An antibacterial high-toughness ceramic material and its preparation method

Abstract

The present invention relates to the technical field of ceramic materials, and specifically relates to an antibacterial high-toughness ceramic material and a preparation method thereof. Step 1: Grind and mix kaolin, quartz, wollastonite, celestite, dolomite, potassium feldspar, zinc oxide, carbon fiber, tungsten powder, and modified polyborosilazane, granulate, and press into tablets, and perform biscuit firing at 800-900 °C for 60-80 min to obtain a green body; Step 2: Mix quartz, dolomite, potassium feldspar, wollastonite, limestone, zinc oxide, carbon fiber, modified polyborosilazane, and modified hydrotalcite to obtain a base glaze; Mix the base glaze with deionized water and grinding balls, and grind to obtain a glaze slurry; Step 3: Uniformly coat the surface of the green body with the glaze slurry, calcine at 750-900 °C for 30-60 min, and then raise the temperature to 1200-1300 °C and calcine for 60-80 min; Cool to room temperature to obtain the antibacterial high-toughness ceramic material.

Description

Technical Field

[0001] The present invention relates to the technical field of ceramic materials, and specifically relates to an antibacterial high-toughness ceramic material and a preparation method thereof. Background Art

[0002] Ceramic materials have excellent wear resistance, corrosion resistance, and high-temperature resistance, and are widely used in fields such as aerospace, automotive manufacturing, and electronic devices. However, ceramics are polycrystalline materials, and grain boundaries hinder displacement, resulting in the inherent brittleness of traditional ceramic materials. One is that the structure often contains a large number of microcracks, and the other is that there are defects such as poor impact resistance and low fracture toughness, which limit their application.

[0003] On the other hand, traditional ceramic materials also have limitations in antibacterial properties, and the increase of this additional property has received increasing attention. Materials such as silver, zinc, titanium, and copper are generally introduced into ceramic materials to enhance antibacterial properties. Among them, silver has a high cost and disadvantages such as oxidation and discoloration when introduced, while zinc and titanium have low antibacterial properties. Copper series antibacterial materials have limited high melting points and high-temperature stability, and their antibacterial properties are also relatively excellent; however, when introduced into ceramic materials, there are problems such as poor dispersion and easy loss, resulting in a decrease in antibacterial properties.

[0004] In summary, to solve the above problems, preparing a ceramic material with high toughness and excellent antibacterial properties will play an important role in fields such as medical devices and food processing, and effectively expand the application fields of ceramic materials. Summary of the Invention

[0005] The purpose of the present invention is to provide an antibacterial high-toughness ceramic material and a preparation method thereof to solve the problems raised in the above background art.

[0006] To solve the above technical problems, the present invention provides the following technical solutions:

[0007] A preparation method of an antibacterial high-toughness ceramic material, comprising the following steps:

[0008] Step 1: Add modified polyborosilazane, zinc oxide, carbon fiber, and tungsten powder to an ethanol solution in sequence, adjust the pH to 3.3 ± 0.2, stir at 60 - 65 °C for 3 - 5 hours, wash, and dry to obtain raw material A; grind, mix, granulate, and press raw material A with kaolin, quartz, wollastonite, celestite, dolomite, and potassium feldspar, and perform biscuit firing at 800 - 900 °C for 60 - 80 min to obtain a biscuit body;

[0009] Step 2: Add the modified polyborosilazane, zinc oxide, and carbon fiber into the ethanol solution in sequence, adjust the pH to 3.3 ± 0.2, stir at 60 - 65 °C for 3 - 5 hours, wash, and dry to obtain raw material B; mix raw material B with quartz, dolomite, potassium feldspar, wollastonite, limestone, and modified hydrotalcite to obtain the base glaze; mix the base glaze with deionized water and grinding balls, and grind to obtain the glaze slurry;

[0010] Step 3: Uniformly coat the glaze slurry on the surface of the green body, calcine at 750 - 900 °C for 20 - 30 min, and then raise the temperature to 1200 - 1300 °C and calcine for 60 - 80 min; cool to room temperature to obtain the antibacterial high-toughness ceramic material.

[0011] In a further embodiment, the green body comprises the following raw materials in parts by mass: 26 - 31 parts of kaolin, 10 - 15 parts of quartz, 15 - 25 parts of wollastonite, 12 - 20 parts of celestine, 5 - 7 parts of dolomite, 6 - 8 parts of potassium feldspar, 3 - 5 parts of zinc oxide, 0.5 - 1.2 parts of carbon fiber, 1 - 2 parts of tungsten powder, and 2.5 - 4.8 parts of modified polyborosilazane.

[0012] In a further embodiment, the base glaze comprises the following raw materials in parts by mass: 28 - 36 parts of quartz, 15 - 25 parts of dolomite, 12 - 20 parts of potassium feldspar, 5 - 7 parts of wollastonite, 10 - 15 parts of limestone, 4 - 6 parts of zinc oxide, 0.5 - 1.2 parts of carbon fiber, 0.5 - 0.8 parts of modified polyborosilazane, and 6 - 8 parts of modified hydrotalcite; the mass ratio of the base glaze, deionized water, and grinding balls is 1:(0.5 - 0.6):3.

[0013] In a further embodiment, the carbon fiber is short cut fiber with a length of 3 - 6 mm and a single filament diameter of 7 - 10 μm.

[0014] In a further embodiment, the preparation of the modified polyborosilazane includes the following steps: uniformly mix liquid polyborosilazane, allyltrimethoxysilane, zirconium dimethacrylate, and dicumyl peroxide, and stir and react at 130 - 135 °C for 12 - 20 hours to obtain the modified polyborosilazane; wherein, allyltrimethoxysilane accounts for 4 - 5 wt% of the liquid polyborosilazane, zirconium dimethacrylate accounts for 1 - 1.5 wt% of the liquid polyborosilazane; the addition amount of dicumyl peroxide is 0.5 - 0.8 wt%.

[0015] In a further embodiment, the preparation of the modified hydrotalcite comprises the following steps: successively adding liquid polyborosilazane and zirconium butoxide into tetrahydrofuran and mixing evenly; adding allyl hydrotalcite, copper methacrylate hydrate, and diisopropylbenzene peroxide, stirring evenly, then placing it in a vacuum reactor, reacting at 120-125 °C for 4-5 hours to obtain a hybrid product, soaking it in ethanol for one week to displace guest molecules, and changing the ethanol twice a day; then drying it in an oven to obtain the modified hydrotalcite.

[0016] In a further embodiment, the modified hydrotalcite comprises the following raw materials in parts by mass: 6-8 parts of liquid polyborosilazane, 2.5-3.2 parts of zirconium butoxide, 5-6 parts of allyl hydrotalcite, 0.6-0.8 parts of copper methacrylate hydrate, and 0.1-0.2 parts of diisopropylbenzene peroxide.

[0017] In a further embodiment, the preparation of the allyl hydrotalcite comprises the following steps: (1) ultrasonically dispersing hydrotalcite in deionized water, adding a mixed solution of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and N-hydroxysuccinimide, and stirring evenly; adding allylamine, reacting at 40-50 °C for 3-4 hours, centrifuging, washing with water, and drying to obtain a solid product; (2) redispersing the solid product in deionized water, adding a mixed aqueous solution of anhydrous copper sulfate and calcium tungstate, adjusting the pH = 5 ± 0.2, stirring and reacting at 70-75 °C for 10-12 hours, cooling, and freeze-drying to obtain allyl hydrotalcite.

[0018] In a further embodiment, in the allyl hydrotalcite, the mass ratio of hydrotalcite to allylamine is 1: (0.05-0.06); the mass ratio of the solid product to anhydrous copper sulfate and calcium tungstate is 10: (1.6-1.8): (0.4-0.6).

[0019] In a further embodiment, an antibacterial and highly tough ceramic material prepared by the preparation method of an antibacterial and highly tough ceramic material, the antibacterial and highly tough ceramic material comprises a green body and a glaze layer, and the thickness of the glaze layer is 2-5 mm.

[0020] Compared with the prior art, the beneficial effects of the present invention are as follows: in the embodiment, by optimizing and improving the components in the green body and glaze, the antibacterial performance is effectively enhanced, and the fracture toughness of the ceramic material is synergistically improved.

[0021] (1) In the solution, zinc oxide and carbon fiber are introduced into the green body. Among them, zinc oxide has antibacterial properties, and at the same time, together with zinc oxide and carbon fiber, they can be used as reinforcing fillers to effectively enhance the strength of the ceramic material. The carbon fiber used is short-fiber carbon fiber. Compared with long fibers, the short-fiber form has better toughness in dispersing stress, preventing crack propagation in the ceramic material, and reducing brittleness. In addition, due to the effective introduction amount of carbon fiber and the problem of the dispersibility of the reinforcing filler, tungsten powder and modified polyborosilazane are further introduced. The introduction of tungsten powder can increase the density of the green body, thereby enhancing the performance of the green body. The modified polyborosilazane is obtained by grafting allyltrimethoxysilane and zirconium dimethacrylate on the basis of liquid polyborosilazane. Since it contains siloxy groups, it can be used as a dispersant to enhance the uniform dispersibility and inhibit aggregation. At the same time, the modified polyborosilazane is grafted with zirconium dimethacrylate, and SiBCN-ZrO2 will be formed after calcination, which can further synergistically toughen with the carbon fiber effectively. In this way, the fracture toughness and antibacterial properties of the green body are effectively enhanced by various substances.

[0022] (2) In the solution, in order to effectively enhance the antibacterial performance of the ceramic material and ensure the fracture toughness of the ceramic material, in the glaze, not only zinc oxide, carbon fiber, and modified polyborosilazane are also introduced; modified hydrotalcite is additionally introduced to enhance the surface antibacterial property and fracture toughness. Among them, the modified hydrotalcite is based on allyl hydrotalcite and is surface-coated with a hybrid gel of liquid polyborosilazane and zirconium n-butoxide. After calcination, SiBCN-ZrO2 porous aerogel can be produced, effectively improving the toughness of the surface glaze layer. The allyl hydrotalcite is obtained by grafting allylamine on the surface of hydrotalcite and loading copper sulfate. Since the surface of the allyl hydrotalcite contains allyl groups, it can be used as a crosslinking agent to crosslink the liquid polyborosilazane to form an aerogel precursor. The loaded copper sulfate can form Ca2CuO3 after calcination, which has excellent antibacterial properties. In addition, since some sites on the surface of the hydrotalcite are occupied by allylamine, the loading of copper ions is reduced, and the antibacterial property still needs to be further increased. Therefore, during the loading of copper sulfate, calcium tungstate is also introduced, and copper methacrylate hydrate is further introduced during the preparation of the modified hydrotalcite. One is to increase the formation amount of Ca2CuO3, and the other is that the high-temperature doping of tungsten can enhance the antibacterial property of the metal compound. In this way, through component optimization, the antibacterial performance of the ceramic material is effectively enhanced on the basis of ensuring the fracture toughness. Detailed implementation manners

[0023] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0024] It should be noted that in the following examples, the parts are by mass; all the raw materials involved in the present invention are commercially available, and there are no special restrictions on the purchasing manufacturers or models, etc. Exemplarily, the carbon fiber is short-cut carbon fiber with a purity of 99%, provided by Raman reagent; the tungsten powder model is W-0050, provided by Yamei Nano Technology; the zinc oxide model is HN-J50W, provided by Hengna New Materials; the hydrotalcite model is DNT-09, and the brand is Korean Danshi; the molecular weight of the liquid polyborosilazane is 1000 g / mol, and the brand is Maidehao; the CAS number of allyltrimethoxysilane is 2551-83-9; the CAS number of allyltrimethoxysilane is 2551-83-9; the CAS number of zirconium oxide dimethacrylate is 97171-79-4; the CAS number of anhydrous copper sulfate is 7758-98-7; the CAS number of calcium tungstate is 7790-75-2; the CAS number of copper methacrylate hydrate is 19662-59-2; the CAS number of zirconium n-butoxide is 1071-76-7.

[0025] Example 1: A preparation method of an antibacterial and highly tough ceramic material, comprising the following steps:

[0026] Step 1: Preparation of modified polyborosilazane: Mix liquid polyborosilazane, allyltrimethoxysilane, zirconium oxide dimethacrylate, and diisopropylbenzene peroxide evenly, and react at 130 °C for 20 hours to obtain modified polyborosilazane; among them, allyltrimethoxysilane accounts for 4.5 wt% of the liquid polyborosilazane, zirconium oxide dimethacrylate accounts for 1.2 wt% of the liquid polyborosilazane; the addition amount of diisopropylbenzene peroxide is 0.8 wt%;

[0027] Preparation of modified hydrotalcite: S1: Ultrasonically disperse 10 parts of hydrotalcite in 90 parts of deionized water, add a mixed solution of 2 parts of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and N-hydroxysuccinimide (in the mixed solution, the content of each component is 0.3 parts of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, 0.2 parts of N-hydroxysuccinimide, and 100 parts of deionized water), and stir evenly; add 0.52 parts of allylamine, react at 50 °C for 3 hours, centrifuge, wash with water, and dry to obtain a solid product; S2: Disperse 10 parts of the solid product again in 50 parts of deionized water, add a mixed aqueous solution of anhydrous copper sulfate and calcium tungstate (1.6 parts of anhydrous copper sulfate, 0.5 parts of calcium tungstate, and 40 parts of deionized water), adjust the pH = 5.1, stir and react at 75 °C for 12 hours, cool, and freeze-dry to obtain allyl hydrotalcite; S3: Add 7 parts of liquid polyborosilazane and 3 parts of zirconium butoxide to tetrahydrofuran in sequence and mix evenly; add 5 parts of allyl hydrotalcite, 0.7 parts of copper methacrylate hydrate, and 0.15 parts of diisopropylbenzene peroxide, stir evenly, then place it in a vacuum reactor, react at 120 °C for 4 hours to obtain a hybrid product, soak it in ethanol to displace the guest molecules for one week, and change the ethanol twice a day; then place it in an oven to dry to obtain the modified hydrotalcite;

[0028] Step 2: Add 3.5 parts of modified polyborosilazane, 4 parts of zinc oxide, 1 part of carbon fiber, and 1.5 parts of tungsten powder to 50wt% ethanol aqueous solution in sequence, adjust the pH = 3.4 with hydrochloric acid, stir at 65 °C for 5 hours, wash, and dry to obtain raw material A; Grind, mix, granulate, and tablet raw material A with 30 parts of kaolin, 12 parts of quartz, 18 parts of wollastonite, 18 parts of celestite, 6 parts of dolomite, and 6 parts of potassium feldspar, and sinter at 800 °C for 60 minutes at a rate of 3 °C / min to obtain a green body;

[0029] Step 3: Add 0.8 parts of modified polyborosilazane, 5 parts of zinc oxide, and 1 part of carbon fiber to 50wt% ethanol aqueous solution in sequence, adjust the pH = 3.3, stir at 65 °C for 5 hours, wash, and dry to obtain raw material B; Mix raw material B with 30 parts of quartz, 20 parts of dolomite, 18 parts of potassium feldspar, 6 parts of wollastonite, 12 parts of limestone, and 7.2 parts of modified hydrotalcite to obtain a base glaze; Mix the base glaze, deionized water, and grinding balls in a mass ratio of 1:0.5:3, and screen to obtain a glaze slurry;

[0030] Step 4: Uniformly coat the glaze slurry on the surface of the green body, sinter at 900 °C for 30 minutes at a rate of 3 °C / min, then sinter at 1250 °C for 60 minutes at a rate of 4 °C / min, and cool to room temperature at a rate of 5 °C / min to obtain an antibacterial and highly tough ceramic material with a 3-mm-thick glaze layer.

[0031] Example 2: A preparation method of an antibacterial and highly tough ceramic material, comprising the following steps:

[0032] Step 1: Preparation of modified polyborosilazane: Mix liquid polyborosilazane, allyltrimethoxysilane, zirconium oxide dimethacrylate, and dicumyl peroxide evenly, and react at 130 °C for 20 hours to obtain modified polyborosilazane; wherein, allyltrimethoxysilane accounts for 4.5 wt% of liquid polyborosilazane, zirconium oxide dimethacrylate accounts for 1.2 wt% of liquid polyborosilazane; the addition amount of dicumyl peroxide is 0.8 wt%;

[0033] Preparation of modified hydrotalcite: S1: Ultrasonically disperse 10 parts of hydrotalcite in 90 parts of deionized water, add a mixed solution of 2 parts of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and N-hydroxysuccinimide (each component content in the mixed solution is 0.3 part of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, 0.2 part of N-hydroxysuccinimide, 100 parts of deionized water), and stir evenly; add 0.52 part of allylamine, react at 50 °C for 3 hours, centrifuge, wash with water, and dry to obtain a solid product; S2: Disperse 10 parts of the solid product again in 50 parts of deionized water, add a mixed aqueous solution of anhydrous copper sulfate and calcium tungstate (1.6 parts of anhydrous copper sulfate, 0.5 part of calcium tungstate, 40 parts of deionized water), adjust the pH = 5.1, stir and react at 75 °C for 12 hours, cool, and freeze-dry to obtain allyl hydrotalcite; S3: Add 7 parts of liquid polyborosilazane and 3 parts of zirconium n-butoxide to tetrahydrofuran in sequence and mix evenly; add 5 parts of allyl hydrotalcite, 0.7 part of copper methacrylate hydrate, and 0.15 part of dicumyl peroxide, stir evenly, then place it in a vacuum reactor, react at 120 °C for 4 hours to obtain a hybrid product, soak it in ethanol to displace the guest molecules for one week, and change the ethanol twice a day; then place it in an oven to dry to obtain modified hydrotalcite;

[0034] Step 2: Add 4.8 parts of modified polyborosilazane, 3 parts of zinc oxide, 1.2 parts of carbon fiber, and 2 parts of tungsten powder to a 50 wt% ethanol aqueous solution in sequence, adjust the pH = 3.4 with hydrochloric acid, stir at 65 °C for 5 hours, wash, and dry to obtain raw material A; Grind, mix, granulate, and tablet raw material A with 26 parts of kaolin, 15 parts of quartz, 25 parts of wollastonite, 12 parts of celestite, 5 parts of dolomite, and 6 parts of potassium feldspar, and sinter at 800 °C for 60 min at a rate of 3 °C / min to obtain a green body;

[0035] Step 3: Add 0.8 parts of modified polyborosilazane, 4 parts of zinc oxide, and 1.2 parts of carbon fiber into 50wt% ethanol aqueous solution in sequence. Adjust the pH to 3.3, stir at 65°C for 5 hours, wash, and dry to obtain raw material B; mix raw material B with 28 parts of quartz, 25 parts of dolomite, 20 parts of potassium feldspar, 5 parts of wollastonite, 10 parts of limestone, and 6 parts of modified hydrotalcite to obtain the base glaze; mix the base glaze, deionized water, and grinding balls with a mass ratio of 1:0.5:3, and screen to obtain the glaze slurry;

[0036] Step 4: Uniformly coat the glaze slurry on the surface of the green body, heat it to 900°C at a rate of 3°C / min and calcine for 30 min, then heat it to 1250°C at a rate of 4°C / min and calcine for 60 min, and set the cooling rate to 5°C / min to cool to room temperature to obtain an antibacterial high-tough ceramic material with a 3-mm-thick glaze layer.

[0037] Example 3: A preparation method of an antibacterial high-tough ceramic material, comprising the following steps:

[0038] Step 1: Preparation of modified polyborosilazane: Mix liquid polyborosilazane, allyltrimethoxysilane, zirconium dimethacrylate, and dicumyl peroxide evenly, and stir and react at 130°C for 20 hours to obtain modified polyborosilazane; among them, allyltrimethoxysilane accounts for 4.5wt% of liquid polyborosilazane, zirconium dimethacrylate accounts for 1.2wt% of liquid polyborosilazane; the addition amount of dicumyl peroxide is 0.8wt%;

[0039] Preparation of modified hydrotalcite: S1: Ultrasonically disperse 10 parts of hydrotalcite in 90 parts of deionized water, add a mixed solution of 2 parts of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and N-hydroxysuccinimide (the content of each component in the mixed solution is 0.3 parts of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, 0.2 parts of N-hydroxysuccinimide, and 100 parts of deionized water), and stir evenly; add 0.52 parts of allylamine, react at 50°C for 3 hours, centrifuge, wash with water, and dry to obtain a solid product; S2: Disperse 10 parts of the solid product in 50 parts of deionized water again, add a mixed aqueous solution of anhydrous copper sulfate and calcium tungstate (1.6 parts of anhydrous copper sulfate, 0.5 parts of calcium tungstate, and 40 parts of deionized water), adjust the PH to 5.1, stir and react at 75°C for 12 hours, cool, and freeze-dry to obtain allyl hydrotalcite; S3: Add 7 parts of liquid polyborosilazane and 3 parts of zirconium n-butoxide into tetrahydrofuran in sequence and mix evenly; add 5 parts of allyl hydrotalcite, 0.7 parts of copper methacrylate hydrate, and 0.15 parts of dicumyl peroxide, stir evenly, then place it in a vacuum reaction kettle, react at 120°C for 4 hours to obtain a hybrid product, soak it in ethanol to displace the guest molecules for one week, and change the ethanol twice a day; then place it in an oven to dry to obtain modified hydrotalcite;

[0040] Step 2: Add 2.5 parts of modified polyborosilazane, 5 parts of zinc oxide, 0.5 part of carbon fiber, and 1 part of tungsten powder into 50wt% ethanol aqueous solution in sequence. Adjust the pH to 3.4 with hydrochloric acid, stir at 65°C for 5 hours, wash, and dry to obtain raw material A. Grind, mix, granulate, and tablet raw material A with 31 parts of kaolin, 10 parts of quartz, 15 parts of wollastonite, 20 parts of celestite, 7 parts of dolomite, and 8 parts of potassium feldspar. Sinter at 800°C for 60 minutes at a rate of 3°C / min to obtain a green body.

[0041] Step 3: Add 0.5 part of modified polyborosilazane, 6 parts of zinc oxide, and 0.5 part of carbon fiber into 50wt% ethanol aqueous solution in sequence. Adjust the pH to 3.3, stir at 65°C for 5 hours, wash, and dry to obtain raw material B. Mix raw material B with 36 parts of quartz, 15 parts of dolomite, 12 parts of potassium feldspar, 7 parts of wollastonite, 15 parts of limestone, and 8 parts of modified hydrotalcite to obtain a base glaze. Mix the base glaze, deionized water, and grinding balls in a mass ratio of 1:0.5:3, and sieve to obtain a glaze slurry.

[0042] Step 4: Uniformly coat the glaze slurry on the surface of the green body, sinter at 900°C for 30 minutes at a rate of 3°C / min, then sinter at 1250°C for 60 minutes at a rate of 4°C / min, and cool to room temperature at a rate of 5°C / min to obtain an antibacterial high-tough ceramic material with a 3-mm-thick glaze layer.

[0043] Comparative Example 1: In the green body, replace the tungsten powder with an equal mass of zinc oxide, and the rest is the same as in Example 1.

[0044] Comparative Example 2: Replace the modified polyborosilazane with an equal mass of allyltrimethoxysilane, and the rest is the same as in Example 1.

[0045] Comparative Example 3: Replace the modified hydrotalcite with an equal mass of copper-based hydrotalcite. The preparation process of copper-based hydrotalcite is as follows: Disperse 10 parts of hydrotalcite in 50 parts of deionized water, add it into an aqueous solution of anhydrous copper sulfate (2 parts of anhydrous copper sulfate, 40 parts of deionized water), adjust the pH to 5.1, stir and react at 75°C for 12 hours, cool, and freeze-dry to obtain copper-based hydrotalcite; the rest is the same as in Example 1.

[0046] Comparative Example 4: Calcium tungstate and copper methacrylate hydrate are not introduced into the modified hydrotalcite; the preparation process of the modified hydrotalcite is as follows: S1: Ultrasonically disperse 10 parts of hydrotalcite in 90 parts of deionized water, add a mixed solution of 2 parts of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and N-hydroxysuccinimide (the content of each component in the mixed solution is 0.3 parts of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, 0.2 parts of N-hydroxysuccinimide, and 100 parts of deionized water), and stir evenly; add 0.52 parts of allylamine, react at 50 °C for 3 hours, centrifuge, wash with water, and dry to obtain a solid product; S2: Disperse 10 parts of the solid product again in 50 parts of deionized water, add a mixed aqueous solution of anhydrous copper sulfate and calcium tungstate (1.6 parts of anhydrous copper sulfate, 40 parts of deionized water), adjust the pH = 5.1, stir and react at 75 °C for 12 hours, cool, and freeze-dry to obtain allyl hydrotalcite; S3: Add 7 parts of liquid polyborosilazane and 3 parts of zirconium n-butoxide to tetrahydrofuran in sequence and mix evenly; add 5 parts of allyl hydrotalcite and 0.15 parts of diisopropylbenzene peroxide, stir evenly, then place in a vacuum reactor, react at 120 °C for 4 hours to obtain a hybrid product, soak it in ethanol to displace the guest molecules for one week, and change the ethanol twice a day; then place it in an oven to dry to obtain the modified hydrotalcite; the rest is the same as in Example 1.

[0047] Experiment: Perform performance tests on the antibacterial and highly tough ceramic materials prepared in Examples 1 to 3 and Comparative Examples 1 to 4. (1) Use the single-edge notched beam method to test the fracture toughness of the ceramic materials at a notch depth of 2.5 mm and a loading rate of 0.05 mm / min. (2) Refer to JC / T 897-2014 Antibacterial Properties of Antibacterial Ceramic Products. Clean the ceramic materials with 75% ethanol, soak them in sterile water for 18 to 24 hours, and dry them with a sterile dry gauze; place them in a sterile petri dish, drop the bacterial solution of Staphylococcus aureus on the surface of the ceramic materials, cover them with a polyethylene film of the same size as the ceramic materials, and incubate them at a constant temperature of 37 °C for 24 hours to detect the antibacterial rate. The results are shown below.

[0048]

[0049] Conclusion: It can be seen from the data in the above table that the ceramic material prepared in this application effectively enhances the toughness of the ceramic material while ensuring high antibacterial performance. From the data of Comparative Examples 1-4, it can be seen that in Comparative Example 1, the fracture toughness decreased due to the reduction of the density by not introducing tungsten powder; in Comparative Example 2, the fracture toughness decreased due to the use of allyltrimethoxysilane as a dispersant; in Comparative Example 3, since the modified hydrotalcite was replaced with an equal mass of copper-based hydrotalcite, copper was lost during the ceramic calcination process, resulting in a decrease in antibacterial performance. At the same time, since the surface of the hydrotalcite was not wrapped with polyborosilazane, the toughening performance decreased. In Comparative Example 4, since calcium tungstate and copper methacrylate hydrate were not introduced into the modified hydrotalcite, the antibacterial performance decreased slightly, and the mechanical properties decreased slightly.

[0050] Finally, it should be noted that the above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements on some of the technical features. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A preparation method of an antibacterial and highly tough ceramic material, characterized in that: It includes the following steps: Step 1: Add modified polyborosilazane, zinc oxide, carbon fiber, and tungsten powder into an ethanol solution in sequence, adjust the pH to 3.3 ± 0.2, stir at 60 - 65 °C for 3 - 5 hours, wash, and dry to obtain raw material A; grind and mix raw material A with kaolin, quartz, wollastonite, celestite, dolomite, and potassium feldspar, granulate, tablet, and perform biscuit firing at 800 - 900 °C for 60 - 80 min to obtain a green body; Step 2: Add modified polyborosilazane, zinc oxide, and carbon fiber into an ethanol solution in sequence, adjust the pH to 3.3 ± 0.2, stir at 60 - 65 °C for 3 - 5 hours, wash, and dry to obtain raw material B; mix raw material B with quartz, dolomite, potassium feldspar, wollastonite, limestone, and modified hydrotalcite to obtain a base glaze; mix the base glaze with deionized water and grinding balls, and grind to obtain a glaze slurry; Step 3: Uniformly coat the surface of the green body with the glaze slurry, calcine at 750 - 900 °C for 20 - 30 min, then raise the temperature to 1200 - 1300 °C and calcine for 60 - 80 min; cool to room temperature to obtain an antibacterial and highly tough ceramic material; The preparation of the modified polyborosilazane includes the following steps: Mix liquid polyborosilazane, allyltrimethoxysilane, zirconium dimethacrylate, and dicumyl peroxide evenly, and stir and react at 130 - 135 °C for 12 - 20 hours to obtain the modified polyborosilazane; among them, allyltrimethoxysilane accounts for 4 - 5 wt% of the liquid polyborosilazane, zirconium dimethacrylate accounts for 1 - 1.5 wt% of the liquid polyborosilazane; the addition amount of dicumyl peroxide is 0.5 - 0.8 wt%; The preparation of the modified hydrotalcite includes the following steps: Add liquid polyborosilazane and zirconium n-butoxide into tetrahydrofuran in sequence and mix evenly; add allyl hydrotalcite, copper methacrylate hydrate, and dicumyl peroxide, stir evenly, then place it in a vacuum reactor and react at 120 - 125 °C for 4 - 5 hours to obtain a hybrid product, soak it in ethanol to displace guest molecules for one week, and change the ethanol twice a day; then place it in an oven to dry to obtain the modified hydrotalcite.

2. The preparation method of an antibacterial and highly tough ceramic material according to claim 1, wherein: The green body includes the following raw materials in parts by mass: 26 - 31 parts of kaolin, 10 - 15 parts of quartz, 15 - 25 parts of wollastonite, 12 - 20 parts of celestite, 5 - 7 parts of dolomite, 6 - 8 parts of potassium feldspar, 3 - 5 parts of zinc oxide, 0.5 - 1.2 parts of carbon fiber, 1 - 2 parts of tungsten powder, and 2.5 - 4.8 parts of modified polyborosilazane.

3. The preparation method of an antibacterial and highly tough ceramic material according to claim 1, characterized in that: The base glaze includes the following raw materials in parts by mass: 28 - 36 parts of quartz, 15 - 25 parts of dolomite, 12 - 20 parts of potassium feldspar, 5 - 7 parts of wollastonite, 10 - 15 parts of limestone, 4 - 6 parts of zinc oxide, 0.5 - 1.2 parts of carbon fiber, 0.5 - 0.8 parts of modified polyborosilazane, and 6 - 8 parts of modified hydrotalcite; The mass ratio of the base glaze to deionized water and grinding balls is 1:(0.5 - 0.6):

3.

4. The preparation method of an antibacterial and highly tough ceramic material according to claim 1, wherein: The carbon fiber is short cut filaments with a length of 3 - 6 mm and a single filament diameter of 7 - 10 μm.

5. The preparation method of an antibacterial and highly tough ceramic material according to claim 1, wherein: The modified hydrotalcite comprises the following raw materials in parts by mass: 6-8 parts of liquid polyborosilazane, 2.5-3.2 parts of zirconium butoxide, 5-6 parts of allyl hydrotalcite, 0.6-0.8 parts of copper methacrylate hydrate, and 0.1-0.2 parts of diisopropylbenzene peroxide.

6. The preparation method of an antibacterial high-toughness ceramic material according to claim 1, characterized in that: The preparation of the allyl hydrotalcite comprises the following steps: (1) Ultrasonically disperse the hydrotalcite in deionized water, add a mixed solution of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and N-hydroxysuccinimide, and stir evenly; add allylamine, react at 40-50°C for 3-4 hours, centrifuge, wash with water, and dry to obtain a solid product; (2) Disperse the solid product again in deionized water, add a mixed aqueous solution of anhydrous copper sulfate and calcium tungstate, adjust the pH to 5±0.2, stir and react at 70-75°C for 10-12 hours, cool, and freeze-dry to obtain the allyl hydrotalcite.

7. The preparation method of an antibacterial and highly tough ceramic material according to claim 6, characterized in that: In the allyl hydrotalcite, the mass ratio of the hydrotalcite to the allylamine is 1:(0.05-0.06); the mass ratio of the solid product to the anhydrous copper sulfate and calcium tungstate is 10:(1.6-1.8):(0.4-0.6).

8. An antibacterial and highly tough ceramic material prepared by the preparation method of an antibacterial and highly tough ceramic material according to any one of claims 1 to 7, characterized in that: The antibacterial high-toughness ceramic material comprises a green body and a glaze layer, and the thickness of the glaze layer is 2-5 mm.

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