CN112830678A - Ceramic antibacterial additive, preparation method thereof and ceramic glaze - Google Patents
Ceramic antibacterial additive, preparation method thereof and ceramic glaze Download PDFInfo
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- CN112830678A CN112830678A CN202110093534.3A CN202110093534A CN112830678A CN 112830678 A CN112830678 A CN 112830678A CN 202110093534 A CN202110093534 A CN 202110093534A CN 112830678 A CN112830678 A CN 112830678A
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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
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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
-
- 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 embodiment of the invention discloses a ceramic antibacterial additive, a preparation method thereof and a ceramic glaze, wherein the additive comprises the following components in percentage by weight: 70-90% of boron-phosphorus glass powder; 10-30% of silver powder; the boron-phosphorus glass powder comprises the following components: na2O, B2O3, P2O5, K2O and Al2O3, wherein the mass ratio of the components is 5-15: 20-30: 20-40: 5-15: 5-15. According to the invention, silver powder and boron-phosphorus glass powder are effectively combined in an embedded manner to form the ceramic antibacterial additive, so that excellent antibacterial performance can be realized on the basis of lower addition amount of silver antibacterial material, and the industrial problem that silver ion antibacterial cost is high and difficult to apply is solved.
Description
Technical Field
The invention relates to the technical field of ceramic production, in particular to a ceramic antibacterial additive, a preparation method thereof and a ceramic glaze.
Background
The bathroom space is always heavily populated by pathogenic microorganisms such as staphylococcus aureus, escherichia coli, various molds and the like because the environment is humid. These bacteria and pathogenic microorganisms are not only transmitted through the air in the form of droplets, through the water in the form of feces, but also through the articles in a surface contact manner. The bathroom has a plurality of bathroom products which are in close contact with the skin of the human body, the most important bathroom products are toilets, bathtubs, hand basins and the like, and when the skin of the human body is in contact with the bacteria and viruses, direct damage is brought to the health of the human body.
The first method is to add an antibacterial material such as silver ions into the raw material of the ceramic, and to form a whole with the ceramic by high-temperature firing, so that the ceramic has an antibacterial function on the surface of the ceramic. The second method is that functional materials such as nano titanium dioxide are attached to the surface of the ceramic in the form of a film layer through a coating by post processing, so that the ceramic has an antibacterial effect.
From the actual product performance and effect, the first method is that the glaze material is usually sintered at 1100-1300 degrees, silver ions are seriously volatilized (silver begins to obviously volatilize at 961 ℃), relatively more silver needs to be added for antibacterial property, so that the cost is very high, the uniformity and the amount of the silver content in the surface layer after the glaze material is calcined are difficult to guarantee, and the silver-containing additive is discolored after high-temperature calcination when the content of the silver-containing additive is too high, so that the glossiness and the appearance are influenced. In the second way, the ceramic product is further processed, for example, by photocatalytic antibacterial coating, and the additional process is added, which is costly, and the antibacterial effect is difficult to guarantee and effective for a long time due to the non-durability of the coating and the insufficient antibacterial effect of the functional material.
It is obvious that the first silver-based antibacterial mode is to add the silver-based antibacterial material directly into the glaze material for high-temperature firing, and the antibacterial coating and the ceramic are integrated into a whole, which is the most feasible choice.
The existing silver-based (including forms of silver, silver ions, silver oxide and the like) antibacterial ceramics still have two problems of high cost and large influence on appearance effect in the actual application process. Firstly, the necessary (99% antibacterial property) addition amount of the existing silver-based antibacterial material is still high, and the cost is too high in the aspects of calculating glaze spraying loss, product yield influence and the like, so that the market application of the antibacterial ceramic is restricted. And when the antibacterial material is added to a certain amount, the appearance of the ceramic surface is more or less affected, for example, the problems of yellowing of color (effect of silver ion), deterioration of glossiness, and the like are caused.
Disclosure of Invention
The technical problem to be solved by the embodiment of the invention is to provide a ceramic antibacterial additive, a preparation method thereof and a ceramic glaze so as to reduce the cost of the silver-based antibacterial glaze.
In order to solve the technical problem, the embodiment of the invention provides a ceramic antibacterial additive, which comprises the following components in percentage by weight: 70-90% of boron-phosphorus glass powder; 10-30% of silver powder; the boron-phosphorus glass powder comprises the following components: na2O, B2O3, P2O5, K2O and Al2O3, wherein the mass ratio of the components is 5-15: 20-30: 20-40: 5-15: 5-15.
Further, the mass ratio of Na2O, B2O3, P2O5, K2O and Al2O3 in the boron-phosphorus glass powder is 10: 30: 40: 10: 10.
further, the silver powder has a particle diameter of about 10-20um and a density of 0.9-1g/cm3The specific surface area is 0.4m2/g。
Furthermore, the particle size specification of the boron-phosphorus glass powder is 10-30 um.
Correspondingly, the embodiment of the invention also provides a preparation method of the ceramic antibacterial additive, which comprises the following steps:
mixing: 70-90 parts of boron phosphorus glass powder and 10-30 parts of silver powder are put into a V-shaped powder mixer according to the parts by weight and mixed to obtain the ceramic antibacterial additive, wherein the mixing speed is 20-25rpm, and the mixing time is 1-3 hours.
Further, the mixing step is preceded by:
the preparation method of the glass powder comprises the following steps: mixing the following components in a mass ratio of 5-15: 20-30: 20-40: 5-15: 5-15 of Na2O, B2O3, P2O5, K2O and Al2O3 are uniformly mixed, and then the mixture is added into a muffle furnace for high-temperature calcination, the temperature is raised to 5 ℃/min, the temperature is raised to 1300 ℃ of 1000 ℃ and the temperature is kept for 0.5-3h, and then the mixture is naturally cooled to the normal temperature; then grinding and crushing are carried out, and sieving is carried out to obtain the boron-phosphorus glass powder with the grain size specification of 10-30 um.
Further, in the step of preparing the glass powder, the mass ratio of Na2O, B2O3, P2O5, K2O and Al2O3 is 10: 30: 40: 10: 10.
further, the silver powder has a particle diameter of about 10-20um and a density of 0.9-1g/cm3The specific surface area is 0.4m2/g。
Correspondingly, the embodiment of the invention also provides a ceramic glaze, which comprises the ceramic antibacterial additive prepared by the preparation method of the ceramic antibacterial additive, wherein the ceramic antibacterial additive accounts for 0.5-2% of the total mass of the ceramic glaze.
The invention has the beneficial effects that: according to the invention, silver powder and boron-phosphorus glass powder are effectively combined in an embedded manner to form the ceramic antibacterial additive, so that excellent antibacterial performance can be realized on the basis of lower addition amount of silver antibacterial material, and the industrial problem that silver ion antibacterial cost is high and difficult to apply is solved.
Drawings
FIG. 1 is an electron micrograph of a ceramic antimicrobial additive according to an embodiment of the present invention.
Fig. 2 is a structure diagram of a boron-phosphorus glass powder-silver three-dimensional molecular network formed under the condition of high-temperature calcination and melting of the ceramic antibacterial additive according to the embodiment of the invention.
Fig. 3 is a schematic view of the floating surface of the borophosphosilicate glass powder-silver component of the ceramic glaze of the embodiment of the invention when melted at high temperature.
Description of the reference numerals
1 is Na or K; 2 is P or B; 3 is O; 4 is Ag.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application can be combined with each other without conflict, and the present invention is further described in detail with reference to the drawings and specific embodiments.
If directional indications (such as up, down, left, right, front, and rear … …) are provided in the embodiment of the present invention, the directional indications are only used to explain the relative position relationship between the components, the movement, etc. in a specific posture (as shown in the drawing), and if the specific posture is changed, the directional indications are changed accordingly.
In addition, the descriptions related to "first", "second", etc. in the present invention are only used for descriptive purposes and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature.
The ceramic antibacterial additive provided by the embodiment of the invention comprises the following components in percentage by weight:
70-90% of boron-phosphorus glass powder;
10-30% of silver powder.
The silver powder has the purity of 99.99 percent, the preferred particle sizes of other specifications are about 10-20um, the density is 0.9-1g/cm3, the specific surface area is 0.4m2/g, and the silver powder is obtained by market purchase.
The boron-phosphorus glass powder comprises the following components: na2O, B2O3, P2O5, K2O and Al2O3, wherein the mass ratio of the components is 5-15: 20-30: 20-40: 5-15: 5-15. The preparation of the boron-phosphorus glass powder adopts high-temperature melting and cooling, and the glass powder is obtained after ball milling and sieving. The specific method comprises the following steps: uniformly mixing the 4 oxides according to a certain proportion, calcining at high temperature in a muffle furnace, heating to 1000 ℃ and 1300 ℃ at a temperature of 5 ℃/min, preserving the temperature for 0.5-3h, and naturally cooling to normal temperature. Then grinding and crushing are carried out until the size of the glass powder is about 10-30um for later use. (4 oxides are all purchased from the market)
According to the embodiment of the invention, high-purity silver powder (purchased by a conventional market way) is effectively embedded and combined with self-made boron-phosphorus glass powder to form an embedded mixture, and silver ions are adsorbed onto a high-temperature resistant material or enter the material in the high-temperature calcination process of the ceramic, so that the volatilization of the silver ions at high temperature is reduced.
In one embodiment, the mass ratio of Na2O, B2O3, P2O5, K2O, and Al2O3 in the borophosphate glass frit is 10: 30: 40: 10: 10.
as an embodiment, the silver powder has a particle diameter of about 10-20um and a density of 0.9-1g/cm3The specific surface area is 0.4m2/g。
In one embodiment, the boron-phosphorus glass powder has a particle size of 10-30 um.
The preparation method of the ceramic antibacterial additive comprises the following mixing steps: 70-90 parts of boron phosphorus glass powder and 10-30 parts of silver powder are put into a V-shaped powder mixer according to the parts by weight and mixed to obtain the ceramic antibacterial additive, wherein the mixing speed is 20-25rpm, and the mixing time is 1-3 hours. Firstly, vibrating and sieving silver powder and boron-phosphorus glass powder respectively by using powder sieving machines to ensure that the particle size specification is uniform before mixing. Secondly, mixing the boron-phosphorus glass powder prepared in advance with silver powder according to the following proportion;
glass powder: 70-90%;
silver powder: 10 to 30 percent;
the two powders were put into a V-type powder mixer to be efficiently mixed under the control of 22rpm for 2 hours. Through utilizing 2 asymmetric barrels of V type mixer, turn over the stirring in-process from top to bottom, realize the horizontal and fore-and-aft convection impact of silver powder and boron phosphorus glass powder, and because of both particle diameters are close, can realize very high mixing degree of consistency finally, form and inlay the compound body. And finally, packaging and storing the mixed powder to obtain the ceramic antibacterial additive.
In the process of efficiently mixing the boron-phosphorus glass powder with the silver powder, the boron-phosphorus glass powder is impacted and mixed by transverse and longitudinal convection, and a mosaic structure is formed microscopically (referring to fig. 1, white is silver, and black is vitreous). The process is very important, the addition amount of the antibacterial additive is only 1%, and when the antibacterial agent is mixed with the glaze, the antibacterial additive can be separated due to stirring dispersion of the glaze slurry if silver and glass powder are not combined into a whole in the stirring process of the glaze slurry, so that the antibacterial performance fails because the antibacterial additive cannot be reacted uniformly and efficiently in the high-temperature calcination melting process after glazing.
As an embodiment, the mixing step further comprises, before:
the preparation method of the glass powder comprises the following steps: mixing the following components in a mass ratio of 5-15: 20-30: 20-40: 5-15: 5-15 of Na2O, B2O3, P2O5, K2O and Al2O3 are uniformly mixed, and then the mixture is added into a muffle furnace for high-temperature calcination, the temperature is raised to 5 ℃/min, the temperature is raised to 1300 ℃ of 1000 ℃ and the temperature is kept for 0.5-3h, and then the mixture is naturally cooled to the normal temperature; then grinding and crushing are carried out, and sieving is carried out to obtain the boron-phosphorus glass powder with the grain size specification of 10-30 um.
In one embodiment, in the step of preparing the glass frit, the mass ratio of Na2O, B2O3, P2O5, K2O, and Al2O3 is 10: 30: 40: 10: 10.
as an embodiment, the silver powder has a particle diameter of about 10-20um and a density of 0.9-1g/cm3The specific surface area is 0.4m2/g。
Referring to fig. 2, fig. 2 is a schematic diagram of a borophosphosilicate glass powder-silver three-dimensional molecular network structure formed under the condition of high-temperature calcination and melting. The boron-phosphorus glass powder has a three-dimensional reticular molecular structure on the microcosmic inside, Na and K in the structure of the boron-phosphorus glass powder are replaced by silver ions under the high-temperature calcination and melting of the ceramic glaze, and the silver ions, boric acid and phosphate radicals form coordination and are combined in the molecular reticular structure of crystal lattices in a replacement mode. Under the conventional condition, the antibacterial ceramic is calcined at the temperature of more than 950 ℃, and silver is lost due to large amount of volatilization, so that the surface of the antibacterial ceramic is free from silver or the silver content is too low, and the antibacterial property is insufficient. Now, the boron-phosphorus glass powder-silver antibacterial composition prepared by the invention has the advantages that the silver is replaced by Na and K and is positioned in a three-dimensional network structure under the high-temperature calcination, so that the excellent high-temperature stability is brought, and the volatilization of the silver is greatly inhibited
The ceramic glaze of the embodiment of the invention comprises a ceramic antibacterial additive, wherein the ceramic antibacterial additive accounts for 0.5-2% of the total mass of the ceramic glaze.
The boron-phosphorus glass powder disclosed by the embodiment of the invention has a three-dimensional reticular molecular structure on the microcosmic inside, Na and K in the structure of the boron-phosphorus glass powder are replaced by silver ions under the condition that the ceramic glaze added with the ceramic antibacterial additive is calcined and melted at high temperature, and the silver ions, boric acid and phosphate radicals form coordination and are combined in the molecular reticular structure of crystal lattices in a replacement mode. Under the conventional condition, the antibacterial ceramic is calcined at the temperature of more than 950 ℃, and silver is lost due to large amount of volatilization, so that the surface of the antibacterial ceramic is free from silver or the silver content is too low, and the antibacterial property is insufficient. The boron-phosphorus glass powder-silver antibacterial composition prepared by the invention has the advantages that the silver is replaced by Na and K under high-temperature calcination and is positioned in a three-dimensional net structure, so that the excellent high-temperature stability is brought, and the volatilization of the silver is greatly inhibited.
Compared with the glaze with SiO2 and Al2O3 as main components, the boron-phosphorus glass powder of the embodiment of the invention has light specific gravity, and under the condition of high-temperature calcination and melting, components forming a molecular net structure by coordination of silver ions, boric acid and phosphate radicals float near the surface of the ceramic glaze, thereby further facilitating less silver addition and realizing excellent antibacterial performance. Referring to fig. 3, when the glaze material on the ceramic surface layer is melted at a high temperature, the borophosphosilicate glass-silver component will float up to the surface when melted due to the low specific gravity.
The preparation process of the antibacterial ceramic sample provided by the embodiment of the invention comprises the following steps: the prepared ceramic antibacterial additive (0.5-2% by mass of glaze slip) is uniformly mixed with dry glaze of ceramic glaze, then water is added, ball milling is carried out to prepare the glaze slip, then spraying glazing is carried out on a square ceramic blank with the thickness of 5cm by 5cm, then high-temperature calcination is carried out, the calcination stability is 1250 ℃, the heating rate is 5 ℃/min, the time is kept for 2h, and finally cooling to the normal temperature is carried out.
The antibacterial performance test flow of the ceramic antibacterial additive comprises the following steps:
the appearance (color, gloss, surface flatness, etc.) of the ceramic sample obtained was first confirmed.
Removing samples with abnormal appearances;
then, the samples with completely normal appearance are tested and analyzed for the antibacterial performance of escherichia coli and staphylococcus aureus according to the antibacterial performance of antibacterial ceramic product 2014 of JCT 897.
Example (c):
first, a boron-phosphorus glass frit was prepared by trial, and the contents of B2O3 and P2O5 were adjusted mainly in accordance with the mass ratio of (na2o.b2O3.P2O5.k2o.al2O 3).
By adjusting the formula, A, B, C, D, E, F, G glass powder samples were prepared.
And then the boron-phosphorus glass powder is used in an antibacterial additive, and the component proportion of the boron-phosphorus glass powder to silver powder is 90: sample 10 was K1, ratio 80: sample 20 was K2, ratio 70: sample 30 was K3.
Mixing the prepared ceramic antibacterial additive samples K1, K2 and K3 with dry glaze materials respectively, adding water, stirring to prepare glaze slurry, glazing on the green ceramic chip, firing and cooling. Preparing ceramic samples with antibacterial function.
First, K1 with the least addition amount of silver powder in the antibacterial agent is selected, and the addition ratio of the antibacterial agent in the glaze is 1% for example, so as to confirm the optimal component ratio of the glass powder. The silver content in the antibacterial ceramic is 0.1%.
The mass percentages are shown in table 1.
TABLE 1
Through the above experiment, it was determined that the optimum composition ratio of the boron-phosphorus glass frit was sample D, and the mass ratio of (na2o.b2o3.p2o5.k2o.al2o3) was 10: 30: 40: 10: 10;
and the antibacterial effect is gradually improved when the boron-phosphorus proportion is increased along with the addition of the boron-phosphorus. When the amount is too high, the appearance of the final ceramic is slightly uneven.
The mass ratio of boron-phosphorus glass powder (Na2O.B2O3.P2O5.K2O.Al2O3) with the optimal component ratio is 10: 30: 40: 10: 10, used in the antibacterial additive, and the component proportion of the silver powder is selected to be 90: sample 10 was K1, ratio 80: sample 20 was K2, ratio 70: sample 30 was K3.
Experiments are carried out on the addition amount of the antibacterial additive;
wherein the addition amounts of the antibacterial agent are respectively set as follows: 0.5%, 0.75%, 1%, 1.25%, 1.5%, 1.75%, 2%.
A total of 7 tests gave the data in table 2:
TABLE 2
As is clear from the experiment, the lowest addition amount of the antimicrobial agent was selected to be 1%, and the type K2 was most preferable. At this time, the amount of silver added was only 0.2%, and according to the test, the number of toilets to which 1Kg of glaze slip can be applied was about 5. The cost of silver powder in 1Kg of glaze slip is about 13 yuan (taking the maximum value of 6500 yuan/Kg in 2020 international silver price as an example), and the cost of silver of a single antibacterial closestool is 2.6 yuan.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (9)
1. The ceramic antibacterial additive is characterized by comprising the following components in percentage by weight: 70-90% of boron-phosphorus glass powder; 10-30% of silver powder; the boron-phosphorus glass powder comprises the following components: na2O, B2O3, P2O5, K2O and Al2O3, wherein the mass ratio of the components is 5-15: 20-30: 20-40: 5-15: 5-15.
2. The ceramic antibiotic additive as claimed in claim 1, wherein the mass ratio of Na2O, B2O3, P2O5, K2O, and Al2O3 in the borophospho-glass frit is 10: 30: 40: 10: 10.
3. the ceramic antibiotic additive according to claim 1, wherein the silver powder has a particle diameter of about 10-20um and a density of 0.9-1g/cm3The specific surface area is 0.4m2/g。
4. The ceramic antibiotic additive as claimed in claim 1, wherein the boron-phosphorus glass powder has a particle size of 10-30 um.
5. A preparation method of a ceramic antibacterial additive is characterized by comprising the following steps:
mixing: 70-90 parts of boron phosphorus glass powder and 10-30 parts of silver powder are put into a V-shaped powder mixer according to the parts by weight and mixed to obtain the ceramic antibacterial additive, wherein the mixing speed is 20-25rpm, and the mixing time is 1-3 hours.
6. The method of preparing a ceramic antimicrobial additive of claim 5, wherein the step of mixing further comprises, prior to the step of mixing:
the preparation method of the glass powder comprises the following steps: mixing the following components in a mass ratio of 5-15: 20-30: 20-40: 5-15: 5-15 of Na2O, B2O3, P2O5, K2O and Al2O3 are uniformly mixed, and then the mixture is added into a muffle furnace for high-temperature calcination, the temperature is raised to 5 ℃/min, the temperature is raised to 1300 ℃ of 1000 ℃ and the temperature is kept for 0.5-3h, and then the mixture is naturally cooled to the normal temperature; then grinding and crushing are carried out, and sieving is carried out to obtain the boron-phosphorus glass powder with the grain size specification of 10-30 um.
7. The method for preparing the ceramic antibiotic additive as claimed in claim 6, wherein in the glass frit preparing step, the mass ratio of Na2O, B2O3, P2O5, K2O, and Al2O3 is 10: 30: 40: 10: 10.
8. the method for preparing the ceramic antibiotic additive according to claim 5, wherein the silver powder has a particle diameter of about 10-20um and a density of 0.9-1g/cm3The specific surface area is 0.4m2/g。
9. A ceramic glaze, comprising the ceramic antibiotic additive prepared by the method for preparing the ceramic antibiotic additive according to any one of claims 5 to 8, wherein the ceramic antibiotic additive accounts for 0.5 to 2% of the total mass of the ceramic glaze.
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Cited By (1)
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| CN115636590A (en) * | 2022-10-08 | 2023-01-24 | 中建材玻璃新材料研究院集团有限公司 | Antibacterial glass powder, preparation method thereof and plastic antibacterial material |
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| CN115636590A (en) * | 2022-10-08 | 2023-01-24 | 中建材玻璃新材料研究院集团有限公司 | Antibacterial glass powder, preparation method thereof and plastic antibacterial material |
| CN115636590B (en) * | 2022-10-08 | 2024-03-12 | 中建材玻璃新材料研究院集团有限公司 | Antibacterial glass powder, preparation method thereof and plastic antibacterial material |
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