CN113248146B - Composite process antibacterial ceramic tile and preparation method thereof - Google Patents
Composite process antibacterial ceramic tile and preparation method thereof Download PDFInfo
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- CN113248146B CN113248146B CN202110616830.7A CN202110616830A CN113248146B CN 113248146 B CN113248146 B CN 113248146B CN 202110616830 A CN202110616830 A CN 202110616830A CN 113248146 B CN113248146 B CN 113248146B
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
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- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
- C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
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- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
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- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
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- 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
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Abstract
The invention relates to the technical field of new building ceramic materials, and particularly discloses a composite process antibacterial ceramic tile and a preparation method thereof. The composite process antibacterial ceramic tile comprises a green body layer and an antibacterial glaze layer, wherein glaze of the antibacterial glaze layer contains a first antibacterial agent, and micropores on the surface of the antibacterial glaze layer are filled with an antibacterial antifouling agent; the first antibacterial agent comprises zinc silicate and/or zinc aluminate, the antibacterial antifouling agent comprises a second antibacterial agent, and the second antibacterial agent comprises nano zinc phosphate and/or nano zinc zirconate. The preparation method comprises the following steps: firstly, preparing a blank layer, then preparing antibacterial glaze slip, spraying the antibacterial glaze slip on the surface of the blank layer, firing to obtain a semi-finished product, polishing the semi-finished product, and polishing the surface of the semi-finished product by using an antibacterial antifouling agent to obtain the antibacterial ceramic tile. The invention adopts the composite antibacterial process of antibacterial in glaze and antibacterial in micropores on the surface of the glaze layer, realizes high-efficiency and lasting antibacterial of ceramic tile products, and the antibacterial components do not influence the permeability of the glaze and can realize the antifouling performance of the glaze.
Description
Technical Field
The invention relates to the technical field of new building ceramic materials, in particular to a functional ceramic material, and specifically relates to a composite process antibacterial ceramic tile and a preparation method thereof.
Background
Currently, for non-polished ceramic tiles, the following types of antibacterial ceramics are mainly used: the first method is to add the antibacterial material into the ceramic tile directly to mix and burn, and the antibacterial agent is silver phosphate generally. The second method is to spray the antibacterial material on the surface of the ceramic tile, and the antibacterial material is prepared by spraying the antibacterial mixed salt solution on the surface of the transparent glaze to form an antibacterial layer and firing the antibacterial layer at high temperature. And thirdly, spraying an antibacterial material on the surface of the finished brick, and then carrying out low-temperature heat treatment to realize the antibacterial effect. Wherein: the first antibacterial ceramic is prepared by directly adding the antibacterial material into a ceramic tile blank or glaze and firing, and the antibacterial effective components of the first antibacterial ceramic are coated in the blank or glaze, so that the antibacterial effect is greatly reduced. The second antibacterial material is sprayed on the surface of the ceramic tile and then is sintered, the structure of the antibacterial material is damaged after high-temperature heat treatment, the antibacterial effect is obviously reduced, and a certain amount of antibacterial material is attached to the surface of the ceramic tile and is easy to react with the glaze surface during high-temperature heat treatment to influence the surface decoration effect. And in the third method, the binding force between the antibacterial layer and the glaze surface is weak by adopting low-temperature heat treatment, the antibacterial layer is easy to fall off in practical application, and the antibacterial durability is poor. The methods are widely applied to non-polished ceramic tiles.
In recent years, polished tile products are very popular, and the antibacterial function of the polished tile products is mainly added in two ways, namely, the antibacterial and antifouling liquid is filled in micropores on the surface of a glaze through a polishing process, and the antibacterial and antifouling liquid is added in a glaze layer and combined with the antibacterial and antifouling liquid, namely, the two processes are combined. Firstly, zinc oxide or silver oxide is used as an antibacterial material in the antibacterial and antifouling liquid adopted in the prior art, the two types of oxides are very easy to react with acid to generate a zinc ion or silver ion salt solution, and the antibacterial material is easily washed off in the washing process, so that the antibacterial durability is poor. Secondly, the antibacterial agent added in the glaze layer is mostly a carrier-loaded zinc-silver material, such as zirconium phosphate doped zinc-silver or zirconium silicate doped zinc-silver, and the carrier material belongs to an opacifier for ceramics and has direct influence on the permeability of glaze polishing.
Disclosure of Invention
The invention provides a composite process antibacterial ceramic tile and a preparation method thereof, which are used for solving one or more technical problems in the prior art and at least providing a beneficial selection or creation condition.
In order to overcome the technical problems, the technical scheme adopted by the invention is as follows:
a composite process antibacterial ceramic tile comprises a green body layer and an antibacterial glaze layer; the glaze of the antibacterial glaze layer contains a first antibacterial agent, and micropores on the surface of the antibacterial glaze layer are filled with an antibacterial antifouling agent;
the first antimicrobial agent comprises zinc silicate and/or zinc aluminate; the antibacterial antifouling agent contains a second antibacterial agent, and the second antibacterial agent comprises nano zinc phosphate and/or nano zinc zirconate.
For the polished glazed ceramic tile, the polished surface of the glaze layer can expose fine micropores which are easy to hide dirt and provide a breeding space for microbial bacteria, so that the glaze layer of the polished glazed ceramic tile needs to be antibacterial, and the micropores on the surface of the glaze layer also need to be antibacterial. According to the invention, the first antibacterial agent is added into the glaze of the antibacterial glaze layer, the antibacterial antifouling agent is filled in the surface micropores of the antibacterial glaze layer, and the antibacterial antifouling agent contains the second antibacterial agent, so that the efficient and lasting antibacterial effect of the ceramic tile is realized by adopting a composite antibacterial process.
Specifically, the first antibacterial agent comprises zinc silicate and/or zinc aluminate, the zinc silicate and/or zinc aluminate is added into the glaze, and when the glaze is fired at high temperature, silica-alumina is used as a glass network structure, and zinc is distributed in the glaze melt as a glass network free component. After polishing, the glaze surface is uniformly distributed with zinc, and the zinc elements can be slowly released into the microbial bacteria body in the form of zinc ions in a humid environment to prevent the microbial bacteria from proliferating, so that the bacteriostatic and antibacterial effects are achieved.
Meanwhile, silicon, aluminum and zinc are common components in the transparent glaze, the antibacterial agent is introduced in the form of zinc silicate and/or zinc aluminate, other elements are not added, the antibacterial agent can be melted into a high-temperature glass melt to form a glass body, and the transparency of a glaze layer is not influenced. Compared with the zirconium phosphate zinc silver doped or zirconium silicate zinc silver doped antibacterial agent adopted in the prior art, the antibacterial agent has the advantages that the zinc silver loading amount is very small, the carrier is mainly added into the glaze, the carriers are mostly high-temperature resistant and stable crystal materials such as zirconium silicate, the crystal materials are not easy to melt in a glass melt and exist in independent crystal forms, the refractive index of the crystal materials is larger than that of the glass melt, the opacifying effect is easily generated, and the transparency of a glaze layer is influenced.
The second antibacterial agent comprises nano zinc phosphate and/or nano zinc zirconate, wherein the nano zinc phosphate and/or nano zinc zirconate contains an antibacterial effective component zinc, and zinc element can be slowly released in a zinc ion form in a humid environment to enter a microbial bacterium body to prevent the microbial bacterium from proliferating, so that the antibacterial effect is achieved.
Meanwhile, the zinc phosphate and the zinc zirconate have stable performance and cannot react with acetic acid substances, and the glaze surface of the antibacterial ceramic tile prepared by the composite process has good acid resistance in the using process, so that the phenomenon of non-antifouling of the glaze surface caused by the reaction consumption of the antibacterial components in the antibacterial antifouling agent by the acetic acid substances is avoided.
In some embodiments of the present application, the antimicrobial antifouling agent further comprises silica sol, and preferably, the silica sol is nano silica sol.
Specifically, the antibacterial and antifouling agent contains solid antibacterial particles, namely nano zinc phosphate and/or nano zinc zirconate, the solid antibacterial particles are filled in micropores on the surface of the glaze layer, and meanwhile, the nano silica sol firmly seals the solid antibacterial particles in the micropores on the surface of the glaze layer in the process of curing to form a film, so that the micropores are filled with the nano-scale solid antibacterial particles, and other pollutants are effectively prevented from entering, and the antifouling and antibacterial effects are realized.
In some embodiments of the present application, the antimicrobial antifouling agent has a solid content of 8 to 12%. Specifically, the solid content is mass percent, and the antibacterial antifouling agent with a certain solid content can effectively guarantee the antibacterial performance of the antibacterial antifouling agent.
In some embodiments of the present application, the chemical composition of the green layer feedstock comprises, in weight percent: SiO 22 65~67%、Al2O3 24~25%、Fe2O3 0.6~0.8%、TiO2 0.05~0.15%、CaO 1.0~1.2%、MgO 0.3~0.5%、K2O 2.9~3.1%、Na2O2.5-3.5%. Specifically, the raw material of the green body layer is selected from the green body raw materials of common polished glazed bricks.
In some embodiments of the present application, the glaze of the antimicrobial glaze layer further comprises a base glaze, and the glaze composition comprises, in parts by weight: 2-8 parts of a first antibacterial agent and 92-98 parts of a basic glaze. Specifically, the specific antibacterial agent and the basic glaze material are prepared according to a formula, so that the antibacterial performance of the glaze layer is guaranteed, and the glaze effect of the basic glaze material is not influenced.
Further, the chemical composition of the base glaze material comprises, by weight: SiO 22 55~57%、Al2O3 19~21%、Fe2O3 0.15~0.25%、TiO2 0.15~0.25%、CaO 10~12%、MgO 3.5~4.5%、ZnO 5.0~6.5%、K2O 0.25~0.55%、Na2O 3.0~4.5%。
Specifically, the basic glaze is composed of transparent zinc-containing glaze polishing, and on one hand, the basic glaze contains the same components of silicon, aluminum and zinc as the first antibacterial agent, so that the first antibacterial agent and the basic glaze are mutually fused at high temperature, and the transparency of the glaze is not influenced; on the other hand, the formula composition of the basic glaze is matched with the formula composition of the green body layer, so that the optimal green glaze adaptability is achieved, and the product performance stability of the antibacterial ceramic tile is guaranteed.
The invention also provides a technical scheme that the preparation method of the composite process antibacterial ceramic tile comprises the following steps:
s1, taking raw materials of the green body layer to obtain the green body layer;
s2, adding a first antibacterial agent into the basic glaze, grinding to obtain antibacterial glaze slurry, spraying the antibacterial glaze slurry on the surface of the green body layer, and sintering to obtain a semi-finished product;
s3, performing surface polishing on the semi-finished product to obtain a polished ceramic tile;
and S4, adding a second antibacterial agent into a dispersing agent, grinding, adding into silica sol, mixing to obtain an antibacterial antifouling agent, dripping the antibacterial antifouling agent on the surface of the polished ceramic tile, and polishing and grinding the surface of the polished ceramic tile to obtain the antibacterial ceramic tile.
In some embodiments of the present application, a method for making a composite process antibacterial ceramic tile comprises the steps of:
s1, uniformly mixing the raw materials of the green body layer, performing ball milling, spray molding, press molding, drying, spraying ground coat, and performing ink-jet pattern printing to obtain the green body layer;
s2, adding a first antibacterial agent into the basic glaze, performing wet ball milling, deironing and homogenization to obtain antibacterial glaze slurry, spraying the antibacterial glaze slurry on the surface of the green body layer, and firing in a kiln to obtain a semi-finished product;
s3, cutting edges of the semi-finished product, and polishing the surface of the semi-finished product to obtain a polished ceramic tile;
s4, adding water and a dispersing agent into the second antibacterial agent, stirring to form slurry, pouring the slurry into a sand mill, grinding at a high speed for 1-2 hours, adding the slurry into the nano silica sol, mixing uniformly, adjusting the pH value of the mixed solution, dispersing the mixed solution into a stable mixed solution by using a high-speed stirring dispersion machine to prepare the antibacterial antifouling agent, dripping the antibacterial antifouling agent on the surface of the polished ceramic tile, polishing the surface of the polished ceramic tile by using a high-pressure grinding disc, and polishing by using common wax water to obtain the antibacterial ceramic tile.
In some embodiments of the present application, the wet ball milling in step S2 is performed for 7 to 9 hours, and the solid content of the antibacterial glaze slip is 60 to 65%.
In some embodiments of the present application, the firing temperature in the firing in step S2 is 1200 to 1230 ℃, and the firing period is 55 to 65 minutes.
In some embodiments of the present application, the dispersant of step S4 is aminopropyltriethoxysilane, and the amount of the dispersant added is 2-3% of the slurry. Particularly, the specific dispersing agent and the appropriate dosage are beneficial to the dispersion and the stable performance of the second antibacterial agent.
In some embodiments of the present application, the volume ratio of the nano antibacterial solution to the aqueous silica sol solution in step S4 is 1: 3-4, the high-speed stirring speed is 1000-1200 r/min, and the pH value of the antibacterial antifouling agent is 7-8. The suspension stability of the silica sol can be ensured by adjusting the pH value of the antibacterial and antifouling agent, and the sol is prevented from precipitating, so that the antifouling and antibacterial performance of the ceramic tile is influenced.
In some embodiments of the present application, the grinding medium of the sand mill in step S4 is yttrium-stabilized zirconia microspheres, the diameter of the microspheres is 0.3 to 0.6 mm, the volume filling rate of the microspheres is 75 to 85%, and the rotation speed of the sand mill is 1850 to 2100 rpm.
Specifically, the combination of grinding by a sand mill and high-speed stirring and dispersion is adopted, and a grinding medium with a specific size, a material ball ratio and a grinding speed are selected, so that the effective and uniform dispersion of the nano antibacterial particles can be ensured, the better antibacterial performance of the nano antibacterial particles can be exerted, and the stability of the antibacterial effect is facilitated.
In some embodiments of the present application, in step S4, the amount of the mixed solution is 50 to 80 g/m, the number of the high-pressure grinding discs is 9, the grinding discs are made of wool felt, the pressure of the grinding discs to the brick surface is 50 to 80Pa, and the common wax is a glycol solution containing silicon resin.
The technical scheme provided by the embodiment of the application at least has the following technical effects or advantages:
according to the invention, zinc silicate and zinc aluminate are used as the antibacterial agent in the glaze, and the components of the zinc silicate and the zinc aluminate are the same as the components of silicon, aluminum and zinc in the glaze, so that the zinc silicate and the zinc aluminate can be mutually fused at high temperature, the transparency of glaze polishing is not influenced, and the defects caused by opalescence of a common carrier type antibacterial agent are avoided.
The invention adopts the nano zinc phosphate and the nano zinc zirconate as the pore-filling antibacterial material of the micropores of the glaze surface, and the antibacterial ceramic tile does not react with acetic acid acidic substances due to the excellent chemical resistance stability, so that the glaze surface has good acid resistance in the using process of the antibacterial ceramic tile, and the problem that the glaze surface is not antifouling due to the fact that the glaze surface is easily consumed by the reaction of the acetic acid acidic substances when zinc oxide, silver oxide and the like are directly adopted as antibacterial agents is avoided.
The invention adopts the composite antibacterial process of antibacterial in glaze and antibacterial in micropores on the surface of the glaze layer, realizes high-efficiency and lasting antibacterial of ceramic tile products, and the antibacterial components do not influence the permeability of the glaze and can realize the antifouling performance of the glaze.
Detailed Description
The present invention is described in detail below by way of examples to facilitate understanding of the present invention by those skilled in the art, and it is to be specifically noted that the examples are provided only for the purpose of further illustrating the present invention and are not to be construed as limiting the scope of the present invention.
Example 1
A composite process antibacterial ceramic tile comprises a green body layer and an antibacterial glaze layer, wherein: the chemical composition of the green body layer raw materials comprises the following components in percentage by weight: SiO 22 66.76%、Al2O3 24.87%、Fe2O3 0.71%、TiO2 0.15%、CaO 1.15%、MgO 0.32%、K2O 3.05%、Na2O 2.89%。
The glaze of the antibacterial glaze layer contains a first antibacterial agent and a basic glaze, wherein the first antibacterial agent is zinc silicate, the addition amount of the zinc silicate is 8 parts, the basic glaze is 92 parts, and the chemical composition of the basic glaze comprises SiO in percentage by mass2 56.07%、Al2O319.77%、Fe2O3 0.24%、TiO2 0.25%、CaO 10.74%、MgO 4.41%、ZnO 5.13%、K2O 0.25%、Na2O 3.14%。
The surface micropores of the antibacterial glaze layer are filled with antibacterial antifouling agents, the antibacterial antifouling agents contain second antibacterial agents and nano silica sol, the second antibacterial agents are nano zinc phosphate, and the solid content of the antibacterial antifouling agents is 12%.
The preparation method of the composite process antibacterial ceramic tile comprises the following steps:
s1, uniformly mixing the raw materials of the green body layer, performing ball milling, spray molding, press molding, drying, spraying ground coat, and performing ink-jet pattern printing to obtain the green body layer;
s2, adding zinc silicate into the basic glaze, performing wet ball milling for 7 hours, removing iron and homogenizing to obtain antibacterial glaze slurry with solid content of 65%, spraying the antibacterial glaze slurry on the surface of the blank, and sintering at 1200 ℃ for 55 minutes in a kiln to obtain a semi-finished product;
s3, cutting edges of the semi-finished product, and polishing the surface of the semi-finished product to obtain a polished ceramic tile;
s4, adding water and 3% of aminopropyltriethoxysilane dispersing agent into nano zinc phosphate, stirring to form slurry, then pouring the slurry into a sand mill, and grinding for 2 hours at high speed, wherein the grinding medium of the sand mill is yttrium stabilized zirconia microspheres, the diameter of the microspheres is 0.3 mm, the volume filling rate of the microspheres is 75%, the rotating speed of the sand mill is 1850 r/min, so as to obtain a nano antibacterial solution, and the volume ratio of the nano antibacterial solution to the aqueous silica sol solution is 1: 3, mixing, adjusting the pH value to 7.5, dispersing the mixture into a stable mixed solution by adopting a high-speed stirring dispersion machine, stirring at the speed of 1000 r/min to prepare the antibacterial antifouling agent, dripping the antibacterial antifouling agent on the surface of the polished ceramic tile according to 70 g/square meter, polishing and grinding at high speed by adopting 9 groups of high-pressure grinding discs, adjusting the pressure of the grinding discs on the surface of the ceramic tile to be 50Pa, and then polishing and grinding by adopting common wax water of glycol solution containing silicon resin to obtain the antibacterial ceramic tile.
Example 2
A composite process antibacterial ceramic tile comprises a green body layer and an antibacterial glaze layer, wherein: the chemical composition of the green body layer raw materials comprises the following components in percentage by weight: SiO 22 66.76%、Al2O3 24.87%、Fe2O3 0.71%、TiO2 0.15%、CaO 1.15%、MgO 0.32%、K2O 3.05%、Na2O 2.89%。
The glaze of the antibacterial glaze layer contains a first antibacterial agent and a basic glaze, wherein the first antibacterial agent is zinc aluminate, the addition amount of the zinc aluminate is 5 parts, the basic glaze is 95 parts, and the chemical composition of the basic glaze comprises SiO in percentage by mass2 56.07%、Al2O319.77%、Fe2O3 0.24%、TiO2 0.25%、CaO 10.74%、MgO 4.41%、ZnO 5.13%、K2O 0.25%、Na2O 3.14%。
The surface micropores of the antibacterial glaze layer are filled with antibacterial antifouling agents, the antibacterial antifouling agents contain second antibacterial agents and nano silica sol, the second antibacterial agents are nano zinc phosphate and nano zinc zirconate, and the solid content of the antibacterial antifouling agents is 8%.
The preparation method of the composite process antibacterial ceramic tile comprises the following steps:
s1, uniformly mixing the raw materials of the green body layer, performing ball milling, spray molding, press molding, drying, spraying ground coat, and performing ink-jet pattern printing to obtain the green body layer;
s2, adding zinc aluminate into the basic glaze, carrying out wet ball milling for 7 hours, deironing and homogenizing to obtain antibacterial glaze slurry with 60% of solid content, spraying the antibacterial glaze slurry on the surface of the blank layer, and firing at the high temperature of 1230 ℃ in a kiln for 65 minutes to obtain a semi-finished product;
s3, cutting edges of the semi-finished product, and polishing the surface of the semi-finished product to obtain a polished ceramic tile;
s4, adding water and 2% of aminopropyltriethoxysilane dispersing agent into nano zinc phosphate and nano zinc zirconate, stirring to form slurry, then pouring the slurry into a sand mill for high-speed grinding for 1 hour, wherein the grinding medium of the sand mill is yttrium stable zirconia microspheres, the diameter of the microspheres is 0.5 mm, the volume filling rate of the microspheres is 80%, the rotating speed of the sand mill is 2100 r/min, and the nano antibacterial solution is obtained, wherein the volume ratio of the nano antibacterial solution to the aqueous silica sol solution is 1: 7, adjusting the pH value to 7, dispersing the mixture into a stable mixed solution by adopting a high-speed stirring dispersion machine, stirring at 1200 rpm to prepare the antibacterial and antifouling agent, dripping the antibacterial and antifouling agent on the surface of the polished ceramic tile according to 70 g/square meter, polishing at high speed by adopting 9 groups of high-pressure grinding discs, adjusting the pressure of the grinding discs on the surface of the tile to be 70Pa, and polishing by adopting common wax water containing a silicon resin glycol solution to obtain the antibacterial ceramic tile.
Example 3
A composite process antibacterial ceramic tile comprises a green body layer and an antibacterial glaze layer, wherein: the chemical composition of the green body layer raw materials comprises the following components in percentage by weight: SiO 22 66.76%、Al2O3 24.87%、Fe2O3 0.71%、TiO2 0.15%、CaO 1.15%、MgO 0.32%、K2O 3.05%、Na2O 2.89%。
The glaze of the antibacterial glaze layer contains a first antibacterial agent and a basic glaze, wherein the first antibacterial agent is zinc silicate and zinc aluminate, the addition amount of the zinc silicate and the zinc aluminate is 7 parts, the basic glaze is 93 parts, and the chemical composition of the basic glaze comprises SiO in percentage by mass2 56.07%、Al2O3 19.77%、Fe2O3 0.24%、TiO2 0.25%、CaO 10.74%、MgO 4.41%、ZnO 5.13%、K2O 0.25%、Na2O 3.14%。
The surface micropores of the antibacterial glaze layer are filled with antibacterial antifouling agents, the antibacterial antifouling agents contain second antibacterial agents and nano silica sol, the second antibacterial agents are nano zinc zirconate, and the solid content of the antibacterial antifouling agents is 10%.
The preparation method of the composite process antibacterial ceramic tile comprises the following steps:
s1, uniformly mixing the raw materials of the green body layer, performing ball milling, spray molding, press molding, drying, spraying ground coat, and performing ink-jet pattern printing to obtain the green body layer;
s2, adding zinc silicate and zinc aluminate into the basic glaze, carrying out wet ball milling for 8 hours, deironing and homogenizing to obtain antibacterial glaze slurry with 68% of solid content, spraying the antibacterial glaze slurry on the surface of the blank layer, and firing at 1210 ℃ in a kiln for 60 minutes to obtain a semi-finished product;
s3, cutting edges of the semi-finished product, and polishing the surface of the semi-finished product to obtain a polished ceramic tile;
s4, adding water and 2.5% of aminopropyltriethoxysilane dispersing agent into nano zinc zirconate, stirring to form slurry, then pouring the slurry into a sand mill for high-speed grinding for 2 hours, wherein the grinding medium of the sand mill is yttrium-stabilized zirconia microspheres, the diameter of the microspheres is 0.3 mm, the volume filling rate of the microspheres is 75%, the rotating speed of the sand mill is 1850 r/min, and a nano antibacterial solution is obtained, wherein the volume ratio of the nano antibacterial solution to the aqueous silica sol solution is 1: 3.5, adjusting the pH value to 7.5, dispersing the mixture into a stable mixed solution by adopting a high-speed stirring dispersion machine, stirring at the speed of 1100 r/min to prepare the antibacterial and antifouling agent, dripping the antibacterial and antifouling agent on the surface of the polished ceramic tile according to 80 g/m, polishing and grinding at a high speed by adopting 9 groups of high-pressure grinding discs, adjusting the pressure of the grinding discs on the surface of the ceramic tile to 80Pa, and then polishing and grinding by adopting common wax water of glycol solution containing silicon resin to obtain the antibacterial ceramic tile.
Comparative example 1
An antibacterial ceramic tile comprising a green body layer and an antibacterial glaze layer, wherein: the chemical composition of the green body layer raw materials comprises the following components in percentage by weight: SiO 22 66.76%、Al2O3 24.87%、Fe2O3 0.71%、TiO2 0.15%、CaO 1.15%、MgO 0.32%、K2O 3.05%、Na2O 2.89%。
The glaze of the antibacterial glaze layer contains a first antibacterial agent and a basic glaze, wherein the first antibacterial agent is zirconium silicate loaded zinc silver, the adding amount of the zirconium silicate loaded zinc silver is 7 parts, the basic glaze is 93 parts, and the basic glaze polishing chemical composition comprises SiO in percentage by mass256.07%、Al2O3 19.77%、Fe2O3 0.24%、TiO2 0.25%、CaO 10.74%、MgO 4.41%、ZnO 5.13%、K2O 0.25%、Na2O 3.14%。
The surface micropores of the antibacterial glaze layer are filled with antibacterial antifouling agents, the antibacterial antifouling agents contain second antibacterial agents and nano silica sol, the second antibacterial agents are nano zinc zirconate, and the solid content of the antibacterial antifouling agents is 10%.
The antibacterial ceramic tile of the comparative example is different from the ceramic tile of example 3 in that the first antibacterial agent is replaced by zirconium silicate loaded with zinc silver, and the other raw material composition and the preparation method are the same as those of example 3.
Comparative example 2
An antibacterial ceramic tile comprising a green body layer and an antibacterial glaze layer, wherein: the chemical composition of the green body layer raw materials comprises the following components in percentage by weight: SiO 22 66.76%、Al2O3 24.87%、Fe2O3 0.71%、TiO2 0.15%、CaO 1.15%、MgO 0.32%、K2O 3.05%、Na2O 2.89%。
The glaze of the antibacterial glaze layer contains a first antibacterial agent and a basic glaze, wherein the first antibacterial agent is zinc silicate and zinc aluminate, the adding amount of the zinc silicate and the zinc aluminate is 7 parts, the basic glaze is 93 parts,the chemical composition of the basic glaze comprises SiO in percentage by mass2 56.07%、Al2O3 19.77%、Fe2O3 0.24%、TiO2 0.25%、CaO 10.74%、MgO 4.41%、ZnO 5.13%、K2O 0.25%、Na2O 3.14%。
The surface micropores of the antibacterial glaze layer are filled with antibacterial antifouling agents, the antibacterial antifouling agents contain second antibacterial agents and nano silica sol, the second antibacterial agents are zinc oxide, and the solid content of the antibacterial antifouling agents is 10%.
The antibacterial ceramic tile of the comparative example is different from example 3 in that the second antibacterial agent is replaced by zinc oxide, and the other raw material composition and the preparation method are the same as those of example 3.
Performance testing
The samples obtained in each example and each comparative example are tested for antibacterial rate and antibacterial durability according to JC/T897-2014 antibacterial ceramic article antibacterial performance standard.
Preparing 10% acetic acid solution, scrubbing the brick surface for 50 times by adopting the acetic acid solution, and after the brick surface is washed clean, detecting the antifouling performance of the brick surface of the sample obtained in the embodiment and the comparative example by adopting cement ink and an oil pen, wherein: the cement ink comprises: mixing carbon-based black water-based common ink with cement, wherein the addition amount of the ink is 15% of the total weight of the cement ink in percentage by weight. The test results are shown in table 1 below.
TABLE 1 comparison table of product performance test of each example and comparative example
From the results of the product performance tests of the examples and comparative examples in table 1, it can be seen that: the samples corresponding to the embodiments 1, 2 and 3 have good antibacterial effect and antibacterial durability to escherichia coli and staphylococcus aureus, and the glaze of the samples is transparent and has good decoration; after acid washing, the antifouling effect is good. In the comparative example 1, the glaze layer is introduced with zirconium silicate doped with zinc silver as an antibacterial agent, and the zirconium silicate carrier is a high-temperature-resistant stable crystal material which is not easy to melt in the glass melt, so that the zirconium silicate carrier exists in an independent crystal form, and the glaze layer is easy to opacify and the transparency is influenced because the refractive index of the zirconium silicate carrier crystal is greatly different from that of the glass melt. In comparative example 2, the antibacterial agent in the antibacterial liquid is zinc oxide, and because the antibacterial agent is not acid-resistant due to oxidation, zinc oxide solid particles in micropores on the surface of the glaze layer are corroded and reacted by acid after acid washing, so that the micropores are hidden with dirt and have poor antifouling property.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are intended to be within the scope of the invention.
Claims (8)
1. A composite process antibacterial ceramic tile is characterized by comprising a green body layer and an antibacterial glaze layer; the glaze of the antibacterial glaze layer consists of a first antibacterial agent and a basic glaze, and the surface micropores of the antibacterial glaze layer are filled with an antibacterial antifouling agent;
the first antibacterial agent is zinc silicate and/or zinc aluminate, and the chemical composition of the basic glaze comprises the following components in percentage by weight: SiO 22 55~57%、Al2O3 19~21%、Fe2O3 0.15~0.25%、TiO2 0.15~0.25%、CaO 10~12%、MgO 3.5~4.5%、ZnO 5.0~6.5%、K2O 0.25~0.55%、Na23.0-4.5% of O; the antibacterial antifouling agent consists of a second antibacterial agent, silica sol and a dispersing agent, wherein the second antibacterial agent is nano zinc phosphate and/or nano zinc zirconate.
2. The composite process antibacterial ceramic tile according to claim 1, wherein the solid content of the antibacterial antifouling agent is 8-12 wt%.
3. The composite process antibacterial ceramic tile according to claim 1, wherein the chemical composition of the raw materials of the green body layer comprises, in weight percent: SiO 22 65~67%、Al2O3 24~25%、Fe2O3 0.6~0.8%、TiO2 0.05~0.15%、CaO 1.0~1.2%、MgO 0.3~0.5%、K2O 2.9~3.1%、Na2O 2.5~3.5%。
4. The composite process antibacterial ceramic tile according to claim 1, wherein the glaze comprises the following components in parts by weight: 2-8 parts of a first antibacterial agent and 92-98 parts of a basic glaze.
5. The method for preparing the composite process antibacterial ceramic tile according to any one of claims 1 to 4, characterized by comprising the following steps:
s1, taking raw materials of the green body layer to obtain the green body layer;
s2, adding a first antibacterial agent into the basic glaze, grinding to obtain antibacterial glaze slurry, spraying the antibacterial glaze slurry on the surface of the green body layer, and sintering to obtain a semi-finished product;
s3, performing surface polishing on the semi-finished product to obtain a polished ceramic tile;
and S4, adding a second antibacterial agent into a dispersing agent, grinding, adding into silica sol, mixing to obtain an antibacterial antifouling agent, dripping the antibacterial antifouling agent on the surface of the polished ceramic tile, and polishing and grinding the surface of the polished ceramic tile to obtain the antibacterial ceramic tile.
6. The preparation method of the composite process antibacterial ceramic tile according to claim 5, wherein the firing temperature in the step S2 is 1200-1230 ℃, and the firing period is 55-65 minutes.
7. The method for preparing the composite process antibacterial ceramic tile according to claim 5, wherein the dispersant in step S4 is aminopropyltriethoxysilane, the amount of the dispersant added is 2-3% by weight of the antibacterial and antifouling agent, and the pH value of the antibacterial and antifouling agent is 7-8.
8. The method for preparing the composite antibacterial ceramic tile according to claim 5, wherein the antibacterial antifouling agent used in step S4 is 50-80 g/m.
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| CN113387726A (en) * | 2021-08-17 | 2021-09-14 | 广东新明珠陶瓷集团有限公司 | Antibacterial ceramic tile and preparation method thereof |
| CN113526873B (en) * | 2021-09-17 | 2021-12-31 | 佛山市三水区康立泰无机合成材料有限公司 | Glass ceramic antibacterial powder and preparation method and application thereof |
| CN113666640B (en) * | 2021-10-21 | 2022-02-22 | 佛山市东鹏陶瓷发展有限公司 | Mesoporous antibacterial frit, preparation method thereof and preparation method of antibacterial ceramic tile |
| CN115490540A (en) * | 2022-10-25 | 2022-12-20 | 科立视材料科技有限公司 | Antibacterial ceramic and antibacterial performance enhanced preparation method thereof |
| CN117247288B (en) * | 2023-11-20 | 2024-02-09 | 佛山欧神诺陶瓷有限公司 | Ceramic tile with antibacterial function and preparation method thereof |
| CN118005431A (en) * | 2024-04-09 | 2024-05-10 | 广东新润成陶瓷有限公司 | Anti-slip antibacterial dry particle brick and preparation method thereof |
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