阅读说明：本技术 介孔抗菌熔块及其制备方法、抗菌陶瓷砖的制备方法 (Mesoporous antibacterial frit, preparation method thereof and preparation method of antibacterial ceramic tile ) 是由 秦汉 徐瑜 钟保民 江彬轩 张智鹏 于 2021-10-21 设计创作，主要内容包括：本发明涉及建筑陶瓷技术领域,尤其涉及一种介孔抗菌熔块及其制备方法、抗菌陶瓷砖的制备方法。一种介孔抗菌熔块的制备方法,包括以下步骤：步骤A、介孔熔块前驱物的制备：步骤A1、按以下质量配比进行制备,每1000g的NaOH溶液中加入100g釉料原料和十六烷基三甲基溴化铵,搅拌混合均匀后进行加热反应；步骤A2、调节经过加热反应后的混合液的pH值至中性,倒去上层清液,进行水洗抽滤后制得介孔熔块前驱物。所述介孔抗菌熔块的制备方法,能够在熔块中形成介孔,制备得到具有介孔结构的介孔抗菌熔块,游离的抗菌金属离子可以通过介孔任意穿梭,抗菌率高,且抗菌耐久性好,使用所述介孔抗菌熔块制得的抗菌陶瓷砖具有优异的抗菌率和耐久抗菌率。(The invention relates to the technical field of building ceramics, in particular to a mesoporous antibacterial frit and a preparation method thereof, and a preparation method of an antibacterial ceramic tile. A preparation method of a mesoporous antibacterial frit comprises the following steps: step A, preparation of a mesoporous frit precursor: step A1, preparing the glaze material and the cetyl trimethyl ammonium bromide according to the following mass ratio, adding 100g of the glaze material and the cetyl trimethyl ammonium bromide into every 1000g of NaOH solution, stirring and mixing uniformly, and then carrying out heating reaction; and A2, adjusting the pH value of the mixed solution after the heating reaction to be neutral, pouring out the supernatant, and performing water washing and suction filtration to obtain the mesoporous frit precursor. The preparation method of the mesoporous antibacterial frit can form mesopores in the frit, prepare the mesoporous antibacterial frit with the mesoporous structure, allow free antibacterial metal ions to freely shuttle through the mesopores, and has high antibacterial rate and good antibacterial durability.)

1. The preparation method of the mesoporous antibacterial frit is characterized by comprising the following steps:

step A, preparation of a mesoporous frit precursor:

step A1, preparing the glaze material and the cetyl trimethyl ammonium bromide according to the following mass ratio, adding 100g of the glaze material and the cetyl trimethyl ammonium bromide into every 1000g of NaOH solution, stirring and mixing uniformly, and then carrying out heating reaction to obtain a mixed solution;

in the step A1, the glaze raw material comprises, by mass, 5-10% of K₂O、5～10%CaO、0～10%MgO、0～5%ZnO、10～40%B₂O₃、10～25%Al₂O₃And 40-70% of water glass, wherein the mass ratio of the water glass to the cetyl trimethyl ammonium bromide is (500-2): 1;

step A2, adjusting the pH value of the mixed solution after the heating reaction to be neutral, pouring out supernatant, and carrying out water washing and suction filtration to obtain a mesoporous frit precursor;

step B, preparation of mesoporous frit:

step B1, heating the mesoporous frit precursor prepared in the step A to a molten state, preserving heat, and pouring into water to obtain a mesoporous frit semi-finished product;

step B2, performing ball milling on the semi-finished mesoporous frit, and filtering and drying to obtain mesoporous frit;

step C, preparation of the acid modified mesoporous frit: placing the mesoporous frit prepared in the step B in dilute nitric acid, carrying out dark water bath, adjusting the pH of the solution to be neutral, and carrying out alcohol washing, water washing, filtering and drying to obtain an acid modified mesoporous frit;

step D, preparation of the mesoporous antibacterial frit: and D, placing the acid modified mesoporous frit prepared in the step C in a silver nitrate solution, carrying out a dark water bath at the temperature of 40-60 ℃, adjusting the pH of the solution to be neutral, and carrying out alcohol washing, water washing, filtering and drying to obtain the mesoporous antibacterial frit.

2. The method for preparing the mesoporous antibacterial frit according to claim 1, wherein in the step A1, the heating reaction temperature is 60-130 ℃ and the reaction time is 1-4 hours.

3. The method of claim 1, wherein in step A1, the concentration of the NaOH solution is 1 mol/L.

4. The method of claim 1, wherein in step B2, the step of ball milling the mesoporous frit semi-finished product is to add the mesoporous frit semi-finished product into a ball mill, and the step of ball milling is performed according to the ratio of the mesoporous frit semi-finished product: ball: the mass ratio of water is 10: 1: and 10, ball-milling until the fineness of the slurry is 80-100 meshes.

5. The method for preparing the mesoporous antibacterial frit according to claim 1, wherein in the step C, the concentration of the dilute nitric acid is 1mol/L, the water bath temperature of the dark water bath is 40-60 ℃, and the water bath time is 12 hours.

6. The method for preparing mesoporous antibacterial frit according to claim 1, wherein in the step D, the silver nitrate concentration is 1mol/L, and the water bath time is 12 h.

7. A mesoporous antibacterial frit, which is prepared by the method for preparing a mesoporous antibacterial frit according to any one of claims 1 to 6.

8. A preparation method of an antibacterial ceramic tile, which is characterized in that the mesoporous antibacterial frit prepared by the preparation method of the mesoporous antibacterial frit according to any one of claims 1 to 6 comprises the following steps:

e1, mixing the mesoporous antibacterial frit, kaolin and water, and then ball-milling until the fineness of the slurry is 125 meshes and the residual is less than 2%, so as to obtain antibacterial frit glaze;

and E2, applying antibacterial fritted glaze on the surface of the green brick, drying and sintering to obtain the antibacterial ceramic brick.

Technical Field

The invention relates to the technical field of building ceramics, in particular to a mesoporous antibacterial frit and a preparation method thereof, and a preparation method of an antibacterial ceramic tile.

Background

Nowadays, people pay more and more attention to health, more and more antibacterial products emerge in the market, the ceramic tile industry is no exception, and products such as antibacterial full-polished glaze and antibacterial marble ceramic tiles are on the market at a glance. At present, the antibacterial ceramic tiles mainly comprise two types: firstly, metal elements with antibacterial performance such as silver, zinc and the like are introduced into the glaze slip, and the glaze slip can show relatively stable antibacterial performance after being sintered; secondly, a layer of antibacterial agent is coated on the surface of the ceramic tile, so that the ceramic tile obtains a strong antibacterial function, and the antibacterial agent is metal ions or nano titanium dioxide and the like. However, both processes have significant limitations:

the first is to introduce metal element into glaze, since the ceramic is silicate material, the glaze material usually contains 40-70% SiO₂Free amorphous SiO after high temperature melting of glaze₂A vitreous glaze layer is formed on the surface of the ceramic tile, and is a compact oxide layer, metal ions are difficult to penetrate through the compact oxide layer to reach the surface of the ceramic tile, and the antibacterial metal ions in the glaze can be released only by throwing off the oxide layer. Therefore, it is difficult to realize a conventional antibacterial ceramic that can produce a good and stable antibacterial property without polishing.

The second method is to coat a layer of antibacterial agent on the surface of the ceramic tile, and the common antibacterial agents are two types: one is metal ion antibacterial agent, and the other is nano titanium dioxide photocatalyst antibacterial agent. The surface coating process of the antibacterial agent can obtain strong antibacterial performance of the ceramic tile, but has the biggest disadvantage of poor durability. Because the antibacterial agent is only coated on the surface of the ceramic tile, once the ceramic tile is worn, the antibacterial agent on the surface is damaged, and the antibacterial effect is lost. In addition, the nano titanium dioxide photocatalyst antibacterial agent can generate antibacterial performance only under the excitation of ultraviolet light, so that the ceramic tile prepared by the process cannot generate antibacterial effect at night and in a dark environment.

Disclosure of Invention

Aiming at the problems in the prior art, the invention aims to provide a preparation method of a mesoporous antibacterial frit, which can form mesopores in the frit and prepare the mesoporous antibacterial frit with a mesoporous structure, so that antibacterial metal ions can freely shuttle in the mesopores, the antibacterial stability is good, the antibacterial effect is good, and the problems of poor antibacterial stability and poor antibacterial effect of the existing antibacterial ceramic tile are solved;

the invention also aims to provide the mesoporous antibacterial frit prepared by the preparation method of the mesoporous antibacterial frit, in the prepared mesoporous antibacterial frit, free antibacterial metal ions can freely shuttle through mesopores, the antibacterial rate is high, and the antibacterial durability is good;

the invention also aims to provide a preparation method of the antibacterial ceramic tile, and the prepared antibacterial ceramic tile has excellent antibacterial rate and durable antibacterial rate, has good and stable antibacterial performance without polishing, also has antibacterial performance at night and in a dark environment, and solves the problems that the existing ceramic tile can realize good antibacterial performance only by polishing, and the antibacterial durability of the antibacterial agent directly coated on the surface of the ceramic tile is poor, and the antibacterial effect cannot be generated at night and in a dark environment.

In order to achieve the purpose, the invention adopts the following technical scheme:

a preparation method of a mesoporous antibacterial frit comprises the following steps:

step A, preparation of a mesoporous frit precursor:

step A1, preparing the glaze material and the cetyl trimethyl ammonium bromide according to the following mass ratio, adding 100g of the glaze material and the cetyl trimethyl ammonium bromide into every 1000g of NaOH solution, stirring and mixing uniformly, and then carrying out heating reaction to obtain a mixed solution;

in the step A1, the glaze raw material comprises, by mass, 5-10% of K₂O、5～10%CaO、0～10%MgO、0～5%ZnO、10～40%B₂O₃、10～25%Al₂O₃And 40-70% of water glass, wherein the mass ratio of the water glass to the cetyl trimethyl ammonium bromide is (500-2): 1;

step A2, adjusting the pH value of the mixed solution after the heating reaction to be neutral, pouring out supernatant, and carrying out water washing and suction filtration to obtain a mesoporous frit precursor;

step B, preparation of mesoporous frit:

step B1, heating the mesoporous frit precursor prepared in the step A to a molten state, preserving heat, and pouring into water to obtain a mesoporous frit semi-finished product;

step B2, performing ball milling on the semi-finished mesoporous frit, and filtering and drying to obtain mesoporous frit;

step C, preparation of the acid modified mesoporous frit: placing the mesoporous frit prepared in the step B in dilute nitric acid, carrying out dark water bath, adjusting the pH of the solution to be neutral, and carrying out alcohol washing, water washing, filtering and drying to obtain an acid modified mesoporous frit;

step D, preparation of the mesoporous antibacterial frit: and D, placing the acid modified mesoporous frit prepared in the step C in a silver nitrate solution, carrying out a dark water bath at the temperature of 40-60 ℃, adjusting the pH of the solution to be neutral, and carrying out alcohol washing, water washing, filtering and drying to obtain the mesoporous antibacterial frit.

In step A1, the heating reaction temperature is 60-130 ℃ and the reaction time is 1-4 h.

In step A1, the concentration of the NaOH solution is 1 mol/L.

Further, in the step B2, the ball milling of the mesoporous frit semi-finished product is specifically to add the mesoporous frit semi-finished product into a ball mill, according to the mesoporous frit semi-finished product: ball: the mass ratio of water is 10: 1: and 10, ball-milling until the fineness of the slurry is 80-100 meshes.

In the step C, the concentration of the dilute nitric acid is 1mol/L, the water bath temperature of the lightproof water bath is 40-60 ℃, and the water bath time is 12 hours.

In step D, the concentration of the silver nitrate is 1mol/L, and the water bath time is 12 h.

A mesoporous antibacterial frit is prepared by using the preparation method of the mesoporous antibacterial frit.

The preparation method of the antibacterial ceramic tile, which is prepared by the preparation method of the mesoporous antibacterial frit, comprises the following steps:

e1, mixing the mesoporous antibacterial frit, kaolin and water, and then ball-milling until the fineness of the slurry is 125 meshes and the residual is less than 2%, so as to obtain antibacterial frit glaze;

and E2, applying antibacterial fritted glaze on the surface of the green brick, drying and sintering to obtain the antibacterial ceramic brick.

Compared with the prior art, the embodiment of the invention has the following beneficial effects:

1. the mesoporous frit precursor is prepared by taking hexadecyl trimethyl ammonium bromide as a surfactant and a template agent, taking water glass in a glaze raw material as a silicon source and using a hydrothermal method under an alkaline environment through the interaction between silicate ions and surfactant molecules. Calcining, crushing, filtering and drying the precursor to obtain mesoporous frit, performing acid modification on the mesoporous frit to obtain acid-modified mesoporous frit, further improving the adsorbability of antibacterial metal ions, then placing the acid-modified mesoporous frit in a silver nitrate solution in a dark water bath to adsorb antibacterial silver ions, adjusting the pH value of the solution to be neutral, and performing alcohol washing, water washing, filtering and drying to obtain the mesoporous antibacterial frit. The preparation method of the mesoporous antibacterial frit can form mesopores in the frit, and the mesoporous antibacterial frit with the mesoporous structure is prepared, so that antibacterial metal ions can freely shuttle in the mesopores, the antibacterial stability is good, the antibacterial effect is good, and the problems of poor antibacterial stability and poor antibacterial effect of the conventional antibacterial ceramic tile are solved;

2. by adding K in step A1₂O、CaO、MgO、ZnO、B₂O₃And Al₂O₃The raw materials are the raw materials in the formula of the glaze, can be adjusted according to the required functions of the glaze and the firing temperature, and the adding amount of each raw material in the glaze raw materials is limited, if K is K₂O, CaO and ZnO are added in too much amount to make the initial melting temperature of the frit too low and further make the mesoporous structure disappear, if MgO is added in too much amount, the glaze is opacified and the color development is not good, if Al is added in too much amount₂O₃If the addition amount of the glaze is too much, the initial melting temperature of the glaze is too high and even the sintering phenomenon occurs, and the glaze is difficult to form transparent glass texture;

3. by limiting the addition amount of the water glass and the cetyltrimethylammonium bromide, if the addition amount of the water glass is excessive, the addition ratio of the cetyltrimethylammonium bromide, which is a templating agent, that is, a substance generating mesopores, is relatively decreased, therefore, the ratio of the cetyl trimethyl ammonium bromide is a key factor for controlling the size and the number of the mesopores, and if the water glass is excessively added, that is, if the amount of cetyltrimethylammonium bromide added is too small, the amount of mesopores is reduced, and the mesopores become small, so that the antibacterial ions are difficult to free and shuttle, thereby affecting the antibacterial effect, and if the amount of water glass added is too small, that is, if the amount of cetyltrimethylammonium bromide added is too large, the mesopores become too large, and antibacterial ions are easily dissociated from the mesopores, thereby affecting the antibacterial stability.

Detailed Description

A preparation method of a mesoporous antibacterial frit comprises the following steps:

step A, preparation of a mesoporous frit precursor:

step A1, preparing the glaze material and the cetyl trimethyl ammonium bromide according to the following mass ratio, adding 100g of the glaze material and the cetyl trimethyl ammonium bromide into every 1000g of NaOH solution, stirring and mixing uniformly, and then carrying out heating reaction to obtain a mixed solution;

in the step A1, the glaze raw material comprises, by mass, 5-10% of K₂O、5～10%CaO、0～10%MgO、0～5%ZnO、10～40%B₂O₃、10～25%Al₂O₃And 40-70% of water glass, wherein the mass ratio of the water glass to the cetyl trimethyl ammonium bromide is (500-2): 1;

step A2, adjusting the pH value of the mixed solution after the heating reaction to be neutral, pouring out supernatant, and carrying out water washing and suction filtration to obtain a mesoporous frit precursor;

step B, preparation of mesoporous frit:

step B1, heating the mesoporous frit precursor prepared in the step A to a molten state, preserving heat, and pouring into water to obtain a mesoporous frit semi-finished product;

step B2, performing ball milling on the semi-finished mesoporous frit, and filtering and drying to obtain mesoporous frit;

step C, preparation of the acid modified mesoporous frit: placing the mesoporous frit prepared in the step B in dilute nitric acid, carrying out dark water bath, adjusting the pH of the solution to be neutral, and carrying out alcohol washing, water washing, filtering and drying to obtain an acid modified mesoporous frit;

step D, preparation of the mesoporous antibacterial frit: and D, placing the acid modified mesoporous frit prepared in the step C in a silver nitrate solution, carrying out a dark water bath at the temperature of 40-60 ℃, adjusting the pH of the solution to be neutral, and carrying out alcohol washing, water washing, filtering and drying to obtain the mesoporous antibacterial frit.

The mesoporous material is a novel material with a pore diameter between a micropore and a macropore and a huge specific surface area and a three-dimensional pore channel structure. Pores with a pore size of less than 2 nm are called micropores according to the definition of the international institute of pure and applied chemistry (IUPAC); macropores with a pore diameter of more than 50 nm; the pores with a diameter of 2-50nm are called mesopores. The mesoporous silica is a porous material capable of realizing efficient adsorption and slow release, and has the characteristics of continuously adjustable uniform mesoporous aperture within the range of 2-50nm, regular pore channels, stable skeleton structure, easily modified inner and outer surfaces, no physiological toxicity and the like. Meanwhile, the mesoporous silica has huge specific surface area and specific pore volume, and is widely applied to the fields of separation and purification, adsorption, catalysis, sensing, drug loading, slow release and the like.

The main component of the ceramic glaze is SiO₂The mesoporous frit precursor is prepared by taking hexadecyl trimethyl ammonium bromide as a surfactant and a template agent, taking water glass in a glaze raw material as a silicon source and adopting a hydrothermal method under an alkaline environment through the interaction between silicate ions and surfactant molecules. Calcining, crushing, filtering and drying the precursor to obtain mesoporous frit, performing acid modification on the mesoporous frit to obtain acid-modified mesoporous frit, further improving the adsorbability of antibacterial metal ions, then placing the acid-modified mesoporous frit in a silver nitrate solution in a dark water bath to adsorb antibacterial silver ions, adjusting the pH value of the solution to be neutral, and performing alcohol washing, water washing, filtering and drying to obtain the mesoporous antibacterial frit. The preparation method of the mesoporous antibacterial frit can form mesopores in the frit, and the mesoporous antibacterial frit with the mesoporous structure is prepared, so that antibacterial metal ions freely shuttle in the mesopores, the antibacterial stability is good, the antibacterial effect is good, and the problems of poor antibacterial stability and poor antibacterial effect of the conventional antibacterial ceramic tile are solved.

In step a2, step C, and step D, adjusting the pH of the solution to neutral means adjusting the pH of the solution to =7, where the solution is neutral, and in step D, by limiting the temperature of the water bath, if the water bath is not performed (direct soaking at normal temperature), or the temperature of the water bath is too low, the adsorption rate of the acid-modified mesoporous frit to the antibacterial metal ions is slow, thereby affecting the antibacterial effect.

Further, in the step a1, the glaze raw material includes, by mass, 5 to 10% of K₂O、5～10%CaO、0～10%MgO、0～5%ZnO、10～40%B₂O₃、10～25%Al₂O₃And 40-70% of water glass, wherein the mass ratio of the water glass to the cetyl trimethyl ammonium bromide is (500-2): 1.

by adding K in step A1₂O、CaO、MgO、ZnO、B₂O₃And Al₂O₃The raw materials are the raw materials in the formula of the glaze, and can be adjusted according to the required functions of the glaze and the firing temperatureBy limiting the addition amount of each raw material in the glaze raw material if K₂O, CaO, the addition of ZnO is too much, which can make the initial melting temperature of the frit too low, and further affect the mesoporous structure, so that the mesoporous structure disappears, if the addition of MgO is too much, the glaze can be opacified, and the color development is not good, if Al is too much₂O₃If the amount of the inorganic filler is too large, the initial melting temperature of the glaze is too high, and the glaze is even burned, so that the glaze is difficult to have a transparent glass texture.

By limiting the addition amount of the water glass and the hexadecyl trimethyl ammonium bromide, the mass ratio of the water glass to the hexadecyl trimethyl ammonium bromide is too large, that is, the proportion of the water glass to the hexadecyl trimethyl ammonium bromide is too large, because the hexadecyl trimethyl ammonium bromide is a template agent, that is, a substance generating mesopores, the proportion of the hexadecyl trimethyl ammonium bromide is a key factor for controlling the size and the quantity of the mesopores, if the mass ratio of the water glass to the hexadecyl trimethyl ammonium bromide is too large, that is, the addition amount of the hexadecyl trimethyl ammonium bromide is too small, the quantity of the mesopores is reduced, the pore diameter of the mesopores is reduced, antibacterial ions are difficult to freely shuttle, the antibacterial effect is influenced, and if the mass ratio of the water glass to the hexadecyl trimethyl ammonium bromide is too small, that is, the addition amount of the hexadecyl trimethyl ammonium bromide is too large, the pore diameter of the frit is too large, antibacterial ions are easy to dissociate from the mesopores, so that the antibacterial stability is influenced, the surface gloss is low after the sintering, and the antifouling property is poor; the pore diameter of the mesoporous antibacterial frit prepared by the invention is 2-30 nm.

Preferably, in the step A1, the heating reaction temperature is 60-130 ℃, and the reaction time is 1-4 hours.

And limiting the reaction temperature of the heating reaction in the step a1, in the step a, cetyl trimethyl ammonium bromide is used as a surfactant and a template agent, water glass in a glaze raw material is used as a silicon source, and a mesoporous frit precursor is prepared by a hydrothermal method under an alkaline environment through interaction between silicate ions and surfactant molecules, wherein the mesoporous frit precursor is a milky viscous jelly, and if the heating reaction is performed at the temperature of a1, the reaction speed is easy to be too slow, and if the heating temperature is too high, the reaction speed is easy to be too fast and uncontrollable.

Preferably, in the step A1, the concentration of the NaOH solution is 1 mol/L.

The mesoporous template and the silicon source can react in an acidic or alkaline environment, the hexadecyl trimethyl ammonium bromide needs to react in an alkaline environment, and a NaOH solution is selected.

Further, in the step a1, the glaze raw material, the cetyl trimethyl ammonium bromide and the NaOH solution are uniformly stirred at 35 to 45 ℃, so that the glaze raw material, the cetyl trimethyl ammonium bromide and the NaOH solution can be uniformly mixed more rapidly.

Further, in the step B2, the ball milling of the mesoporous frit semi-finished product is specifically to add the mesoporous frit semi-finished product into a ball mill, according to the mesoporous frit semi-finished product: ball: the mass ratio of water is 10: 1: and 10, ball-milling until the fineness of the slurry is 80-100 meshes.

In the step B, the precursor is calcined and heated to a molten state, ball milling and crushing are carried out, filtration and drying are carried out to obtain mesoporous frit, and then acid modification is carried out on the mesoporous frit to obtain acid-modified mesoporous frit, so that the adsorbability of antibacterial metal ions is further improved, wherein the heating temperature of the heating to the molten state is determined by the formula of the frit and is required to be 100-200 ℃ above the melting temperature of the formula of the frit, if the heating temperature is lower than the melting temperature of the formula of the frit, a glassy frit cannot be formed, and if the heating temperature exceeds 200 ℃ above the melting temperature of the formula of the frit, the mesoporous structure is influenced.

In step B2, the method further includes a step of removing iron after filtering, and then drying the mesoporous frit to obtain a mesoporous frit, wherein the step of removing iron can remove impurities during the preparation process.

In the step C, the concentration of the dilute nitric acid is 1mol/L, the water bath temperature of the lightproof water bath is 40-60 ℃, and the water bath time is 12 hours.

The acid modified mesoporous frit is prepared by carrying out acid modification on the mesoporous frit, the adsorbability to antibacterial metal ions is further improved, the adsorbability to silver ions can be improved, if the concentration of the dilute nitric acid is too high, the dilute nitric acid solution is easy to be unstable and easy to decompose into oxygen and nitrogen dioxide, the gas is toxic and has pungent smell and great harm, and in addition, the ceramic glaze/frit does not react with strong acid, so the concentration of the dilute nitric acid is 1 mol/L.

In step D, the concentration of the silver nitrate is 1mol/L, and the water bath time is 12 h.

And the lucifugal water bath is the constant-temperature water bath soaking.

In the step D, the pH of the solution is adjusted to be neutral by using a sodium hydroxide solution with the concentration of 0.1 mol/L.

A mesoporous antibacterial frit is prepared by using the preparation method of the mesoporous antibacterial frit.

In the mesoporous antibacterial frit prepared by the preparation method of the mesoporous antibacterial frit, free antibacterial metal ions can freely shuttle through mesopores, so that the antibacterial rate is high, and the antibacterial durability is good.

The preparation method of the antibacterial ceramic tile, which is prepared by the preparation method of the mesoporous antibacterial frit, comprises the following steps:

e1, mixing the mesoporous antibacterial frit, kaolin and water, and then ball-milling until the fineness of the slurry is 125 meshes and the residual is less than 2%, so as to obtain antibacterial frit glaze;

and E2, applying antibacterial fritted glaze on the surface of the green brick, drying and sintering to obtain the antibacterial ceramic brick.

The antibacterial ceramic tile has the advantages that the mesoporous antibacterial frit, kaolin and water are mixed and then subjected to ball milling to obtain the antibacterial frit glaze, then the antibacterial frit glaze is applied to the surface of a green brick, the antibacterial component is in the glaze layer, the durability of the antibacterial frit glaze is better than that of the ceramic tile coated with the antibacterial agent on the surface, the prepared antibacterial ceramic tile has excellent antibacterial rate and durable antibacterial rate, the antibacterial ceramic tile has good and stable antibacterial performance without polishing, the antibacterial ceramic tile also has antibacterial performance at night and in a dark environment, the problems that the existing ceramic tile can realize good antibacterial performance only by polishing, the antibacterial durability of the antibacterial agent directly coated on the surface of the ceramic tile is poor, and the antibacterial effect cannot be generated at night and in a dark environment are solved.

In step E1, the mass ratio of the mesoporous antibacterial frit to the kaolin is 95: 5; in the step E1, sodium tripolyphosphate and sodium carboxymethylcellulose are further added, the mesoporous antibacterial frit, kaolin, sodium tripolyphosphate, sodium carboxymethylcellulose and water are mixed and then ball-milled, and the addition amount of the sodium tripolyphosphate, the addition amount of the sodium carboxymethylcellulose and the addition amount of the water are calculated according to the weight percentage of the total weight of the mesoporous antibacterial frit and the kaolin, in the step E1, the addition amount of the sodium tripolyphosphate is 0.1-0.6%, the addition amount of the sodium carboxymethylcellulose is 0.05-0.2%, and the addition amount of the water is 30-40%.

Specifically, the frit with the frit content of more than 90% is called pure frit glaze, the frit is glaze, namely the mesoporous antibacterial frit disclosed by the invention is glaze, but 100% of the pure frit has no glazes, and the mesoporous antibacterial frit is extremely easy to settle without adding a suspending agent, so that the kaolin and the sodium carboxymethyl cellulose are added as the suspending agent, the stability of the glaze is improved, the components in the glaze are uniformly dispersed, the sodium tripolyphosphate is added as a debonding agent, and the sodium tripolyphosphate is used together with the suspending agent to suspend particles in the glaze, so that the leveling property is good, and the obtained glaze is smooth and flat.

The technical solution of the present invention is further explained by the following embodiments.

In order to facilitate an understanding of the present invention, a more complete description of the present invention is provided below. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.

The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.

Examples 1 to 5

A preparation method of a mesoporous antibacterial frit comprises the following steps:

step A, preparation of a mesoporous frit precursor:

step A1, preparing the glass fiber by the following mass ratio, adding 100g of glaze raw materials (wherein, the composition of the glaze raw materials is shown in the following table 1) and cetyl trimethyl ammonium bromide into 1000g of NaOH solution, wherein the mass ratio of the water glass to the cetyl trimethyl ammonium bromide is 50: 1, stirring and mixing uniformly at 40 ℃, and then placing the mixture in a reaction kettle for heating reaction, wherein the reaction temperature of the heating reaction is 100 ℃, and the reaction time is 2 hours, so as to obtain a mixed solution;

step A2, taking out the mixed solution after the heating reaction, adjusting the pH value of the mixed solution after the heating reaction to be neutral, pouring out the supernatant, and performing water washing and suction filtration to obtain a mesoporous frit precursor;

step B, preparation of mesoporous frit:

step B1, placing the mesoporous frit precursor prepared in the step A in a high-temperature frit furnace, heating to a molten state, preserving heat for 30min, and pouring into water to obtain a mesoporous frit semi-finished product;

step B2, adding the mesoporous frit semi-finished product into a ball mill, and mixing the mesoporous frit semi-finished product: ball: the mass ratio of water is 10: 1: 10, ball-milling until the fineness of the slurry is 100 meshes, and filtering and drying to obtain mesoporous frit;

step C, preparation of the acid modified mesoporous frit: placing the mesoporous frit prepared in the step B in dilute nitric acid with the concentration of 1mol/L, carrying out light-proof water bath at the temperature of 50 ℃ for 12 hours, adjusting the pH of the solution to be neutral, and carrying out alcohol washing, water washing, filtering and drying to prepare an acid modified mesoporous frit;

step D, preparation of the mesoporous antibacterial frit: and D, placing the acid modified mesoporous frit prepared in the step C in a silver nitrate solution with the concentration of 1mol/L, carrying out water bath in a dark place at the temperature of 50 ℃ for 12 hours, adjusting the pH of the solution to be neutral, and carrying out alcohol washing, water washing, filtering and drying to obtain the mesoporous antibacterial frit.

Example 6

Compared with the example 4, in the present example, the temperature of the water bath in the dark water bath in the step D is 40 ℃, and the rest of the raw materials and the preparation method are the same as those in the example 4, so as to obtain the mesoporous antibacterial frit.

Example 7

Compared with the example 4, in the present example, the temperature of the water bath in the dark water bath in the step D is 60 ℃, and the rest of the raw materials and the preparation method are the same as those in the example 4, so as to obtain the mesoporous antibacterial frit.

Example 8

Compared with example 4, in this example, the mass ratio of the water glass to the cetyltrimethylammonium bromide in the step a1 is 500: 1, the other raw materials and the preparation method are the same as those of the example 4, and the mesoporous antibacterial frit is prepared.

Example 9

Compared with example 4, in this example, the mass ratio of the water glass to the cetyltrimethylammonium bromide in the step a1 is 2: 1, the other raw materials and the preparation method are the same as those of the example 4, and the mesoporous antibacterial frit is prepared.

Comparative example 1

In comparison with example 4, in this comparative example, the mass ratio of water glass to cetyltrimethylammonium bromide in step a1 was 1: 1, the other raw materials and the preparation method are the same as those of the example 4, and the mesoporous antibacterial frit is prepared.

Comparative example 2

In comparison with example 4, in this comparative example, the mass ratio of water glass to cetyltrimethylammonium bromide in step a1 was 600: 1, the other raw materials and the preparation method are the same as those of the example 4, and the mesoporous antibacterial frit is prepared.

Comparative example 3

In comparison with example 4, in this comparative example, in step a1, the composition of the glaze raw material was 12% by mass K₂O、12%CaO、6%ZnO、10%B₂O₃、20%Al₂O₃And 40% of water glass, the rest raw materials and the preparation method and the examples4, obtaining the mesoporous antibacterial frit.

Comparative example 4

Compared with the example 4, in the comparative example, the water bath temperature of the dark water bath in the step D is 30 ℃, and the rest raw materials and the preparation method are the same as the example 4, so that the mesoporous antibacterial frit is prepared.

The mesoporous antibacterial frits prepared in the embodiments 1-9 and the comparative examples 1-4 are respectively used for preparing antibacterial ceramic tiles, and the preparation steps are as follows:

step E1, mixing the mesoporous antibacterial frit, kaolin, sodium tripolyphosphate, sodium carboxymethylcellulose and water, and then ball-milling until the fineness of the slurry is 125 meshes and the residual is less than 2%, so as to obtain the antibacterial frit glaze, wherein the mass ratio of the mesoporous antibacterial frit to the kaolin is 95: 5, according to the weight percentage of the total weight of the mesoporous antibacterial frit and the kaolin, in the step E1, the addition amount of sodium tripolyphosphate is 0.3%, the addition amount of sodium carboxymethylcellulose is 0.1%, and the addition amount of water is 35%;

and E2, applying antibacterial fritted glaze on the surface of the green brick, drying and sintering to obtain the antibacterial ceramic brick.

And (3) performance testing: the antibacterial rate and the antibacterial durability are measured according to the test method of JC/T897-2014 antibacterial ceramic product antibacterial performance, antibacterial rate and antibacterial durability are tested on antibacterial ceramic tiles respectively prepared by using the mesoporous antibacterial frits prepared in examples 1-9 and comparative examples 1-4, and the performance test results are shown in the following table:

as can be seen from examples 1 to 9, the antibacterial ceramic tile prepared by preparing the mesoporous antibacterial frit, preparing the antibacterial frit glaze using the mesoporous antibacterial frit, and applying the antibacterial frit glaze on the surface of the green tile, after firing, has a good antibacterial effect, a high antibacterial rate and antibacterial durability, can achieve a good and stable antibacterial effect without polishing, and does not directly cause the antibacterial effect to fail due to abrasion of the surface of the ceramic tile;

comparative example 1 the frit pore size was too large, the surface gloss after firing was low, and the antifouling performance was poor, because the mass ratio of water glass to cetyltrimethylammonium bromide was too small, i.e. the ratio of cetyltrimethylammonium bromide was too large; in comparative example 2, the mass ratio of the water glass to the cetyl trimethyl ammonium bromide is too large, that is, the ratio of the water glass to the cetyl trimethyl ammonium bromide is too large, so that the quantity of mesopores in the mesoporous antibacterial frit is small, the pore diameter of the mesopores is reduced, and the antibacterial ions are difficult to free and shuttle, so that the antibacterial rate of the antibacterial ceramic tile is reduced compared with that of example 4;

comparative example 3K added to frit material of step a1₂O, CaO and ZnO are too much, so that the initial melting temperature of the frit is too low, the mesoporous structure of the frit is influenced, and the antibacterial performance of the antibacterial ceramic tile is poorer than that of the antibacterial ceramic tile in the embodiment 4;

in comparative example 4, the temperature of the water bath in the dark water bath in step D is too low, so that the adsorption speed of the acid-modified mesoporous frit to the antibacterial metal ions is slow, that is, the amount of the antibacterial metal ions adsorbed by the acid-modified mesoporous frit is less, so that the antibacterial rate of the prepared antibacterial ceramic tile is reduced compared with that of example 4, and the antibacterial effect is poorer than that of example 4.

The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.

The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.