Antibacterial easy-to-clean ceramic and preparation method thereof

Abstract

The invention discloses antibacterial easy-to-clean ceramic and a preparation method thereof.The antibacterial easy-to-clean ceramic comprises glaze and a blank, the glaze comprises 30-60 parts of potassium feldspar, 30-60 parts of albite, 44-60 parts of phosphate, 20-28 parts of a first antibacterial agent and the like; the first antibacterial agent comprises an active component and a carrier, and the active component comprises zirconium oxide nano powder and zinc oxide nano powder; the blank comprises 45-75 parts of rutile titanium dioxide, 50-60 parts of sodium alginate, 50-70 parts of composite fibers, 20-36 parts of a surfactant, 40-50 parts of a second antibacterial agent and the like; the second antibacterial agent comprises cuprous oxide; the composite fiber comprises a first fiber body and a second fiber body, and the first fiber body comprises TiB fiber. Zirconium oxide and zinc oxide nano powder with efficient antibacterial ability is added into the glaze, and phosphate is combined to consolidate the glaze, so that antibacterial substances are prevented from flowing out; cuprous oxide is used as a second antibacterial active component in the blank and is combined with the TiB non-continuous reinforced fibers to obtain excellent antibacterial performance and mechanical strength.

Description

Technical Field

[0001] This application relates to the technical field of ceramic materials, and particularly to an antibacterial and easy-to-clean ceramic and its preparation method. Background Art

[0002] Ceramic materials are a type of solid materials mainly composed of inorganic non-metallic substances and made through processes such as high-temperature sintering. Traditional ceramics mainly use natural minerals such as clay, quartz, and feldspar as raw materials. The firing temperature of traditional ceramics is generally between 1000°C and 1300°C, and its products are widely used in building ceramics (such as ceramic tiles), daily-use ceramics (such as tableware, tea sets, etc.), sanitary wares (such as toilets, etc.). However, traditional ceramics have some limitations, such as relatively low strength and hardness, large brittleness, single function, and no antibacterial and easy-to-clean functions.

[0003] The raw materials of modern ceramic materials are no longer limited to natural minerals, but more use synthetic high-purity powders, such as alumina, zirconia, silicon carbide, silicon nitride, etc., and synthetic composite material powders, such as synthetic bone powder, shell composite mineral functional materials, etc. These added materials have a more uniform particle size distribution and higher purity, and can precisely control the microstructure and special properties of ceramics, so as to produce many types of functional ceramics according to requirements. Nowadays, there is a large market demand for antibacterial ceramics. Antibacterial ceramics have antibacterial effects through physical, chemical and other means, mainly including methods such as coating, impregnation, and mixed sintering. Among them, coating and impregnation only make the antibacterial material adhere to the surface of the ceramic to make it antibacterial, but the antibacterial property cannot last long, and the antibacterial material is easy to flow out during use, affecting human health.

[0004] Regarding the above technology, the applicant believes that the existing antibacterial ceramics cannot have long-term and efficient antibacterial performance, and the antibacterial active ingredients in the ceramic materials cannot maintain good stability, resulting in poor antibacterial performance of the ceramic materials. Summary of the Invention

[0005] In order to enable ceramic materials to obtain high antibacterial performance and long-lasting antibacterial stability, while taking into account the characteristics of easy cleaning, this application provides an antibacterial and easy-to-clean ceramic and its preparation method.

[0006] In the first aspect, an antibacterial and easy-to-clean ceramic provided by this application adopts the following technical solution: An antibacterial and easy-to-clean ceramic, comprising a glaze and a blank. By weight, the glaze comprises 50 - 90 parts of calcite, 60 - 120 parts of wollastonite, 30 - 60 parts of potassium feldspar, 30 - 60 parts of sodium feldspar, 44 - 60 parts of phosphate, and 20 - 28 parts of a first antibacterial agent; the first antibacterial agent comprises an active ingredient and a carrier, and the active ingredient comprises zirconia nanopowder and zinc oxide nanopowder; The blank material comprises 100 - 200 parts of kaolin, 120 - 180 parts of bentonite, 100 - 120 parts of dolomite, 580 - 600 parts of shell powder, 60 - 90 parts of potassium feldspar, 50 - 70 parts of albite, 80 - 100 parts of quartz, 45 - 75 parts of rutile type titanium dioxide, 50 - 60 parts of sodium alginate, 50 - 70 parts of composite fiber, 20 - 36 parts of surfactant and 40 - 50 parts of second antibacterial agent; the second antibacterial agent comprises cuprous oxide; the composite fiber comprises a first fiber body and a second fiber body, and the first fiber body comprises TiB fiber.

[0007] By adopting the above technical solution, for the glaze composition, zirconium oxide and zinc oxide nano - powders are loaded on the stable mesoporous material, which can dissolve zinc ions in the glaze layer to adsorb on the cell membrane and enter the interior of the bacteria, combine with the sulfhydryl groups of proteins, resulting in the bacteria losing the ability of fission reproduction and finally dying. When the bacteria lose their activity, the zinc ions will dissociate and repeat the sterilization, thus maintaining a lasting antibacterial effect. Moreover, the zirconium oxide nano - material can greatly improve the flexural strength and fracture toughness of the ceramic glaze layer, and cooperate with zinc oxide for antibacterial. By reasonably occupying the pores on the mesoporous carrier, zinc oxide is evenly dispersed, so that the first antibacterial agent composite particles have higher mechanical strength without affecting the antibacterial effect, further ensuring the long - term antibacterial performance of the glaze layer. Adding phosphate can not only effectively fix the nano - antibacterial agent powder, but also form a glassy thin layer in the glaze layer to improve the easy - cleaning performance.

[0008] For the blank material composition, by selecting cuprous oxide as the effective antibacterial component, when it contacts bacteria in a humid environment, it can be attracted by the negative charge carried by the cell membrane, enabling copper ions to penetrate the cell membrane to disrupt the internal electrical balance of the bacteria, causing micro - environmental disorder and leading to its death. The surfactant can effectively prevent the aggregation of cuprous oxide particles and induce them to distribute along the fiber structure. The TiB fiber in the composite fiber, as a discontinuous reinforced titanium matrix composite, has excellent high specific strength, specific stiffness and high - temperature resistance. It can not only combine well with other inorganic components in the blank material, but also efficiently carry cuprous oxide through the fiber - like structure of TiB whiskers, serving as the attachment skeleton of the antibacterial active substance in the blank material system. Different from other reinforcing fiber structures, the three - dimensional composite structure jointly constructed by it and the antibacterial particles can effectively reduce the obvious non - uniform strain distribution between the matrix and the fiber region, making the antibacterial particles more evenly dispersed and having higher antibacterial activity. At the same time, to cover the color deviation caused by copper ions in the blank body, rutile type titanium dioxide is introduced to enhance the overall whiteness; by introducing sodium alginate, while improving the high - temperature resistance of the blank material system, it can also chelate copper ions under high - temperature conditions, thereby regulating the reaction activity of copper ions and enhancing its stability, macroscopically making it have a long - term antibacterial effect.

[0009] For the overall ceramic composition, a high-activity and long-term stable antibacterial effect is obtained by combining the first antibacterial agent in the glaze layer and the second antibacterial agent in the body; meanwhile, potassium feldspar, sodium feldspar, and calcite in the glaze layer can act as fluxes to lower the firing temperature of the glaze, promote the melting and flow of the glaze, and cooperate with the phosphate component to make the glaze layer smoother and flatter, reducing the adsorption and residue of stains, thereby improving the easy-cleaning performance.

[0010] Preferably, the carrier includes one or more of activated carbon, multi-walled carbon nanotubes, and silica white.

[0011] By adopting the above technical solution, a suitable mesoporous material is selected to effectively load the nano antibacterial particles. The high specific surface area and porosity of the mesoporous material can provide a large number of uniform active loading sites for the nano antibacterial particles to prevent the aggregation of zirconia and zinc oxide nano powders, making them highly dispersed to obtain a better antibacterial effect, and can also reduce the adverse effects of other ceramic matrix materials on the antibacterial effect of the active ingredients. Specifically, activated carbon (carbon molecular sieve), as a functional carbon adsorption material, has characteristics such as a large specific surface area, regular pore structure, and strong adsorption, so it can effectively adsorb zirconia and zinc oxide nano powders; multi-walled carbon nanotubes, as a one-dimensional quantum material, have a tight hexagonal structure and show obvious chemical inertness on the surface, and can cooperate with different nano antibacterial particles to form a lamellar structure with different loadings and provide high mechanical strength; silica white is mainly hydrated amorphous silica, which has high temperature resistance, a large specific surface area, is not easily decomposed by heat, has chemical stability and good dispersion, so while being an effective carrier, it can also reinforce the ceramic glaze layer.

[0012] Preferably, the particle size of the zirconia nano powder is 50 - 500 nm, and / or the particle size of the zinc oxide is 50 - 100 nm.

[0013] By adopting the above technical solutions, on the one hand, zirconia nanopowder and zinc oxide nanopowder are jointly added into the ceramic glaze layer for mutual modification by the composite powder method. Both of them have strong antibacterial and bacteriostatic effects. The zinc ions in zinc oxide can combine with the negatively charged groups on the surface of bacterial cells, destroy the microscopic structure and biological functions of the cell membrane, cause the leakage of cell contents, and can also interfere with the enzyme system of bacteria, inhibit their growth and reproduction, so as to achieve the bactericidal effect. Since zirconia will undergo volume expansion under specific conditions (martensitic transformation), and zinc oxide can act as a stabilizer to form a solid solution with zirconia through high-temperature sintering, effectively avoiding the volume effect and obtaining high-temperature stability. After returning to room temperature, both can still maintain the tetragonal or cubic phase stability, so that the ceramic glaze layer can maintain a long-term and synergistic antibacterial effect; on the other hand, zirconia and zinc oxide with nano-powders of a specific particle size range are selected, which can have a special surface effect and cooperate with the carrier synergistically. Also, due to the high atomic diffusion coefficient and unsaturated atomic coordination in the interfacial atomic region of the nanoparticles, the two have higher antibacterial activity in the glaze system. At the same time, the zirconia and zinc oxide powders in this range have smaller particle sizes and are evenly distributed in the ceramic glaze layer, with a weak light scattering effect, which can make the glaze layer still have good transparency and meet higher requirements for dyeing and processing.

[0014] Preferably, the phosphate includes one or more of ammonium dihydrogen phosphate and diammonium hydrogen phosphate.

[0015] By adopting the above technical solutions, on the one hand, both ammonium dihydrogen phosphate and diammonium hydrogen phosphate have low melting points and high surface tensions, and can cooperate with the potassium feldspar and sodium feldspar components in the glaze to form a uniform glassy film on the surface, so that stains are difficult to adhere and are easier to clean; on the other hand, when ammonium dihydrogen phosphate and diammonium hydrogen phosphate react with the antibacterial agent components in advance, they form a structure similar to a glass phase or a mineral phase and wrap around the metal ions (such as zinc ions, etc.) in the system to form a stable structure, so as to greatly improve the stability of the antibacterial agent components on the glaze surface.

[0016] Preferably, the second fiber body includes one or more of silicon carbide fibers and alumina fibers.

[0017] By adopting the above technical solution, on the one hand, silicon carbide fibers and alumina fibers can be mixed into the ceramic green body as reinforcing fibers to greatly enhance toughness. When the ceramic is subjected to external forces, the second fiber body can hinder the propagation of cracks and absorb energy through the bridging and pulling-out effects of the fiber structure, thereby improving the overall strength of the ceramic material. On the other hand, both silicon carbide fibers and alumina fibers have good high-temperature resistance, can assist the active ingredients in the second antibacterial agent to maintain a stable inherent structure in a high-temperature environment, and reduce the thermal expansion coefficient of the ceramic matrix, thereby improving the thermal stability of the ceramic material and further preventing high temperature from damaging the antibacterial structure in the green body.

[0018] Preferably, the mass ratio of the first fiber body to the second fiber body is 1:(0.2 - 0.5).

[0019] By adopting the above technical solution, setting the specific mass ratio range of the first fiber body and the second fiber body in the blank system can not affect the uniform dispersion and regulation of the antibacterial active substance by the first fiber body, nor affect the effective regulation of the mechanical properties and high-temperature resistance of the green body by the second fiber body. When the mass ratio range of the first fiber body and the second fiber body is unreasonable, not only the above technical effects cannot be achieved, but also the fiber body structure is prone to form a disordered and irregular structure inside the green body, which hinders the function of other functional components and has an adverse impact on the structural stability of the green body.

[0020] Preferably, the surfactant includes one or more of polyvinylpyrrolidone (PVP) and cetyltrimethylammonium bromide (CTAB).

[0021] By adopting the above technical solution, polyvinylpyrrolidone (PVP) and cetyltrimethylammonium bromide (CTAB) are used as surfactants. The carbonyl or nitrogen atom in the PVP molecule or the amphiphilic structure of CTAB can be adsorbed and combined with the surface of the antibacterial active ingredient cuprous oxide particles to form a protective film on its surface, preventing the cuprous oxide particles from aggregating or precipitating due to collision, static electricity, etc., so that it can maintain a stable dispersion state in the blank system, thereby ensuring that the green body still has a long-term antibacterial effect after molding. At the same time, both PVP and CTAB can also have a guiding effect on the forming shape of cuprous oxide in the blank system, and can affect the growth of cuprous oxide particles along the fiber body (especially TiB fibers) structure, so as to form a uniform antibacterial agent distribution structure in the green body to exert a uniform and stable antibacterial effect.

[0022] In a second aspect, a method for preparing an antibacterial and easy-to-clean ceramic provided by the present application includes the following steps: S1. Glaze Slurry Preparation: Calcite, wollastonite, potassium feldspar, and sodium feldspar are ball-milled and mixed evenly to obtain glaze powder. Then, the active ingredient in the first antibacterial agent is loaded onto the carrier through vacuum infiltration. The first antibacterial agent, phosphate, and water are added to the glaze powder, and the temperature is raised to 55 - 65°C, followed by high-speed stirring at 1000 - 1100 r / min for 1 - 2 h. After standing, the glaze slurry is obtained. S2. Green Body Preparation: Kaolin, bentonite, dolomite, shell powder, potassium feldspar, sodium feldspar, and quartz are mixed evenly and wet ball-milled to obtain green body powder. The composite fiber is pretreated, and surfactant, rutile titanium dioxide, sodium alginate, and the second antibacterial agent are added and dissolved and mixed. Then, the green body powder and water are added and stirred and mixed. The temperature is raised to 90 - 100°C, and it is pressed into shape to obtain the green body. S3. Preliminary Firing: The green body is naturally left standing for 20 - 24 h, and the water content inside the green body is controlled to be 1% - 6%. Then, the green body is calcined at 1200 - 1400°C for 12 - 24 h and naturally cooled to obtain the biscuit body. S4. Glazing: The glaze slurry is sprayed and coated on the surface of the biscuit body to obtain the initial ceramic product. S5. Secondary Firing: The initial ceramic product is calcined at 1150 - 1350°C for 6 - 12 h and naturally cooled to obtain the finished ceramic product.

[0023] By adopting the above technical solution, in the process of glaze slurry preparation, the step-by-step method is used to first prepare the glaze powder, and then the first antibacterial agent and other functional materials are introduced, which can ensure the subsequent antibacterial effect and easy-cleaning performance of the glaze layer, and prevent the occurrence of microstructural damage or inactivation in the previous steps. For the first antibacterial agent, the vacuum infiltration method is used, and the antibacterial nanoparticles penetrate into the mesoporous carrier under the action of the pressure difference in the vacuum environment to achieve effective loading and mixing, which can form a stable and high-loading composite antibacterial structure; then the green body is also prepared by the step-by-step method to ensure that the second antibacterial agent and other functional materials can play a stable role; finally, the glaze slurry is evenly coated on the surface of the green body by spraying, and combined with high-temperature sintering, a finished ceramic product with both antibacterial efficacy and easy cleaning is prepared. This preparation method is stable and controllable and can form industrial production and processing.

[0024] Preferably, in the step S2, the pretreatment of the composite fiber includes cutting the first fiber body and the second fiber body into short fibers. The aspect ratio of the first fiber body is 20 - 40, and / or the length of the second fiber body is 0.1 - 0.5 mm.

[0025] By adopting the above technical solution, both the first fiber body and the second fiber body are mechanically cut into short fiber forms, which can improve the uniformity of the distribution of the fiber body material in the ceramic green body without affecting the respective functions of the fiber bodies. Setting the aspect ratio of the first fiber body, TiB fiber, within a specific range can ensure its enhanced effect on regulating the activity of antibacterial particles. While setting the length of the second fiber body, silicon carbide fiber / aluminum oxide fiber, within a specific range can improve its compatibility and bonding strength in the green body system while taking into account the strengthening effect.

[0026] Preferably, in the step S2, the green body is pressed by an isostatic pressing method, and the isostatic pressing pressure is 180 - 260 MPa.

[0027] By adopting the above technical solution, the green body is prepared by an isostatic pressing method, and the appropriate isostatic pressing pressure is regulated. Then, the pressure is transmitted through a liquid or gas medium to ensure that the green body is uniformly pressured in all directions, thereby avoiding problems such as uneven density and deformation of the green body caused by uneven pressure. Moreover, the processing method of isostatic pressing can also effectively eliminate the voids between the antibacterial particles and the fiber structure, significantly improving the density and strength of the green body, reducing shrinkage and deformation in the subsequent high-temperature sintering step, and thus improving the dimensional accuracy and production quality of the ceramic product. At the same time, other forming methods such as rolling, grouting, or others can also be used to achieve a better green body forming effect.

[0028] In summary, the present application has the following beneficial effects: 1. In the present application, cuprous oxide is selected as the antibacterial active ingredient in the green body composition. When it comes into contact with bacteria in a humid environment, it can be attracted by the negative charge carried by the cell membrane, enabling copper ions to penetrate the cell membrane to disrupt the internal electrical balance of the bacteria, causing microenvironmental disorders and leading to their death. The surfactant can effectively prevent the aggregation of cuprous oxide particles and induce their distribution along the fiber structure. The TiB fiber in the composite fiber, as a discontinuous reinforced titanium matrix composite, has excellent high specific strength, specific stiffness, and high-temperature resistance. It can not only combine well with other inorganic components in the green body but also efficiently carry cuprous oxide through the fiber-like structure of TiB whiskers to serve as the attachment skeleton of the antibacterial active substance in the green body system. Different from other reinforcing fiber structures, the three-dimensional composite structure jointly constructed by it and the antibacterial particles can effectively reduce the obvious non-uniform strain distribution between the matrix and the fiber region, thus making the antibacterial particles more uniformly dispersed and having higher antibacterial activity. At the same time, to cover the color deviation caused by copper ions in the green body, rutile titanium dioxide is introduced to enhance the overall whiteness; while introducing sodium alginate can improve the high-temperature resistance of the green body system and can also chelate copper ions under high-temperature conditions, thereby regulating the reaction activity of copper ions and enhancing its stability, macroscopically making it have a long-term antibacterial effect.

[0029] 2. This application adds phosphate components to the glaze. On the one hand, ammonium dihydrogen phosphate and diammonium hydrogen phosphate both have a low melting point and high surface tension, and can cooperate with the potassium feldspar and sodium feldspar components in the glaze to form a uniform glassy film on the surface, making it difficult for stains to adhere and easier to clean. On the other hand, ammonium dihydrogen phosphate and diammonium hydrogen phosphate form a glass-like or mineral phase when reacting with the antibacterial agent component in advance, and form a stable structure around the metal ions (such as zinc ions) in the system, thereby greatly improving the stability of the antibacterial agent component of the glaze.

[0030] 3. This application uses polyvinylpyrrolidone (PVP) and cetyltrimethylammonium bromide (CTAB) as surfactants. The carbonyl group or nitrogen atom in the PVP molecule or the amphiphilic structure of CTAB can be adsorbed and bonded to the surface of the antimicrobial active ingredient cuprous oxide particles, forming a protective film on the surface. This prevents the cuprous oxide particles from agglomerating or precipitating due to collisions, static electricity, etc., allowing them to maintain a stable dispersion state within the blank system, thereby ensuring that the blank has a long-lasting antimicrobial effect after molding. At the same time, both PVP and CTAB can also guide the molding shape of cuprous oxide within the blank system, affecting the extension and growth of cuprous oxide particles along the fiber body (especially TiB fiber) structure, thereby forming a uniform antimicrobial agent distribution structure within the blank body to exert a uniform and stable antimicrobial effect. DETAILED DESCRIPTION

[0031] The present application can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure of the present application more thorough and comprehensive.

[0032] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which this application pertains. The terms used herein in the specification of this application are for the purpose of describing specific embodiments only and are not intended to limit this application. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0033] In this application, terms such as "further," "further," "particularly," "for example," "such as," "example," and "for instance" are used for descriptive purposes to indicate that the preceding and following technical solutions are related in terms of their coverage. However, they should not be construed as limiting the preceding technical solution or the scope of protection of this application. In this application, unless otherwise specified, "A (such as B)" means that B is a non-limiting example of A, and it should be understood that A is not limited to B.

[0034] In this application, in the technical features or technical solutions described in an open language, it includes the closed technical features or technical solutions composed of the listed contents, and also includes the open technical features or technical solutions containing the listed contents.

[0035] In this application, the exemplary descriptions such as "in some embodiments" or "in one embodiment" may cover, but are not limited to, the following meanings: These solutions can be combined with other solutions in a suitable manner to form new technical solutions.

[0036] In this application, for a method process involving multiple steps, unless there are clear different descriptions in this article, the execution of these steps has no strict order limit, and it can be executed in an order other than the described one. Moreover, any step may include multiple sub-steps or multiple stages. These sub-steps or stages do not necessarily need to be completed at the same moment, but can be executed at different moments, and their execution order does not necessarily need to be sequential, but can be executed alternately or simultaneously with other steps or a part of the sub-steps or stages of other steps.

[0037] The raw materials used in the examples and comparative examples can all be obtained commercially.

[0038] The first antibacterial agent includes an active ingredient with antibacterial efficacy and a carrier with the characteristics of a mesoporous material. Among them, the active ingredient is selected as a mixed powder of zirconia nanopowder and zinc oxide nanopowder. The particle size range of the zirconia nanopowder is 50 - 500 nm, preferably 50 - 300 nm; the particle size range of the zinc oxide nanopowder is 50 - 100 nm, preferably 50 - 60 nm. When the compounding mass ratio of the zirconia nanopowder to the zinc oxide nanopowder is 1:(1.80 - 3.40), keeping the effective component of zinc oxide slightly higher than that of zirconia to ensure antibacterial performance, especially for Staphylococcus aureus and Escherichia coli.

[0039] The second antibacterial agent needs to cooperate with the composite fiber to act on the green body together. The active ingredient with antibacterial efficacy in the second antibacterial agent is selected as cuprous oxide. There is no specific limitation on the particles of cuprous oxide. It is preferably prepared by a solid-phase method. For example, under high-temperature conditions, cuprous oxide is reduced from cupric oxide using copper powder as a reducing agent; or cuprous oxide is obtained by annealing and oxidizing copper powder in an aerobic environment. Then, mechanical processing is performed on the prepared cuprous oxide material to precisely control its purity, composition, structure, and morphology.

[0040] For the first fiber body TiB fiber in the composite fiber, raw materials Ti and TiB2 powders are used for preparation. Among them, the particle size of Ti powder is preferably 100 - 200 μm, while the particle size of TiB2 powder is preferably 5 - 10 μm. The Ti powder and TiB2 powder are mixed by a ball milling process at a rotation speed of 100 r / min for 4 h. Then, by making a mold composed of hundreds of tubes and substrates to control the distribution of the composite material powder, the mixed powder of the composite material is filled into the array tubes, and pure Ti powder is filled into the voids outside the tube walls, finally forming an array-confined distribution of the mixed powder of the composite material, presenting a fiber-like structure. Then, the fiber-like structure mold filled with powder is placed into a steel cold pressing mold for cold pressing molding, with a pressing pressure of 300 - 400 MPa and a pressure holding time of 5 min. Finally, vacuum hot pressing sintering is carried out, with a sintering process of 1500 K, 1 h, a pressure of 40 MPa, and a vacuum degree maintained at 0.01 Pa; and hot extrusion (extrusion ratio of 14:1) is carried out to obtain the first fiber body TiB fiber.

[0041] Preparation Example 1. Preparation of Glaze Slip Preparation Example 1 - 1, a method for preparing a ceramic glaze slip, adopts the following steps: (1) 70 kg of calcite, 90 kg of wollastonite, 45 kg of potassium feldspar, and 45 kg of sodium feldspar are ball milled and mixed evenly to obtain a glaze powder; (2) 24 kg of the first antibacterial agent, 52 kg of phosphate, and 4.6 L of deionized water are added to the glaze powder, heated to 6℃, and stirred at a high speed of 1100 r / min for 1.5 h, and then left standing to obtain the glaze slip.

[0042] Among them, for the first antibacterial agent, the compounding mass ratio of zirconia nanopowder to zinc oxide nanopowder is 1:2.60, the carrier is selected as multi-walled carbon nanotubes, and the phosphate is selected as ammonium dihydrogen phosphate.

[0043] Preparation Example 1 - 2, a method for preparing a ceramic glaze slip, adopts the following steps: (1) 90 kg of calcite, 120 kg of wollastonite, 60 kg of potassium feldspar, and 60 kg of sodium feldspar are ball milled and mixed evenly to obtain a glaze powder; (2) 28 kg of the first antibacterial agent, 60 kg of phosphate, and 5.4 L of deionized water are added to the glaze powder, heated to 65℃, and stirred at a high speed of 1100 r / min for 2 h, and then left standing to obtain the glaze slip.

[0044] Among them, for the first antibacterial agent, the compounding mass ratio of zirconia nanopowder to zinc oxide nanopowder is 1:2.60, the carrier is selected as multi-walled carbon nanotubes, and the phosphate is selected as ammonium dihydrogen phosphate.

[0045] Preparation Example 1 - 3, a method for preparing a ceramic glaze slip, adopts the following steps: (1) Mix 50 kg of calcite, 60 kg of wollastonite, 30 kg of potassium feldspar, and 30 kg of albite by ball milling to obtain a uniformly mixed glaze powder. (2) Add 20 kg of the first antibacterial agent, 44 kg of phosphate, and 3.8 L of deionized water to the glaze powder, heat up to 55 °C, stir at a high speed of 1000 r / min for 1 h, and let it stand to obtain a glaze slurry.

[0046] Among them, for the first antibacterial agent, the compounding mass ratio of zirconia nanopowder to zinc oxide nanopowder is 1:2.60, the carrier is selected as multi-walled carbon nanotubes, and the phosphate is selected as ammonium dihydrogen phosphate.

[0047] Preparation Example 1-4, a method for preparing a ceramic glaze slurry, which is different from Preparation Example 1-1 in that the carrier in the first antibacterial agent is selected as activated carbon.

[0048] Preparation Example 1-5, a method for preparing a ceramic glaze slurry, which is different from Preparation Example 1-1 in that the carrier in the first antibacterial agent is selected as silica white.

[0049] Preparation Example 1-6, a method for preparing a ceramic glaze slurry, which is different from Preparation Example 1-1 in that the phosphate is selected as diammonium hydrogen phosphate.

[0050] Preparation Example 1-7, a method for preparing a ceramic glaze slurry, which is different from Preparation Example 1-1 in that the compounding mass ratio of zirconia nanopowder to zinc oxide nanopowder in the first antibacterial agent is 1:3.40.

[0051] Preparation Example 1-8, a method for preparing a ceramic glaze slurry, which is different from Preparation Example 1-1 in that the compounding mass ratio of zirconia nanopowder to zinc oxide nanopowder in the first antibacterial agent is 1:1.80.

[0052] 2. Preparation of the green body Preparation Example 2-1, a method for preparing a ceramic green body, which adopts the following steps: (1) Mix 150 kg of kaolin, 150 kg of bentonite, 110 kg of dolomite, 590 kg of shell powder, 75 kg of potassium feldspar, 60 kg of albite, and 90 kg of quartz uniformly, and obtain the green body powder through wet ball milling. (2) Pretreat 60 kg of composite fibers, add 28 kg of surfactant, 60 kg of rutile-type titanium dioxide, 55 kg of sodium alginate, and 45 kg of the second antibacterial agent to dissolve and mix, then add the green body powder and 6.8 L of water to stir and mix, heat up to 95 °C, and press by isostatic pressing to obtain the green body.

[0053] Among them, for the composite fiber, the second fiber body is made of silicon carbide fiber, and the mass ratio of the first fiber body to the second fiber body is 1:0.35; the surfactant is polyvinylpyrrolidone (PVP); and the isostatic pressure is 220 MPa.

[0054] Preparation Example 2-2, a method for preparing a ceramic green body, comprising the following steps: (1) Mix 200 kg of kaolin, 180 kg of bentonite, 120 kg of dolomite, 600 kg of shell powder, 90 kg of potassium feldspar, 70 kg of sodium feldspar, and 100 kg of quartz evenly, and obtain the green body powder through wet ball milling; (2) Pretreat 70 kg of composite fiber, add 36 kg of surfactant, 75 kg of rutile titanium dioxide, 60 kg of sodium alginate, and 50 kg of the second antibacterial agent, dissolve and mix them, then add the green body powder and 7.4 L of water, stir and mix, heat up to 100 °C, and obtain the green body by isostatic pressing.

[0055] Among them, for the composite fiber, the second fiber body is made of silicon carbide fiber, and the mass ratio of the first fiber body to the second fiber body is 1:0.35; the surfactant is polyvinylpyrrolidone (PVP); and the isostatic pressure is 220 MPa.

[0056] Preparation Example 2-3, a method for preparing a ceramic green body, comprising the following steps: (1) Mix 100 kg of kaolin, 120 kg of bentonite, 100 kg of dolomite, 580 kg of shell powder, 60 kg of potassium feldspar, 50 kg of sodium feldspar, and 80 kg of quartz evenly, and obtain the green body powder through wet ball milling; (2) Pretreat 50 kg of composite fiber, add 20 kg of surfactant, 45 kg of rutile titanium dioxide, 50 kg of sodium alginate, and 40 kg of the second antibacterial agent, dissolve and mix them, then add the green body powder and 6.2 L of water, stir and mix, heat up to 90 °C, and obtain the green body by isostatic pressing.

[0057] Among them, for the composite fiber, the second fiber body is made of silicon carbide fiber, and the mass ratio of the first fiber body to the second fiber body is 1:0.35; the surfactant is polyvinylpyrrolidone (PVP); and the isostatic pressure is 220 MPa.

[0058] Preparation Example 2-4, a method for preparing a ceramic green body, which is different from Preparation Example 2-1 in that the second fiber body is made of alumina fiber.

[0059] Preparation Example 2-5, a method for preparing a ceramic green body, which is different from Preparation Example 2-1 in that the mass ratio of the first fiber body to the second fiber body is 1:0.5.

[0060] Preparation Example 2-6. The method for preparing the ceramic green body is different from that of Preparation Example 2-1 in that the mass ratio of the first fiber body to the second fiber body is 1:0.2.

[0061] Preparation Example 2-7. The method for preparing the ceramic green body is different from that of Preparation Example 2-1 in that the surfactant is cetyltrimethylammonium bromide (CTAB).

[0062] Preparation Example 2-8. The method for preparing the ceramic green body is different from that of Preparation Example 2-1 in that the isostatic pressure is 260 MPa.

[0063] Preparation Example 2-9. The method for preparing the ceramic green body is different from that of Preparation Example 2-1 in that the isostatic pressure is 180 MPa.

[0064] Examples Example 1. An antibacterial and easy-to-clean ceramic and its preparation method, which include the following steps: (1) Naturally stand the green body prepared in Preparation Example 2-1 for 22 h, control the moisture content inside the green body to 4%, then calcine the green body at 1300 °C for 18 h, and naturally cool it to obtain a biscuit body; (2) Spray and coat the glaze slurry prepared in Preparation Example 1-1 on the surface of the biscuit body to obtain a preliminary ceramic product; (3) Calcinate the preliminary ceramic product at 1250 °C for 9 h, and naturally cool it to obtain a finished ceramic product.

[0065] Example 2. An antibacterial and easy-to-clean ceramic and its preparation method, which include the following steps: (1) Naturally stand the green body prepared in Preparation Example 2-1 for 24 h, control the moisture content inside the green body to 1%, then calcine the green body at 1400 °C for 24 h, and naturally cool it to obtain a biscuit body; (2) Spray and coat the glaze slurry prepared in Preparation Example 1-1 on the surface of the biscuit body to obtain a preliminary ceramic product; (3) Calcinate the preliminary ceramic product at 1350 °C for 12 h, and naturally cool it to obtain a finished ceramic product.

[0066] Example 3. An antibacterial and easy-to-clean ceramic and its preparation method, which include the following steps: (1) Naturally stand the green body prepared in Preparation Example 2-1 for 20 h, control the moisture content inside the green body to 6%, then calcine the green body at 1200 °C for 12 h, and naturally cool it to obtain a biscuit body; (2) Spray and coat the glaze slurry prepared in Preparation Example 1-1 on the surface of the biscuit body to obtain a preliminary ceramic product; (3) Calcinate the preliminary ceramic product at 1150 °C for 6 h, and naturally cool it to obtain a finished ceramic product.

[0067] Example 4. An antibacterial and easy-to-clean ceramic, which is different from Example 1 in that the glaze slurry is derived from Preparation Example 1-2.

[0068] Example 5. An antibacterial and easy-to-clean ceramic, which is different from Example 1 in that the glaze slurry is derived from Preparation Example 1-3.

[0069] Example 6. An antibacterial and easy-to-clean ceramic, which is different from Example 1 in that the glaze slurry is derived from Preparation Example 1-4.

[0070] Example 7. An antibacterial and easy-to-clean ceramic, which is different from Example 1 in that the glaze slurry is derived from Preparation Example 1-5.

[0071] Example 8. An antibacterial and easy-to-clean ceramic, which is different from Example 1 in that the glaze slurry is derived from Preparation Example 1-6.

[0072] Example 9. An antibacterial and easy-to-clean ceramic, which is different from Example 1 in that the glaze slurry is derived from Preparation Example 1-7.

[0073] Example 10. An antibacterial and easy-to-clean ceramic, which is different from Example 1 in that the glaze slurry is derived from Preparation Example 1-8.

[0074] Example 11. An antibacterial and easy-to-clean ceramic, which is different from Example 1 in that the green body is derived from Preparation Example 2-2.

[0075] Example 12. An antibacterial and easy-to-clean ceramic, which is different from Example 1 in that the glaze slurry is derived from Preparation Example 2-3.

[0076] Example 13. An antibacterial and easy-to-clean ceramic, which is different from Example 1 in that the glaze slurry is derived from Preparation Example 2-4.

[0077] Example 14. An antibacterial and easy-to-clean ceramic, which is different from Example 1 in that the glaze slurry is derived from Preparation Example 2-5.

[0078] Example 15. An antibacterial and easy-to-clean ceramic, which is different from Example 1 in that the glaze slurry is derived from Preparation Example 2-6.

[0079] Example 16. An antibacterial and easy-to-clean ceramic, which is different from Example 1 in that the glaze slurry is derived from Preparation Example 2-7.

[0080] Example 17. An antibacterial and easy-to-clean ceramic, which is different from Example 1 in that the glaze slurry is derived from Preparation Example 2-8.

[0081] Example 18. An antibacterial and easy-to-clean ceramic, which is different from Example 1 in that the glaze slurry is derived from Preparation Example 2-9.

[0082] Comparative Example Comparative Example 1, an antibacterial and easy-to-clean ceramic, which is different from Example 1 in that the zirconia powder and zinc oxide powder, the active ingredients of the first antibacterial agent in the glaze, are not nano-scale powders.

[0083] Comparative Example 2, an antibacterial and easy-to-clean ceramic, which is different from Example 1 in that the compound mass ratio of the zirconia nano-powder and zinc oxide nano-powder in the first antibacterial agent in the glaze is 2:0.8.

[0084] Comparative Example 3, an antibacterial and easy-to-clean ceramic, which is different from Example 1 in that the carrier of the first antibacterial agent in the glaze is replaced with glass particles with an equal amount of dense and smooth surfaces.

[0085] Comparative Example 4, an antibacterial and easy-to-clean ceramic, which is different from Example 1 in that the phosphate in the glaze is replaced with an equal amount of calcite.

[0086] Comparative Example 5, an antibacterial and easy-to-clean ceramic, which is different from Example 1 in that the first fiber body TiB fiber of the composite fiber in the blank is replaced with an equal amount of silicon carbide fiber.

[0087] Comparative Example 6, an antibacterial and easy-to-clean ceramic, which is different from Example 1 in that the mass ratio of the first fiber body to the second fiber body of the composite fiber in the blank is 0.2:1.

[0088] Comparative Example 7, an antibacterial and easy-to-clean ceramic, which is different from Example 1 in that the surfactant in the blank is replaced with an equal amount of kaolin.

[0089] Comparative Example 8, an antibacterial and easy-to-clean ceramic, which is different from Example 1 in that the sodium alginate in the blank is replaced with an equal amount of kaolin.

[0090] Comparative Example 9, an antibacterial and easy-to-clean ceramic, which is different from Example 1 in that the composite fiber in the blank preparation process does not go through the pre-treatment processing step.

[0091] Comparative Example 10, an antibacterial and easy-to-clean ceramic, which is different from Example 1 in that the isostatic pressing molding method is not used in the blank preparation process, but the conventional pressing method is used.

[0092] Performance Detection Test 1. Antibacterial Performance

[0093] The 50 mm × 50 mm ceramic specimens prepared in each of the examples and comparative examples were tested according to "JC / T 897-2014 Antibacterial Properties of Antibacterial Ceramic Products". The test strains were Staphylococcus aureus AS1.89 and Escherichia coli AS1.90, to test whether the antibacterial rate of the ceramic specimens prepared in this application meets the national standard Class I determination criterion (99%). The test results are shown in Table 1.

[0094] 2. Durable antibacterial rate After the 50 mm × 50 mm ceramic specimens prepared in each of the examples and comparative examples were scrubbed 500 times, their durable antibacterial rates against Staphylococcus aureus AS1.89 and Escherichia coli AS1.90 were tested. The test results are shown in Table 1.

[0095] 3. Easy-to-clean performance The easy-to-clean performance of the 50 mm × 50 mm ceramic specimens prepared in each of the examples and comparative examples was tested according to "GB / T 31859-2015 Test Method for Easy Cleanability of Domestic Porcelain". A is used to represent the residual amount of oil stain per unit area: A ≤ 0.50 g / m 2 , indicating "easy to clean"; 0.50 g / m 2 < A ≤ 1.00 g / m 2 , indicating "relatively easy to clean"; 1.00 g / m 2 < A ≤ 1.50 g / m 2 , indicating "cleanable"; A > 1.50 g / m 2 , indicating "not cleanable". The test results are shown in Table 1.

[0096] Table 1

[0097] Combined with Examples 1-3, Comparative Example 1 and Table 1, the antibacterial rate and durable antibacterial rate of the ceramic specimens prepared in Examples 1-3 are significantly better than those of the ceramic specimens prepared in Comparative Example 1, while the easy-to-clean performance of the two is not much different. From the test results, it can be seen that when the active ingredient zirconia powder and zinc oxide powder are not in nano-scale powder, on the one hand, it is difficult to exert the high antibacterial activity of nano-particles in the system, and on the other hand, the too large particles are difficult to be loaded into the mesoporous structure of the carrier used in this application, which will affect the release of metal ions and be inactivated by the hindrance of other components in the system. Therefore, Comparative Example 1 cannot obtain the expected antibacterial effect and antibacterial long-term performance.

[0098] Combined with Examples 1-3, Comparative Example 2 and Table 1, the antibacterial rate and durable antibacterial rate of the ceramic specimens prepared in Examples 1-3 are significantly better than those of the ceramic specimens prepared in Comparative Example 2. From the test results, it can be seen that the content of zinc oxide nanoparticles in Comparative Example 2 is too low relative to the overall proportion of the active ingredients, resulting in low activity of zinc ions in the glaze, and further unable to achieve effective antibacterial and bacteriostatic effects.

[0099] Combined with Examples 1-3, Comparative Example 3 and Table 1, the antibacterial rate and durable antibacterial rate of the ceramic specimens prepared in Examples 1-3 are significantly better than those of the ceramic specimens prepared in Comparative Example 3, but it has little effect on the easy-to-clean performance of the ceramic specimens in Comparative Example 3. From the test results, it can be seen that the first antibacterial agent in the glaze of Comparative Example 3 lacks a mesoporous carrier to effectively carry the nano-antibacterial particles, thus unable to exert the expected antibacterial effect. And it has a great impact on the long-term antibacterial stability of the ceramic specimens. The antibacterial active substances lacking a carrier will flow out during long-term use. However, the dense glass material on the surface can improve the hydrophobic and oleophobic properties of the glaze layer to a certain extent.

[0100] Combined with Examples 1-3, Comparative Example 4 and Table 1, the antibacterial rate and durable antibacterial rate of the ceramic specimens prepared in Examples 1-3 are significantly better than those of the ceramic specimens prepared in Comparative Example 4, and the easy-to-clean performance of Comparative Example 4 is significantly reduced. From the test results, it can be seen that the phosphate in the glaze layer not only has a great impact on the fixation of the antibacterial active ingredients, but also has a great impact on the formation of a uniform and stable glassy structure layer on the surface of the glaze layer, further affecting the easy-to-clean performance of the ceramic material.

[0101] Combined with Examples 1-3, Comparative Examples 5-6 and Table 1, the antibacterial rate and durable antibacterial rate of the ceramic specimens prepared in Examples 1-3 are significantly better than those of the ceramic specimens prepared in Comparative Examples 5-6. From the test results, it can be seen that the first fiber body TiB fiber in the composite fiber plays an indispensable role in the antibacterial performance and long-term antibacterial stability of the glaze layer. The fiber-like structure of the TiB whiskers can efficiently carry cuprous oxide and jointly construct a three-dimensional composite structure with the antibacterial particles, effectively reducing the obvious non-uniform strain distribution between the matrix and the fiber region, so that the antibacterial particles are more evenly dispersed and have higher antibacterial activity.

[0102] Combined with Examples 1-3, Comparative Examples 7-8 and Table 1, the antibacterial rate and durable antibacterial rate of the ceramic specimens prepared in Examples 1-3 are significantly better than those of the ceramic specimens prepared in Comparative Examples 7-8. From the test results, it can be seen that both the surfactant and sodium alginate, which are functional components in the green body system, play important roles. Specifically, the surfactant can prevent the copper oxide particles in the second antibacterial agent from agglomerating or precipitating, keeping them in a stable dispersion state, so as to ensure a long-lasting antibacterial effect after the green body is formed. And sodium alginate can preliminarily chelate copper ions in the previous processing steps, thereby regulating the reaction activity of copper ions.

[0103] Combined with Examples 1-3, Comparative Example 9 and Table 1, the antibacterial rate and durable antibacterial rate of the ceramic specimens prepared in Examples 1-3 are significantly better than those of the ceramic specimens prepared in Comparative Example 9, and the easy-cleaning performance of Comparative Example 9 is significantly reduced. From the test results, it can be seen that since the composite fibers in the green body preparation process do not go through the pre-treatment processing steps, the parameters such as the length and aspect ratio of the fiber body structure are all within an unreasonable range. In particular, the too-long and intricate filamentous fiber structure has a great adverse effect on the green body forming, and indirectly affects the spraying and adhesion effect of the glaze slip, so that a ceramic product with antibacterial and easy-cleaning effects cannot be formed.

[0104] Combined with Examples 1-3, Comparative Example 10 and Table 1, the antibacterial rate and durable antibacterial rate of the ceramic specimens prepared in Examples 1-3 are significantly better than those of the ceramic specimens prepared in Comparative Example 10, and the easy-cleaning performance of Comparative Example 10 is somewhat reduced. From the test results, it can be seen that the isostatic pressing forming method can also effectively eliminate the gaps between the antibacterial particles and the fiber body structure, significantly improving the density and strength of the green body, thus preventing the antibacterial agent in the glaze layer or green body from flowing out during long-term use, and having an important impact on the appearance forming quality of the ceramic product.

[0105] This specific embodiment is only an interpretation of the present application, and it is not a limitation of the present application. After reading this specification, those skilled in the art can make modifications to this embodiment without creative contributions as needed, but as long as they are within the scope of the claims of the present application, they are protected by the patent law.

Claims

1. An antibacterial and easily cleanable ceramic, characterized in that It includes glaze and body. By weight parts, the glaze includes 50-90 parts of calcite, 60-120 parts of wollastonite, 30-60 parts of potassium feldspar, 30-60 parts of albite, 44-60 parts of phosphate, and 20-28 parts of the first antibacterial agent; the first antibacterial agent includes an active ingredient and a carrier, and the active ingredient includes zirconia nanopowder and zinc oxide nanopowder; The body includes 100-200 parts of kaolin, 120-180 parts of bentonite, 100-120 parts of dolomite, 580-600 parts of shell powder, 60-90 parts of potassium feldspar, 50-70 parts of albite, 80-100 parts of quartz, 45-75 parts of rutile titanium dioxide, 50-60 parts of sodium alginate, 50-70 parts of composite fiber, 20-36 parts of surfactant, and 40-50 parts of the second antibacterial agent; the second antibacterial agent includes cuprous oxide; the composite fiber includes a first fiber body and a second fiber body, and the first fiber body includes TiB fiber.

2. The antibacterial and easy-to-clean ceramic according to claim 1, wherein The carrier includes one or more of activated carbon, multi-walled carbon nanotubes, and silica white.

3. The antibacterial and easy-to-clean ceramic according to claim 2, characterized in that, The particle size of the zirconia nanopowder is 50-500nm, and / or the particle size of the zinc oxide is 50-100nm.

4. An antibacterial and easy-to-clean ceramic according to claim 1, characterized in that, The phosphate includes one or more of ammonium dihydrogen phosphate and diammonium hydrogen phosphate.

5. An antibacterial and easy-to-clean ceramic according to claim 1, characterized in that, The second fiber body includes one or more of silicon carbide fiber and alumina fiber.

6. The antibacterial and easy-to-clean ceramic according to claim 5, wherein, The mass ratio of the first fiber body to the second fiber body is 1:(0.2-0.5).

7. An antibacterial and easy-to-clean ceramic according to claim 1, characterized in that, The surfactant includes one or more of polyvinylpyrrolidone (PVP) and cetyltrimethylammonium bromide (CTAB).

8. A method for preparing an antibacterial and easily cleanable ceramic according to any one of claims 1-7, characterized in that, It includes the following steps: S1. Glaze slurry preparation: Mix calcite, wollastonite, potassium feldspar, and albite by ball milling to obtain glaze powder. Then, load the active ingredient in the first antibacterial agent onto the carrier through vacuum infiltration. Add the first antibacterial agent, phosphate, and water to the glaze powder, heat to 55-65°C, and stir at a high speed of 1000-1100r / min for 1-2h, and then let it stand to obtain the glaze slurry; S2. Body preparation: Mix kaolin, bentonite, dolomite, shell powder, potassium feldspar, albite, and quartz evenly, and obtain body powder through wet ball milling; Pretreat the composite fiber, and add surfactant, rutile titanium dioxide, sodium alginate, and the second antibacterial agent to dissolve and mix, then add the body powder and water and stir and mix, heat to 90-100°C, and press into shape to obtain the body; S3. Preliminary firing: Let the body stand naturally for 20-24h, control the moisture content inside the body to be 1%-6%, then calcine the body at 1200-1400°C for 12-24h, and cool naturally to obtain the biscuit; S4. Glazing: Spray and coat the glaze slurry on the surface of the biscuit to obtain the initial ceramic product; S5. Secondary firing: Calcinate the initial ceramic product at 1150-1350°C for 6-12h, and cool naturally to obtain the finished ceramic product.

9. The preparation method of an antibacterial and easy-to-clean ceramic according to claim 8, characterized in that, In the step S2, the pretreatment of the composite fiber includes cutting the first fiber body and the second fiber body into short fibers, the aspect ratio of the first fiber body being 20-40, and / or the length of the second fiber body being 0.1-0.5 mm.

10. The preparation method of an antibacterial and easy-to-clean ceramic according to claim 8, characterized in that, In the step S2, an isostatic pressing forming method is adopted to press and obtain a green body, and the isostatic pressing pressure is 180-260 MPa.

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