozone, and after stirring, pass through a mold and cool to obtain the composite ceramic.

[0018] Furthermore, the particle size of the mixture obtained by grinding in S41 is 150 mesh.

[0019] Furthermore, the heating rate of the muffle furnace in S42 is 3°C / min.

[0020] Furthermore, in S43, the heating rate of the polyvinyl alcohol from room temperature to 200° C. is 5° C. / min.

[0021] Furthermore, the ozone introduction flow rate in S43 is 10 m / s.

[0022] The present invention adds a modified antibacterial material to the biocomposite ceramic material, so that the prepared composite ceramic has a better antibacterial effect. Thymol and sodium alginate in the modified antibacterial material have natural antibacterial properties and can effectively inhibit the growth of various bacteria. When these two components are combined with the biocomposite ceramic material, the antibacterial ability of the material can be significantly improved; thymol can destroy the cell wall or cell membrane of bacteria, causing the death of bacteria, and at the same time, thymol can also inhibit the metabolic activity of bacteria, thereby further inhibiting the growth and reproduction of bacteria; sodium alginate, as a natural polymer material, can be gradually degraded and absorbed and utilized in a living body, reducing stimulation and rejection reactions to the living body; sodium alginate can form a high-viscosity solution in water, play a thickening role, improve the stability of the system, and prevent separation or precipitation between components.

[0023] Sodium tripolyphosphate has good solubility and complexing properties in water, which enables thymol to be more evenly dispersed in the solution and prevents it from aggregation and precipitation.

[0024] The molecular structure of hydroxyapatite is similar to the inorganic components in human bones and teeth, so it can form a good bond with human tissues and has good biocompatibility. In modified antibacterial materials, it can also provide additional biological activity and enhance the mechanical properties and stability of the material. Hydroxyapatite can also form a good interface bond with the bioceramic matrix, which can transfer and disperse stress and improve the overall mechanical properties of the material. At the same time, the addition of inorganic materials can also fill the defects and pores in the bioceramic matrix and improve the density and strength of the material.

[0025] And hydroxyapatite itself is porous, and this porous structure provides abundant space for the loading of antibacterial ingredients. During the preparation process, sodium alginate and thymol can penetrate into the porous structure of hydroxyapatite to form a stable complex. This structure not only helps the sustained release of antibacterial ingredients, but also increases the contact area between antibacterial ingredients and microorganisms, thereby improving the antibacterial effect. In addition, the surface of hydroxyapatite has a certain adsorption capacity, which can adsorb and fix sodium alginate and thymol molecules. This adsorption helps to maintain the stability of antibacterial ingredients and prevent them from being quickly released or degraded in the environment. The calcium ions in hydroxyapatite can undergo ion exchange reactions with the carboxyl groups in sodium alginate to form stable chemical bonds. The formation of this chemical bond helps to enhance the binding force between hydroxyapatite and sodium alginate, and also helps to fix and release antibacterial ingredients. Thymol, as a broad-spectrum antibacterial agent, can inhibit the growth of a variety of bacteria, fungi and yeasts. Hydroxyapatite itself also has certain antibacterial properties, which is mainly attributed to the interaction between the positive charge on its surface and the negative charge of the bacterial cell membrane. When hydroxyapatite is combined with sodium alginate and thymol, the three can act together on microbial cells and exert synergistic antibacterial effects through multiple pathways such as destroying cell membranes and inhibiting enzyme activity.

[0026] The main components of beeswax are compounds such as esters, free fatty acids, free fatty alcohols and hydrocarbons, which give beeswax good antibacterial properties. Therefore, adding beeswax can further improve the antibacterial properties of the composite material.

[0027] In the ceramic material of the present invention, multiple antibacterial components such as nano silver particles, nano alumina, nano titanium dioxide in the composite ceramic work together to form a powerful antibacterial barrier, which can effectively inhibit the growth of multiple bacteria; due to the use of biocompatible materials zirconium oxide and polyvinyl alcohol, the composite ceramic can reduce rejection reactions and inflammatory reactions when used in vivo, thereby improving safety and effectiveness; the addition of inorganic materials such as nano alumina and zirconium oxide significantly improves the mechanical strength and wear resistance of the composite ceramic, enabling it to withstand greater stress and impact; during the high-temperature sintering process, stable chemical bonds and phase structures are formed between the components, so that the composite ceramic has excellent chemical stability and corrosion resistance; the materials used in the preparation process are all environmentally friendly materials, and no harmful substances are generated during the sintering process, which meets environmental protection requirements.

[0028] Nano-alumina has high hardness, high wear resistance and good dispersibility. It can be evenly distributed in composite ceramics to form a hard skeleton structure. Zirconia has excellent phase change toughening effect. When subjected to external force, it can undergo phase change to absorb energy, thereby preventing crack expansion and fracture. Under light conditions, nano-titanium dioxide can generate electron-hole pairs, and react with hydroxide ions and oxygen ions adsorbed on its surface to generate hydroxyl radicals and superoxide anion radicals. These free radicals can directly attack the cell wall and cell membrane of bacteria, destroy its structure and cause bacterial death. At the same time, titanium dioxide can also decompose organic pollutants and harmful gases in the air. Zinc oxide has certain antibacterial properties. Zinc oxide can also adjust the pH value of the composite ceramic surface to put it in an environment that is not conducive to bacterial growth; nanosilver particles can release silver ions, which have strong oxidizing properties and high permeability. They can quickly penetrate the cell walls and cell membranes of bacteria to enter the cells and destroy the respiratory system and DNA structure of the cells, thereby causing bacterial death. Nanosilver particles also have broad-spectrum antibacterial properties and can inhibit the growth of a variety of bacteria, fungi and viruses; polyvinyl alcohol has good bonding and film-forming properties, and can tightly bond the components together to form an overall structure. At the same time, polyvinyl alcohol can also improve the density and water resistance of composite ceramics.

[0029] Beneficial effects of the present invention:

[0030] The present invention adds a modified antibacterial material to the biocomposite ceramic material, so that the prepared composite ceramic has a better antibacterial effect. The thymol and sodium alginate in the modified antibacterial material have natural antibacterial properties, can effectively inhibit the growth of various bacteria, and significantly improve the antibacterial ability of the material; sodium tripolyphosphate has good solubility and complexing properties in water, which enables thymol to be more evenly dispersed in the solution to prevent its aggregation and precipitation; and in the preparation process, sodium alginate and thymol can penetrate into the porous structure of hydroxyapatite to form a stable composite, which not only helps the sustained release of antibacterial components, but also increases the contact area between the antibacterial components and microorganisms, thereby improving the antibacterial effect; the beeswax added to the antibacterial material also has good antibacterial properties, which can further improve the antibacterial performance of the composite material. DETAILED DESCRIPTION

[0031] In order to further illustrate the technical means and effects adopted by the present invention to achieve the predetermined invention purpose, the specific implementation methods, structures, features and effects of the present invention are described in detail below in combination with the embodiments.

[0032] Formula ratio 1: polyvinyl alcohol 21%, nano-alumina 30%, zirconium oxide 10%, nano-titanium dioxide 15%, zinc oxide 10%, modified antibacterial material 7%, nano-silver particles 5%, polyethylene glycol-20002%;

[0033] Formula ratio 2: polyvinyl alcohol 25%, nano-alumina 40%, zirconium oxide 10%, nano-titanium dioxide 10%, zinc oxide 5%, modified antibacterial material 5%, nano-silver particles 3%, polyethylene glycol-40002%;

[0034] Formula ratio 3: polyvinyl alcohol 30%, nano-alumina 35%, zirconium oxide 10%, nano-titanium dioxide 10%, zinc oxide 5%, modified antibacterial material 5%, nano-silver particles 3%, polyethylene glycol-50002%;

[0035] Formula ratio 4: polyvinyl alcohol 20%, nano-alumina 30%, zirconium oxide 15%, nano-titanium dioxide 20%, zinc oxide 5%, modified antibacterial material 4%, nano-silver particles 5%, polyethylene glycol-20001%;

[0036] Example 1

[0037] The preparation method of the modified antibacterial material is as follows:

[0038] S1: Sodium tripolyphosphate is dissolved in deionized water to prepare a sodium tripolyphosphate solution with a mass fraction of 30%, thymol is dispersed in the sodium tripolyphosphate solution, the mass ratio of thymol to sodium tripolyphosphate is 1:2, 1wt% Tween-80 is added, and ultrasonic treatment is performed for 0.5h to obtain a solid-liquid mixture A;

[0039] S2: Sodium alginate is dissolved in deionized water to prepare a sodium alginate solution with a mass fraction of 20%, the sodium alginate solution and the solid-liquid mixture A are mixed in a volume ratio of 1:1, stirred at a speed of 200 r / min for 1 h, and then ultrasonicated for 0.5 h to obtain a solid-liquid mixture B;

[0040] S3: freeze-dry the solid-liquid mixture B in liquid nitrogen for 10 minutes, and then use a freeze dryer to vacuum dry the mixture at a temperature of -70°C, and grind the freeze-dried solid to obtain a mixture C;

[0041] S4: Mix the mixture C and hydroxyapatite in a mass ratio of 1:2, add 1wt% beeswax, put into a ball mill and grind at a speed of 400r / min for 0.5h to obtain the modified antibacterial material. The particle size of the modified antibacterial material obtained by grinding is 150 mesh.

[0042] The specific process of the preparation method of the composite ceramic is as follows:

[0043] S41: according to the formula ratio 1, nano-alumina, zirconium oxide, nano-titanium dioxide and zinc oxide are put into a ball mill for grinding, the speed of the ball mill is 300r / min, the grinding time is 0.5h, and the particle size of the mixture obtained by grinding is 150 mesh;

[0044] S42: sintering the ground mixture in a muffle furnace at 300° C. for 3 h, with a heating rate of 3° C. / min, and cooling to room temperature after sintering to obtain a mixture D;

[0045] S43: Heat polyvinyl alcohol from room temperature to 200°C in a blender at a heating rate of 5°C / min, and stir at a speed of 200r / min for 1h. Then put mixture D, nanosilver particles, modified antibacterial material, and dispersant into the blender, and continue stirring at a speed of 300r / min for 2h. While stirring, introduce ozone at a flow rate of 10m / s. After stirring, pass through a mold and cool to obtain the composite ceramic.

[0046] Example 2

[0047] The preparation method of the modified antibacterial material is as follows:

[0048] S1: Sodium tripolyphosphate is dissolved in deionized water to prepare a sodium tripolyphosphate solution with a mass fraction of 20%, thymol is dispersed in the sodium tripolyphosphate solution, the mass ratio of thymol to sodium tripolyphosphate is 1:2, 1wt% Tween-80 is added, and ultrasonic treatment is performed for 0.5h to obtain a solid-liquid mixture A;

[0049] S2: Sodium alginate is dissolved in deionized water to prepare a sodium alginate solution with a mass fraction of 20%, the sodium alginate solution and the solid-liquid mixture A are mixed in a volume ratio of 1:1, stirred at a speed of 200 r / min for 1 h, and then ultrasonicated for 0.5 h to obtain a solid-liquid mixture B;

[0050] S3: freeze-dry the solid-liquid mixture B in liquid nitrogen for 10 minutes, and then use a freeze dryer to vacuum dry the mixture at a temperature of -70°C, and grind the freeze-dried solid to obtain a mixture C;

[0051] S4: Mix the mixture C and hydroxyapatite in a mass ratio of 1:1, add 1wt% beeswax, put into a ball mill and grind at a speed of 400r / min for 0.5h to obtain the modified antibacterial material. The particle size of the modified antibacterial material obtained by grinding is 150 mesh.

[0052] The specific process of the preparation method of the composite ceramic is as follows:

[0053] S41: according to the formula ratio 2, nano-alumina, zirconium oxide, nano-titanium dioxide and zinc oxide are put into a ball mill for grinding, the speed of the ball mill is 300r / min, the grinding time is 0.5h, and the particle size of the mixture obtained by grinding is 150 mesh;

[0054] S42: sintering the ground mixture in a muffle furnace at 300° C. for 3 h, with a heating rate of 3° C. / min, and cooling to room temperature after sintering to obtain a mixture D;

[0055] S43: Heat polyvinyl alcohol from room temperature to 200°C in a blender at a heating rate of 5°C / min, and stir at a speed of 200r / min for 1h. Then put mixture D, nanosilver particles, modified antibacterial material, and dispersant into the blender, and continue stirring at a speed of 300r / min for 2h. While stirring, introduce ozone at a flow rate of 10m / s. After stirring, pass through a mold and cool to obtain the composite ceramic.

[0056] Example 3

[0057] The preparation method of the modified antibacterial material is as follows:

[0058] S1: Sodium tripolyphosphate is dissolved in deionized water to prepare a sodium tripolyphosphate solution with a mass fraction of 30%, thymol is dispersed in the sodium tripolyphosphate solution, the mass ratio of thymol to sodium tripolyphosphate is 1:2, 1wt% Tween-80 is added, and ultrasonic treatment is performed for 0.5h to obtain a solid-liquid mixture A;

[0059] S2: Sodium alginate is dissolved in deionized water to prepare a sodium alginate solution with a mass fraction of 20%, the sodium alginate solution and the solid-liquid mixture A are mixed in a volume ratio of 1:1, stirred at a speed of 200 r / min for 1 h, and then ultrasonicated for 0.5 h to obtain a solid-liquid mixture B;

[0060] S3: freeze-dry the solid-liquid mixture B in liquid nitrogen for 10 minutes, and then use a freeze dryer to vacuum dry the mixture at a temperature of -70°C, and grind the freeze-dried solid to obtain a mixture C;

[0061] S4: Mix the mixture C and hydroxyapatite in a mass ratio of 1:0.5, add 1wt% beeswax, put into a ball mill and grind at a speed of 400r / min for 0.5h to obtain the modified antibacterial material. The particle size of the modified antibacterial material obtained by grinding is 150 mesh.

[0062] The specific process of the preparation method of the composite ceramic is as follows:

[0063] S41: according to the formula ratio 3, nano-alumina, zirconium oxide, nano-titanium dioxide and zinc oxide are put into a ball mill for grinding, the speed of the ball mill is 300 r / min, the grinding time is 0.5 h, and the particle size of the mixture obtained by grinding is 150 mesh;

[0064] S42: sintering the ground mixture in a muffle furnace at 300° C. for 3 h, with a heating rate of 3° C. / min, and cooling to room temperature after sintering to obtain a mixture D;

[0065] S43: Heat polyvinyl alcohol from room temperature to 200°C in a blender at a heating rate of 5°C / min, and stir at a speed of 200r / min for 1h. Then put mixture D, nanosilver particles, modified antibacterial material, and dispersant into the blender, and continue stirring at a speed of 300r / min for 2h. While stirring, introduce ozone at a flow rate of 10m / s. After stirring, pass through a mold and cool to obtain the composite ceramic.

[0066] Example 4

[0067] The preparation method of the modified antibacterial material is as follows:

[0068] S1: Sodium tripolyphosphate is dissolved in deionized water to prepare a sodium tripolyphosphate solution with a mass fraction of 20%, thymol is dispersed in the sodium tripolyphosphate solution, the mass ratio of thymol to sodium tripolyphosphate is 1:2, 1wt% Tween-80 is added, and ultrasonic treatment is performed for 0.5h to obtain a solid-liquid mixture A;

[0069] S2: Sodium alginate is dissolved in deionized water to prepare a sodium alginate solution with a mass fraction of 20%, the sodium alginate solution and the solid-liquid mixture A are mixed in a volume ratio of 1:1, stirred at a speed of 200 r / min for 1 h, and then ultrasonicated for 0.5 h to obtain a solid-liquid mixture B;

[0070] S3: freeze-dry the solid-liquid mixture B in liquid nitrogen for 10 minutes, and then use a freeze dryer to vacuum dry the mixture at a temperature of -70°C, and grind the freeze-dried solid to obtain a mixture C;

[0071] S4: Mix the mixture C and hydroxyapatite in a mass ratio of 1:2, add 1wt% beeswax, put into a ball mill and grind at a speed of 400r / min for 0.5h to obtain the modified antibacterial material. The particle size of the modified antibacterial material obtained by grinding is 150 mesh.

[0072] The specific process of the preparation method of the composite ceramic is as follows:

[0073] S41: according to the formula ratio 4, nano-alumina, zirconium oxide, nano-titanium dioxide and zinc oxide are put into a ball mill for grinding, the speed of the ball mill is 300r / min, the grinding time is 0.5h, and the particle size of the mixture obtained by grinding is 150 mesh;

[0074] S42: sintering the ground mixture in a muffle furnace at 300° C. for 3 h, with a heating rate of 3° C. / min, and cooling to room temperature after sintering to obtain a mixture D;

[0075] S43: Heat polyvinyl alcohol from room temperature to 200°C in a blender at a heating rate of 5°C / min, and stir at a speed of 200r / min for 1h. Then put mixture D, nanosilver particles, modified antibacterial material, and dispersant into the blender, and continue stirring at a speed of 300r / min for 2h. While stirring, introduce ozone at a flow rate of 10m / s. After stirring, pass through a mold and cool to obtain the composite ceramic.

[0076] Comparative Example 1

[0077] In this comparative example, thymol was not added to the modified antibacterial material, and the remaining steps were consistent with those in Example 1.

[0078] Comparative Example 2

[0079] In this comparative example, sodium alginate was not added to the modified antibacterial material, and the remaining steps were consistent with those in Example 1.

[0080] Comparative Example 3

[0081] In this comparative example, hydroxyapatite was not added to the modified antibacterial material, and the remaining steps were consistent with those in Example 1.

[0082] Comparative Example 4

[0083] In this comparative example, beeswax was not added to the modified antibacterial material, and the remaining steps were consistent with those in Example 1.

[0084] Comparative Example 5

[0085] In this comparative example, no nanosilver particles were added during the preparation of the composite ceramic, and the remaining steps were consistent with those of Example 1.

[0086] The antibacterial properties of the embodiments and comparative examples were tested.

[0087] Antibacterial test: Place the sample on an agar plate containing Escherichia coli, then culture it at 37°C for 24h, 36h, and 72h, observe the colony formation on the sample surface, and analyze its antibacterial rate.

[0088]

[0089] It can be seen from the experimental data that the modified antibacterial material added in the present invention makes the prepared composite ceramic have better antibacterial properties and its antibacterial effect is more stable.

[0090] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any form. Although the present invention has been disclosed as a preferred embodiment as above, it is not used to limit the present invention. Any technical personnel in this field can make some changes or modify the technical contents disclosed above into equivalent embodiments without departing from the scope of the technical solution of the present invention. However, any brief modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention are still within the scope of the technical solution of the present invention.

Claims

1. An antibacterial biocomposite ceramic, characterized in that: The composite ceramic is formulated as follows: by mass percentage, polyvinyl alcohol 20-30%, nano-alumina 30-40%, zirconium oxide 10-15%, nano-titanium dioxide 10-20%, zinc oxide 5-10%, modified antibacterial material 4-7%, nano-silver particles 3-5%, dispersant 1-2%, Wherein, the preparation method of the modified antibacterial material is as follows: S1: dissolving sodium tripolyphosphate in deionized water to obtain a sodium tripolyphosphate solution with a mass fraction of 20-30%, dispersing thymol in the sodium tripolyphosphate solution, with the mass ratio of thymol to sodium tripolyphosphate being 1:2, adding 1wt% Tween-80, and ultrasonicating for 0.5h to obtain a solid-liquid mixture A; S2: Sodium alginate is dissolved in deionized water to prepare a sodium alginate solution with a mass fraction of 20%, the sodium alginate solution and the solid-liquid mixture A are mixed in a volume ratio of 1:1, stirred at a speed of 200 r / min for 1 h, and then ultrasonicated for 0.5 h to obtain a solid-liquid mixture B; S3: freeze-dry the solid-liquid mixture B in liquid nitrogen for 10 minutes, and then use a freeze dryer to vacuum dry the mixture at a temperature of -70°C, and grind the freeze-dried solid to obtain a mixture C; S4: Mix the mixture C and hydroxyapatite in a mass ratio of 1:(0.5-2), add 1wt% beeswax, put into a ball mill and grind at a speed of 400r / min for 0.5h to obtain the modified antibacterial material.

2. The antibacterial biocomposite ceramic according to claim 1, characterized in that: The dispersant is polyethylene glycol, and the number average molecular weight thereof is 2000-5000.

3. The antibacterial biocomposite ceramic according to claim 1, characterized in that: The particle size of the modified antibacterial material obtained by grinding in S4 is 150 mesh.

4. A method for preparing an antibacterial biocomposite ceramic, based on the antibacterial biocomposite ceramic according to any one of claims 1 to 3, characterized in that: The specific process of the preparation method of composite ceramics is as follows: S41: according to the formula ratio, nano-alumina, zirconium oxide, nano-titanium dioxide and zinc oxide are put into a ball mill for grinding, the speed of the ball mill is 300r / min, and the grinding time is 0.5h; S42: sintering the ground mixture in a muffle furnace at 300° C. for 3 h, and cooling to room temperature after sintering to obtain a mixture D; S43: Heat polyvinyl alcohol from room temperature to 200°C in a blender, and stir at a speed of 200 r / min for 1 hour, then put mixture D, nanosilver particles, modified antibacterial material, and dispersant into the blender, and continue stirring at a speed of 300 r / min for 2 hours. While stirring, introduce ozone, and after stirring, pass through a mold and cool to obtain the composite ceramic.

5. The method for preparing an antibacterial biocomposite ceramic according to claim 4, characterized in that: The particle size of the mixture obtained by grinding in S41 is 150 mesh.

6. The method for preparing an antibacterial biocomposite ceramic according to claim 4, characterized in that: The heating rate of the muffle furnace in S42 is 3°C / min.

7. The method for preparing an antibacterial biocomposite ceramic according to claim 4, characterized in that: In the S43, the heating rate of the polyvinyl alcohol from room temperature to 200° C. is 5° C. / min.

8. The method for preparing an antibacterial biocomposite ceramic according to claim 4, characterized in that: The ozone introduction flow rate in S43 is 10 m / s.

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