Antibacterial porous ceramic material capable of controllable release of silver ions and preparation method and application thereof

Abstract

The application discloses a kind of controllable release silver ion antibacterial porous ceramic materials and preparation method and application thereof, belong to ceramic material field, the antibacterial porous ceramic material is prepared by the mass ratio of 1:4-18:0.3-3 antibacterial agent, ceramic material and binding material;Wherein, the preparation method of antibacterial agent is: aluminum hydroxide is added to soluble silver salt solution, is uniformly obtained mixture, the mixture is heated at 300-350 DEG C 2-3h, obtain the antibacterial agent;Specific component is compounded simultaneously to obtain ceramic material and binding material.The antibacterial porous ceramic material has good pore structure, can effectively regulate antibacterial component silver element from sustained and effective dissolution, and has certain strength, water resistance, can play constant and effective antibacterial, sterilization and inhibit the role of algal growth.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of ceramic materials, and particularly relates to an antibacterial porous ceramic material capable of controlled release of silver ions and a preparation method and application thereof. BACKGROUND

[0002] Silver has the advantages of strong antibacterial ability, good durability, wide antibacterial spectrum and high safety, and has been widely used in the medical field as a long-acting antibacterial material. Common silver antibacterial agents include nano-silver antibacterial agents and silver ion antibacterial agents. For example, CN106513704A discloses a nano-silver capable of controlled release of silver ions and an antibacterial agent prepared therefrom, and CN103222477A discloses a silver ion inorganic antibacterial agent. The dispersion and wettability of silver in the antibacterial agent system have a great influence on its antibacterial effect, and if the silver ions or nano-silver entering the environment are not effectively controlled within a certain concentration range, they will have an impact on human health and the ecological environment.

[0003] In the prior art, in order to achieve controlled release of silver ions, control the release concentration thereof in the environment and ensure its bactericidal effect, some researchers have attempted to use a reducing graphene layer (rGO) to protect nano-silver particles (CN117106197A). Under the protection of the reducing graphene layer, the release of silver ions is controlled to a certain extent. However, the reducing graphene layer cannot completely protect the nano-silver particles, and can only maintain an effective bactericidal concentration for a short period of time, resulting in frequent replacement of the nano-silver particles.

[0004] CN108939174A discloses a pH-responsive polyoxazoline-nano-silver layer-by-layer self-assembly multilayer film. The invention first prepares a functional monomer: 2-(2-methoxycarbonyl) ethyl-2-oxazoline, and then obtains a negatively charged anionic polyoxazoline by copolymerization. Meanwhile, silver ions are reduced by catechol grafted chitosan to obtain a nano-silver composite sol (CSS-AgNPs). Finally, the negatively charged polyoxazoline and the positively charged nano-silver are alternately assembled on the starting layer by electrostatic layer-by-layer self-assembly to obtain a pH-responsive polyoxazoline-nano-silver layer-by-layer self-assembly multilayer film. The self-assembly film has anti-adhesion and pH responsiveness, thereby realizing controlled release of the antibacterial agent nano-silver. However, the preparation method of the film material is relatively complex and requires the action of multiple raw material carriers.

[0005] The Chinese patent document with the publication number CN111849233A discloses a kind of super wear-resistant long-acting antibacterial and antiviral nano coating and its preparation method, the super wear-resistant long-acting antibacterial and antiviral nano coating includes, according to weight fraction: composite silicate 30-75 parts, antibacterial agent 2-6 parts, antiviral agent 1-3 parts, defoaming agent 1-3 parts, leveling agent 1-3 parts and deionized water 150-350 parts, antibacterial agent includes 1-3 parts of EK50 and 1-3 parts of silver nitrate according to weight fraction.The coating prepared by the nano coating can continuously and slowly release silver ions from the inside, thereby obtaining rapid and long-term antibacterial ability.

[0006] Porous ceramic materials have the advantages of high temperature resistance, heat insulation, high hardness, wear resistance, etc., and are widely used in filtration materials, thermal insulation materials, wave absorbing materials, building decoration, etc. Nowadays, the application field and market prospect of antibacterial ceramic products are also increasingly expanding. For example, the Chinese patent document with the publication number CN110698227A discloses an antibacterial ceramic tile and a preparation method thereof. The antibacterial ceramic tile includes an antibacterial glaze layer arranged on the upper surface of the ceramic tile. The antibacterial glaze layer is composed of a base transparent glaze and a zirconium phosphate loaded composite antibacterial agent. The zirconium phosphate loaded composite antibacterial agent includes a zirconium phosphate carrier and a composite antibacterial agent. The zirconium phosphate loaded composite antibacterial agent is accumulated on the upper part of the antibacterial glaze layer. The antibacterial effective components of the composite antibacterial agent are antibacterial oxides and antibacterial ions. However, the problems of antibacterial layer falling off and the bonding force between the antibacterial layer and the substrate are urgent technical problems to be solved. SUMMARY

[0007] The present application provides an antibacterial porous ceramic material capable of controlled release of silver ions. The preparation process is simple and efficient, and the sintering forming temperature is relatively low. The antibacterial porous ceramic material has a good pore structure, can release silver ions in a controlled manner, and has good antibacterial and algae growth inhibition ability.

[0008] The specific technical solutions adopted are as follows:

[0009] An antibacterial porous ceramic material is prepared from an antibacterial agent, a ceramic material and a binding material in a mass ratio of 1:4-18:0.3-3.

[0010] The preparation method of the antibacterial agent is as follows: aluminum hydroxide is added to a soluble silver salt solution, mixed uniformly, and silver ions are uniformly loaded onto the surface of the aluminum hydroxide to obtain a mixture. The mixture is heated at 300-350℃ for 2-3h to obtain the antibacterial agent.

[0011] The ceramic material includes, in mass parts, 40-56 parts of aluminum hydroxide, 0-5 parts of ammonium carbonate, 0-5 parts of sodium carbonate, 3-6 parts of calcium hydroxide and 20-33 parts of sodium metasilicate. The ammonium carbonate and sodium carbonate are not both 0 parts.

[0012] The binding material comprises feldspar 30-45 parts by mass, kaolin 2-6 parts by mass, limestone 15-20 parts by mass, quartz 25-30 parts by mass and sodium carbonate 6-10 parts by mass.

[0013] The application uses alumina crystals uniformly loaded with silver elements as an antibacterial agent, and combines with a specific component of the ceramic body and the binding material to prepare the antibacterial porous ceramic material.

[0014] Preferably, in the soluble silver salt solution, the mass ratio of the soluble silver salt to water is 1:1.0-2.2, and the mass ratio of the soluble silver salt to aluminum hydroxide is 1:8.5-12.5. Under the above parameters, the uniformity of the silver elements loaded on the alumina crystals in the product antibacterial agent is improved.

[0015] Preferably, the soluble silver salt is silver nitrate or silver acetate.

[0016] Preferably, the particle size of the antibacterial agent, the ceramic body and the binding material is ≤300 mesh.

[0017] The application also provides a preparation method of the antibacterial porous ceramic material, which comprises the following steps: preparing the antibacterial agent, the ceramic body and the binding material respectively, mixing the antibacterial agent, the ceramic body and the binding material in a mass ratio of 1:4-18:0.3-3 to obtain a composite powder, dry-pressing the composite powder to obtain a ceramic green body, and high-temperature calcining the ceramic green body and naturally cooling it to obtain the antibacterial porous ceramic material.

[0018] Preferably, the dry-pressing pressure is 25-30 MPa, and the dry-pressing time is 1-5 minutes.

[0019] Preferably, the high-temperature calcination of the ceramic green body is carried out in an air atmosphere, and the calcination is carried out in a gradient temperature mode, that is, first calcination at 105-110 ℃ for 1-1.5 h, then second calcination at 300-310 ℃ for 2-2.5 h, third calcination at 850-860 ℃ for 1-1.5 h, and finally fourth calcination at 1200-1250 ℃ for 1-1.5 h. The above four stages of calcination respectively evaporate water, form pores, partially sinter and sinter the ceramic green body.

[0020] Further preferably, the temperature rising rate is 10-15 ℃ / min.

[0021] The application also provides an application of the antibacterial porous ceramic material in the field of antibacterial materials.

[0022] Compared with the prior art, the application has the following beneficial effects:

[0023] (1) The average specific surface area of the antibacterial porous ceramic material is greater than or equal to 10.804 m 2 / g, the average pore volume is greater than or equal to 0.054 cc / g, and the average pore size is greater than or equal to 9.004 nm. Due to the good pore structure, the silver element can be effectively and continuously dissolved out, and the antibacterial porous ceramic material has certain strength and water resistance, and can play a constant and effective role of antibacterial, sterilization and inhibition of algae growth.

[0024] (2) The antibacterial agent, the ceramic material and the binding material have good compatibility, and the silver is dispersed in the ceramic crystal lattice during the ceramic sintering process, so that the antibacterial material is not precipitated.

[0025] (3) The addition of the antibacterial agent prepared by the specific method in the present application will not cause the discoloration, gloss change and durability change of the ceramic surface. BRIEF DESCRIPTION OF DRAWINGS

[0026] Figure 1 The sample diagram of the antibacterial porous ceramic material prepared in Example 2.

[0027] Figure 2 The scanning electron microscope diagram of the antibacterial porous ceramic material sample prepared in Example 2. DETAILED DESCRIPTION

[0028] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the present application.

[0029] Example 1

[0030] (1) Preparation of the antibacterial agent: at room temperature, 8 parts of silver nitrate are added to 12 parts of water to dissolve, to obtain a silver nitrate solution, and then the silver nitrate solution is uniformly mixed with 80 parts of aluminum hydroxide to uniformly load silver ions on the surface of the aluminum hydroxide, to obtain a mixture, and the mixture is heated at 350 DEG C for 3 hours, and then ground and crushed to 300 mesh for standby;

[0031] (2) Preparation of the ceramic material: at room temperature, 55 parts of aluminum hydroxide, 5 parts of ammonium carbonate, 5 parts of sodium carbonate, 5 parts of calcium hydroxide and 30 parts of sodium metasilicate are mixed, and then ground to 300 mesh for standby;

[0032] (3) Preparation of the binding material: at room temperature, 40 parts of feldspar, 5 parts of kaolin, 20 parts of limestone, 25 parts of quartz and 10 parts of sodium carbonate are mixed, and then ground to 300 mesh for standby;

[0033] (4) 5 parts of the antibacterial agent prepared in the above step, 90 parts of the ceramic material, and 5 parts of the binding material were uniformly mixed in terms of mass parts, and then dry-pressed into a cylindrical ceramic body with a diameter of 2 cm and a thickness of 0.3 cm on a molding machine at 30 MPa;

[0034] (5) The cylindrical ceramic body was calcined in an air atmosphere at a temperature increasing rate of 10 ℃ / min, first calcined at 105 ℃ for 1 h in a first stage, then calcined at 300 ℃ for 2 h in a second stage, then calcined at 850 ℃ for 1 h in a third stage, and finally calcined at 1200 ℃ for 1 h in a fourth stage. After high-temperature calcination, the cylindrical ceramic body was naturally cooled to room temperature to obtain the antibacterial porous ceramic material.

[0035] Example 2

[0036] (1) Preparation of the antibacterial agent: 8 parts of silver nitrate were dissolved in 12 parts of water at room temperature to obtain a silver nitrate solution, and then the silver nitrate solution was uniformly mixed with 80 parts of aluminum hydroxide to uniformly load silver ions onto the surface of the aluminum hydroxide to obtain a mixture. The mixture was heated at 350 ℃ for 3 h, ground and pulverized to 300 mesh, and then used;

[0037] (2) Preparation of the ceramic material: 55 parts of aluminum hydroxide, 5 parts of ammonium carbonate, 5 parts of sodium carbonate, 5 parts of calcium hydroxide, and 30 parts of sodium metasilicate were mixed at room temperature, ground to 300 mesh, and then used as a ceramic material;

[0038] (3) Preparation of the binding material: 40 parts of feldspar, 5 parts of kaolin, 20 parts of limestone, 25 parts of quartz, and 10 parts of sodium carbonate were mixed at room temperature, ground to 300 mesh, and then used as a binding material;

[0039] (4) 10 parts of the antibacterial agent prepared in the above step, 85 parts of the ceramic material, and 5 parts of the binding material were uniformly mixed in terms of mass parts, and then dry-pressed into a cylindrical ceramic body with a diameter of 2 cm and a thickness of 0.3 cm on a molding machine at 30 MPa;

[0040] (5) The cylindrical ceramic body was calcined in an air atmosphere at a temperature increasing rate of 10 ℃ / min, first calcined at 105 ℃ for 1 h in a first stage, then calcined at 300 ℃ for 2 h in a second stage, then calcined at 850 ℃ for 1 h in a third stage, and finally calcined at 1200 ℃ for 1 h in a fourth stage. After high-temperature calcination, the cylindrical ceramic body was naturally cooled to room temperature to obtain the antibacterial porous ceramic material.

[0041] The optical picture of the antibacterial porous ceramic material is shown in Figure 1 The scanning electron microscope picture is shown in Figure 2 It can be seen that the antibacterial porous ceramic material has a good porous structure and uniformly loaded antibacterial components.

[0042] Example 3

[0043] (1) Preparation of the antibacterial agent: 8 parts of silver nitrate was dissolved in 12 parts of water at room temperature to obtain a silver nitrate solution, and then the silver nitrate solution was mixed with 80 parts of aluminum hydroxide to uniformly load silver ions onto the surface of the aluminum hydroxide to obtain a mixture. The mixture was heated at 350°C for 3h, and then ground and crushed to 300 mesh for standby;

[0044] (2) Preparation of the ceramic material: 55 parts of aluminum hydroxide, 5 parts of ammonium carbonate, 5 parts of sodium carbonate, 5 parts of calcium hydroxide, and 30 parts of sodium metasilicate were mixed at room temperature, and then ground to 300 mesh for standby;

[0045] (3) Preparation of the binding material: 40 parts of feldspar, 5 parts of kaolin, 20 parts of limestone, 25 parts of quartz, and 10 parts of sodium carbonate were mixed at room temperature, and then ground to 300 mesh for standby;

[0046] (4) 15 parts of the antibacterial agent, 80 parts of the ceramic material, and 5 parts of the binding material prepared in the above steps were uniformly mixed, and then dry-pressed into a cylindrical ceramic body with a diameter of 2 cm and a thickness of 0.3 cm at 30 MPa on a molding machine;

[0047] (5) The cylindrical ceramic body was calcined in an air atmosphere with a temperature rising rate of 10°C / min. First, it was calcined at 105°C for 1h in the first stage, then at 300°C for 2h in the second stage, then at 850°C for 1h in the third stage, and finally at 1200°C for 1h in the fourth stage. After high-temperature calcination, it was naturally cooled to room temperature to obtain the antibacterial porous ceramic material.

[0048] Sample analysis

[0049] (1) Antibacterial performance test

[0050] The antibacterial porous ceramic material prepared in Examples 1-3 was used for antibacterial experiments. The antibacterial porous ceramic material was immersed in deionized water, and the immersion liquid was subjected to antibacterial experiments. The test bacteria was Staphylococcus aureus.

[0051] The specific experimental operation was as follows:

[0052] An antibacterial porous ceramic material sample (1.52g) was taken and placed in a 500mL brown bottle. 200mL of deionized water was added for immersion for 24h, and the immersion liquid was sampled for the first time. Then, sampling was performed every 24h.

[0053] The activated S. aureus single colony was inoculated into a 50 mL sterilized liquid medium in a triangular flask, which was fixed on a shaking table, and expanded for 12 h at 200 rpm and 37°C. The cultured bacteria solution was diluted to 10 5 -10 6 cfu / mL standby;

[0054] 100 μL of the above bacteria solution and 100 μL of sterile water were punched into three holes of a sterile 96-hole plate as blank controls, and 100 μL of the above bacteria solution and 100 μL of the leaching solution were punched into another three holes as test samples.

[0055] The 96-hole plate after the sample was put into an enzyme marker, and the OD value was measured, and the antibacterial rate was calculated by the following formula.

[0056]

[0057] The results shown in Table 1 prove that the antibacterial porous ceramic material can controllably release silver ions, and has long-acting antibacterial performance.

[0058] Table 1: Antibacterial experiment results

[0059]

[0060] The above examples have described the technical solutions of the present application in detail, and it should be understood that the above description is only a specific embodiment of the present application, and is not used to limit the present application. Any modification, supplement or similar replacement within the principle range of the present application should be included in the protection range of the present application.

Claims

1. An antibacterial porous ceramic material, characterized in that, It is prepared from antibacterial agent, ceramic material and binder in a mass ratio of 1:4-18:0.3-3; The method for preparing the antibacterial agent is as follows: aluminum hydroxide is added to a soluble silver salt solution and mixed evenly to obtain a mixture. The mixture is then heated at 300-350℃ for 2-3 hours to obtain the antibacterial agent. The ceramic material, by weight, comprises 40-56 parts aluminum hydroxide, 0-5 parts ammonium carbonate, 0-5 parts sodium carbonate, 3-6 parts calcium hydroxide and 20-33 parts sodium metasilicate, wherein ammonium carbonate and sodium carbonate are not both 0 parts. The binder, by weight, comprises 30-45 parts feldspar, 2-6 parts kaolin, 15-20 parts limestone, 25-30 parts quartz, and 6-10 parts sodium carbonate. In soluble silver salt solutions, the mass ratio of soluble silver salt to water is 1:1.0-2.2; the mass ratio of soluble silver salt to aluminum hydroxide is 1:8.5-12.

5. The soluble silver salt is silver nitrate or silver acetate; The preparation method of the antibacterial porous ceramic material includes the following steps: preparing antibacterial agent, ceramic material and binder separately, then mixing the antibacterial agent, ceramic material and binder in a mass ratio of 1:4-18:0.3-3 to obtain a composite powder, dry pressing the composite powder to obtain a ceramic body, calcining the ceramic body at high temperature and then naturally cooling it to obtain the antibacterial porous ceramic material; the dry pressing pressure is 25-30 MPa; the high temperature calcination of the ceramic body is carried out in an air atmosphere, with gradient temperature calcination. First, the first stage calcination is carried out at 105-110℃ for 1-1.5h, then the temperature is raised to 300-310℃ for 2-2.5h, then the temperature is raised to 850-860℃ for 1-1.5h, and finally the fourth stage calcination is carried out at 1200-1250℃ for 1-1.5h.

2. The antibacterial porous ceramic material according to claim 1, characterized in that, The particle size of the antibacterial agent, ceramic material, and binder is ≤300 mesh.

3. The antibacterial porous ceramic material according to claim 1, characterized in that, When preparing antibacterial porous ceramic materials, the heating rate is 10-15℃ / min.

4. The application of the antibacterial porous ceramic material according to any one of claims 1-3 in the field of antibacterial.

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