CN111377613A - Antibacterial ceramic glaze and preparation method thereof - Google Patents
Antibacterial ceramic glaze and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
- C03C8/20—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing titanium compounds; containing zirconium compounds
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5022—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with vitreous materials
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/86—Glazes; Cold glazes
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2204/00—Glasses, glazes or enamels with special properties
- C03C2204/02—Antibacterial glass, glaze or enamel
Abstract
The invention relates to the field of ceramic preparation, in particular to a preparation method of an antibacterial ceramic glaze; according to the preparation method of the antibacterial ceramic glaze, the antibacterial ceramic glaze produced by the invention adopts a sol antibacterial agent compounded by silver and titanium dioxide, has double antibacterial effects of a photocatalytic antibacterial agent and a silver antibacterial agent, and silver can promote the separation of electron-hole pairs in titanium dioxide and enhance the photocatalytic performance; the titanium dioxide can solve the problems of slow release and blackening of the silver-based antibacterial agent, and provides more durable and stable antibacterial performance for the material. The antibacterial ceramic glaze material has the advantages of low cost, strong antibacterial effect and durable antibacterial performance, and is hopeful to be applied to the fields of various daily ceramics, ceramic cups, ceramic tableware products and the like with antibacterial, mildew-resistant and corrosion-resistant properties.
Description
Technical Field
The invention relates to the field of ceramic preparation, in particular to an antibacterial ceramic glaze and a preparation method thereof.
Background
In recent years, people adopt various compounding methods to prepare composite antibacterial materials, the defects of limitation of antibacterial spectrum of inorganic antibacterial agents, easy elution of organic antibacterial agents and heat resistance are overcome, and the antibacterial sanitary ceramic products are used in hospitals, restaurants and high-grade houses in industrially developed countries.
CN204687461U discloses an antibacterial ceramic comprising a ceramic substrate layer; at least one antibacterial layer attached to the surface of the ceramic substrate layer, wherein the antibacterial layer is a titanium dioxide layer; at least one auxiliary antibacterial layer attached between the ceramic substrate layer and the antibacterial layer, wherein the auxiliary antibacterial layer is a silver ion antibacterial layer; and the adhesion-promoting layer is attached to the outer surface of the antibacterial ceramic.
CN105036804A discloses a health-preserving antibacterial ceramic glaze which is composed of the following materials in parts by weight: 10-30 parts of shells, 5-15 parts of bone meal, 5-10 parts of aluminum oxide, 0.1-0.5 part of ferric oxide, 5-15 parts of spodumene, 3-10 parts of tin oxide, 10-30 parts of germanized ore, 5-10 parts of crystal, 1-5 parts of talc and 2-10 parts of diatom ooze; and additionally adding a basic formula of common transparent glaze: 10-15 parts of limestone, 20-30 parts of feldspar, 1-5 parts of zinc, 20-30 parts of quartz and 1-4 parts of magnesium carbonate; the antibacterial ceramic prepared from the antibacterial glaze disclosed by the invention is compatible with a human body, and various elements are required by the human body; the cost is lower than that of silver-based antibacterial control, the application range is wide, and the antibacterial ceramic can be made into antibacterial ceramics with various colors; the sterilization rate is high, the antibacterial rate to escherichia coli reaches 98.7% -99.3%, and the antibacterial rate to staphylococcus aureus reaches 99.95%; the antibacterial ceramic glaze is suitable for various daily-use ceramics, various sanitary wares, technical ceramics and the like, and can also be used for producing antibacterial ceramics with various colors.
CN1240643C relates to a glaze liquid for endowing the surface of a ceramic or enamel article with an antibacterial function and application thereof. The antibacterial glaze liquid comprises 1-7 parts of low-temperature antibacterial agent or high-temperature antibacterial agent, 0.2-4 parts of adhesive, 0.1-0.5 part of dispersing agent, 0.1-1 part of defoaming agent, 7-10 parts of solvent and 90-100 parts of water. The antibacterial agent can be used on blanks, semi-finished products and finished products of various ceramics or enamel articles, and the articles have good and lasting antibacterial function by adopting the modes of spraying, brushing, soaking and the like.
The effective component of the antibacterial ceramic glaze material in the above patents and the prior art is photosensitive titanium dioxide, but the limitation of the antibacterial ceramic glaze material by illumination is large, particularly, titanium dioxide distributed on the surface in the antibacterial ceramic material doped with titanium glaze material is relatively less, and most of titanium dioxide is converted into rutile type with poor photocatalytic activity after being fired at high temperature, so that the antibacterial effect is greatly influenced.
Disclosure of Invention
The invention provides an antibacterial ceramic glaze and a preparation method thereof.
An antibacterial ceramic glaze and a preparation method thereof, wherein the scheme is as follows:
adding 13-17 parts of silicon dioxide, 1-4 parts of copper oxide, 0.5-8 parts of chromium oxide, 0.5-2 parts of boron trioxide, 5-10 parts of sodium silicate, 0.1-0.5 part of cerium oxide, 0.2-0.8 part of manganese oxide, 5-9 parts of lime glaze, 4-12 parts of wollastonite and 1-7 parts of dolomite into a crusher according to the mass parts, and crushing to obtain a mixture; smelting the mixture at the temperature of 700-; mixing 20-35 parts of the obtained glaze with 40-65 parts of graphene copper doped nano titanium dioxide sol, performing wet ball milling for 10-30h, sieving to remove impurities to obtain glaze slurry, coating the glaze slurry on the surface of a ceramic biscuit, drying at 40-80 ℃ for 30-60min, taking out, standing at room temperature for 20-30h, repeatedly coating for 3-5 times, firing at 1000-1200 ℃ for 15-45min under the protection of protective gas, and cooling to obtain the antibacterial ceramic glaze.
The graphene copper doped nano titanium dioxide sol is a graphene copper doped nano titanium dioxide sol, and the preparation method comprises the following steps:
adding 11.5-18.6 parts of metatitanic acid into 300 parts of water by mass, stirring and mixing uniformly, heating to boil, then slowly adding 10.2-15.4 parts of concentrated sulfuric acid into the reaction kettle, controlling the adding for 20-60min, then continuing to react for 60-90min, standing and aging for 24-36h after the reaction is finished, adjusting the pH value to 5-7 by using ammonia water after filtering, generating white precipitate, aging for 10-20h, filtering, dispersing the obtained precipitate in 180 parts of 1% -5% nitric acid for reacting for 60-120min after washing, then 0.18-1.4 parts of graphene doped copper silane and 0.3-2.4 parts of hydrazine hydrate are added, and the irradiation intensity is controlled at 100-240W/m by using ultraviolet rays with the wavelength range of 280-385 nm.2Irradiating for 24-48h to obtain the graphene copper doped nano titanium dioxide sol.
The graphene doped copper silane is prepared by pretreating graphene oxide with R-vinyl triethoxysilane, grafting allyl silane on the surface of the graphene oxide, reducing the graphene oxide, carrying out polymerization reaction under the action of ammonium persulfate by taking copper methacrylate as a monomer, introducing a hyperbranched structure on the surface of graphene, carrying out suction filtration, and washing. The principle is as follows:
the preparation method of the graphene doped copper silane comprises the following steps:
step 1: mixing 2-7 parts of graphite oxide and 20-36 parts of R-vinyltriethoxysilane by mass, adding 100-1000 parts of white oil, adjusting the pH value to 3-6, dispersing for 1-4 h by ultrasonic waves, and then reacting for 2-6h at 40-80 ℃; then adding 20-31 parts of hydrazine hydrate and 10-18 parts of ammonia water, reducing at 50-80 ℃, reacting for 2-6h, performing suction filtration, washing, and vacuum drying to obtain vinyl silane grafted graphene;
step 2: mixing 10-20 parts of vinyl silane grafted graphene and 40-50 parts of copper methacrylate according to the mass parts, adding 0.05-0.4 part of ammonium persulfate, 500-1000 parts of solvent oil and 0.5-2 parts of gelatin, reacting for 3-10 hours at 80-90 ℃ under the protection of nitrogen, filtering, washing and drying to obtain the graphene doped copper silane.
The protective gas is high-purity nitrogen with 0.1-0.5% of hydrogen.
The average grain diameter of the mixture is 50-200 microns.
The glaze slurry coating mode is brushing or spraying.
The temperature of the quenching water is 10-30 ℃.
The content of the lime glaze calcium oxide is 14-19%.
According to the antibacterial ceramic glaze and the preparation method thereof, the sol antibacterial agent compounded by graphene doped copper silane and titanium dioxide is adopted, the dual antibacterial effects of a photocatalytic antibacterial agent and graphene doped copper silane are achieved, and the photocatalytic performance of the graphene doped copper silane can be enhanced; the titanium dioxide can solve the problems of slow release and blackening of the silver-based antibacterial agent, and the synergistic effect of the combination of the vinyl silane grafted graphene, the copper methacrylate and the titanium dioxide provides the material with more lasting and stable antibacterial performance. The antibacterial ceramic glaze material has the advantages of low cost, strong antibacterial effect and long antibacterial property, and is hopeful to be applied to the fields of various ceramic products such as antibiosis, mildew resistance, corrosion resistance and the like.
Drawings
Fig. 1 is an SEM scanning electron microscope photograph of the antibacterial ceramic sheet prepared in example 1, magnified 4000 times.
Detailed Description
The invention is further illustrated by the following specific examples:
and (3) detecting the antibacterial performance of the prepared ceramic according to 'antibacterial performance JC/T897-2014 of the antibacterial ceramic product instead of JC/T897-2002', wherein the test strains are staphylococcus aureus and escherichia coli.
And respectively putting the glazed ceramic wafer into 3% hydrochloric acid, 5% caustic soda, 5% detergent and clear water in sequence, soaking for one week, and detecting the antibacterial performance of the prepared ceramic according to the antibacterial performance JC/T897-2014 of antibacterial ceramic products instead of JC/T897-2002, wherein the test strains are staphylococcus aureus and escherichia coli. And (4) detecting the sterilization effect of the ceramic glaze to evaluate the corrosion resistance of the ceramic glaze.
Example 1
An antibacterial ceramic glaze and a preparation method thereof, wherein the scheme is as follows:
adding 13 g of silicon dioxide, 1 g of copper oxide, 0.5 g of chromium oxide, 0.5 g of boron trioxide, 5 g of sodium silicate, 0.1 g of cerium oxide, 0.2 g of manganese oxide, 5 g of lime glaze, 4 g of wollastonite and 1 g of dolomite into a pulverizer for pulverization treatment to obtain a mixture; smelting the mixture at 700 ℃ for 60min under the protection of protective gas, then heating to 1000 ℃, continuing to melt for 60min, and quenching and water quenching after smelting is finished to obtain a block glaze; mixing 20 g of the obtained glaze with 40 g of graphene copper doped nano titanium dioxide sol, performing wet ball milling for 10h, sieving to remove impurities to obtain glaze slurry, coating the glaze slurry on the surface of a ceramic biscuit, drying at 40 ℃ for 60min, taking out, standing at room temperature for 20h, repeatedly coating for 3 times, firing at 1000 ℃ for 15min under the protection of protective gas, and cooling to obtain the antibacterial ceramic glaze.
Adding 11.5 g of metatitanic acid into 200 g of water, stirring and mixing uniformly, heating to boiling, slowly adding 10.2 g of concentrated sulfuric acid into a reaction kettle, controlling the addition to be finished for 20min, continuing to react for 60min, standing and aging for 24h after the reaction is finished, adjusting the pH value to 5 by using ammonia water after filtering, generating white precipitate, aging for 10h, filtering, dispersing the obtained precipitate into 180 g of 1% nitric acid after washing, reacting for 60min, then adding 0.18 g of graphene-doped copper silane and 0.3 g of hydrazine hydrate, and controlling the irradiation intensity to be 100W/m by using ultraviolet rays with the wavelength of 280nm2And irradiating for 24 hours to obtain the graphene copper doped nano titanium dioxide sol.
The shielding gas is high-purity nitrogen with 0.1 percent of hydrogen.
The average grain diameter of the mixture is 50 microns.
The glaze slip coating mode is brushing.
The temperature of the quenching water is 10 ℃.
The content of the lime glaze calcium oxide is 14 percent.
The preparation method of the graphene doped copper silane comprises the following steps:
step 1: mixing 2 g of graphite oxide and 20 g of R-vinyltriethoxysilane, adding 100 g of white oil, adjusting the pH value to 3, dispersing for 1h by using ultrasonic waves, and then reacting for 2h at 40 ℃; then adding 20 g of hydrazine hydrate and 10 g of ammonia water, reducing at 50 ℃, after reacting for 2h, carrying out suction filtration, washing, and vacuum drying to obtain vinyl silane grafted graphene;
step 2: 10 g of vinyl silane grafted graphene and 40 g of copper methacrylate are mixed, 0.05 g of ammonium persulfate, 500 g of solvent oil and 0.5 g of gelatin are added, the mixture reacts for 3 hours at 80 ℃ under the protection of nitrogen, and then the mixture is filtered, washed and dried to obtain the graphene doped copper silane.
The ceramic glaze prepared by the experiment has the advantages that the sterilization rate of escherichia coli is 100%, the sterilization rate of the material subjected to a corrosivity test is 89.1%, the sterilization rate of staphylococcus aureus is 100%, and the sterilization rate of the material subjected to the corrosivity test is 85.9%.
Example 2
An antibacterial ceramic glaze and a preparation method thereof, wherein the scheme is as follows:
adding 15 g of silicon dioxide, 2 g of copper oxide, 4 g of chromium oxide, 1 g of boron trioxide, 8 g of sodium silicate, 0.3 g of cerium oxide, 0.5 g of manganese oxide, 7 g of lime glaze, 8 g of wollastonite and 3 g of dolomite into a pulverizer to perform pulverization treatment, thereby obtaining a mixture; smelting the mixture at 750 ℃ for 90min under the protection of protective gas, then heating to 1100 ℃, continuing to melt for 120min, and quenching and water quenching after smelting is finished to obtain a block glaze; mixing 28 g of the obtained glaze with 55 g of graphene copper doped nano titanium dioxide sol, performing wet ball milling for 20h, sieving to remove impurities to obtain glaze slurry, coating the glaze slurry on the surface of a ceramic biscuit, drying at 60 ℃ for 40min, taking out, standing at room temperature for 25h, repeatedly coating for 4 times, firing at 1100 ℃ for 35min under the protection of protective gas, and cooling to obtain the antibacterial ceramic glaze.
Adding 15 g of metatitanic acid into 220 g of water, stirring and mixing uniformly, heating to boiling, then slowly adding 14.5 g of concentrated sulfuric acid into a reaction kettle, controlling the addition to be finished for 40min, then continuing to react for 70min, standing and aging for 28h after the reaction is finished, adjusting the pH value to 5.5 by using ammonia water after filtering, generating white precipitate, aging for 16h, filtering, dispersing the obtained precipitate into 190 g of 3% nitric acid after washing, reacting for 110min, then adding 0.6 g of graphene-doped copper silane and 0.9 g of hydrazine hydrate, and controlling the irradiation intensity to be 150W/m by using ultraviolet rays with the wavelength of 322nm2And irradiating for 30h to obtain the graphene copper doped nano titanium dioxide sol.
The preparation method of the graphene doped copper silane comprises the following steps:
step 1: mixing 5 g of graphite oxide and 26 g of R-vinyltriethoxysilane, adding 400 g of white oil, adjusting the pH value to 4, dispersing for 2h by using ultrasonic waves, and then reacting for 5h at 60 ℃; then adding 24 g of hydrazine hydrate and 15 g of ammonia water, reducing at 60 ℃, reacting for 4 hours, performing suction filtration, washing, and drying in vacuum to obtain vinyl silane grafted graphene;
step 2: mixing 15 g of vinyl silane grafted graphene and 42 g of copper methacrylate, adding 0.1 g of ammonium persulfate, 600 g of solvent oil and 0.9 g of gelatin, reacting at 85 ℃ for 5 hours under the protection of nitrogen, filtering, washing and drying to obtain the graphene doped copper silane.
The shielding gas is high-purity nitrogen with 0.3 percent of hydrogen.
The average grain diameter of the mixture is 100 microns.
The glaze slip coating mode is spraying.
The temperature of the quenching water is 20 ℃.
The content of the lime glaze calcium oxide is 15%.
The ceramic glaze prepared by the experiment has the advantages that the sterilization rate of escherichia coli is 100%, the sterilization rate of the material subjected to a corrosivity test is 85.2%, the sterilization rate of staphylococcus aureus is 100%, and the sterilization rate of the material subjected to the corrosivity test is 83.1%.
Example 3
An antibacterial ceramic glaze and a preparation method thereof, wherein the scheme is as follows:
adding 17 g of silicon dioxide, 4 g of copper oxide, 8 g of chromium oxide, 2 g of boron trioxide, 10 g of sodium silicate, 0.5 g of cerium oxide, 0.8 g of manganese oxide, 9 g of lime glaze, 12 g of wollastonite and 7 g of dolomite into a pulverizer to perform pulverization treatment, thereby obtaining a mixture; smelting the mixture at 800 ℃ for 120min under the protection of protective gas, then heating to 1200 ℃, continuing to melt for 180min, and quenching and water quenching after smelting is finished to obtain a block glaze; mixing 35 g of the obtained glaze with 65 g of graphene copper doped nano titanium dioxide sol, performing wet ball milling for 30h, sieving to remove impurities to obtain glaze slurry, coating the glaze slurry on the surface of a ceramic biscuit, drying at 80 ℃ for 60min, taking out, standing at room temperature for 30h, repeatedly coating for 5 times, firing at 1200 ℃ for 45min under the protection of protective gas, and cooling to obtain the antibacterial ceramic glaze.
The graphene copper doped nano titanium dioxide sol is a silver-loaded nano titanium dioxide sol, and the preparation method comprises the following steps:
adding 18.6 g of metatitanic acid into 300 g of water, stirring and mixing uniformly, heating to boiling, then slowly adding 15.4 g of concentrated sulfuric acid into a reaction kettle, controlling the addition for 60min, continuing to react for 90min, standing and aging for 36h after the reaction is finished, adjusting the pH value to 7 by using ammonia water after filtering, generating white precipitate, aging for 20h, filtering, dispersing the obtained precipitate into 260 g of 5% nitric acid after washing, reacting for 120min, then adding 1.4 g of graphene-doped copper silane and 2.4 g of hydrazine hydrate, and controlling the irradiation intensity to be 240W/m by using ultraviolet rays with the wavelength of 385nm2And irradiating for 48 hours to obtain the graphene copper doped nano titanium dioxide sol.
The shielding gas is high-purity nitrogen with 0.5 percent of hydrogen.
The average grain diameter of the mixture is 200 microns.
The glaze slip coating mode is spraying.
The temperature of the quenching water is 30 ℃.
The content of the lime glaze calcium oxide is 19 percent.
The preparation method of the graphene doped copper silane comprises the following steps:
step 1: mixing 7 g of graphite oxide and 36 g of R-vinyltriethoxysilane, adding 1000 g of white oil, adjusting the pH value to 6, dispersing for 4h by using ultrasonic waves, and then reacting for 6h at 80 ℃; then adding 31 g of hydrazine hydrate and 18 g of ammonia water, carrying out reduction at 80 ℃, carrying out suction filtration, washing and vacuum drying after 6h of reaction to obtain vinyl silane grafted graphene;
step 2: mixing 20 g of vinyl silane grafted graphene and 50 g of copper methacrylate, adding 0.4 g of ammonium persulfate, 1000 g of solvent oil and 2 g of gelatin, reacting at 90 ℃ for 10 hours under the protection of nitrogen, filtering, washing and drying to obtain the graphene doped copper silane.
The ceramic glaze prepared by the experiment has the advantages that the sterilization rate of escherichia coli is 100%, the sterilization rate of the material subjected to a corrosivity test is 93.6%, the sterilization rate of staphylococcus aureus is 100%, and the sterilization rate of the material subjected to the corrosivity test is 90.8%.
Comparative example 1
An antibacterial ceramic glaze and a preparation method thereof, wherein the scheme is as follows:
adding 13 g of silicon dioxide, 1 g of copper oxide, 0.5 g of chromium oxide, 0.5 g of boron trioxide, 5 g of sodium silicate, 0.1 g of cerium oxide, 0.2 g of manganese oxide, 5 g of lime glaze, 4 g of wollastonite and 1 g of dolomite into a pulverizer for pulverization treatment to obtain a mixture; smelting the mixture at 700 ℃ for 60min under the protection of protective gas, then heating to 1000 ℃, continuing to melt for 60min, and quenching and water quenching after smelting is finished to obtain a block glaze; mixing 20 g of the obtained glaze with 40 g of graphene copper doped nano titanium dioxide sol, performing wet ball milling for 10h, sieving to remove impurities to obtain glaze slurry, coating the glaze slurry on the surface of a ceramic biscuit, drying at 40 ℃ for 60min, taking out, standing at room temperature for 20h, repeatedly coating for 3 times, firing at 1000 ℃ for 15min under the protection of protective gas, and cooling to obtain the antibacterial ceramic glaze.
Adding 11.5 g of metatitanic acid into 200 g of water, stirring and mixing uniformly, heating to boiling, slowly adding 10.2 g of concentrated sulfuric acid into a reaction kettle, controlling the addition to be finished for 20min, continuing to react for 60min, standing and aging for 24h after the reaction is finished, adjusting the pH value to 5 by using ammonia water after filtering, generating white precipitate, aging for 10h, filtering, dispersing the obtained precipitate into 180 g of 1% nitric acid after washing, reacting for 60min, then adding 0.18 g of graphene-doped copper silane and 0.3 g of hydrazine hydrate, and controlling the irradiation intensity to be 100W/m by using ultraviolet rays with the wavelength of 280nm2And irradiating for 24 hours to obtain the graphene copper doped nano titanium dioxide sol.
The shielding gas is high-purity nitrogen with 0.1 percent of hydrogen.
The average grain diameter of the mixture is 50 microns.
The glaze slip coating mode is brushing.
The temperature of the quenching water is 10 ℃.
The content of the lime glaze calcium oxide is 14 percent.
The preparation method of the graphene doped copper silane comprises the following steps:
step 1: mixing 2 g of graphite oxide and 20 g of R-vinyltriethoxysilane, adding 100 g of white oil, adjusting the pH value to 3, dispersing for 1h by using ultrasonic waves, and then reacting for 2h at 40 ℃; then adding 20 g of hydrazine hydrate and 10 g of ammonia water, reducing at 50 ℃, after reacting for 2h, carrying out suction filtration, washing, and vacuum drying to obtain vinyl silane grafted graphene;
step 2: mixing 10 g of vinyl silane grafted graphene, adding 0.05 g of ammonium persulfate, 500 g of solvent oil and 0.5 g of gelatin, reacting for 3 hours at 80 ℃ under the protection of nitrogen, filtering, washing and drying to obtain the graphene doped copper silane.
The ceramic glaze prepared by the experiment has the advantages that the sterilization rate of escherichia coli is 93.3%, the sterilization rate of the material after the corrosivity test is 78.5%, and the sterilization rate of staphylococcus aureus is 90%. 5 percent, and the sterilization rate of the material after the corrosion test is 73.3 percent.
Comparative example 2
An antibacterial ceramic glaze and a preparation method thereof, wherein the scheme is as follows:
adding 13 g of silicon dioxide, 1 g of copper oxide, 0.5 g of chromium oxide, 0.5 g of boron trioxide, 5 g of sodium silicate, 0.1 g of cerium oxide, 0.2 g of manganese oxide, 5 g of lime glaze, 4 g of wollastonite and 1 g of dolomite into a pulverizer for pulverization treatment to obtain a mixture; smelting the mixture at 700 ℃ for 60min under the protection of protective gas, then heating to 1000 ℃, continuing to melt for 60min, and quenching and water quenching after smelting is finished to obtain a block glaze; mixing 20 g of the obtained glaze with 40 g of water, carrying out wet ball milling for 10h, sieving to remove impurities to obtain glaze slurry, coating the glaze slurry on the surface of a ceramic biscuit, drying at 40 ℃ for 60min, taking out, standing at room temperature for 20h, repeatedly coating for 3 times, firing at 1000 ℃ for 15min under the protection of protective gas, and cooling to obtain the antibacterial ceramic glaze.
The shielding gas is high-purity nitrogen with 0.1 percent of hydrogen.
The average grain diameter of the mixture is 50 microns.
The glaze slip coating mode is brushing.
The temperature of the quenching water is 10 ℃.
The content of the lime glaze calcium oxide is 14 percent.
The ceramic glaze prepared by the experiment has the advantages that the escherichia coli sterilization rate is 54.7%, the sterilization rate of the material subjected to the corrosion test is 36.2%, the sterilization rate of staphylococcus aureus is 51.9%, and the sterilization rate of the material subjected to the corrosion test is 28.9%.
Comparative example 3
Adding 13 g of silicon dioxide, 1 g of copper oxide, 0.5 g of chromium oxide, 0.5 g of boron trioxide, 5 g of sodium silicate, 0.1 g of cerium oxide, 0.2 g of manganese oxide, 5 g of lime glaze, 4 g of wollastonite and 1 g of dolomite into a pulverizer for pulverization treatment to obtain a mixture; smelting the mixture at 700 ℃ for 60min under the protection of protective gas, then heating to 1000 ℃, continuing to melt for 60min, and quenching and water quenching after smelting is finished to obtain a block glaze; mixing 20 g of the obtained glaze with 40 g of water, carrying out wet ball milling for 10h, sieving to remove impurities to obtain glaze slurry, coating the glaze slurry on the surface of a ceramic biscuit, drying at 40 ℃ for 60min, taking out, standing at room temperature for 20h, repeatedly coating for 3 times, firing at 1000 ℃ for 15min under the protection of protective gas, and cooling to obtain the antibacterial ceramic glaze.
Adding 11.5 g of metatitanic acid into 200 g of water, stirring and mixing uniformly, heating to boiling, slowly adding 10.2 g of concentrated sulfuric acid into a reaction kettle, controlling the addition to be finished for 20min, continuing to react for 60min, standing and aging for 24h after the reaction is finished, adjusting the pH value to 5 by using ammonia water after filtering, generating white precipitate, aging for 10h, filtering, dispersing the obtained precipitate into 180 g of 1% nitric acid after washing, reacting for 60min, then adding 0.18 g of graphene-doped copper silane and 0.3 g of hydrazine hydrate, and controlling the irradiation intensity to be 100W/m by using ultraviolet rays with the wavelength of 280nm2And irradiating for 24 hours to obtain the graphene copper doped nano titanium dioxide sol.
The shielding gas is high-purity nitrogen with 0.1 percent of hydrogen.
The average grain diameter of the mixture is 50 microns.
The glaze slip coating mode is brushing.
The temperature of the quenching water is 10 ℃.
The content of the lime glaze calcium oxide is 14 percent.
The preparation method of the graphene doped copper silane comprises the following steps:
step 2: mixing 10 g of graphene and 40 g of copper methacrylate, adding 0.05 g of ammonium persulfate, 500 g of solvent oil and 0.5 g of gelatin, reacting for 3 hours at 80 ℃ under the protection of nitrogen, filtering, washing and drying to obtain the graphene doped copper silane.
The ceramic glaze prepared by the experiment has the advantages that the sterilization rate of escherichia coli is 90.6%, the sterilization rate of the material subjected to a corrosivity test is 83.9%, the sterilization rate of staphylococcus aureus is 89.9%, and the sterilization rate of the material subjected to the corrosivity test is 80.6%.
Claims (10)
1. An antibacterial ceramic glaze and a preparation method thereof, wherein the scheme is as follows:
adding 13-17 parts of silicon dioxide, 1-4 parts of copper oxide, 0.5-8 parts of chromium oxide, 0.5-2 parts of boron trioxide, 5-10 parts of sodium silicate, 0.1-0.5 part of cerium oxide, 0.2-0.8 part of manganese oxide, 5-9 parts of lime glaze, 4-12 parts of wollastonite and 1-7 parts of dolomite into a crusher according to the mass parts, and crushing to obtain a mixture; smelting the mixture at the temperature of 700-; mixing 20-35 parts of the obtained glaze with 40-65 parts of graphene copper doped nano titanium dioxide sol, performing wet ball milling for 10-30h, sieving to remove impurities to obtain glaze slurry, coating the glaze slurry on the surface of a ceramic biscuit, drying at 40-80 ℃ for 30-60min, taking out, standing at room temperature for 20-30h, repeatedly coating for 3-5 times, firing at 1000-1200 ℃ for 15-45min under the protection of protective gas, and cooling to obtain the antibacterial ceramic glaze.
2. The antibacterial ceramic glaze material and the preparation method thereof according to claim 1, wherein the graphene copper doped nano titanium dioxide sol is a graphene copper doped nano titanium dioxide sol, and the preparation method thereof comprises:
adding 11.5-18.6 parts of metatitanic acid into 300 parts of 200-phase water according to the mass parts, stirring and mixing uniformly, heating to boiling, then slowly adding 10.2-15.4 parts of concentrated sulfuric acid into a reaction kettle, controlling the addition for 20-60min, then continuing to react for 60-90min, standing and aging for 24-36h after the reaction is finished, adjusting the pH value to 5-7 by using ammonia water after filtering, generating white precipitate, aging for 10-20h, filtering, dispersing the obtained precipitate into 1-5% nitric acid of 180-phase 260 parts after washing, reacting for 60-120min, then adding 0.18-1.4 parts of graphene doped copper silane and 0.3-2.4 parts of hydrazine hydrate, and controlling the irradiation intensity to be 240W/m by using ultraviolet rays with the wavelength range of 280-385 nm2Irradiating for 24-48h to obtain the graphene copper doped nano titanium dioxide sol.
3. The antibacterial ceramic glaze and the preparation method thereof according to claim 1, wherein the antibacterial ceramic glaze is characterized in that: and the graphene doped copper silane is obtained by pretreating graphene oxide by using R-vinyl triethoxysilane, grafting allyl silane on the surface, and reducing to obtain vinyl silane grafted graphene.
4. The antibacterial ceramic glaze and the preparation method thereof according to claim 3, wherein the antibacterial ceramic glaze is characterized in that: and carrying out polymerization reaction on the vinyl silane grafted graphene by taking copper methacrylate as a monomer under the action of ammonium persulfate, introducing a hyperbranched structure on the surface of the graphene, carrying out suction filtration, and washing to obtain the graphene doped copper silane.
5. The antibacterial ceramic glaze and the preparation method thereof according to claim 1, wherein the antibacterial ceramic glaze is characterized in that: the preparation method of the graphene doped copper silane comprises the following steps:
step 1: mixing 2-7 parts of graphite oxide and 20-36 parts of R-vinyltriethoxysilane by mass, adding 100-1000 parts of white oil, adjusting the pH value to 3-6, dispersing for 1-4 h by ultrasonic waves, and then reacting for 2-6h at 40-80 ℃; then adding 20-31 parts of hydrazine hydrate and 10-18 parts of ammonia water, reducing at 50-80 ℃, reacting for 2-6h, performing suction filtration, washing, and vacuum drying to obtain vinyl silane grafted graphene;
step 2: mixing 10-20 parts of vinyl silane grafted graphene and 40-50 parts of copper methacrylate according to the mass parts, adding 0.05-0.4 part of ammonium persulfate, 500-1000 parts of solvent oil and 0.5-2 parts of gelatin, reacting for 3-10 hours at 80-90 ℃ under the protection of nitrogen, filtering, washing and drying to obtain the graphene doped copper silane.
6. The antibacterial ceramic glaze and the preparation method thereof according to claim 1, wherein the antibacterial ceramic glaze is characterized in that: the protective gas is high-purity nitrogen with 0.1-0.5% of hydrogen.
7. The antibacterial ceramic glaze and the preparation method thereof according to claim 1, wherein the antibacterial ceramic glaze is characterized in that: the average grain diameter of the mixture is 50-200 microns.
8. The antibacterial ceramic glaze and the preparation method thereof according to claim 1, wherein the antibacterial ceramic glaze is characterized in that: the glaze slurry coating mode is brushing or spraying.
9. The antibacterial ceramic glaze and the preparation method thereof according to claim 1, wherein the antibacterial ceramic glaze is characterized in that: the temperature of the quenching water is 10-30 ℃.
10. The antibacterial ceramic glaze and the preparation method thereof according to claim 1, wherein the antibacterial ceramic glaze is characterized in that: the content of the lime glaze calcium oxide is 14-19%.
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| CN114230267A (en) * | 2021-12-01 | 2022-03-25 | 深圳大学 | Hyperbranched graphene oxide cement-based composite material and preparation method thereof |
| CN114351142A (en) * | 2021-11-26 | 2022-04-15 | 格力电器（武汉）有限公司 | Preparation method of antibacterial enamel liner, antibacterial enamel liner and water heater comprising antibacterial enamel liner |
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