CN115925388B - Preparation method of long-acting antibacterial domestic ceramic - Google Patents
Preparation method of long-acting antibacterial domestic ceramic Download PDFInfo
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Abstract
The invention discloses a preparation method of a long-acting antibacterial domestic ceramic, which is implemented according to the following steps: step 1, preparing a photocatalysis nano rod; step 2, coaxial cladding modification; step 3, blending and compounding treatment; step 4, grouting molding; and 5, preparing the long-acting antibacterial ceramic. The long-acting antibacterial ceramic prepared by the preparation method solves the problems of high cost, poor antibacterial effect and poor persistence of the antibacterial agent in the conventional antibacterial ceramic products, and has good application prospect in the field of daily ceramics.
Description
Technical Field
The invention belongs to the technical field of preparation methods of antibacterial ceramics, and particularly relates to a preparation method of a long-acting antibacterial domestic ceramic.
Background
With the development of society and the improvement of living standard of people, people put higher demands on living quality, and prevention of pathogenic bacteria from entering and invading human body is urgent. The research and the development of daily ceramic products with antibacterial function are widely supported and focused by society. The antibacterial ceramic is a novel functional ceramic with antibacterial effect on the surface of the ceramic by adding an antibacterial agent in the production process of ceramic products. The existing preparation method of the antibacterial ceramic product mainly comprises the steps of adding metal ion elution type inorganic antibacterial agents such as silver with antibacterial effect or adding photocatalyst materials with photocatalytic sterilization effect into ceramic, wherein the antibacterial ceramic obtained by the method has good sterilization effect, but has the defects of high production cost, harm to human body due to excessive ion elution, poor antibacterial effect and persistence, high requirements on illumination conditions and the like in daily life.
The Chinese patent (application number: 201911340842.0, application publication number: CN 110818261A, publication date: 2019.12.23) proposes an antibacterial ceramic glaze which can realize uniform dispersion of an antibacterial agent in a ceramic overglaze and has efficient and sustainable antibacterial and bacteriostatic effects, but has the problems of high cost, easy oxidation and inactivation of the antibacterial agent, excessive dissolution of silver ions, harm to human bodies and short antibacterial duration.
The Chinese patent (application number: 2016046818. X, application publication number: CN 106082959A, publication date: 2016.11.09) designs a preparation method of a long-acting composite antibacterial ceramic, which not only can ensure the structural integrity of silver ions under high-temperature firing, but also has long-acting antibacterial effect, but also has the problems of higher cost, excessive silver ion dissolution, harm to human body and reduced antibacterial effect of materials along with the dissolution of silver ions.
Chinese patent (application No. 202111461615.0, application publication No. CN 114315136A, publication No. 2022.04.12) discloses a low-cost antibacterial ceramic glaze, which has low cost and can realize better antibacterial effect, but ZnO has poor thermal stability, and can not exert better antibacterial effect when oxidized and lost at high Wen Zhongyi; meanwhile, znO cannot exert catalytic sterilization effect under dark condition and cannot continuously resist bacteria.
Chinese patent (202111279682.0, CN 113929306A, 2022.01.14) discloses a photocatalyst antibacterial ceramic glaze and a lightweight ceramic tile, which widen the application range of the antibacterial ceramic glaze and enhance the antibacterial effect, but the antibacterial ceramic is difficult to realize the antibacterial effect in a dark environment and cannot realize long-acting antibacterial effect.
The Chinese patent (application number: 202111460126.3, application publication number: CN 113998996A, publication date: 2022.02.01) provides a mildew-proof antibacterial ceramic material and a preparation method thereof, which improve mildew-proof antibacterial effect, and the long-afterglow light accumulating material emits light to continuously promote the photocatalytic sterilization effect of nano titanium oxide at night or in a dark environment, but the titanium oxide has a larger band gap and only responds to ultraviolet light, even if the wavelength of light is changed by rare earth ions, the light utilization rate of the titanium oxide is still poorer, and the catalytic antibacterial effect is poorer.
Disclosure of Invention
The invention aims to provide a preparation method of a long-acting antibacterial domestic ceramic, which solves the problems of high cost, poor antibacterial effect and poor persistence of an antibacterial agent in an antibacterial ceramic product prepared by the existing method.
The technical scheme adopted by the invention is as follows:
the preparation method of the long-acting antibacterial domestic ceramic comprises the following steps:
step 1, uniformly mixing and stirring a photocatalyst precursor, a pH regulator and deionized water, then placing the mixed solution in a reaction kettle for hydrothermal reaction, cooling to room temperature, washing and suction filtering for three times by using deionized water and ethanol, and drying to obtain a photocatalytic nanorod;
step 2, placing the photocatalysis nano rod into a mixed solution composed of butyl titanate, rare earth salt, zinc nitrate hexahydrate, solvent and surfactant, stirring at high speed, aging for 12-24 hours, and drying to obtain modified TiO 2 A coaxially coated photocatalyst;
step 3, the coaxial coated photocatalyst obtained in the step 2 is mixed with Sr 2 MgSi 2 O 7 :Eu 2+ ,Dy 3+ (SMSO) long afterglow materials are blended and ground uniformly, and then calcined at high temperature to obtain a composite photocatalyst;
step 4, mixing and stirring the composite photocatalyst, the ceramic material and the binder to obtain a mixed material, adding water into the mixed material, stirring, grouting for molding, and drying and dehydrating to obtain an antibacterial ceramic blank;
and 5, sintering the antibacterial ceramic blank to 1000 ℃ in air, and then sintering for 70-90 min in a reducing atmosphere to obtain the long-acting antibacterial ceramic.
The invention is also characterized in that:
the temperature of the hydrothermal reaction in the step 1 is 90-120 ℃, the time of the hydrothermal reaction is 4-10 h, the temperature of the drying treatment is 60-80 ℃, and the drying treatment time in the step 1 is 6-12 h.
In the step 1, the concentration of the photocatalyst precursor is 20 mmol/L-100 mmol/L, and the concentration ratio of the pH regulator to the photocatalyst precursor is 1:1.
the photocatalyst precursor is one of zinc salt or copper salt, wherein the zinc salt is any one of zinc nitrate and zinc acetate, the copper salt is copper nitrate, and the pH regulator is any one of hexamethylenetetramine and sodium hydroxide.
The stirring speed in the step 2 is 500-800 r/min, the stirring time is 3-5 h, the drying treatment temperature in the step 2 is 60-80 ℃ and the drying treatment time is 8-12 h.
In the step 2, the mass percentages of the substances of the photocatalytic nanorod and the mixed solution are as follows: 20 to 24 percent of photocatalysis nanorod, 10 to 12 percent of butyl titanate, 0.3 to 0.6 percent of rare earth salt, 0.3 to 0.7 percent of zinc nitrate hexahydrate, 62 to 69 percent of solvent, 0.4 to 0.7 percent of surfactant, any one of cerium nitrate hexahydrate and yttrium nitrate, one or more of absolute ethyl alcohol, deionized water, acetic acid, hydrochloric acid and nitric acid as solvent, and one of sodium dodecyl benzene sulfonate and stearic acid as surfactant.
The high-temperature calcination temperature in the step 3 is 550-600 ℃, the calcination time is 2-3 h, and the mass ratio of the coaxial coated photocatalyst to the SMSO is 1 (1.2-1.5).
And in the step 4, water is added and stirred for 4-6 hours, the drying and dehydrating temperature in the step 4 is 100-130 ℃, and the drying and dehydrating time is 1-2 hours.
In the step 4, the mass percentages of the materials in the mixed materials are as follows: 20-30% of composite photocatalyst, 26-34% of kaolin, 20-30% of potassium feldspar powder, 20-25% of quartz powder, 3-4% of quicklime and 0.1-0.2% of binder, wherein the sum of the mass percentages of the components is 100%. Wherein the binder is sodium carboxymethyl cellulose, and the mass ratio of the mixed material to water is 2:1-4:1.
In the step 5, the reducing atmosphere is mixed gas of nitrogen and hydrogen in a volume ratio of 95:5, and the sintering temperature is 1250-1300 ℃.
The beneficial effects of the invention are as follows:
the preparation method of the long-acting antibacterial domestic ceramic can obtain the antibacterial ceramic with continuous, efficient antibacterial performance, good mechanical performance and chemical stability, and adopts modified TiO 2 The coaxial coated photocatalysis nano rod is used as an antibacterial agent, can reduce the high Wen Sunhao of the photocatalyst, widens the application range of antibacterial ceramics, and can activate rare earth metals and Zn 2+ The leaching antibacterial effect of the nano photocatalyst is combined with the catalytic antibacterial performance of the nano photocatalyst, so that the antibacterial ceramic can be high-efficiency and long-acting antibacterial; meanwhile, the composite long afterglow material enables the antibacterial ceramic to have a light storage function, so that the antibacterial ceramic can be ensured to be antibacterial under the dark condition, and the antibacterial duration time is prolonged. The long-acting antibacterial ceramic prepared by the invention solves the problems of high cost, poor antibacterial effect and poor persistence of the antibacterial agent in the conventional antibacterial ceramic products, and has good application prospect in the field of daily ceramics.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
The technical scheme adopted by the invention is that the preparation method of the long-acting antibacterial domestic ceramic is implemented according to the following steps:
step 1, preparing a photocatalysis nano rod
Uniformly stirring a solution consisting of a photocatalyst precursor, a pH regulator and deionized water, then placing the solution into a reaction kettle, carrying out hydrothermal reaction for 4-10 hours at 90-120 ℃, cooling to room temperature, using the deionized water and ethanol for three times of washing and suction filtration, and drying at 60-80 ℃ for 6-12 hours to obtain the photocatalytic nanorod;
in the step 1, the concentration of the photocatalyst precursor is 20 mmol/L-100 mmol/L, and the concentration ratio of the pH regulator to the photocatalyst precursor is 1:1, a photocatalyst precursor is one of zinc salt or copper salt, wherein the zinc salt is any one of zinc nitrate and zinc acetate, the copper salt is copper nitrate, and the pH regulator is any one of hexamethylenetetramine and sodium hydroxide;
step 2, coaxial coating modification
Adding the photocatalysis nano rod into a mixed solution composed of butyl titanate, rare earth salt, zinc nitrate hexahydrate, solvent and surfactant, vigorously stirring for 3-5 h at 500-800 r/min, aging for 12-24 h, and drying for 8-12 h at 60-80 ℃ to obtain modified TiO 2 A coaxially coated photocatalyst;
in the step 2, the mass percentages of the substances of the photocatalytic nanorod and the mixed solution are as follows: 20% -24% of photocatalysis nanorod, 10% -12% of butyl titanate, 0.3% -0.6% of rare earth salt, 0.3% -0.7% of zinc nitrate hexahydrate, 62% -69% of solvent, 0.4% -0.7% of surfactant, any one of cerium nitrate hexahydrate and yttrium nitrate, one or more of absolute ethyl alcohol, deionized water, acetic acid, hydrochloric acid and nitric acid as solvent, and one of sodium dodecyl benzene sulfonate and stearic acid as surfactant;
step 3, blending and compounding treatment
Mixing the coaxial coating modified photocatalyst prepared in the step 2 with Sr 2 MgSi 2 O 7 :Eu 2+ ,Dy 3+ (SMSO) long afterglow materials are mixed and ground uniformly, and then calcined for 2 to 3 hours at 550 to 600 ℃ to obtain the composite photocatalyst;
the mass ratio of the coaxial coated photocatalyst to the SMSO in the step 3 is 1 (1.2-1.5)
Step 4, slip casting
Mixing and stirring the composite photocatalyst obtained in the step 3, ceramic materials and binders to obtain a mixed material, adding water into the mixed material, stirring for 4-6 hours, grouting, and drying and dehydrating at 100-130 ℃ for 1-2 hours to obtain an antibacterial ceramic blank;
in the step 4, the mass percentages of the materials of the mixed materials are as follows: 20-30% of composite photocatalyst, 26-34% of kaolin, 20-30% of potassium feldspar powder, 20-25% of quartz powder, 3-4% of quicklime and 0.1-0.2% of binder, wherein the sum of the mass percentages of the components is 100%. Wherein the binder is sodium carboxymethyl cellulose, and the mass ratio of the mixed material to water is 2:1-4:1;
step 5, preparing the long-acting antibacterial ceramic
And (3) sintering the antibacterial ceramic blank obtained in the step (4) to 1000 ℃ under an oxidizing atmosphere (air), and then sintering at 1250-1300 ℃ for 70-90 min under a reducing atmosphere (mixed gas of nitrogen and hydrogen in a volume ratio of 95:5) to obtain the long-acting antibacterial ceramic product.
According to the preparation method of the long-acting antibacterial ceramic, the photocatalytic nanorods which are uniform in diameter, high in specific surface area and large in length-diameter ratio are obtained by adjusting the concentration of the precursor solution, the hydrothermal temperature and the time, and the purposes of sterilizing and reinforcing the toughened ceramic with multiple active sites are achieved; by Zn 2+ And rare earth ion co-doped modified TiO 2 The photocatalyst nano rod is coaxially coated to obtain a modified photocatalyst with good high-temperature stability and response to visible light, the purposes of reducing the photocatalyst height Wen Sunhao and widening the application range of the antibacterial ceramic can be realized, and the activation effect and Zn of rare earth metal can be realized 2+ The leaching antibacterial effect of the catalyst is combined with the photocatalytic antibacterial performance of the composite photocatalyst, so that the aims of high efficiency and long-acting antibacterial are achieved; blending and compounding the modified photocatalyst and a long afterglow material SMSO to obtain a composite photocatalyst with a light storage function, and ensuring that the catalyst can play a role in catalytic sterilization under the dark condition, thereby realizing a continuous antibacterial effect; proper ceramic materials and binders are selected, and sintering is carried out in a reducing atmosphere to ensure that the ceramic materials and binders have good mechanical propertyAn antimicrobial ceramic which is capable of chemically stabilizing and smoothing surfaces.
Example 1
The preparation method of the long-acting antibacterial domestic ceramic comprises the following steps:
step 1, adding 30g of zinc nitrate and 14g of hexamethylenetetramine into 1000mL of deionized water, uniformly stirring, placing into a reaction kettle, performing hydrothermal reaction for 10 hours at 90 ℃, cooling to room temperature, taking out precipitate, washing with ethanol and deionized water for three times, performing suction filtration, and drying at 60 ℃ for 12 hours to obtain ZnO nanorods;
step 2, adding 20g of ZnO nano rod into a mixed solution consisting of 10mL of butyl titanate, 0.3g of yttrium nitrate, 0.3g of zinc nitrate hexahydrate, 70mL of ethanol, 2mL of acetic acid, 10mL of deionized water and 0.4g of sodium dodecyl benzene sulfonate, vigorously stirring for 5h at 500r/min, aging for 12h, and drying at 60 ℃ for 12h to obtain modified TiO 2 Coaxially coated ZnO photocatalyst;
step 3. 20g of the coaxial coating modified ZnO photocatalyst and 24gSr 2 MgSi 2 O 7 :Eu 2+ ,Dy 3+ (SMSO) long afterglow materials are mixed and ground uniformly, and then calcined for 2 hours at 550 ℃ to obtain a composite photocatalyst;
step 4, mixing and stirring 40g of composite photocatalyst with 52g of kaolin, 50g of potassium feldspar powder, 50g of quartz powder, 6g of quicklime, 2g of dolomite powder and 0.2g of sodium carboxymethyl cellulose to obtain a mixed material, adding 100g of water, stirring for 4 hours, grouting for molding, drying at 100 ℃ for 2 hours, and dehydrating to obtain an antibacterial ceramic blank;
and 5, sintering the antibacterial ceramic blank to 1000 ℃ in an oxidizing atmosphere (air), and then sintering at 1250 ℃ for 90min in a reducing atmosphere (mixed gas of nitrogen and hydrogen in a volume ratio of 95:5) to obtain the long-acting antibacterial ceramic product.
Example 2
The preparation method of the long-acting antibacterial domestic ceramic comprises the following steps:
step 1, adding 25.9g of zinc acetate and 19.6g of hexamethylenetetramine into 7000mL of deionized water, uniformly stirring, placing into a reaction kettle, performing hydrothermal reaction for 8 hours at 95 ℃, cooling to room temperature, taking out precipitate, washing with ethanol and deionized water for three times, performing suction filtration, and drying for 6 hours at 80 ℃ to obtain ZnO nanorods;
step 2, adding 10g of ZnO nano rod into a mixed solution consisting of 6mL of butyl titanate, 0.3g of cerium nitrate, 0.35g of zinc nitrate hexahydrate, 30mL of ethanol, 1mL of hydrochloric acid, 10mL of deionized water and 0.3g of sodium dodecyl benzene sulfonate, vigorously stirring for 3h at 800r/min, aging for 24h, and drying at 80 ℃ for 8h to obtain modified TiO 2 Coaxially coated ZnO photocatalyst;
step 3. 10g of the coaxial coating modified ZnO photocatalyst and 15gSr 2 MgSi 2 O 7 :Eu 2+ ,Dy 3+ (SMSO) long afterglow materials are mixed and ground uniformly, and then calcined for 3 hours at 550 ℃ to obtain a composite photocatalyst;
step 4, mixing and stirring 20g of composite photocatalyst with 34g of kaolin, 20g of potassium feldspar powder, 20g of quartz powder, 4g of quicklime, 2g of dolomite powder and 0.2g of sodium carboxymethyl cellulose to obtain a mixed material, adding 50g of water, stirring for 4 hours, grouting for molding, drying at 130 ℃ for 1 hour, and dehydrating to obtain an antibacterial ceramic blank;
and 5, sintering the antibacterial ceramic blank to 1000 ℃ in an oxidizing atmosphere (air), and then sintering at 1300 ℃ for 70min in a reducing atmosphere (mixed gas of nitrogen and hydrogen in a volume ratio of 95:5) to obtain the long-acting antibacterial ceramic product.
Example 3
The preparation method of the long-acting antibacterial domestic ceramic comprises the following steps:
step 1, adding 36.24g of copper nitrate and 21g of hexamethylenetetramine into 6000mL of deionized water, uniformly stirring, placing into a reaction kettle, performing hydrothermal reaction for 6 hours at 90 ℃, cooling to room temperature, taking out precipitate, performing three times of washing with ethanol and deionized water, performing suction filtration, and drying for 12 hours at 60 ℃ to obtain a CuO nano rod;
step 2, adding 10g of CuO nano rod into a mixed solution consisting of 5mL of butyl titanate, 0.2g of yttrium nitrate, 0.3g of zinc nitrate hexahydrate, 35mL of ethanol, 1mL of acetic acid, 5mL of deionized water and 0.35g of stearic acid, vigorously stirring for 4h at 600r/min, aging for 12h, and drying at 60 ℃ for 10h to obtain modified TiO 2 Coaxially coated CuO photocatalyst;
step 3. 10g of the coaxial coating modified CuO photocatalyst and 12gSr 2 MgSi 2 O 7 :Eu 2+ ,Dy 3+ (SMSO) long afterglow materials are mixed and ground uniformly, and then calcined at 600 ℃ for 2 hours to obtain a composite photocatalyst;
step 4, mixing and stirring 15g of the composite photocatalyst with 13g of kaolin, 10g of potassium feldspar powder, 10g of quartz powder, 1.5g of quicklime, 0.5g of dolomite powder and 0.05g of sodium carboxymethyl cellulose to obtain a mixed material, adding 20g of water, stirring for 6 hours, grouting for molding, drying at 100 ℃ for 2 hours, and dehydrating to obtain an antibacterial ceramic blank;
and 5, sintering the antibacterial ceramic blank to 1000 ℃ in an oxidizing atmosphere (air), and sintering at 1250 ℃ for 80 minutes in a reducing atmosphere (mixed gas of nitrogen and hydrogen in a volume ratio of 95:5) to obtain the long-acting antibacterial ceramic product.
Example 4
The preparation method of the long-acting antibacterial domestic ceramic comprises the following steps:
step 1, adding 44.63g of zinc nitrate and 21.03g of hexamethylenetetramine into 2500mL of deionized water, uniformly stirring, placing into a reaction kettle, performing hydrothermal reaction for 10 hours at 90 ℃,
cooling to room temperature, taking out the precipitate, washing with ethanol and deionized water for three times, suction filtering, and drying at 60 ℃ for 12 hours to obtain ZnO nanorods;
step 2, adding 12g of ZnO nano rod into a mixed solution consisting of 6mL of butyl titanate, 0.3g of cerium nitrate, 0.2g of zinc nitrate hexahydrate, 35mL of ethanol, 1mL of nitric acid, 5mL of deionized water and 0.35g of sodium dodecyl benzene sulfonate, vigorously stirring for 5h at 600r/min, aging for 24h, and drying at 70 ℃ for 10h to obtain modified TiO 2 Coaxially coated ZnO photocatalyst;
step 3. 12g of the coaxial coating modified ZnO photocatalyst and 18gSr 2 MgSi 2 O 7 :Eu 2+ ,Dy 3+ (SMSO) long afterglow materials are mixed and ground uniformly, and then calcined for 2 hours at 550 ℃ to obtain a composite photocatalyst;
step 4, mixing and stirring 20g of the composite photocatalyst with 24g of kaolin, 16g of potassium feldspar powder, 16g of quartz powder, 2.4g of quicklime, 1.6g of dolomite powder and 0.16g of sodium carboxymethyl cellulose to obtain a mixed material, adding 20g of water, stirring for 4 hours, grouting for molding, drying at 100 ℃ for 1 hour, and dehydrating to obtain an antibacterial ceramic blank;
and 5, sintering the antibacterial ceramic blank to 1000 ℃ in an oxidizing atmosphere (air), and then sintering at 1250 ℃ for 90min in a reducing atmosphere (mixed gas of nitrogen and hydrogen in a volume ratio of 95:5) to obtain the long-acting antibacterial ceramic product.
Example 5
The preparation method of the long-acting antibacterial domestic ceramic comprises the following steps:
step 1, adding 36.24g of copper nitrate and 21g of hexamethylenetetramine into 6000mL of deionized water, uniformly stirring, placing into a reaction kettle, performing hydrothermal reaction for 4 hours at 120 ℃, cooling to room temperature, taking out precipitate, performing three times of washing with ethanol and deionized water, performing suction filtration, and drying for 10 hours at 60 ℃ to obtain a CuO nano rod;
step 2, adding 10g of CuO nano rod into a mixed solution consisting of 5.5mL of butyl titanate, 0.3g of cerium nitrate, 0.15g of zinc nitrate hexahydrate, 35mL of ethanol, 1mL of acetic acid, 5mL of deionized water and 0.2g of sodium dodecyl benzene sulfonate, vigorously stirring for 5h at 500r/min, aging for 20h, and drying at 60 ℃ for 12h to obtain modified TiO 2 Coaxially coated CuO photocatalyst;
step 3. 10g of the coaxial coating modified CuO photocatalyst and 15gSr 2 MgSi 2 O 7 :Eu 2+ ,Dy 3+ (SMSO) long afterglow materials are mixed and ground uniformly, and then calcined for 2 hours at 550 ℃ to obtain a composite photocatalyst;
step 4, mixing and stirring 20g of composite photocatalyst with 28g of kaolin, 25g of potassium feldspar powder, 22g of quartz powder, 4g of quicklime, 1g of dolomite powder and 0.1g of sodium carboxymethyl cellulose to obtain a mixed material, adding 30g of water, stirring for 5 hours, grouting for molding, drying at 120 ℃ for 2 hours, and dehydrating to obtain an antibacterial ceramic blank;
and 5, sintering the antibacterial ceramic blank to 1000 ℃ in an oxidizing atmosphere (air), and sintering at 1250 ℃ for 80 minutes in a reducing atmosphere (mixed gas of nitrogen and hydrogen in a volume ratio of 95:5) to obtain the long-acting antibacterial ceramic product.
The antibacterial test method of the long-acting antibacterial ceramic refers to JC/T897-2014 antibacterial property of antibacterial ceramic products, wherein the antibacterial test method is characterized in that the long-acting antibacterial ceramic is firstly placed under illumination for 6 hours and then placed in a dark environment for 12 hours, and finally the antibacterial rate is counted, and the comparison of the antibacterial properties of the long-acting antibacterial ceramic obtained in the examples 1-5 and the antibacterial properties of the conventional antibacterial ceramic is shown in the following table 1:
TABLE 1
As can be seen from table 1, the metal ion type antibacterial ceramic has an antibacterial effect >90%, but its continuous antibacterial effect is poor; the photocatalytic antibacterial ceramic has a continuous antibacterial property, but has a low overall antibacterial rate due to the difficulty in achieving an antibacterial effect in a dark environment. The initial antibacterial rate and the antibacterial rate of the long-acting antibacterial ceramic prepared by the invention on escherichia coli and staphylococcus aureus can be kept above 98 percent after 5 days, which is higher than the index of JC/T897-2014 antibacterial ceramic product antibacterial performance (antibacterial rate is more than or equal to 90 percent), and the ceramic has excellent antibacterial effect in natural light and dark environment, and can realize continuous antibacterial. The invention has good application prospect in improving the antibacterial effect and the persistence of ceramics.
Claims (7)
1. The preparation method of the long-acting antibacterial domestic ceramic is characterized by comprising the following steps of:
step 1, uniformly mixing and stirring a photocatalyst precursor, a pH regulator and deionized water, then placing the mixed solution in a reaction kettle for hydrothermal reaction, cooling to room temperature, washing and suction filtering for three times by using deionized water and ethanol, and drying to obtain a photocatalytic nanorod;
step 2, placing the photocatalysis nano rod into a mixed solution composed of butyl titanate, rare earth salt, zinc nitrate hexahydrate, a solvent and a surfactant, stirring at a high speed, aging for 12-24 hours, and drying to obtain modified TiO 2 A coaxially coated photocatalyst;
step 3, coaxially cladding the obtained in the step 2Photocatalyst and Sr of (2) 2 MgSi 2 O 7 :Eu 2+ ,Dy 3+ The long afterglow materials are blended and ground uniformly, and then calcined at high temperature to obtain a composite photocatalyst;
step 4, mixing and stirring the composite photocatalyst, the ceramic material and the binder to obtain a mixed material, adding water into the mixed material, stirring, grouting for molding, and drying and dehydrating to obtain an antibacterial ceramic blank;
step 5, sintering the antibacterial ceramic blank to 1000 ℃ in air, and then sintering for 70-90 min at 1250-1300 ℃ in a reducing atmosphere to obtain the long-acting antibacterial ceramic;
the photocatalyst precursor is one of zinc salt or copper salt, wherein the zinc salt is any one of zinc nitrate and zinc acetate, the copper salt is copper nitrate, and the pH regulator is any one of hexamethylenetetramine and sodium hydroxide;
in the step 2, the mass percentages of the substances of the photocatalytic nanorods and the mixed solution are as follows: 20% -24% of photocatalysis nanorod, 10% -12% of butyl titanate, 0.3% -0.6% of rare earth salt, 0.3% -0.7% of zinc nitrate hexahydrate, 62% -69% of solvent, 0.4% -0.7% of surfactant, any one of cerium nitrate hexahydrate and yttrium nitrate, one or more of absolute ethyl alcohol, deionized water, acetic acid, hydrochloric acid and nitric acid, and one of sodium dodecyl benzene sulfonate and stearic acid;
the high-temperature calcination temperature in the step 3 is 550-600 ℃, the calcination time is 2-3 h, and the photocatalyst and Sr are coaxially coated 2 MgSi 2 O 7 :Eu 2+ ,Dy 3+ The mass ratio of the long afterglow material is 1 (1.2-1.5).
2. The method for preparing the long-acting antibacterial domestic ceramic according to claim 1, wherein the temperature of the hydrothermal reaction in the step 1 is 90-120 ℃, the time of the hydrothermal reaction is 4-10 hours, the temperature of the drying treatment is 60-80 ℃, and the time of the drying treatment in the step 1 is 6-12 hours.
3. The method for preparing the long-acting antibacterial domestic ceramic according to claim 1, wherein the concentration of the photocatalyst precursor in the step 1 is 20 mmol/L-100 mmol/L, and the concentration ratio of the pH regulator to the photocatalyst precursor is 1:1.
4. the method for preparing the long-acting antibacterial domestic ceramic according to claim 1, wherein in the step 2, the stirring speed is 500 r/min-800 r/min, the stirring time is 3-5 h, the drying treatment temperature is 60-80 ℃ and the drying treatment time is 8-12 h.
5. The method for preparing the long-acting antibacterial domestic ceramic according to claim 1, wherein the water adding and stirring time in the step 4 is 4-6 hours, the drying and dehydrating temperature in the step 4 is 100-130 ℃, and the drying and dehydrating time is 1-2 hours.
6. The preparation method of the long-acting antibacterial domestic ceramic according to claim 1, wherein the mass percentage of each material in the mixed materials in the step 4 is as follows: 20-30% of composite photocatalyst, 26-34% of kaolin, 20-30% of potassium feldspar powder, 20-25% of quartz powder, 3-4% of quicklime and 0.1-0.2% of binder, wherein the sum of the mass percentages of the components is 100%, the binder is sodium carboxymethyl cellulose, and the mass ratio of the mixed material to water is 2:1-4:1.
7. The method for preparing the long-acting antibacterial domestic ceramic according to claim 1, wherein the reducing atmosphere in the step 5 is a mixed gas of nitrogen and hydrogen in a volume ratio of 95:5.
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