CN113526873B - Glass ceramic antibacterial powder and preparation method and application thereof - Google Patents

Glass ceramic antibacterial powder and preparation method and application thereof Download PDF

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Publication number
CN113526873B
CN113526873B CN202111090070.7A CN202111090070A CN113526873B CN 113526873 B CN113526873 B CN 113526873B CN 202111090070 A CN202111090070 A CN 202111090070A CN 113526873 B CN113526873 B CN 113526873B
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glass ceramic
antibacterial powder
powder
glass
antibacterial
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CN113526873A (en
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彭小晋
王祥乾
张天杰
王衔雯
赵本茂
章承华
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Foshan Sanshui Create Tide Co ltd
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Foshan Sanshui Create Tide Co ltd
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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
    • C03C12/00—Powdered glass; Bead compositions
    • 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
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • 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 discloses glass ceramic antibacterial powder and a preparation method and application thereof, relates to the technical field of antibacterial materials, and particularly relates to glass ceramic antibacterial powder and a preparation method and application thereof. The method comprises the following steps: weighing and mixing the raw materials to obtain a first mixture; mixing the first mixture with a dispersion liquid to obtain a first slurry; grinding, drying and powdering the first slurry to obtain a first powder material; melting the first powder at high temperature to obtain a first glass body; and heating and crystallizing the first glass body, and then crushing, grinding and sieving to obtain a finished product. The preparation method has the advantages of simple process, low cost, high yield, no agglomeration of the obtained powder particles and good filling property. Correspondingly, the prepared glass ceramic antibacterial powder has good high-temperature resistance and stable antibacterial performance, and can be used as an antibacterial agent to be added into ceramic glaze.

Description

Glass ceramic antibacterial powder and preparation method and application thereof
Technical Field
The invention relates to the technical field of antibacterial materials, in particular to glass ceramic antibacterial powder and a preparation method and application thereof.
Background
The demand of consumers for ceramics with antibacterial function is increasing, and the antibacterial function of ceramics is often realized by adding antibacterial powder in the ceramic industry. Most of the antibacterial powder used in the current antibacterial ceramics is Ag loaded by porous materials+、Zn+And Cu2+Or doped with TiO2Rare earth compounds, and the like. For example, chinese invention patent CN 110547302B discloses an antibacterial powder, a preparation method and use thereof, wherein the antibacterial powder uses silicon oxide as a carrier to load silver, copper and zinc composite metal elements. The antibacterial powder has the basic particle size of less than 10um, low cost and excellent antibacterial performance, contains various antibacterial metal ions, and can be widely applied to various materials such as plastics, textiles and the like to realize the antibacterial function. But the aboveThe antibacterial powder has complex preparation process, high cost and no high temperature resistance, and is not suitable for preparing the antibacterial ceramic tiles. In addition, rare earth compounds are selectively doped into part of the antibacterial powder, radiation can be generated to a human body while the antibacterial function is realized, the human body health is seriously injured, the development of the antibacterial ceramic tile is seriously limited by the problems, and the development of the high-temperature resistant antibacterial powder for the glaze, which is economical and practical and is suitable for large-scale production, is urgently needed.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of glass ceramic antibacterial powder, which has the advantages of simple process, low cost, high yield, no agglomeration of the obtained powder particles and good filling property.
The invention also aims to solve the technical problem of providing the glass ceramic antibacterial powder which has good high-temperature resistance and stable antibacterial performance.
The invention also aims to solve the technical problems that the application of the glass ceramic antibacterial powder is provided, and the obtained glaze surface has the advantages of thin thickness, uniform distribution, pure color development and good texture.
In order to achieve the technical effects, the invention provides a preparation method of glass ceramic antibacterial powder, which comprises the following steps:
s1, weighing the raw materials and mixing to obtain a first mixture;
s2, mixing the first mixture with a dispersion liquid to obtain a first slurry;
s3, grinding, drying and powdering the first slurry to obtain first powder;
s4, melting the first powder at high temperature to obtain a first glass body;
s5, heating and crystallizing the first glass body, and then crushing, grinding and sieving to obtain a finished product;
the prepared glass ceramic antibacterial powder comprises the following chemical components in percentage by mass:
SiO2 41~51%、ZrO2 1~2%、Al2O3 10~20%、B2O3 2~5%、ZnO 10~20%、MgO 1~4%、CaO 4~8%、Na2O 1~7%、K2O 3~4%。
preferably, 30 to 60 parts by weight of the dispersion is added per 100 parts by weight of the first mixture.
Preferably, the dispersion comprises, in mass percent: 80-90% of water, 10-20% of ethylene glycol and 1-5% of polyacrylate.
Preferably, in step S3, the first slurry is ground by ball milling at a rotation speed of 10 to 500r/min for 1 to 3 hours;
the drying conditions are as follows: keeping the temperature at 100-250 ℃ for 2-3.5 h.
Preferably, in step S4, the high-temperature melting conditions of the first powder lot are: preserving heat for 3-5 h at 1380-1650 ℃;
in step S5, the conditions for the heat crystallization process of the first glass body are: preserving the heat for 1-3 h at 950-1150 ℃.
Preferably, in step S5, a sand mill is used for grinding, the grinding speed of the sand mill is 2000-2800 rpm, and the grinding time is 1-3 hours;
the screening is carried out by adopting a screen with 300-350 meshes.
Preferably, the main crystal phase of the prepared glass ceramic antibacterial powder is spinel ZnAl2O4。
The invention also provides the glass ceramic antibacterial powder prepared by the method, which comprises the following chemical components in percentage by mass: SiO 22 41~51%、ZrO2 1~2%、Al2O3 10~20%、B2O3 2~5%、ZnO 10~20%、MgO 1~4%、CaO 4~8%、Na2O 1~7%、K2O 3~4%。
Preferably, the main crystal phase of the glass ceramic antibacterial powder is spinel type ZnAl2O4；
The maximum tolerance temperature of the glass ceramic antibacterial powder is 1100-1300 ℃.
The invention also provides application of the glass ceramic antibacterial powder, which is used as an antibacterial agent to be added into ceramic glaze.
The implementation of the invention has the following beneficial effects:
1. the invention provides a high-resistanceThe preparation method of the glass ceramic antibacterial powder for the warm glaze has the advantages of simple process, low cost and high yield, and is suitable for large-scale production. In the preparation process, simple high-temperature melting is utilized to obtain a basic glass body, and then specific heating crystallization treatment is carried out to obtain ZnAl with spinel type main crystal phase2O4The glass ceramic is crushed and ground to obtain the high-temperature resistant glass ceramic antibacterial powder for glaze.
2. The glass ceramic antibacterial powder provided by the invention has the advantages of no agglomeration of particles, regular shape, uniform size and narrow particle size distribution range. The main crystalline phase of the glass ceramic antibacterial powder is spinel ZnAl2O4And the spinel structure effectively ensures the high-temperature stability of ZnO and effectively improves the high-temperature antibacterial stability of the glass ceramic antibacterial powder.
3. The glass ceramic antibacterial powder provided by the invention can be used as an antibacterial agent to be applied to ceramic glaze, the performance of glaze slip is not influenced, and the glaze surface has pure color development and good texture. Under the condition of small addition amount of the glass ceramic antibacterial powder, the antibacterial ceramic tile prepared by using the ceramic glaze still has continuous and efficient antibacterial performance.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail below.
The invention provides a preparation method of glass ceramic antibacterial powder, which comprises the following steps:
s1, weighing the raw materials and mixing to obtain a first mixture;
s2, mixing the first mixture with a dispersion liquid to obtain a first slurry;
s3, grinding, drying and powdering the first slurry to obtain first powder;
s4, melting the first powder at high temperature to obtain a first glass body;
s5, heating and crystallizing the first glass body, and then crushing, grinding and sieving to obtain a finished product;
the prepared glass ceramic antibacterial powder comprises the following chemical components in percentage by mass:
SiO2 41~51%、ZrO2 1~2%、Al2O3 10~20%、B2O3 2~5%、ZnO 10~20%、MgO 1~4%、CaO 4~8%、Na2O 1~7%、K2O 3~4%。
the preparation method of the glass ceramic antibacterial powder has the advantages of simple process, low cost and high yield, and is suitable for large-scale production. In the preparation process, simple high-temperature melting is utilized to obtain a basic glass body, and then the ZnAl with spinel type main crystal phase is obtained by specific heating crystallization treatment2O4The glass ceramic is crushed and ground to obtain the high-temperature resistant glass ceramic antibacterial powder for glaze.
The above preparation steps are specifically described as follows.
S1, weighing the raw materials and mixing to obtain a first mixture. Preferably, the prepared glass ceramic antibacterial powder comprises the following chemical components in percentage by mass:
SiO2 41~51%、ZrO2 1~2%、Al2O3 10~20%、B2O3 2~5%、ZnO 10~20%、MgO 1~4%、CaO 4~8%、Na2O 1~7%、K2O 3~4%。
in the prior art, Ag is often loaded by porous materials+、Zn+And Cu2+Or doped with TiO2And rare earth compounds, etc. to achieve the antibacterial purpose. However, the additive has high cost, is not high temperature resistant and has unstable antibacterial effect, and particularly, the rare earth compound can also generate radiation to a human body. Therefore, the invention provides the glass ceramic antibacterial powder which can resist high temperature and has continuous and stable antibacterial effect, and the glass ceramic antibacterial powder specifically comprises the following chemical components:
ZnO is a main substance with antibacterial effect, and the antibacterial mechanism of ZnO is mainly as follows: when the light irradiation energy exceeds the forbidden band width of ZnO, electrons (e) on the valence band-) Excited to transit to the conduction band, leaving a positively charged hole (h) in the valence band+) The electrons and holes react with oxygen, hydroxyl and water adsorbed on the surface of the material to generate OH and O with strong oxidation activity2 -And H2O2And the like, which destroy the cell walls of bacteria, fungi and viruses, cause the outflow of organic matters such as proteins in cells and the like, influence the metabolic process of the organic matters, and finally kill various bacteria, fungi and viruses. However, the single ZnO component is a glaze flux, and can be melted at high temperature and lose antibacterial performance when directly added into the ceramic glaze, in order to take account of the glaze and the antibacterial performance, ZnO must be firstly melted in a basic vitreous body system, and then spinel phase zinc aluminate is separated out through a crystallization process, so as to ensure the high-temperature antibacterial performance of ZnO. More preferably, the content of ZnO in the basic glass body component is controlled to be 15-19%.
Crystallizing and separating out spinel type ZnAl by adopting a basic glass body system2O4The high temperature resistance matrix phase and the low temperature resistance function are combined, so that the high temperature resistance of ZnO can be improved, the ZnO is prevented from being melted by glaze at high temperature, and a stable and durable antibacterial effect is achieved. The Al is2O3When the content of (A) is too low, ZnAl is precipitated2O4The content is less, which is not beneficial to the antibacterial effect. When said Al is present2O3When the content of (A) is too high, the high-temperature viscosity of a glass system is large, the energy required in the crystallization process is higher, and the ZnAl cannot be easily precipitated2O4The crystal seriously affects the antibacterial effect of the glass ceramic antibacterial powder. Therefore, Al needs to be controlled2O3More preferably, the Al content2O3The content of (A) is 15-19%.
SiO2Is an important network skeleton component of the glass phase, SiO2The content is too small, a glass phase cannot be formed, and the subsequent crystallization process cannot be realized; however, the content of the silicon dioxide is too high, the crystallization degree of a basic vitreous body system is too low, and the content of spinel type zinc aluminate is too small, so that the antibacterial performance of the glass ceramic antibacterial powder is influenced. Therefore, it is more preferable to control the SiO2The content is 45-50%.
ZrO2Is a crystal nucleating agent and can induce a glass system to separate out spinel type ZnAl2O4More preferably, the ZrO2The content of (A) is controlled to be 1-2%.
B2O3Is an important fusing agent in the high-temperature melting process of a glass system, and preferably,b is2O3The content of (A) is controlled to be 3-4%.
The addition of MgO is favorable for improving the elasticity and the thermal shock resistance of the glass ceramic antibacterial powder, and preferably, the content of MgO is controlled to be 2-3%.
The CaO can improve the hand feeling of the glaze surface of the ceramic tile doped with the glass ceramic antibacterial powder, and preferably, the content of the CaO is controlled to be 5-7%.
Na2O and K2O reduces the melting temperature of the whole glass system, is favorable for quickly forming a glass liquid phase and facilitating the subsequent crystallization process, and better, the Na2O and K2The content of O is controlled to be 2-6% and 3.5-4% respectively.
In conclusion, the ZnAl with spinel type main crystal phase is obtained by heating and crystallizing the basic glass body with specific chemical components2O4The glass ceramic antibacterial powder for the high-temperature resistant glaze. The glass ceramic antibacterial powder has good and stable antibacterial effect, and tests show that the glass ceramic antibacterial powder is used as an antibacterial agent and added into ceramic glaze, so that the antibacterial effect of the prepared antibacterial ceramic tile on staphylococcus aureus is more than or equal to 99.99%, and the antibacterial effect of the prepared antibacterial ceramic tile on escherichia coli is more than or equal to 99.99%. Moreover, the glass ceramic antibacterial powder provided by the invention is applied to ceramic glaze as an antibacterial agent, the performance of glaze slip is not affected, and the glaze surface has pure color and good texture.
S2, mixing the first mixture with a dispersion liquid to obtain a first slurry;
specifically, the addition amount of the dispersion liquid is not too large, which will increase the subsequent grinding and drying treatment amount, but the addition amount of the dispersion liquid is too small, which will affect the dispersion effect, and preferably, 30 to 60 parts by weight of the dispersion liquid is added per 100 parts by weight of the first mixture.
The dispersion comprises three components of water, glycol and polyacrylate. Preferably, the dispersion comprises, in mass percent: 80-90% of water, 10-20% of ethylene glycol and 1-5% of polyacrylate. The polyacrylate is a dispersant, and for the grinding-aid effect in the slurry grinding process, the polyacrylate is preferably sodium polyacrylate, and more preferably, the mass percentage of the polyacrylate is 2-4%.
In addition, in order to further reduce the Zeta potential of the whole dispersion system and improve the dispersion stability of the first slurry, the pH of the dispersion liquid is controlled to be 6-7.
S3, grinding, drying and powdering the first slurry to obtain first powder;
the invention adopts a melting crystallization method to prepare the glass ceramic antibacterial powder, and wet grinding and mixing are an important process in order to ensure that the components of the first slurry are uniformly distributed. Specifically, the first slurry is ground by ball milling, preferably, the ball milling speed is 10-500 r/min, and the ball milling time is 1-3 h. And screening the slurry after ball milling, preferably, enabling the first slurry prepared by the ball milling process to pass through a 300-400-mesh screen.
The first slurry after grinding needs to be dried, preferably, the drying conditions are as follows: keeping the temperature at 100-250 ℃ for 2-3.5 h.
S4, melting the first powder at high temperature to obtain a first glass body;
in the process of preparing the glass ceramic antibacterial powder by the melting crystallization method, high-temperature melting is one of the most critical processes, and in order to ensure that the ion migration of a glass system is complete, the component distribution is complete, and the component volatilization is effectively reduced in a high-temperature melting state, preferably, the high-temperature melting conditions of the first powder are as follows: preserving the heat for 3-5 h at 1380-1650 ℃. Under the high-temperature melting condition, ions in the high-temperature glass melt are more convenient to migrate and more uniform in distribution, so that the subsequent crystallization process is convenient to realize. More preferably, the high-temperature melting conditions of the first powder are as follows: preserving the heat for 3-5 h at 1400-1600 ℃.
S5, heating and crystallizing the first glass body again, and then crushing, grinding and sieving to obtain a finished product;
and (3) heating the first glass body obtained after high-temperature melting for crystallization treatment: promoting zinc aluminate ZnAl in glass system2O4Separating out spinel crystals; increasing ZnAl content in zinc aluminate2O4The crystallinity of (2) and the phase ratio of (3) are improved. Preferably, the first glass body is subjected toThe conditions of the crystallization treatment are as follows: preserving the heat for 1-3 h at 950-1150 ℃.
And crushing, grinding and sieving the first glass body after crystallization treatment to obtain a finished product. Preferably, a sand mill is adopted for wet grinding, the particle size of the final glass ceramic antibacterial powder is influenced by the technological parameters of the sand mill, the grinding speed of the sand mill is 2000-2800 rpm, and the grinding time is 1-3 h. And finally, sieving the sanded semi-finished product to obtain a finished product, wherein the finished product is preferably sieved by using a 300-350-mesh sieve. Preferably, D is finally obtained100Glass ceramic antibacterial powder less than or equal to 25 um.
In conclusion, the preparation method provided by the invention has the advantages of simple process, low cost and high yield, and is suitable for large-scale production. In the preparation process, the glass ceramic antibacterial powder which is high temperature resistant and has zinc aluminate as the main crystal phase is obtained by a simple high-temperature melting crystallization method. And the glass ceramic antibacterial powder with uniform particle size, no agglomeration and narrow particle size distribution range is obtained by adopting a water milling mode of combining ball milling and sanding.
The glass ceramic antibacterial powder is obtained according to the preparation method, and preferably comprises the following chemical components in percentage by mass: SiO 22 41~51%、ZrO2 1~2%、Al2O3 10~20%、B2O3 2~5%、ZnO 10~20%、MgO 1~4%、CaO 4~8%、Na2O 1~7%、K2O 3~4%。
Further, the glass ceramic antibacterial powder has good high temperature resistance and antibacterial performance, and preferably, the main crystal phase of the glass ceramic antibacterial powder is spinel type ZnAl2O4(ii) a The maximum tolerance temperature of the glass ceramic antibacterial powder is 1100-1300 ℃.
Tests prove that the antibacterial effect of the prepared antibacterial ceramic tile on staphylococcus aureus is more than or equal to 99.99% and the antibacterial effect on escherichia coli is more than or equal to 99.99% when the antibacterial powder of glass ceramic is used as an antibacterial agent and added into ceramic glaze. Moreover, the glass ceramic antibacterial powder provided by the invention is applied to ceramic glaze as an antibacterial agent, the performance of glaze slip is not affected, and the glaze surface has pure color and good texture. The invention is further illustrated by the following specific examples:
example 1
A preparation method of glass ceramic antibacterial powder comprises the following steps:
s1, weighing the raw materials and mixing to obtain a first mixture;
s2, mixing the first mixture with a dispersion liquid to obtain a first slurry;
30 parts by weight of the dispersion are added per 100 parts by weight of the first mix. The dispersion comprises the following components in percentage by mass: 80% of water, 19% of ethylene glycol and 1% of sodium polyacrylate.
S3, grinding, drying and powdering the first slurry to obtain first powder;
carrying out wet grinding on the first slurry by adopting ball milling, wherein the ball milling rotation speed is 450 r/min, and the ball milling time is 1 h;
the drying conditions are as follows: the temperature is kept at 100 ℃ for 3.5 h.
S4, melting the first powder at high temperature to obtain a first glass body;
the high-temperature melting conditions of the first powder are as follows: the temperature is kept at 1400 ℃ for 5 h.
S5, heating and crystallizing the first glass body, and then crushing, grinding and sieving to obtain a finished product;
the crystallization processing conditions of the first glass body are as follows: the temperature is kept at 1000 ℃ for 3 h.
Wet grinding is carried out by adopting a sand mill, the grinding rotating speed of the sand mill is 2100rpm, and the grinding time is 3 hours;
sieving with 325 mesh sieve to obtain the final product.
The chemical composition of the finally prepared glass ceramic antibacterial powder comprises the following components in percentage by mass:
SiO2 42%、ZrO2 1.2%、Al2O3 20%、B2O3 4%、ZnO 18%、MgO 3%、CaO 6%、Na2O 2%、K2O 3.8%。
example 2
A preparation method of glass ceramic antibacterial powder comprises the following steps:
s1, weighing the raw materials and mixing to obtain a first mixture;
s2, mixing the first mixture with a dispersion liquid to obtain a first slurry;
50 parts by weight of the dispersion are added per 100 parts by weight of the first mix. The dispersion comprises the following components in percentage by mass: 80% of water, 15% of ethylene glycol and 5% of sodium polyacrylate.
S3, grinding, drying and powdering the first slurry to obtain first powder;
carrying out wet grinding on the first slurry by adopting ball milling, wherein the ball milling rotation speed is 50 r/min, and the ball milling time is 3 h;
the drying conditions are as follows: the temperature is kept at 250 ℃ for 2 h.
S4, melting the first powder at high temperature to obtain a first glass body;
the high-temperature melting conditions of the first powder are as follows: keeping the temperature at 1380 ℃ for 3.5 h.
S5, heating and crystallizing the first glass body, and then crushing, grinding and sieving to obtain a finished product;
the crystallization processing conditions of the first glass body are as follows: the temperature is kept at 950 ℃ for 2 h.
Carrying out wet grinding by using a sand mill, wherein the grinding rotating speed of the sand mill is 2000rpm, and the grinding time is 1 h;
sieving with 350 mesh sieve to obtain the final product.
The chemical composition of the finally prepared glass ceramic antibacterial powder comprises the following components in percentage by mass:
SiO2 46%、ZrO2 1.8%、Al2O3 17%、B2O3 3%、ZnO 16%、MgO 3%、CaO 5%、Na2O 5%、K2O 3.2%。
example 3
A preparation method of glass ceramic antibacterial powder comprises the following steps:
s1, weighing the raw materials and mixing to obtain a first mixture;
s2, mixing the first mixture with a dispersion liquid to obtain a first slurry;
60 parts by weight of the dispersion are added per 100 parts by weight of the first mix. The dispersion comprises the following components in percentage by mass: 80% of water, 16% of ethylene glycol and 4% of potassium polyacrylate.
S3, grinding, drying and powdering the first slurry to obtain first powder;
carrying out wet grinding on the first slurry by adopting ball milling, wherein the ball milling rotation speed is 500r/min, and the ball milling time is 1 h;
the drying conditions are as follows: the temperature is kept at 200 ℃ for 2.5 h.
S4, melting the first powder at high temperature to obtain a first glass body;
the high-temperature melting conditions of the first powder are as follows: the temperature was maintained at 1650 ℃ for 5 h.
S5, heating and crystallizing the first glass body, and then crushing, grinding and sieving to obtain a finished product;
the crystallization processing conditions of the first glass body are as follows: keeping the temperature at 1150 ℃ for 2.5 h.
Carrying out wet grinding by using a sand mill, wherein the grinding rotating speed of the sand mill is 2400rpm, and the grinding time is 1.5 h;
and sieving the mixture by using a 300-mesh sieve to obtain a finished product.
The chemical composition of the finally prepared glass ceramic antibacterial powder comprises the following components in percentage by mass:
SiO2 50%、ZrO2 2%、Al2O3 12%、B2O3 5%、ZnO 12%、MgO 2%、CaO 7%、Na2O 6%、K2O 4%。
example 4
A preparation method of glass ceramic antibacterial powder comprises the following steps:
s1, weighing the raw materials and mixing to obtain a first mixture;
s2, mixing the first mixture with a dispersion liquid to obtain a first slurry;
60 parts by weight of the dispersion are added per 100 parts by weight of the first mix. The dispersion comprises the following components in percentage by mass: 85% of water, 10% of ethylene glycol and 5% of sodium polyacrylate.
S3, grinding, drying and powdering the first slurry to obtain first powder;
carrying out wet grinding on the first slurry by adopting ball milling, wherein the ball milling rotation speed is 450 r/min, and the ball milling time is 1 h;
the drying conditions are as follows: the temperature is kept at 150 ℃ for 3 h.
S4, melting the first powder at high temperature to obtain a first glass body;
the high-temperature melting conditions of the first powder are as follows: the temperature is kept at 1450 ℃ for 4.5 h.
S5, crystallizing the first glass body, crushing, grinding and sieving to obtain a finished product;
the crystallization processing conditions of the first glass body are as follows: the temperature is kept for 1.5h at 1150 ℃.
Wet grinding is carried out by adopting a sand mill, the grinding rotating speed of the sand mill is 2100rpm, and the grinding time is 3 hours;
sieving with 350 mesh sieve to obtain the final product.
The chemical composition of the finally prepared glass ceramic antibacterial powder comprises the following components in percentage by mass:
SiO2 51%、ZrO2 2%、Al2O3 10%、B2O3 5%、ZnO 10%、MgO 3%、CaO 8%、Na2O 7%、K2O 4%。
example 5
Example 5 the same preparation method as in example 1 was used, except that the firing conditions in step S4 were different. The firing conditions in step S4 of example 5 are as follows:
the high-temperature melting conditions of the first powder are as follows: keeping the temperature at 1200 ℃ for 2 h.
Example 6
Example 6 the same preparation method as that of example 1 was used, except that the firing conditions in step S4 were different. The firing conditions in step S4 of example 6 are as follows:
the high-temperature melting conditions of the first powder are as follows: the temperature is kept at 1800 ℃ for 3 h.
Example 7
Example 7 was prepared in the same manner as example 1, except that the crystallization conditions in step S5 were different. The crystallization conditions of step S5 of example 7 are as follows:
the crystallization processing conditions of the first glass body are as follows: the temperature is kept at 800 ℃ for 3 h.
Example 8
Example 8 was conducted in the same manner as example 1 except that the crystallization conditions in step S5 were different. The crystallization conditions of step S5 of example 8 are as follows:
the crystallization processing conditions of the first glass body are as follows: incubate at 1300 ℃ for 3 h.
Comparative example 1
A preparation method of antibacterial powder comprises the following steps:
s1, weighing the raw materials and mixing to obtain a first mixture;
s2, mixing the first mixture with a dispersion liquid to obtain a first slurry;
30 parts by weight of the dispersion are added per 100 parts by weight of the first mix. The dispersion comprises the following components in percentage by mass: 80% of water, 19% of ethylene glycol and 1% of sodium polyacrylate.
S3, grinding, drying and powdering the first slurry to obtain first powder;
carrying out wet grinding on the first slurry by adopting ball milling, wherein the ball milling rotation speed is 450 r/min, and the ball milling time is 1 h;
the drying conditions are as follows: the temperature is kept at 100 ℃ for 3.5 h.
S4, carrying out water quenching on the first powder after high-temperature melting to obtain a frit;
the high-temperature melting conditions of the first powder are as follows: keeping the temperature at 1400 ℃ for 5h, then carrying out water quenching treatment, and rapidly cooling to normal temperature.
S5, crushing, grinding and sieving the frit to obtain a finished product;
grinding by a sand mill, wherein the grinding speed of the sand mill is 2100rpm, and the grinding time is 3 h;
sieving with 325 mesh sieve to obtain the final product.
The glass ceramic antibacterial powder obtained in examples 1 to 8 and comparative example 1 was used as an antibacterial agent and added to ceramic glaze, antibacterial ceramic tile samples were prepared, and the samples were subjected to antibacterial effect tests of staphylococcus aureus and escherichia coli, respectively, and the specific test results are shown in table 1. Test results show that the high-temperature resistant glass ceramic antibacterial powder prepared by the preparation method provided by the invention has a good antibacterial effect in ceramic glaze.
Table 1 results of antibiotic test of antibiotic tile samples to which the glass ceramic antibiotic powders of examples 1 to 8 and comparative example 1 were added (%)
Figure 153744DEST_PATH_IMAGE001
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.

Claims (9)

1. The preparation method of the glass ceramic antibacterial powder is characterized by comprising the following steps:
s1, weighing the raw materials and mixing to obtain a first mixture;
s2, mixing the first mixture with a dispersion liquid to obtain a first slurry;
s3, grinding, drying and powdering the first slurry to obtain first powder;
s4, melting the first powder at high temperature to obtain a first glass body;
s5, heating and crystallizing the first glass body, and then crushing, grinding and sieving to obtain a finished product;
the chemical composition of the prepared glass ceramic antibacterial powder comprises the following components in percentage by mass:
SiO2 41~51%、ZrO2 1~2%、Al2O3 10~20%、B2O3 2~5%、ZnO 10~20%、MgO 1~4%、CaO 4~8%、Na2O 1~7%、K2O 3~4%；
in step S4, the high-temperature melting conditions of the first powder material are: preserving heat for 3-5 h at 1380-1650 ℃;
in step S5, the conditions for the heat crystallization process of the first glass body are: preserving the heat for 1-3 h at 950-1150 ℃.
2. The method for preparing glass ceramic antibacterial powder according to claim 1, wherein 30 to 60 parts by weight of the dispersion is added per 100 parts by weight of the first mixture.
3. The method for preparing glass ceramic antibacterial powder according to claim 1, wherein the dispersion comprises, by mass: 80-90% of water, 10-20% of ethylene glycol and 1-5% of polyacrylate.
4. The preparation method of glass ceramic antibacterial powder according to claim 1, wherein in step S3, the first slurry is ground by ball milling, the rotation speed of the ball milling is 10 to 500r/min, and the ball milling time is 1 to 3 hours;
the drying conditions are as follows: keeping the temperature at 100-250 ℃ for 2-3.5 h.
5. The method for preparing glass ceramic antibacterial powder according to claim 1, wherein in step S5, a sand mill is adopted for grinding, the grinding speed of the sand mill is 2000-2800 rpm, and the grinding time is 1-3 h;
the screening is carried out by adopting a screen with 300-350 meshes.
6. The method for preparing glass ceramic antibacterial powder according to claim 1, wherein the main crystal phase of the prepared glass ceramic antibacterial powder is spinel type ZnAl2O4。
7. The glass ceramic antibacterial powder is characterized by being prepared by the preparation method of any one of claims 1 to 6, and comprising the following chemical components in percentage by mass: SiO 22 41~51%、ZrO2 1~2%、Al2O3 10~20%、B2O3 2~5%、ZnO 10~20%、MgO 1~4%、CaO 4~8%、Na2O 1~7%、K2O 3~4%。
8. The glass-ceramic antibacterial powder according to claim 7, wherein the main crystal phase of the glass-ceramic antibacterial powder is spinel type ZnAl2O4；
The maximum tolerance temperature of the glass ceramic antibacterial powder is 1100-1300 ℃.
9. Use of a glass ceramic antibacterial powder, characterized in that the glass ceramic antibacterial powder according to any one of claims 7 to 8 is used as an antibacterial agent added to ceramic glazes.
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