Antibacterial self-cleaning domestic ceramic and preparation method thereof

Abstract

The invention relates to the technical field of ceramic materials, and discloses antibacterial self-cleaning domestic ceramic and a preparation method thereof. The preparation method comprises the following steps: S1, mixing a ceramic green body raw material, an antibacterial precursor and an auxiliary agent, performing ball milling to obtain slurry, performing slip casting on the slurry to obtain a green body, and drying to obtain the green body; s2, carrying out gradient in-situ reaction sintering on the green body, and sintering at the temperature of 400-600 DEG C; then sintering at the temperature of 800 to 1000 DEG C; then sintering at the temperature of 1100 to 1250 DEG C; s3, after sintering, micron-sized pits are formed in the surface of the ceramic body through plasma etching; and S4, glazing: sintering at 700-900 DEG C to combine the glaze with the biscuit, thereby obtaining the antibacterial self-cleaning domestic ceramic. The preparation process is simple, long-acting synergism of antibacterial and self-cleaning performance is achieved, and firm combination of the functional layer and the ceramic matrix is achieved.

Description

Technical Field

[0001] This invention relates to the field of ceramic materials technology, specifically to an antibacterial self-cleaning daily-use ceramic and its preparation method. Background Technology

[0002] Existing antibacterial ceramics often rely on the addition of antibacterial agents such as silver and zinc. However, these agents suffer from problems such as easy aggregation, inactivation during high-temperature firing, and weak adhesion to the ceramic matrix leading to rapid degradation of antibacterial performance. Self-cleaning ceramics often depend on surface coating with photocatalysts such as TiO2, but the coating is prone to peeling off, and because they require ultraviolet light excitation, their self-cleaning effect is poor in low-light environments such as indoors. Alternatively, they may achieve hydrophobic self-cleaning by etching micro-nano structures on the surface, but this lacks antibacterial properties, and the structure is easily damaged by oil stains. Antibacterial and self-cleaning functions are often achieved through step-by-step processing (such as firing the ceramic first and then coating the functional layer), which is complex, costly, and results in weak adhesion between the functional layer and the substrate, leading to poor durability. Summary of the Invention

[0003] To address the aforementioned problems in the existing technology, the present invention aims to provide an antibacterial self-cleaning daily ceramic and its preparation method, which has a simple process, long-lasting synergistic antibacterial and self-cleaning properties, and a strong bond between the functional layer and the ceramic matrix.

[0004] To address the above problems, the present invention provides the following technical solution: In a first aspect, this application provides a method for preparing antibacterial self-cleaning daily-use ceramics, comprising the following steps: S1. Mix the ceramic body raw materials, antibacterial precursors and additives, ball mill them to obtain a slurry, and then cast the slurry to obtain a green body. After drying, the green body is obtained. S2. The green body is subjected to gradient in-situ reaction sintering, first sintering at 400-600℃; then sintering at 800-1000℃; and then sintering at 1100-1250℃. S3. After sintering, micron-level pits are formed on the surface of the ceramic blank by plasma etching; S4. Glaze the ceramic and sinter it at 700-900℃ to bond the glaze with the unglazed body, thus producing antibacterial and self-cleaning daily ceramics.

[0005] In one embodiment of this application, the raw materials for the ceramic body include clay, quartz, and feldspar.

[0006] In one embodiment of this application, the ceramic body raw material comprises the following raw materials in the following weight ratios: 35-50 wt% clay, 20-35 wt% quartz and 20-30 wt% feldspar.

[0007] In one embodiment of this application, the antibacterial precursor is a composite sol of silver nitrate and tetrabutyl titanate.

[0008] In one embodiment of this application, the mass ratio of silver nitrate to tetrabutyl titanate is 1:5 to 1:10.

[0009] In one embodiment of this application, the antibacterial precursor accounts for 1-5 wt% of the ceramic green body raw material.

[0010] In one embodiment of this application, the additives include dispersants and photoresponsive additives.

[0011] In one embodiment of this application, the dispersant is silica sol.

[0012] In one embodiment of this application, the silica sol accounts for 0.5-2 wt% of the ceramic green body raw material.

[0013] In one embodiment of this application, the nano-SiO2 particles in the silica sol have a large specific surface area and surface energy, which can be adsorbed on the particle surface formed by the antibacterial precursor (silver nitrate and tetrabutyl titanate composite sol), preventing the particles from agglomerating during sintering and playing a role in dispersion and stabilization.

[0014] In one embodiment of this application, the photoresist is a visible light responder.

[0015] In one embodiment of this application, the visible light responsive additive is a rare earth element.

[0016] In one embodiment of this application, the rare earth element is selected from lanthanum and cerium.

[0017] In one embodiment of this application, rare earth elements account for 0.1-1 wt% of the ceramic body raw material.

[0018] In one embodiment of this application, sintering is carried out at 400-600°C for 1-3 hours.

[0019] In one embodiment of this application, sintering is carried out at 800-1000°C for 1-3 hours.

[0020] In one embodiment of this application, sintering is carried out at 1100-1250°C for 1-4 hours.

[0021] In one embodiment of this application, sintering is performed at a low temperature of 400-600°C, during which the precursor decomposes into Ag. + And TiO2 nanoparticles.

[0022] In one embodiment of this application, sintering is performed at a medium temperature of 800-1000°C, Ag + It reacts with SiO2 in the ceramic matrix to form a stable Ag-Si-O solid solution, thereby avoiding Ag + It volatilizes, while TiO2 crystallizes into the anatase phase.

[0023] In one embodiment of this application, sintering is carried out at a high temperature of 1100-1250℃, and nano-sized TiO2 / Ag-Si-O particles are grown in situ and uniformly distributed on the ceramic surface with a distribution depth of 5-20μm, forming chemical bonds with the ceramic matrix.

[0024] In one embodiment of this application, the plasma may be Ar plasma.

[0025] In one embodiment of this application, the power of plasma etching is 100-300W.

[0026] In one embodiment of this application, the plasma etching time is 5-15 minutes.

[0027] In one embodiment of this application, the diameter of the formed micron-sized pit is 5-20 μm.

[0028] In one embodiment of this application, nano-sized TiO2 / Ag-Si-O particles are distributed within the pit.

[0029] In one embodiment of this application, the thickness of the glaze is 50-100 μm.

[0030] In one embodiment of this application, the glaze is sintered at 700-900°C for 1-3 hours to bond the glaze with the unglazed body.

[0031] In one embodiment of this application, the glaze includes a base glaze and functional additives.

[0032] In one embodiment of this application, the base glaze comprises feldspar, quartz, and zinc oxide.

[0033] In one embodiment of this application, the mass ratio of feldspar, quartz and zinc oxide is 3:2:1.

[0034] In one embodiment of this application, the functional additive is Ag-loaded. + Mesoporous SiO2 and fluorine-modified TiO2 nanotubes.

[0035] In one embodiment of this application, Ag is loaded. + Mesoporous SiO2 accounts for 3-8 wt% of the glaze.

[0036] In one embodiment of this application, fluorine-modified TiO2 nanotubes account for 2-5 wt% of the glaze.

[0037] In one embodiment of this application, the fluorine content in the fluorine-modified TiO2 nanotubes is 1-3 wt%.

[0038] In one embodiment of this application, sintering is carried out at 700-900℃, and the fluxing effect of zinc oxide is used to bond the glaze with the green body. At the same time, functional additives are uniformly dispersed in the glaze layer, so that the functional layer and the glaze layer are integrally formed.

[0039] Secondly, this application provides antibacterial self-cleaning daily ceramics prepared by the above-mentioned method.

[0040] Compared with the prior art, the present invention has the following beneficial effects: (1) This application provides an antibacterial self-cleaning daily-use ceramic and its preparation method, which achieves long-term synergistic effect of antibacterial and self-cleaning properties by generating an antibacterial-photocatalytic bifunctional phase in situ. The Ag-Si-O solid solution slowly releases Ag... + To achieve long-lasting antibacterial effects, hydroxyl radicals generated by TiO2 photocatalysis assist in sterilization; the micro-nano structure enhances hydrophobicity and reduces stain adhesion; TiO2 can degrade residual organic matter under visible light, achieving dual self-cleaning through hydrophobic and antifouling properties and photocatalytic degradation.

[0041] (2) This application provides an antibacterial self-cleaning daily ceramic and its preparation method. The energy consumption is reduced by low-temperature sintering, high-temperature damage is avoided, the functional layer and glaze layer are integrally formed, and the wear resistance is improved.

[0042] (3) This application provides an antibacterial self-cleaning daily ceramic and its preparation method, which achieves an antibacterial rate of ≥99.9%, a self-cleaning rate of ≥90%, and the antibacterial and self-cleaning properties remain ≥95% after 500 water washes. Detailed Implementation

[0043] The technical solutions in the embodiments of this application will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of this application, and not all embodiments. Based on the embodiments in this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application.

[0044] Unless otherwise specified, all materials and reagents used in the following examples are commercially available.

[0045] The preparation method of the composite sol of silver nitrate and tetrabutyl titanate used in the following implementation is as follows: Prepare a 0.1 mol / L nitric acid solution and adjust the pH to 2.0-2.5; Tetrabutyl titanate was added to ethanol and stirred until homogeneous to obtain a tetrabutyl titanate solution with a concentration of 0.8 mol / L. Place the tetrabutyl titanate solution in a 500mL three-necked flask, heat it in a water bath to 30°C, and stir magnetically. Under light-protected conditions, silver nitrate solution was slowly added dropwise to tetrabutyl titanate solution at a rate of 1-2 mL / min; During the dropwise addition process, the mixture should be continuously stirred and the temperature maintained at 30±2℃; After the addition is complete, continue stirring for 2 hours to ensure the two components are fully mixed. Add silica sol (0.5-2 wt% of total sol mass) as a dispersion stabilizer; Transfer the mixed sol to a brown glass bottle and seal for storage; The prepared composite sol was aged at room temperature (25±2℃) in the dark for 24 hours. Shake gently 2-3 times during the aging process to promote even mixing; The final product is a transparent or translucent pale yellow composite sol.

[0046] The load Ag used in the following implementation + The preparation method of mesoporous SiO2 is as follows: Mesoporous SiO2 was immersed in AgNO3 solution (0.1-0.5 mol / L) by impregnation, stirred for 12 h, dried at 60 °C, and reduced at 300 °C for 2 h. The silver loading was adjusted to 5 wt% by the AgNO3 concentration.

[0047] The preparation method of fluorine-modified TiO2 nanotubes used in the following implementation is as follows: TiO2 nanotubes were immersed in NH4F solution, dried at 80℃, and heat-treated at 300℃ for 2 hours. The fluorine content was adjusted to 2wt% by adjusting the NH4F concentration. Example 1

[0048] This embodiment 1 provides an in-situ generated antibacterial self-cleaning ceramic with dual antibacterial and photocatalytic functions, and its preparation method.

[0049] formula: Ceramic body raw materials: clay 50wt%, feldspar 30wt%, quartz 20wt%; Antibacterial precursor: a composite sol of silver nitrate and tetrabutyl titanate (mass ratio 1:8), accounting for 3 wt% of the ceramic body raw materials; Additives; silica sol accounts for 1 wt% of the raw material; rare earth element La 3+ It accounts for 0.5 wt% of the raw material of the billet.

[0050] Preparation method: The ceramic green body raw material, antibacterial precursor and additives are mixed and ball-milled for 24 hours to obtain a slurry; The slurry is poured into molds to obtain a green body; The green body was dried at 80℃ for 24 hours to obtain the raw green body; The green blank is placed in the furnace and sintered using a gradient heating process: sintering at 500℃ for 2 hours, then heating to 900℃ at a rate of 5℃ / min and sintering for 2 hours, and finally heating to 1200℃ at a rate of 5℃ / min and sintering for 3 hours, and then cooling to room temperature with the furnace. The sintered green body was subjected to plasma etching using Ar plasma at a power of 200W for 10 minutes to form micron-sized pits on the ceramic surface. Example 2

[0051] This embodiment 2 provides an in-situ generated antibacterial self-cleaning ceramic with dual antibacterial and photocatalytic functions and its preparation method.

[0052] formula: Ceramic body raw materials: clay 50wt%, feldspar 30wt%, quartz 20wt%; Antibacterial precursor: a composite sol of silver nitrate and tetrabutyl titanate (mass ratio 1:5), accounting for 1 wt% of the ceramic body raw materials; Additives; silica sol accounts for 0.5 wt% of the raw material; rare earth element La 3+ It accounts for 0.1 wt% of the raw material of the billet.

[0053] Preparation method: The ceramic green body raw material, antibacterial precursor and additives are mixed and ball-milled for 24 hours to obtain a slurry; The slurry is poured into molds to obtain a green body; The green body was dried at 80℃ for 24 hours to obtain the raw green body; The green blank is placed in the furnace and sintered using a gradient heating process: sintering at 400℃ for 1 hour, then heating to 800℃ at a rate of 5℃ / min and sintering for 1 hour, and finally heating to 1100℃ at a rate of 5℃ / min and sintering for 2 hours, and then cooling to room temperature with the furnace. The sintered green blank was subjected to plasma etching using Ar plasma at a power of 100W for 5 minutes to form micron-sized pits on the ceramic surface. Example 3

[0054] This embodiment 3 provides an in-situ generated antibacterial-photocatalytic dual-functional antibacterial self-cleaning ceramic and its preparation method.

[0055] formula: Ceramic body raw materials: clay 50wt%, feldspar 30wt%, quartz 20wt%; Antibacterial precursor: a composite sol of silver nitrate and tetrabutyl titanate (mass ratio 1:10), accounting for 5 wt% of the ceramic body raw materials; Additives; silica sol accounts for 2 wt% of the raw material; rare earth element La 3+It accounts for 1 wt% of the raw material of the billet.

[0056] Preparation method: The ceramic green body raw material, antibacterial precursor and additives are mixed and ball-milled for 24 hours to obtain a slurry; The slurry is poured into molds to obtain a green body; The green body was dried at 80℃ for 24 hours to obtain the raw green body; The green blank is placed in the furnace and sintered using a gradient heating process: sintering at 600℃ for 3 hours, then heating to 1000℃ at a rate of 5℃ / min and sintering for 3 hours, and finally heating to 1250℃ at a rate of 5℃ / min and sintering for 4 hours, and then cooling to room temperature with the furnace. The sintered green body was subjected to plasma etching using Ar plasma at a power of 300W for 15 minutes to form micron-sized pits on the ceramic surface. Example 4

[0057] This embodiment 4 provides a ceramic with a low-temperature co-fired functional glaze layer and its preparation method.

[0058] formula: Ceramic body raw materials: clay 50wt%, feldspar 30wt%, quartz 20wt%; Base glaze: feldspar 60wt%, quartz 20wt%, zinc oxide 20wt%; Functional additives: Ag-loaded + Mesoporous SiO2 accounts for 5 wt% of the glaze; fluorine-modified TiO2 nanotubes account for 3 wt% of the glaze, of which the fluorine content in the fluorine-modified TiO2 nanotubes is 2 wt%.

[0059] Preparation method: The ceramic body raw materials are mixed, ball-milled for 24 hours, and then slip-cast to obtain the body. The green body was dried at 80℃ for 24 hours to obtain the raw green body; The green blank is placed in the furnace and sintered at 1200℃ for 3 hours. It is then cooled to room temperature with the furnace to obtain the sintered green blank. The base glaze and functional additives are mixed and ball-milled for 24 hours to obtain the glaze slurry; The glaze slurry is sprayed onto the surface of the unglazed body, and the glaze layer thickness is 75μm. The glazed bisque was sintered at 800℃ for 2 hours and then cooled to room temperature in the kiln. Example 5

[0060] This embodiment 5 provides a ceramic with a low-temperature co-fired functional glaze layer and its preparation method.

[0061] formula: Ceramic body raw materials: clay 50wt%, feldspar 30wt%, quartz 20wt%; Base glaze: feldspar 60wt%, quartz 20wt%, zinc oxide 20wt%; Functional additives: Ag-loaded + Mesoporous SiO2 accounts for 3 wt% of the glaze; fluorine-modified TiO2 nanotubes account for 2 wt% of the glaze, of which the fluorine content in the fluorine-modified TiO2 nanotubes is 1 wt%.

[0062] Preparation method: The ceramic body raw materials are mixed, ball-milled for 24 hours, and then slip-cast to obtain the body. The green body was dried at 80℃ for 24 hours to obtain the raw green body; The green blank is placed in the furnace and sintered at 1200℃ for 3 hours. It is then cooled to room temperature with the furnace to obtain the sintered green blank. The base glaze and functional additives are mixed and ball-milled for 24 hours to obtain the glaze slurry; The glaze slurry is sprayed onto the surface of the unglazed body, and the glaze layer thickness is 50μm. The glazed bisque was sintered at 700°C for 1 hour and then cooled to room temperature in the kiln. Example 6

[0063] This embodiment 6 provides a ceramic with a low-temperature co-fired functional glaze layer and its preparation method.

[0064] formula: Ceramic body raw materials: clay 50wt%, feldspar 30wt%, quartz 20wt%; Base glaze: feldspar 60wt%, quartz 20wt%, zinc oxide 20wt%; Functional additives: Ag-loaded + Mesoporous SiO2 accounts for 8 wt% of the glaze; fluorine-modified TiO2 nanotubes account for 5 wt% of the glaze, of which the fluorine content in the fluorine-modified TiO2 nanotubes is 3 wt%.

[0065] Preparation method: The ceramic body raw materials are mixed, ball-milled for 24 hours, and then slip-cast to obtain the body. The green body was dried at 80℃ for 24 hours to obtain the raw green body; The green blank is placed in the furnace and sintered at 1200℃ for 3 hours. It is then cooled to room temperature with the furnace to obtain the sintered green blank. The base glaze and functional additives are mixed and ball-milled for 24 hours to obtain the glaze slurry; The glaze slurry is sprayed onto the surface of the unglazed body, and the glaze layer thickness is 100μm. The glazed bisque was sintered at 900℃ for 3 hours and then cooled to room temperature in the kiln. Example 7

[0066] This embodiment 7 provides an in-situ generated antibacterial self-cleaning ceramic with dual antibacterial and photocatalytic functions, and its preparation method.

[0067] formula: Ceramic body raw materials: clay 50wt%, feldspar 30wt%, quartz 20wt%; Antibacterial precursor: a composite sol of silver nitrate and tetrabutyl titanate (mass ratio 1:8), accounting for 3 wt% of the ceramic body raw materials; Additives; silica sol accounts for 1 wt% of the raw material; rare earth element La 3+ It accounts for 0.5 wt% of the raw material of the billet.

[0068] Glazes consist of a base glaze and functional additives; Base glaze: feldspar 60wt%, quartz 20wt%, zinc oxide 20wt%; Functional additives: Ag-loaded + Mesoporous SiO2 accounts for 5 wt% of the glaze; fluorine-modified TiO2 nanotubes account for 3 wt% of the glaze, of which the fluorine content in the fluorine-modified TiO2 nanotubes is 2 wt%.

[0069] Preparation method: The ceramic green body raw material, antibacterial precursor and additives are mixed and ball-milled for 24 hours to obtain a slurry; The slurry is poured into molds to obtain a green body; The green body was dried at 80℃ for 24 hours to obtain the raw green body; The green blank is placed in the furnace and sintered using a gradient heating process: sintering at 500℃ for 2 hours, then heating to 900℃ at a rate of 5℃ / min and sintering for 2 hours, and finally heating to 1200℃ at a rate of 5℃ / min and sintering for 3 hours, and then cooling to room temperature with the furnace. The sintered green body was subjected to plasma etching using Ar plasma at a power of 200W for 10 minutes to form micron-sized pits on the ceramic surface.

[0070] The base glaze and functional additives are mixed and ball-milled for 24 hours to obtain the glaze slurry; The glaze slurry is sprayed onto the surface of the unglazed body, and the glaze layer thickness is 75μm. The glazed bisque was sintered at 800℃ for 2 hours and then cooled to room temperature in the kiln. Example 8

[0071] This embodiment 8 provides an in-situ generated antibacterial-photocatalytic dual-function antibacterial self-cleaning ceramic and its preparation method.

[0072] formula: Ceramic body raw materials: clay 50wt%, feldspar 30wt%, quartz 20wt%; Antibacterial precursor: a composite sol of silver nitrate and tetrabutyl titanate (mass ratio 1:10), accounting for 5 wt% of the ceramic body raw materials; Additives; silica sol accounts for 2 wt% of the raw material; rare earth element La 3+ It accounts for 1 wt% of the raw material of the billet.

[0073] Glazes consist of a base glaze and functional additives; Base glaze: feldspar 60wt%, quartz 20wt%, zinc oxide 20wt%; Functional additives: Ag-loaded + Mesoporous SiO2 accounts for 8 wt% of the glaze; fluorine-modified TiO2 nanotubes account for 5 wt% of the glaze, of which the fluorine content in the fluorine-modified TiO2 nanotubes is 3 wt%.

[0074] Preparation method: The ceramic green body raw material, antibacterial precursor and additives are mixed and ball-milled for 24 hours to obtain a slurry; The slurry is poured into molds to obtain a green body; The green body was dried at 80℃ for 24 hours to obtain the raw green body; The green blank is placed in the furnace and sintered using a gradient heating process: sintering at 600℃ for 3 hours, then heating to 1000℃ at a rate of 5℃ / min and sintering for 3 hours, and finally heating to 1250℃ at a rate of 5℃ / min and sintering for 4 hours, and then cooling to room temperature with the furnace. The sintered green body was subjected to plasma etching using Ar plasma at a power of 300W for 15 minutes to form micron-sized pits on the ceramic surface.

[0075] The base glaze and functional additives are mixed and ball-milled for 24 hours to obtain the glaze slurry; The glaze slurry is sprayed onto the surface of the unglazed body, and the glaze layer thickness is 100μm. The glazed bisque was sintered at 900℃ for 3 hours and then cooled to room temperature in the kiln.

[0076] Comparative Example 1 Comparative Example 1 is a traditional antibacterial ceramic, with only an antibacterial agent added. The specific preparation method is as follows: 3 wt% nano-Ag2O was added as an antibacterial agent to the ceramic body raw materials (50 wt% clay, 30 wt% feldspar, 20 wt% quartz). After mixing, the mixture was ball-milled for 24 hours, slip-cast, dried at 80℃ for 24 hours, and then sintered at 1200℃ for 3 hours.

[0077] Comparative Example 2 Comparative Example 2 is a traditional self-cleaning ceramic with only a TiO2 photocatalyst coated on its surface. The specific preparation method is as follows: The raw materials for ceramic body (50wt% clay, 30wt% feldspar, and 20wt% quartz) were mixed, ball-milled for 24 hours, slip-cast, dried at 80℃ for 24 hours, and then sintered at 1200℃ for 3 hours to obtain a green body. TiO2 nanoparticles were dispersed in ethanol to form a 5wt% suspension, which was sprayed onto the surface of the green body, dried, and then heat-treated at 500℃ for 1 hour to form a TiO2 coating.

[0078] Comparative Example 3 Comparative Example 3 is a traditional antibacterial self-cleaning ceramic, and the specific preparation method is as follows: 3 wt% nano-Ag₂O was added as an antibacterial agent to the raw materials of ceramic body (50 wt% clay, 30 wt% feldspar, and 20 wt% quartz). After mixing, the mixture was ball-milled for 24 hours, slip-cast, dried at 80℃ for 24 hours, and then sintered at 1200℃ for 3 hours. TiO₂ nanoparticles were dispersed in ethanol to form a 5 wt% suspension, which was sprayed onto the surface of the green body. After drying, it was heat-treated at 500℃ for 1 hour to form a TiO₂ coating.

[0079] Comparative Example 4 Comparative Example 4 provides a ceramic with a conventional glaze firing temperature and its preparation method.

[0080] formula: 3 wt% nano-Ag₂O was added as an antibacterial agent to the ceramic body raw materials (50 wt% clay, 30 wt% feldspar, and 20 wt% quartz). After mixing, the mixture was ball-milled for 24 hours, slip-cast, dried at 80℃ for 24 hours, and then sintered at 1200℃ for 3 hours. TiO₂ nanoparticles were dispersed in ethanol to form a 5 wt% suspension, which was sprayed onto the surface of the green body. After drying, it was heat-treated at 1200℃ for 2 hours to form a TiO₂ coating.

[0081] The ceramics prepared in the above embodiments and comparative examples were subjected to performance tests. The test methods are as follows, and the results are shown in Table 1.

[0082] Referring to GB / T21510-2008 "Test Method for Antibacterial Properties of Nano-Inorganic Materials", Escherichia coli (ATCC25922) and Staphylococcus aureus (ATCC 6538) were used as test strains. The antibacterial rate (R) was calculated by colony counting method. The calculation formula is: R = (A - B) / A × 100%, where A is the average colony count of the control group sample and B is the average colony count of the test group sample.

[0083] Oil degradation rate: Oleic acid (simulated oil) was uniformly coated onto the sample surface at a concentration of 1 mg / cm², and then left under visible light irradiation (5000 lux) for 24 hours. The oil degradation rate was calculated by weighing. The formula is: Degradation rate = (W0 - W) / (W0 - W0) / W0. 24 ) / W0 × 100%, where W0 is the initial oil contamination mass, W 24 The remaining oil quality after 24 hours.

[0084] Water contact angle: The water contact angle of the sample surface was measured using a contact angle meter. Five different locations were measured for each sample, and the average value was taken.

[0085] Friction test: The friction test was conducted using a friction and wear tester under the conditions of a load of 500g and a friction speed of 50 times / minute. After 1000 cycles, the antibacterial rate and the retention rate of self-cleaning performance were tested.

[0086] Water washing test: The sample was placed in deionized water and washed with shaking at 40℃ and 100rpm for 500 cycles. The antibacterial rate and the retention rate of self-cleaning performance were then tested.

[0087] Table 1 Antibacterial rate (%) Oil degradation rate (%) Water contact angle (°) Functional retention rate (%) after 1000 cycles of friction Function retention rate (%) after 500 water washes Example 1 ≥99.9 ≥90 ≥140 ≥95 ≥95 Example 2 ≥99.5 ≥85 ≥135 ≥90 ≥90 Example 3 ≥99.9 ≥92 ≥145 ≥96 ≥96 Example 4 ≥99.9 ≥90 ≥135 ≥95 ≥95 Example 5 ≥99.6 ≥85 ≥130 ≥90 ≥90 Example 6 ≥99.9 ≥92 ≥140 ≥96 ≥96 Example 7 ≥99.9 ≥95 ≥145 ≥97 ≥97 Example 8 ≥99.9 ≥96 ≥150 ≥98 ≥98 Comparative Example 1 ≥99.9 ≤20 ≤90 ≤70 ≤60 Comparative Example 2 ≤50 ≥80 ≤100 ≤50 ≤40 Comparative Example 3 ≥99.9 ≥80 ≤100 ≤60 ≤50 Comparative Example 4 ≤80 ≤60 ≤100 ≤50 ≤40 As shown in Table 1, Examples 1-8 all exhibited excellent antibacterial and self-cleaning properties, and good durability. Examples 7-8, in particular, showed the best overall performance. In contrast, Comparative Example 1, while exhibiting good antibacterial properties, had poor self-cleaning properties; Comparative Example 2, while having relatively good self-cleaning properties, had poor antibacterial properties; and Comparative Example 3, while possessing both antibacterial and self-cleaning properties, had poor durability and low functional retention. Compared to Comparative Example 3, Comparative Example 4 showed that high temperature disrupted the bond between the functional layer and the glaze layer.

[0088] The present application has been described in detail above with reference to specific embodiments and exemplary examples; however, these descriptions should not be construed as limiting the present application. Those skilled in the art will understand that various equivalent substitutions, modifications, or improvements can be made to the technical solutions and implementation methods of the present application without departing from the spirit and scope of the present application, and all such modifications and improvements fall within the scope of the present application. The scope of protection of the present application is determined by the appended claims.

Claims

1. A method for preparing an antibacterial, self-cleaning daily-use ceramic, characterized in that, Includes the following steps: S1. Mix the ceramic body raw materials, antibacterial precursors and additives, ball mill them to obtain a slurry, and then cast the slurry to obtain a green body. After drying, the green body is obtained. S2. The green body is subjected to gradient in-situ reaction sintering, first sintering at 400-600℃; then sintering at 800-1000℃; and then sintering at 1100-1250℃. S3. After sintering, micron-level pits are formed on the surface of the ceramic blank by plasma etching; S4. Glaze the ceramic and sinter it at 700-900℃ to bond the glaze with the unglazed body, thus producing antibacterial and self-cleaning daily ceramics.

2. The method for preparing antibacterial self-cleaning daily-use ceramics according to claim 1, characterized in that, The ceramic body raw material comprises the following raw materials in the following weight ratios: 35-50 wt% clay, 20-35 wt% quartz and 20-30 wt% feldspar; the antibacterial precursor is a composite sol of silver nitrate and tetrabutyl titanate; the mass ratio of silver nitrate to tetrabutyl titanate is 1:5-1:10; the antibacterial precursor accounts for 1-5 wt% of the ceramic body raw material.

3. The method for preparing antibacterial self-cleaning daily-use ceramics according to claim 1, characterized in that, The additives include dispersants and photoresponsive additives; the dispersant is silica sol; and the photoresponsive additives are rare earth elements.

4. The method for preparing antibacterial self-cleaning daily-use ceramics according to claim 3, characterized in that, The silica sol accounts for 0.5-2 wt% of the ceramic body raw material; the rare earth element is selected from lanthanum and cerium; the rare earth element accounts for 0.1-1 wt% of the ceramic body raw material.

5. The method for preparing antibacterial self-cleaning daily-use ceramics according to claim 1, characterized in that, The green body is subjected to in-situ reaction sintering, first sintering at 400-600℃ for 1-3 hours; then sintering at 800-1000℃ for 1-3 hours; and then sintering at 1100-1250℃ for 1-4 hours.

6. The method for preparing antibacterial self-cleaning daily-use ceramics according to claim 1, characterized in that, The plasma etching power is 100-300W, and the plasma etching time is 5-15min.

7. The method for preparing antibacterial self-cleaning daily-use ceramics according to claim 1, characterized in that, The diameter of the formed micron-sized pits is 5-20 μm; nano-sized TiO2 / Ag-Si-O particles are distributed within the pits.

8. The method for preparing antibacterial self-cleaning daily-use ceramics according to claim 1, characterized in that, The glaze thickness is 50-100 μm; it is sintered at 700-900℃ for 1-3 hours; the glaze comprises a base glaze and functional additives, the base glaze comprising feldspar, quartz, and zinc oxide; the functional additives are Ag-loaded... + Mesoporous SiO2 and fluorine-modified TiO2 nanotubes.

9. The method for preparing antibacterial self-cleaning daily-use ceramics according to claim 8, characterized in that, The mass ratio of feldspar, quartz, and zinc oxide is 3:2:1; the Ag-loaded... + The mesoporous SiO2 accounts for 3-8 wt% of the glaze; the fluorine-modified TiO2 nanotubes account for 2-5 wt% of the glaze; and the fluorine content in the fluorine-modified TiO2 nanotubes is 1-3 wt%.

10. Antibacterial self-cleaning daily ceramic prepared by the preparation method according to any one of claims 1-9.