Antibacterial glaze and preparation method thereof

Abstract

The invention provides antibacterial glaze and a preparation method thereof.The antibacterial glaze is composed of basic glaze and antibacterial functional glaze, and the antibacterial functional glaze is prepared from, by weight, 40-60 parts of frit and 5-15 parts of antibacterial components; wherein the antibacterial component is lanthanum-gadolinium co-doped zinc-loaded mesoporous zirconia, the molar ratio of lanthanum to gadolinium is (2.5-3.5): 1, and the zinc loading capacity is 5-10 wt%. The antibacterial glaze provided by the invention has excellent high-temperature stability and multiple synergistic antibacterial mechanisms, and effectively solves the key technical bottlenecks of unstable performance, poor action persistence and the like of an existing antibacterial ceramic product.

Description

Technical Field

[0001] This application relates to the technical field of ceramic glazes, and specifically, to an antibacterial glaze and a preparation method thereof. Background Art

[0002] Glazes are functional materials that mainly consist of mineral raw materials (such as feldspar, quartz, kaolin, etc.). After being finely ground into slurries, they form a vitreous thin layer on the surface of ceramic bodies through high-temperature sintering. The main functions of traditional glazes are to enhance the aesthetics and surface protection performance of ceramic products. However, with the improvement of people's living standards and the enhancement of health awareness, the single decorative and protective function can no longer meet the modern consumption needs. Especially in usage environments where bacteria are likely to breed, such as kitchens, bathrooms, and medical facilities, ceramic products with special functions such as antibacterial and self-cleaning are increasingly favored by the market.

[0003] The key technology of antibacterial ceramics lies in the introduction of antibacterial agents into the glaze formula. Currently, the antibacterial effect is mainly achieved through three action mechanisms: (1) The slow release and sterilization of metal ions such as Ag + , Zn 2+ , Cu 2+ , etc.; (2) Photocatalytic materials such as TiO2 generate reactive oxygen species for sterilization under light illumination; (3) Contact sterilization of nanomaterials. However, the high-temperature stability of antibacterial components is insufficient. Under the conditions of the conventional firing temperature of ceramic glazes (1200 - 1300 °C), active antibacterial components such as silver are extremely prone to oxidation, volatilization, or reaction with the glaze matrix, resulting in a large loss of effective antibacterial components. Secondly, there are obvious limitations in the existing antibacterial mechanisms. The antibacterial systems relying on ion release generally have the problem of uncontrollable release rates. Excessive initial release may lead to local concentration exceeding the standard, posing potential toxicity risks, while in the later stage, the antibacterial performance rapidly decays due to the depletion of effective components. Photocatalytic antibacterial materials are limited by light illumination conditions, and their antibacterial effects are significantly reduced in dark or weak light environments, making it difficult to meet the actual application requirements. Therefore, how to achieve the organic combination of different antibacterial mechanisms and develop a new type of glaze with excellent high-temperature stability and multiple synergistic antibacterial mechanisms is of great significance for promoting the upgrading of the functional ceramic industry. Summary of the Invention

[0004] In the embodiments of this application, an antibacterial glaze and a preparation method thereof are provided. This antibacterial glaze has both excellent high-temperature stability and multiple synergistic antibacterial mechanisms, effectively solving the key technical bottlenecks such as the unstable performance and poor action persistence of existing antibacterial ceramic products.

[0005] To achieve the above object, in a first aspect, the present application provides the following technical solution: An antibacterial glaze, which is composed of a base glaze and an antibacterial functional glaze. The antibacterial functional glaze comprises the following raw materials in parts by weight: 40-60 parts of frit, 5-15 parts of an antibacterial component; wherein, the antibacterial component is lanthanum-gadolinium co-doped zinc-loaded mesoporous zirconia, and the molar ratio of lanthanum to gadolinium is (2.5-3.5):1, and the zinc loading amount is 5-10 wt%.

[0006] In the present application, mesoporous zirconia is used as a carrier. Its high melting point and chemical stability can effectively isolate the destruction of the antibacterial active ingredient by high temperature. The high specific surface area of the mesoporous structure provides rich anchoring sites and diffusion channels for the active component; and zinc ions are used as the antibacterial active ingredient to replace traditional silver / copper ions, reducing the raw material cost and avoiding the problem of glaze discoloration caused by copper ions; the present application also introduces a specific ratio of lanthanum-gadolinium double rare earth elements to achieve a triple protection mechanism. Lanthanum can expand the zirconia lattice to form a zinc ion embedding channel, improving the thermal stability of the mesoporous structure. Gadolinium fills the lattice gap to inhibit the migration of zinc ions, and reduces the oxygen vacancy concentration through magnetic moment coupling, reducing the oxidation sites of zinc ions. Moreover, the electron cloud overlapping effect between lanthanum and gadolinium can form stable Zn-O-La / Gd multi-coordination bonds, ensuring the controllable release of zinc ions while achieving high-density loading.

[0007] The antibacterial component provided by the present application has a multiple synergistic antibacterial mechanism. On the one hand, the zinc ions confined in the mesopores destroy the bacterial membrane structure through electrostatic interaction; on the other hand, the highly active hydroxyl radicals generated by the catalysis of lanthanum / gadolinium ions further enhance the antibacterial effect. And the present application realizes the long-term slow release of zinc ions by precisely regulating the lattice channel and the interstitial filling effect: the lattice channel expanded by lanthanum ions ensures the diffusion of zinc ions as needed, while the interstitial filling of gadolinium ions forms a zero-order release kinetics through energy barrier regulation, maintaining an effective antibacterial concentration for a long time.

[0008] In any of the above technical solutions, further, the base glaze comprises the following raw materials in parts by weight: 35-45 parts of potassium feldspar powder, 20-30 parts of quartz powder, 15-20 parts of kaolin, 5-10 parts of calcium carbonate, 2-5 parts of zinc oxide, and 3-8 parts of talc powder.

[0009] In any of the above technical solutions, further, the mass ratio of the base glaze to the antibacterial functional glaze is 1:0.15-0.25.

[0010] In any of the above technical solutions, further, the frit is a borosilicate frit, which is composed of 58-63 wt% of SiO2, 15-25 wt% of B2O3, 5-10 wt% of Na2O, and 3-8 wt% of CaO.

[0011] In any of the above technical solutions, further, the preparation method of the antibacterial component comprises the following steps:

[0012] S1. Dissolve lanthanum salt, gadolinium salt and inorganic zirconium salt precursor in an aqueous solution containing a chelating agent according to a molar ratio of 2.5 - 3.5:1:8 - 12, add a templating agent, adjust the pH value to 8.5 - 10, stir until a homogeneous sol is formed, and then carry out a hydrothermal crystallization reaction at 140 - 180 °C for 12 - 24 h to obtain a mesoporous zirconia precursor.

[0013] S2. Calcinate the mesoporous zirconia precursor at a high temperature to remove the templating agent, then immerse it in a zinc salt solution and react for 2 - 8 h, and then calcine it in an inert atmosphere to obtain the antibacterial component.

[0014] In any of the above technical solutions, further, in step S1, the lanthanum salt and gadolinium salt are each independently selected from at least one of nitrates, chlorides or organometallic complexes.

[0015] In any of the above technical solutions, further, in step S1, the inorganic zirconium salt precursor is selected from at least one of zirconium oxychloride and zirconyl nitrate.

[0016] In any of the above technical solutions, further, in step S1, the templating agent is a surfactant, selected from at least one of cationic cetyltrimethylammonium bromide, nonionic block copolymer or zwitterionic surfactant.

[0017] In any of the above technical solutions, further, in step S1, the chelating agent is selected from at least one of carboxylic acids, aminocarboxylic acids, polyhydroxy acids or polymer polymers, and the concentration is 0.1 - 0.3 mol / L.

[0018] In any of the above technical solutions, further, in step S1, the mass ratio of the templating agent to the inorganic zirconium salt precursor is 1:(0.8 - 1.5).

[0019] The preferred mass ratio can ensure that the templating agent micelles form a homogeneous complex with the hydrolysis product of the zirconium salt precursor. If the templating agent is insufficient, the number of micelles is insufficient, resulting in an incomplete mesoporous structure; if the templating agent is excessive, the micelles are densely packed, easily causing mesoporous collapse.

[0020] In any of the above technical solutions, further, in step S2, the temperature of the high-temperature calcination is 500 - 700 °C, and the time is 2 - 6 h.

[0021] The preferred calcination temperature and time can regulate the degree of templating agent removal and the degree of crystal phase transformation, ensuring the integrity, thermal stability of the mesoporous structure and the uniform doping of rare earth ions.

[0022] In any of the above technical solutions, further, in step S2, the temperature of the calcination is 300 - 500 °C, and the time is 1 - 4 h.

[0023] In any of the above technical solutions, further, in step S2, the zinc salt is selected from at least one of zinc nitrate, zinc acetate or zinc sulfate.

[0024] In any of the above technical solutions, further, in step S2, the concentration of the zinc salt solution is 0.2 - 0.6 mol / L.

[0025] In any of the above technical solutions, further, the preparation method of the antibacterial component includes the following steps:

[0026] Step a: Mix lanthanum nitrate, gadolinium nitrate and zirconium oxynitrate in a molar ratio of 2.5 - 3.5:1:8 - 12 and dissolve them in deionized water containing ethylenediaminetetraacetic acid. Add the template agent cetyltrimethylammonium bromide, adjust the pH value to 9 - 10 with ammonia water, stir at 58 - 62 °C until a homogeneous sol is formed, then transfer it to a hydrothermal reaction kettle and hydrothermally crystallize at 140 - 180 °C for 12 - 24 hours to form a rare earth - doped mesoporous zirconia precursor.

[0027] Step b: Centrifuge and wash the mesoporous zirconia precursor until it is neutral, calcine it at 500 - 700 °C for 2 - 6 h to remove the template agent to obtain a powder; adopt the equal - volume impregnation method, immerse the powder in a zinc nitrate solution, ultrasonically assist the impregnation for 2 - 8 h, dry at 80 °C, and then heat - treat it at 300 - 500 °C for 1 - 4 h under nitrogen protection to obtain the antibacterial component.

[0028] Adopting one provided in the embodiment of the present application, compared with the prior art, it has the following technical effects:

[0029] The technical solution of the present application designs an innovative lanthanum - gadolinium co - doped mesoporous zirconia carrier. Using high - melting - point mesoporous zirconia as the carrier, its stable crystal structure provides effective protection for the antibacterial active ingredient; through the synergistic effect of lanthanum ions expanding the lattice and gadolinium ions filling the gaps, a stable Zn - O - La / Gd multi - coordination bond is formed, significantly improving the high - temperature stability of zinc ions; at the same time, the unique mesoporous structure and rare earths jointly construct a zinc ion slow - release system, realizing a multiple antibacterial mechanism of contact sterilization and active oxygen catalysis. This solution not only overcomes the defects of traditional silver / copper - based antibacterial agents being prone to volatilization and oxidation at high temperatures, but also significantly reduces the production cost by replacing precious metals with zinc, and finally obtains an antibacterial glaze product with excellent high - temperature stability, long - lasting antibacterial property and economic practicality.

[0030] In the second aspect, the present application also provides a preparation method of the above antibacterial glaze, including the following steps:

[0031] S3: Mix the frit and the antibacterial component, ball - mill and screen them to obtain the antibacterial functional glaze.

[0032] S4. Mix the antibacterial functional glaze with the base glaze and obtain the antibacterial glaze through a gradient sintering process.

[0033] In any of the above technical solutions, further, in step S3, during the ball milling process, the ball-to-material ratio is 1.5 - 2:1, and the ball milling time is 30 - 60 min.

[0034] In any of the above technical solutions, further, in step S4, the gradient sintering process includes: in the first stage, heating to 600 - 800 °C at a rate of 5 - 8 °C / min and holding for 30 - 60 min; in the second stage, heating to 1100 - 1250 °C at a rate of 2 - 4 °C / min and holding for 1 - 2 h.

[0035] The preferred gradient sintering process realizes the effective encapsulation and protection of the frit against the antibacterial component through staged temperature control, which not only ensures the glaze surface quality, but also maximally retains the antibacterial activity of zinc ions, while reducing the glaze layer defects.

[0036] It should be understood that both the foregoing general description and the following specific embodiments are for the purpose of illustration and example and do not necessarily limit the present disclosure. At the same time, the specification is used to explain the principles of the present disclosure. Specific Embodiments

[0037] In order to make the technical solutions and advantages in the embodiments of the present application clearer, the following further details the exemplary embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than an exhaustive list of all embodiments. It should be noted that, without conflict, the embodiments in the present application and the features in the embodiments can be combined with each other.

[0038] The term "and / or" in the present application is merely a description of the association relationship of the associated objects, indicating that three relationships may exist. For example, A and / or B is specifically understood as: it may simultaneously include both A and B, A may exist alone, or B may exist alone, and any of the above three situations can be satisfied.

[0039] Example 1

[0040] This embodiment provides an antibacterial glaze, which is composed of a base glaze and an antibacterial functional glaze with a mass ratio of 1:0.2. The antibacterial functional glaze includes the following raw materials in parts by weight: 50 parts of frit (composition: 63.0 wt% SiO2, 22.0 wt% B2O3, 8.0 wt% Na2O, 7.0 wt% CaO), 10 parts of antibacterial component; wherein, the antibacterial component is lanthanum-gadolinium co-doped zinc-loaded mesoporous zirconia, and the molar ratio of lanthanum to gadolinium is 3:1; the base glaze includes the following raw materials in parts by weight: 40 parts of potassium feldspar powder, 25 parts of quartz powder, 18 parts of kaolin, 8 parts of calcium carbonate, 4 parts of zinc oxide, and 6 parts of talc powder:

[0041] It is prepared by the following method:

[0042] (1) Lanthanum nitrate, gadolinium nitrate and zirconium oxynitrate are mixed in a molar ratio of 3:1:10 and dissolved in deionized water containing ethylenediaminetetraacetic acid (the concentration of ethylenediaminetetraacetic acid is 0.2 mol / L). Cetyltrimethylammonium bromide as a template agent is added (the mass ratio of the template agent to zirconium oxynitrate is 1:1). Stir for 30 min until homogeneous, adjust the pH value to 9.5 with ammonia water, continue to stir in a constant temperature water bath at 60 °C for 4 h until a homogeneous sol is formed. Then transfer it to a polytetrafluoroethylene-lined reaction kettle, hydrothermally crystallize at 160 °C for 18 h, cool to room temperature to obtain a mesoporous zirconia precursor, and after centrifugal separation, wash it 3 times with deionized water;

[0043] (2) The above-mentioned mesoporous zirconia precursor is placed in a muffle furnace and calcined at 600 °C for 4 h at a heating rate of 2 °C / min to remove the template agent, obtaining tetragonal mesoporous zirconia (powder). Prepare a 0.5 mol / L zinc nitrate solution, impregnate the powder by the equal-volume impregnation method (liquid-solid ratio 10 mL / g), ultrasonically assist impregnation for 6 h, vacuum dry at 80 °C for 12 h, and then heat-treat at 400 °C for 2 h under nitrogen protection to obtain the antibacterial component, and the zinc loading is 8.5 wt%;

[0044] (3) Mix the frit and the antibacterial component in proportion, wet mill at a ball-to-material ratio of 1.8:1 for 45 min, and pass through a 200-mesh sieve to obtain the antibacterial functional glaze;

[0045] (4) Mix the antibacterial functional glaze and the base glaze in proportion, and obtain the antibacterial glaze through a gradient sintering process; first rise to 750 °C at a rate of 6 °C / min and hold for 45 min to soften the frit and wrap the antibacterial component, then rise to 1200 °C at a rate of 3 °C / min, hold for 1.5 h in a nitrogen atmosphere to promote the densification of the glaze layer, and naturally cool to room temperature to obtain the antibacterial glaze.

[0046] Example 2

[0047] This example provides an antibacterial glaze, which is composed of a base glaze and an antibacterial functional glaze with a mass ratio of 1:0.15. The antibacterial functional glaze includes the following raw materials in parts by weight: 40 parts of frit (composition: 62.5 wt% SiO2, 22.7 wt% B2O3, 9.1 wt% Na2O, 5.7 wt% CaO), 5 parts of antibacterial component; wherein, the antibacterial component is lanthanum-gadolinium co-doped zinc-loaded mesoporous zirconia, and the molar ratio of lanthanum to gadolinium is 2.5:1; the base glaze includes the following raw materials in parts by weight: 35 parts of potassium feldspar powder, 20 parts of quartz powder, 15 parts of kaolin, 5 parts of calcium carbonate, 2 parts of zinc oxide and 3 parts of talc powder:

[0048] It is prepared by the following method:

[0049] (1) Lanthanum nitrate, gadolinium nitrate and zirconium oxynitrate are mixed in a molar ratio of 2.5:1:8 and dissolved in deionized water containing ethylenediaminetetraacetic acid (the concentration of ethylenediaminetetraacetic acid is 0.2 mol / L). Cetyltrimethylammonium bromide as a template agent is added (the mass ratio of the template agent to zirconium oxynitrate is 1:0.8). Stir for 30 min until homogeneous, adjust the pH value to 9.3 with ammonia water, and continue to stir in a constant temperature water bath at 60 °C for 4 h until a uniform sol is formed. Subsequently, transfer it to a polytetrafluoroethylene-lined reaction kettle and hydrothermally crystallize at 140 °C for 12 h. Cool to room temperature to obtain a mesoporous zirconia precursor, and after centrifugal separation, wash it 3 times with deionized water;

[0050] (2) The above-mentioned mesoporous zirconia precursor is placed in a muffle furnace and calcined at 500 °C for 2 h at a heating rate of 2 °C / min to remove the template agent, obtaining tetragonal mesoporous zirconia (powder). Prepare a 0.2 mol / L zinc nitrate solution, impregnate the powder by the equal-volume impregnation method (liquid-solid ratio 10 mL / g), ultrasonically assist the impregnation for 2 h, vacuum dry at 80 °C for 12 h, and then heat-treat at 300 °C for 1 h under nitrogen protection to obtain the antibacterial component, and the zinc loading is 5.8 wt%;

[0051] (3) Mix the frit and the antibacterial component in proportion, wet mill for 30 min with a ball-to-material ratio of 1.5:1, and pass through a 200-mesh sieve to obtain the antibacterial functional glaze;

[0052] (4) Mix the antibacterial functional glaze and the base glaze in proportion and obtain the antibacterial glaze through a gradient sintering process; first, raise the temperature to 600 °C at 5 °C / min and hold for 30 min to soften the frit and wrap the antibacterial component, then raise the temperature to 1100 °C at 2 °C / min and hold for 1 h in a nitrogen atmosphere to promote the densification of the glaze layer, and naturally cool to room temperature to obtain the antibacterial glaze.

[0053] Example 3

[0054] This example provides an antibacterial glaze, which is composed of a base glaze and an antibacterial functional glaze with a mass ratio of 1:0.25. The antibacterial functional glaze includes the following raw materials in parts by weight: 60 parts of frit (composition: 59 wt% SiO2, 24 wt% B2O3, 9 wt% Na2O, 8 wt% CaO), 15 parts of antibacterial component; among them, the antibacterial component is lanthanum-gadolinium co-doped zinc-loaded mesoporous zirconia, and the molar ratio of lanthanum to gadolinium is 3.5:1; the base glaze includes the following raw materials in parts by weight: 45 parts of potassium feldspar powder, 30 parts of quartz powder, 20 parts of kaolin, 10 parts of calcium carbonate, 5 parts of zinc oxide and 8 parts of talc powder:

[0055] It is prepared by the following method:

[0056] (1) Lanthanum nitrate, gadolinium nitrate and zirconium oxynitrate are mixed in a molar ratio of 3.5:1:12 and dissolved in deionized water containing ethylenediaminetetraacetic acid (the concentration of ethylenediaminetetraacetic acid is 0.2 mol / L). Cetyltrimethylammonium bromide as a template agent is added (the mass ratio of the template agent to zirconium oxynitrate is 1:1.5). Stir for 30 min until homogeneous, adjust the pH value to 9.7 with ammonia water, continue to stir in a constant temperature water bath at 60 °C for 4 h until a homogeneous sol is formed. Then transfer it to a polytetrafluoroethylene-lined reaction kettle and hydrothermally crystallize at 180 °C for 24 h. Cool to room temperature to obtain a mesoporous zirconia precursor. After centrifugal separation, wash it 3 times with deionized water;

[0057] (2) Place the above mesoporous zirconia precursor in a muffle furnace, heat it to 700 °C at a rate of 2 °C / min and calcine for 6 h to remove the template agent, obtaining tetragonal mesoporous zirconia (powder). Prepare a 0.6 mol / L zinc nitrate solution, impregnate the powder by the equal-volume impregnation method (liquid-solid ratio 10 mL / g), ultrasonically assist the impregnation for 8 h, vacuum dry at 80 °C for 12 h, and then heat-treat at 500 °C for 4 h under nitrogen protection to obtain the antibacterial component, with a zinc loading of 9.1 wt%;

[0058] (3) Mix the frit and the antibacterial component in proportion, wet mill for 60 min with a ball-to-material ratio of 2:1, and pass through a 200-mesh sieve to obtain the antibacterial functional glaze;

[0059] (4) Mix the antibacterial functional glaze and the base glaze in proportion, and obtain the antibacterial glaze through a gradient sintering process; First, heat it to 800 °C at a rate of 8 °C / min and hold for 60 min to soften the frit and wrap the antibacterial component. Then, heat it to 1250 °C at a rate of 4 °C / min and hold for 2 h in a nitrogen atmosphere to promote the densification of the glaze layer, and naturally cool to room temperature to obtain the antibacterial glaze.

[0060] Comparative Example 1

[0061] The antibacterial glaze provided in this comparative example is the same as that in Example 1 except for the following parameter settings: the molar ratio of lanthanum to gadolinium in the antibacterial component is 4:1.

[0062] Comparative Example 2

[0063] The antibacterial glaze provided in this comparative example is the same as that in Example 1 except for the following parameter settings: the molar ratio of lanthanum to gadolinium in the antibacterial component is 2:1.

[0064] Comparative Example 3

[0065] The antibacterial glaze provided in this comparative example is the same as that in Example 1 except for the following parameter settings: the antibacterial component is cerium-gadolinium co-doped zinc-loaded mesoporous zirconia, and the molar ratio of cerium to gadolinium is 3:1.

[0066] Comparative Example 4

[0067] The antibacterial glaze provided in this comparative example is the same as that in Example 1 except for the following parameter settings: the antibacterial component (lanthanum-gadolinium co-doped zinc-loaded mesoporous zirconia) is replaced with an equal amount of silver-loaded mesoporous zirconia, and the silver loading is 8.5 wt%.

[0068] Comparative Example 5

[0069] The antibacterial glaze provided in this comparative example is the same as that in Example 1 except for the following parameter settings: gadolinium is not doped in the antibacterial component, and only lanthanum is used for doping, that is, lanthanum nitrate and zirconium oxynitrate react according to a molar ratio of 2:5 in step (1).

[0070] Experimental Example

[0071] Take a ceramic green body with a specification of 10 cm × 10 cm × 5 mm, place it in a sintering furnace, take it out after sintering at 650 °C for 3 h to form a green body, immerse the green body in the antibacterial glazes of Examples 1-3 and Comparative Examples 1-4 of the present invention respectively, and control the thickness of the glaze layer to 0.1 mm through multiple immersions. After the immersion is completed, place it in a kiln for firing, control the temperature to 1350 °C, take it out after firing for 6 h, and after cooling, form a test sample.

[0072] Antibacterial performance: The antibacterial rate was tested with reference to the standard of JC / T 897-2014, using Escherichia coli and Staphylococcus aureus as the test strains, the bacterial solution concentration: 1×10 5 CFU / mL, contact temperature 37 ± 1 °C;

[0073] Antibacterial persistence: The antibacterial rate was tested after the sample was washed 30 times, using Escherichia coli as the test strain, and the washing solution was an aqueous solution containing 1.0 wt% sodium dodecylbenzenesulfonate, pH = 10 ± 0.5. The results are shown in Table 1.

[0074] Table 1

[0075]

[0076] Sustained-release performance: The test sample was immersed in PBS with pH = 7.4 at a constant temperature of 37 °C, and the zinc ion concentration at different time points was measured using an atomic absorption spectrometer. The results are shown in Table 2.

[0077] Table 2

[0078]

[0079]

[0080] As can be seen from Table 1 and Table 2, in Examples 1-3, through the precise ratio of lanthanum-gadolinium and combined with the lattice regulation of mesoporous zirconia, the synergistic effect of multiple antibacterial mechanisms was achieved. Among them, the antibacterial rate of Escherichia coli at 24 hours in Example 1 reached 99.98%, and the antibacterial rate of Staphylococcus aureus was 99.95%. After 30 washes, the antibacterial persistence remained at 99.23%. The zinc ion slow-release data showed that the cumulative release amount in the example group was only 3.82-4.05 ppm within 30 days, which conformed to the zero-order kinetic model, indicating its controllable long-term release characteristics.

[0081] In Comparative Examples 1-2, the molar ratio of lanthanum-gadolinium deviated from the optimal range, resulting in the imbalance between lattice channels and interstitial filling. The 24-hour antibacterial rate decreased to 85.65-88.32%, and the 30-day zinc cumulative release amount reached 5.81-7.25 ppm, showing first-order kinetic characteristics. In Comparative Example 3, cerium was used to replace lanthanum, and in Comparative Example 5, only lanthanum was doped, which could not effectively expand the zirconia lattice, resulting in a low zinc loading and poor antibacterial persistence. In Comparative Example 4, a silver-loaded system was used. Although the initial antibacterial rate was high, silver ions were oxidized and inactivated during high-temperature sintering, and the 30-day slow-release amount dropped sharply to 8.57 ppm, and the release curve showed the characteristics of sudden release followed by oxidative decay. In Comparative Example 5, only lanthanum was doped, resulting in out-of-control zinc ion release and showing first-order kinetic characteristics.

[0082] Detection of reactive oxygen species (ROS) generation ability: The specific detection process is as follows: Grind the glaze sample into powder (particle size ≤ 5 μm), disperse it in PBS buffer (1 mg / mL), add DCFH-DA fluorescent probe (10 μM), react in the dark for 30 min, simulate light (ultraviolet-visible light, λ = 365 nm) and dark conditions respectively, and use a microplate reader to detect the fluorescence intensity (DCFH-DA: Ex / Em = 488 / 525 nm) to judge the catalytic generation effect of reactive oxygen species. The results are shown in Table 3.

[0083] Table 3

[0084]

[0085] As can be seen from Table 3, the antibacterial components provided by this application can continuously generate reactive oxygen species through non-photocatalytic pathways, and still maintain more than 50% ROS activity under dark conditions, solving the problem of the failure of traditional photocatalytic materials (such as TiO2) in the dark environment.

[0086] Based on the embodiments in this disclosure, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the scope of protection of this disclosure.

[0087] Although the preferred embodiments of the present application have been described, additional changes and modifications can be made by those skilled in the art once they learn the basic creative concept. Therefore, the appended claims are intended to be construed to include the preferred embodiments as well as all changes and modifications falling within the scope of the present application.

[0088] Obviously, those skilled in the art can make various changes and modifications to the present application without departing from the spirit and scope of the present application. Thus, if these modifications and variations of the present application fall within the scope of the claims of the present application and their equivalent technologies, the present application is also intended to include these modifications and variations.

Claims

1. An antibacterial glaze, characterized in that, It consists of a base glaze and an antibacterial functional glaze. The antibacterial functional glaze comprises raw materials in the following parts by weight: 40 - 60 parts of frit, 5 - 15 parts of antibacterial component; wherein, the antibacterial component is lanthanum-gadolinium co-doped zinc-loaded mesoporous zirconia, and the molar ratio of lanthanum to gadolinium is (2.5 - 3.5):1, and the zinc loading is 5 - 10 wt%.

2. The antibacterial glaze according to claim 1, characterized in that The base glaze comprises raw materials in the following parts by weight: 35 - 45 parts of potassium feldspar powder, 20 - 30 parts of quartz powder, 15 - 20 parts of kaolin, 5 - 10 parts of calcium carbonate, 2 - 5 parts of zinc oxide, and 3 - 8 parts of talc powder.

3. The antibacterial glaze according to claim 1, characterized in that, The mass ratio of the base glaze to the antibacterial functional glaze is 1:0.15 - 0.

25.

4. The antibacterial glaze according to claim 1, characterized in that The preparation method of the antibacterial component comprises the following steps: S1. Dissolve lanthanum salt, gadolinium salt and inorganic zirconium salt precursor in an aqueous solution containing a chelating agent according to a molar ratio of 2.5 - 3.5:1:8 - 12, add a template agent, adjust the pH value to 8.5 - 10, stir to form a homogeneous sol, and then carry out a hydrothermal crystallization reaction at 140 - 180 °C for 12 - 24 h to obtain a mesoporous zirconia precursor; S2. Calcinate the mesoporous zirconia precursor at a high temperature to remove the template agent, then immerse it in a zinc salt solution and react for 2 - 8 h, and then calcine it in an inert atmosphere to obtain the antibacterial component.

5. The antibacterial glaze according to claim 4, characterized in that, In step S1, the lanthanum salt and gadolinium salt are each independently selected from at least one of nitrates, chlorides or organometallic complexes; and / or The inorganic zirconium salt precursor is selected from at least one of zirconium oxychloride and zirconium oxynitrate; and / or The template agent is a surfactant, selected from at least one of cationic cetyltrimethylammonium bromide, non-ionic block copolymer or zwitterionic surfactant; and / or The chelating agent is selected from at least one of carboxylic acids, aminocarboxylic acids, polyhydroxy acids or polymer polymers, and the concentration is 0.1 - 0.3 mol / L.

6. The antibacterial glaze according to claim 4, characterized in that In step S1, the mass ratio of the template agent to the inorganic zirconium salt precursor is 1:(0.8 - 1.5).

7. The antibacterial glaze according to claim 4, wherein, In step S2, the temperature of the high-temperature calcination is 500 - 700 °C, and the time is 2 - 6 h; and / or The temperature of the calcination is 300 - 500 °C, and the time is 1 - 4 h.

8. The antibacterial glaze according to claim 4, wherein In step S2, the zinc salt is selected from at least one of zinc nitrate, zinc acetate or zinc sulfate; and / or The concentration of the zinc salt solution is 0.2 - 0.6 mol / L.

9. A method for preparing the antibacterial glaze according to any one of claims 1-8, characterized in that, It comprises the following steps: S3. Mix, ball mill and screen the frit and the antibacterial component to obtain the antibacterial functional glaze; S4. Mix the antibacterial functional glaze with the base glaze and obtain the antibacterial glaze through a gradient sintering procedure.

10. The preparation method according to claim 9, characterized in that, In step S3, during the ball milling process, the ball-to-material ratio is 1.5 - 2:1, and the ball milling time is 30 - 60 min; and / or In step S4, the gradient sintering procedure includes: the first stage is heated to 600 - 800 °C at 5 - 8 °C / min and kept warm for 30 - 60 min; the second stage is heated to 1100 - 1250 °C at 2 - 4 °C / min and kept warm for 1 - 2 h.

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