An antibacterial, high-strength and tough copper-modified Jianshui purple pottery and its preparation method

Abstract

The present invention relates to an antibacterial high-strength and tough copper-modified Jianshui purple pottery and a preparation method thereof. The copper-modified pottery is composed of 40-98 parts by mass of Jianshui purple pottery clay and 2-60 parts by mass of copper and copper alloy, totaling 100 parts. Among them, the Jianshui purple pottery clay is a mixture of Yunnan Jianshui purple pottery clay and one or more of white clay, green clay, yellow clay, and variegated clay. The copper is micron-sized or nano-sized pure copper powder or a mixture of both. The preparation method mainly includes steps of molecular-level mixing, vacuum filtration, atmospheric drying, mechanical grinding, degreasing, and hot-pressing sintering. In the obtained copper-modified pottery, the copper and the Jianshui pottery are evenly mixed, and the particle size is 10.0-30.0 μm. The hardness of the composite material is 180-305 HV0.5, the cross-sectional shrinkage rate is not less than 5.0%, the surface is rich in the metallic luster of copper, and the antibacterial rate after 12.0 hours exceeds 85.0%. The composite material can be used for manufacturing health-preserving teapots and tea sets, storage containers such as basins, bowls, and vats, components of water purification systems, and the four treasures of the study, etc. Compared with the existing technologies, the technological process designed by the present invention is simple and easy to implement. The prepared material has good comprehensive mechanical properties, has a sterilization function, and has a beautiful surface luster. The present invention can contribute to the product and technological innovation of Yunnan Jianshui pottery, and is beneficial to the economic and industrial development in the central and western regions and the inheritance and promotion of traditional cultural techniques.

Description

Technical Field

[0001] The present invention relates to the technical field of composite material manufacturing, and in particular to a cermet composite material and a preparation method thereof. Background Art

[0002] Jianshui ceramics, also known as the "Jade of Southern Yunnan", are special products of Jianshui, Yunnan. They are China's National Geographical Indication Products. Jianshui ceramics combine practicality and ornamental value. The clay contains rich minerals, has good plasticity, a low sintering shrinkage rate, a wide firing temperature range, a low deformation rate, and good affinity with metal materials, and a high interfacial bonding strength between ceramics and metals. The main products include teapots, tea sets, the four treasures of the study, etc. In recent years, with the development of the cultural industry and tourism in Jianshui, the Jianshui ceramics industry has developed rapidly, with its influence continuously increasing nationwide and gradually realizing the transformation into cultural products. However, at the same time, due to the relatively remote production area, lack of product innovation, and lack of uniqueness compared with competing products, the current related industries also face considerable difficulties in further development and need to continuously innovate and iterate products and processes to solve the problems.

[0003] In recent years, cermet composite materials have gradually entered the public social life from applications in key fields. The addition of metals can improve the deficiencies in the comprehensive mechanical properties of ceramic materials, making their application scenarios broader. At the same time, the addition of metals can endow ceramics with the luster of metals, with a bright and beautiful appearance, while retaining the heaviness and texture of ceramic materials, which can meet the preferences of most people. Among many cermet composite materials, copper is most suitable for making materials for daily necessities. It has a heavy texture, a beautiful luster, precious properties and a moderate cost. Copper is a high-quality matrix material for metal composite materials and can produce a good bonding effect with hard materials such as ceramics, which can significantly improve the comprehensive mechanical properties of ceramic materials. Copper daily necessities themselves also have a long history, are widely used, and are deeply loved by the general public.

[0004] At the same time, copper is also the most representative metal with bactericidal effects. Research results show that copper ions have the effect of inhibiting the growth of various health-harming bacteria, viruses and microorganisms in water (such as algae). The mechanism of action is as follows: copper ions can penetrate the cell membrane and reach the interior of the cell, and can denature certain enzymes in the cell, thereby disrupting the cell's metabolism and killing microorganisms. Abroad, people widely use food utensils made of copper alloys to hold food because the surface of copper can effectively inhibit bacteria, such as being able to prevent the growth of Salmonella and Campylobacter strains and reduce the incidence of microbial food poisoning.

[0005] Currently, some technologies have been developed for copper and other metal matrix ceramic composites. Patent CN113462945A discloses a cermet composite material and its preparation method, which mixes metal elements such as Ni, Mo, Ag, Y with ceramic materials such as ZrC, VC, and C to obtain a composite material with high strength and good corrosion resistance. However, the composition of this material is relatively complex and the cost is relatively high. Patent CN114315368A discloses a metal copper and MoAlB ceramic composite material and its preparation method. This invention uses the method of electroless plating surface coating to composite the metal ceramics, focusing on the barrier effect of the Cu coating layer on the ceramic material, and does not achieve uniform mixing. Patent CN114540754A discloses a Cu / Ti-W / ceramic composite material. First, the ion bombardment technology is used to improve the surface activity of the ceramic matrix, and then the surface coating is added through the magnetron sputtering coating technology. This invention is mainly for the production of initiators and can improve the bonding force between the exploding foil and the ceramic. Generally speaking, the above technologies mostly adopt the surface layer bonding process and do not carry out uniform mixing, so the mechanical properties of the composite material cannot be improved as a whole. The ceramics used are also mostly bulk components for specific application scenarios. Currently, there are few material innovation technologies that focus on local industrial development and select ceramics for specific production areas.

[0006] In recent years, some related technologies have also been applied to the development of antibacterial metal ceramic composites for daily necessities. For example, Patent CN113925331A discloses a method for manufacturing a trace element slow-release component with a sterilization function, which mainly coats a composite material containing trace elements on the inner wall of the ceramic kettle body and coats an outer sterilization material on some positions of the kettle body to achieve resistance to external bacteria and supplement trace elements in the internal tea soup. This invention has distinct features and strong functional properties, but it does not innovate the material itself, and the coating ingredients used are complex and the process cost is also relatively high. Patent CN111517828A discloses a nano-antibacterial ceramic tea set and its manufacturing process. The antibacterial ability of the kettle body itself is mainly improved by relying on two nano-antibacterial glaze layers. However, this invention also does not innovate the material itself and focuses on the special functional properties brought by the product structure. Summary of the Invention

[0007] In view of the above-mentioned gaps in the existing technologies, the present invention focuses on the ceramic industry in Jianshui, Yunnan, conducts product and technological innovation research and development, and provides a high-strength and tough copper-Jianshui ceramic composite material with a sterilization function and its preparation method, aiming to provide new impetus for the local industrial development and contribute to the development of local industries in the central and western regions.

[0008] The object of the present invention can be achieved by the following technical solutions: An antibacterial, high-strength and tough copper-modified Jianshui purple clay, by mass, the raw materials include the following components: 40-98 parts of Jianshui purple clay; 2-60 parts of copper and copper alloy, a total of 100 parts, wherein the Jianshui purple clay is a mixture of Yunnan Jianshui purple clay and one or more of white clay, green clay, yellow clay, and variegated clay.

[0009] Preferably, the raw materials include the following components: 70-98 parts; 2-30 parts of copper and copper alloy, a total of 100 parts, wherein the Jianshui purple clay is a mixture of Yunnan Jianshui purple clay and one or more of white clay, green clay, yellow clay, and variegated clay.

[0010] Preferably, the raw materials include the following components: 85-95 parts; 5-15 parts of copper and copper alloy, a total of 100 parts, wherein the Jianshui purple clay is a mixture of Yunnan Jianshui purple clay and one or more of white clay, green clay, yellow clay, and variegated clay.

[0011] Furthermore, the copper in the raw materials is powdered pure copper, and the particle size of the selected powder can be micron-sized, nano-sized, or a mixture of both.

[0012] Furthermore, the copper and copper alloy in the raw materials can be one or more of Cu-Cr alloy, aluminum bronze alloy, and iron bronze alloy.

[0013] A preparation method of an antibacterial, high-strength and tough copper-modified Jianshui purple clay includes the following steps:

[0014] (1) Molecular-level mixing: Put the Jianshui clay and copper powder into the mixed solution, and carry out mechanical stirring and ultrasonic vibration to obtain a uniformly mixed mud of the clay and copper powder;

[0015] (2) Vacuum filtration: Use a suction pump and a suction flask to carry out vacuum filtration on the mixed mud, and peel it off from the microporous filter membrane to obtain a relatively dry thin slice of the mud mixture;

[0016] (3) Atmospheric drying: Place the thin slice of the mud mixture in step (2) in an atmospheric drying oven for drying, control the temperature at 60.0-120.0 °C, and the time at 3.0-6.0 h;

[0017] (4) Mechanical grinding: Grind the mud to 600-1200 mesh by physical methods;

[0018] (5) Degreasing: Place the green compact in a vacuum sintering furnace for degreasing, the degreasing temperature is 300.0-400.0 °C, and the holding time is 1.0-10.0 h;

[0019] (6) Hot pressing and sintering: Place the degreased blank in a vacuum hot pressing furnace for sintering, carry out temperature raising and pressure applying treatments, and the sintered shape can be a teapot, tea set, basin, bowl, cylinder, etc.

[0020] Preferably, a preparation method of antibacterial high-strength and tough copper-modified Jianshui purple pottery comprises the following steps:

[0021] (1) Molecular-level mixing: Put Jianshui clay and copper powder into a mixed solution, carry out mechanical stirring and ultrasonic vibration to obtain a uniformly mixed mud of clay and copper powder;

[0022] (2) Vacuum filtration: Use a suction filtration pump and a suction filtration flask to conduct vacuum filtration on the mixed mud, and peel it off from the microporous filter membrane to obtain a relatively dry thin slice of mud mixture;

[0023] (3) Atmospheric drying: Place the thin slice of the mud mixture in step (2) in an atmospheric drying oven for drying, control the temperature at 90.0 - 100.0 °C, and the time at 3.0 - 5.0 h;

[0024] (4) Mechanical grinding: Grind the mud to 600 - 1200 meshes by physical methods;

[0025] (5) Debinding: Place the green compact in a vacuum sintering furnace for debinding, the debinding temperature is 350.0 - 400.0 °C, and the holding time is 4.0 - 7.0 h;

[0026] (6) Hot pressing sintering: Place the debound blank in a vacuum hot pressing furnace for sintering, carry out temperature rising and pressure applying treatments, and the sintered shapes can be teapots, tea sets, basins, bowls, vats, etc.

[0027] Further, in step (1), the mixed solution used for mixing and stirring is deionized water or absolute ethanol;

[0028] Further, the device used for vacuum filtration in step (2) includes a suction filtration flask, a funnel, and a vacuum pump, and the vacuum degree of filtration is 0.01 - 0.1 MPa;

[0029] Further, the pore size of the microporous filter membrane used for the vacuum filtration in step (2) is nanoscale. To ensure the filtration effect, the thickness of each thin slice obtained by filtration does not exceed 3.0 mm;

[0030] Further, in step (4), put the thin slice obtained by filtration, cemented carbide balls, and absolute ethanol into a nylon bottle, carry out ball milling on a planetary ball mill, the ball-to-material ratio is between 5:1 and 15:1, the ball milling time is 2.0 - 48.0 h, and the ball milling speed is 150 - 300 rpm;

[0031] Further, in the hot pressing sintering in step (6), under vacuum conditions, heat the blank to 800 - 1100 °C at a heating rate of 2 - 10 °C / min, apply pressure to 5.0 - 50.0 MPa, and hold for 0.8 - 1.5 h;

[0032] The average particle size of the sintered copper-modified Jianshui purple pottery composite material is 10.0 - 30.0 μm, the hardness of the composite material is 180 - 305 HV0.5, the cross-sectional shrinkage rate is not less than 5.0%, and in addition, the surface of the prepared copper-pottery composite material has the metallic luster of copper, and the antibacterial rate exceeds 85.0% in 12.0 hours.

[0033] An antibacterial, high-strength and tough copper-modified Jianshui purple pottery prepared by this process can be used for health-preserving teapots and tea sets, storage containers such as basins, bowls, and vats, components of water purification systems, and the Four Treasures of the Study, etc.

[0034] The present invention uses Jianshui pottery clay and pure copper as raw materials for the composite material. The materials are simple to obtain, focus on the development of local industries, and the cost is not high. Both materials are widely used in the production of daily necessities such as teapots and containers, and have a good foundation among the general public. The prepared copper-pottery composite material retains the heaviness of ceramic materials and also has a metallic luster, which is a new and beautiful material. In terms of performance, copper-based ceramic composite materials have been widely used. The interface between the matrix and Jianshui purple pottery clay is well-connected, which can ensure excellent comprehensive mechanical properties. Mainly, it can improve the relatively lacking plasticity of ceramic materials and broaden the application scenarios of the prepared materials. In addition, copper also has good antibacterial properties, which can enhance the food safety attribute of daily necessities.

[0035] The composite powder mixing and sintering process adopted by the present invention is beneficial to obtaining a uniformly dispersed composite material powder. Through molecular-level mixing, the uniform mixing of Jianshui purple pottery clay and copper powder particles can be ensured, making the particle size of the alloy as uniform as possible, and the particle size is further refined by ball milling. During the vacuum filtration process, copper and pottery clay powders can also be arranged orderly according to the gravity, making the distribution of the hard and soft components more uniform. Finally, through the hot pressing sintering process, the material can be made more dense, the copper-pottery particles are connected more tightly, and the material has better comprehensive mechanical properties. The prepared copper-pottery material can be directly used for the preparation of daily necessities, or can be made into powder and then remolded into mud for the firing of daily necessities with complex shapes such as teapots and tea sets.

[0036] Compared with the prior art, the present invention has the following advantages:

[0037] 1. The high-strength and tough copper-modified Jianshui purple pottery prepared by the method of the present invention has good comprehensive mechanical properties. Through molecular-level mixing and hot pressing sintering, the copper powder and ceramic powder can be evenly distributed, the particle size is refined to 10.0 - 30.0 μm, and at the same time, the interface between copper and ceramic particles is well-connected. All of the above are due to the improvement of the comprehensive mechanical properties of the copper-pottery composite material. The hardness of the material can reach 200 - 300 HV0.5, and at the same time, the very unsatisfactory plasticity of ceramic materials is improved, and the cross-sectional shrinkage rate can reach more than 5.0%.

[0038] 2. The novel copper-modified Jianshui purple pottery prepared by the method of the present invention has good bactericidal performance. The ultrafine copper particles can be converted into copper ions in liquid and air environments. The copper ions can enter the cells of microorganisms and kill the active enzymes in the cells, thereby killing bacteria. The antibacterial rate can reach more than 85.0% in 12 hours. Compared with process methods such as antibacterial coatings, the prepared material of the present invention has antibacterial properties itself, which can reduce complex processes such as coatings and can achieve the protection of all positions of the containers manufactured. Since the copper particles are evenly distributed in the material, the situation of protection failure due to coating peeling can be avoided.

[0039] 3. The novel copper-modified Jianshui purple pottery prepared by the method of the present invention combines copper metal with Jianshui purple pottery with rich local characteristics. It not only retains the heaviness and texture of purple pottery but also endows purple pottery with the beautiful luster of copper metal. Both of the two materials selected in the present invention have a long application foundation as daily-use materials and are deeply loved by the general public. They are ideal innovative materials for making daily-use products such as teapots, tea sets, and the four treasures of the study. The present invention focuses on local industrial products and technological innovation, which can contribute to the development and upgrading of the economy and cultural industries in the central and western regions and contribute to rural revitalization. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] Figure 1 is a typical microstructural photograph of the antibacterial high-strength and tough copper-modified Jianshui purple pottery prepared by the present invention;

[0041] Figure 2 is a physical photograph of the antibacterial high-strength and tough copper-modified Jianshui purple pottery prepared by the present invention;

[0042] Figure 3 is the change trend of the microhardness and sintering temperature of the antibacterial high-strength and tough copper-modified Jianshui purple pottery prepared by the present invention.

[0043] Figure 4 is the change trend of the microhardness and hot-pressing sintering pressure of the antibacterial high-strength and tough copper-modified Jianshui purple pottery prepared by the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0044] The present invention will be described in detail below with reference to the drawings and embodiments. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present invention, several deformations and improvements can still be made. These all belong to the protection scope of the present invention. Embodiment

[0045] The steps of an antibacterial high-strength and tough copper-modified Jianshui purple pottery and its preparation method are as follows:

[0046] Step 1: Molecular-level mixing: Put Jianshui clay and copper powder into the mixed solution, with 60 parts of clay and 40 parts of copper powder, and carry out mechanical stirring and ultrasonic vibration to obtain a mud material with evenly mixed clay and copper powder;

[0047] Step 2: Vacuum filtration: Use a suction pump and a suction flask to conduct vacuum filtration on the mixed mud, with a suction vacuum of 0.03 MPa, and peel it off from the microporous filter membrane to obtain a relatively dry thin slice of the mud mixture;

[0048] Step 3: Atmospheric drying: Place the thin slice of the mud mixture described in step (2) in an atmospheric drying oven for drying, with the temperature controlled at 99.0 °C and the time being 5.6 h;

[0049] Step 4: Mechanical grinding: Put the thin slice obtained by suction filtration, cemented carbide balls, and absolute ethanol into a nylon bottle, and conduct ball milling on a planetary ball mill, with the ball-to-material ratio between 13:1, the ball milling time being 24.0 h, and the ball milling speed being 177.0 rpm;

[0050] Step 5: Debinding: Place the green compact in a vacuum sintering furnace for debinding, with the debinding temperature being 367.0 °C and the holding time being 9.0 h;

[0051] Step 6: Hot pressing sintering: Place the debound blank in a vacuum hot pressing furnace for sintering, heat the blank to 950 °C at a heating rate of 9.0 °C / min, apply a pressure of 20.0 MPa, and hold for 0.9 h.

[0052] The physical diagram of the sintered high-strength and tough copper-Jianshui ceramic composite material is as Figure 1 shown, and the microstructural diagram is as Figure 2 shown. The Vickers hardness is 285 HV0.5, the cross-sectional shrinkage rate is 6.9%, and the antibacterial rate for 12 hours is 96.0%. In addition, the inventor found that as the content of clay increases, the hardness of the copper-ceramic composite material first increases and then decreases, and the hardness reaches the maximum value at 1000 °C, as Figure 3 shown. Example

[0053] The steps of an antibacterial high-strength and tough copper-modified Jianshui purple pottery and its preparation method are as follows:

[0054] Step 1: Molecular-level mixing: Put Jianshui clay and copper powder into the mixed solution, with 60 parts of clay and 40 parts of copper powder, and conduct mechanical stirring and ultrasonic vibration to obtain a uniformly mixed mud of clay and copper powder;

[0055] Step 2: Vacuum filtration: Use a suction pump and a suction flask to conduct vacuum filtration on the mixed mud, with a suction vacuum of 0.05 MPa, and peel it off from the microporous filter membrane to obtain a relatively dry thin slice of the mud mixture;

[0056] Step 3: Atmospheric drying: Place the thin slice of the mud mixture described in step (2) in an atmospheric drying oven for drying, with the temperature controlled at 90.0 °C and the time being 5.0 h;

[0057] Step 4. Mechanical grinding: Put the thin slices obtained by suction filtration, cemented carbide balls, and absolute ethanol into a nylon bottle, and perform ball milling on a planetary ball mill. The ball-to-material ratio is between 9:1, the ball milling time is 4.0 h, and the ball milling speed is 202 rpm;

[0058] Step 5. Debinding: Place the green compact in a vacuum sintering furnace for debinding. The debinding temperature is 350 °C, and the holding time is 3.0 h;

[0059] Step 6. Sinter the debound blank in a vacuum hot pressing furnace. Heat the blank to 1000 °C at a heating rate of 6.0 °C / min, apply a pressure of 40.0 MPa, and hold for 1.2 h.

[0060] The physical diagram of the high-strength and tough copper-Jianshui ceramic composite material is sintered, with a Vickers hardness of 305 HV0.5, a cross-sectional shrinkage rate of 7.4%, and a 12-hour antibacterial rate of 96%. In addition, the inventor found that as the sintering pressure increases, the hardness of the copper-ceramic composite material shows a trend of increasing first and then stabilizing. The hardness stabilizes after 30.0 MPa, as Figure 4 shown. Example

[0061] The steps of an antibacterial high-strength and tough copper-modified Jianshui purple pottery and its preparation method are as follows:

[0062] Step 1. Molecular-level mixing: Put Jianshui clay and copper powder into the mixed solution. There are 86 parts of clay and 14 parts of copper powder. Perform mechanical stirring and ultrasonic vibration to obtain a uniformly mixed mud of clay and copper powder;

[0063] Step 2. Vacuum suction filtration: Use a suction pump and a suction flask to perform vacuum filtration on the mixed mud. The suction filtration vacuum degree is 0.09 MPa and it is peeled off from the microporous filter membrane to obtain a relatively dry mud mixture thin slice;

[0064] Step 3. Atmospheric drying: Place the mud mixture thin slice described in step (2) in an atmospheric drying oven for drying. The temperature is controlled at 117 °C, and the time is 3.1 h;

[0065] Step 4. Mechanical grinding: Put the thin slices obtained by suction filtration, cemented carbide balls, and absolute ethanol into a nylon bottle, and perform ball milling on a planetary ball mill. The ball-to-material ratio is between 6:1, the ball milling time is 47.0 h, and the ball milling speed is 153 rpm;

[0066] Step 5. Debinding: Place the green compact in a vacuum sintering furnace for debinding. The debinding temperature is 317 °C, and the holding time is 7.0 h;

[0067] Step 6: Place the degreased blank in a vacuum hot press furnace for sintering. Heat the blank to 881°C at a heating rate of 3.0°C / min, apply a pressure of 24.0 MPa, and hold for 1.5 h.

[0068] Sinter a high-strength and tough copper-Jianshui ceramic composite material with a Vickers hardness of 300 HV0.5, a cross-sectional shrinkage rate of 5.1%, and a 12-hour antibacterial rate of 90%. Example

[0069] The steps of a method for preparing an antibacterial high-strength and tough copper-modified Jianshui purple pottery are as follows:

[0070] Step 1: Molecular-level mixing: Put Jianshui clay and copper powder into a mixed solution, with 47 parts of clay and 53 parts of copper powder. Conduct mechanical stirring and ultrasonic vibration to obtain a uniformly mixed mud of clay and copper powder.

[0071] Step 2: Vacuum filtration: Use a suction pump and a suction flask to conduct vacuum filtration on the mixed mud. The vacuum degree of suction filtration is 0.07 MPa and it is peeled off from the microporous filter membrane to obtain a relatively dry mud mixture thin slice.

[0072] Step 3: Atmospheric drying: Place the mud mixture thin slice described in step (2) in an atmospheric drying oven for drying, control the temperature at 98°C, and the time is 3.9 h.

[0073] Step 4: Mechanical grinding: Put the thin slice obtained by suction filtration, cemented carbide balls, and absolute ethanol into a nylon bottle, and conduct ball milling on a planetary ball mill. The ball-to-material ratio is between 11:1, the ball milling time is 13.0 h, and the ball milling speed is 238 rpm.

[0074] Step 5: Degreasing: Place the green compact in a vacuum sintering furnace for degreasing, with a degreasing temperature of 315°C and a holding time of 1.0 h.

[0075] Step 6: Place the degreased blank in a vacuum hot press furnace for sintering. Heat the blank to 930°C at a heating rate of 8.0°C / min, apply a pressure of 49.0 MPa, and hold for 1.2 h.

[0076] Sinter a high-strength and tough copper-Jianshui ceramic composite material with a Vickers hardness of 182 HV0.5, a cross-sectional shrinkage rate of 7.5%, and a 12.0-hour antibacterial rate of 95%. Example

[0077] The steps of a method for preparing an antibacterial high-strength and tough copper-modified Jianshui purple pottery are as follows:

[0078] Step 1: Molecular-level mixing: Put Jianshui clay and copper powder into a mixed solution, with 84 parts of clay and 16 parts of copper powder. Conduct mechanical stirring and ultrasonic vibration to obtain a uniformly mixed mud of clay and copper powder.

[0079] Step 2. Vacuum filtration: Use a suction pump and a suction flask to conduct vacuum filtration on the mixed mud material. The vacuum degree for suction filtration is 0.06 MPa, and then peel it off from the microporous filter membrane to obtain a relatively dry thin slice of the mud material mixture;

[0080] Step 3. Atmospheric drying: Place the thin slice of the mud material mixture described in step (2) in an atmospheric drying oven for drying. Control the temperature at 119 °C and the time at 4.3 h;

[0081] Step 4. Mechanical grinding: Put the thin slice obtained by suction filtration, cemented carbide balls, and absolute ethanol into a nylon bottle, and conduct ball milling on a planetary ball mill. The ball-to-material ratio is between 10:1, the ball milling time is 40.0 h, and the ball milling speed is 248 rpm;

[0082] Step 5. Debinding: Place the green compact in a vacuum sintering furnace for debinding. The debinding temperature is 337 °C and the holding time is 10.0 h;

[0083] Step 6. Sinter the debound blank in a vacuum hot pressing furnace. Heat the blank to 819 °C at a heating rate of 5.0 °C / min, apply a pressure of 31.0 MPa, and hold for 1.2 h.

[0084] Sinter a high-strength and tough copper-Jianshui ceramic composite material with a Vickers hardness of 274 HV0.5, a cross-sectional shrinkage rate of 5.3%, and a 12-hour antibacterial rate of 91%. Example

[0085] The steps of a method for preparing an antibacterial high-strength and tough copper-modified Jianshui purple pottery are as follows:

[0086] Step 1. Molecular-level mixing: Put Jianshui clay and copper powder into a mixed solution, with 40 parts of clay and 60 parts of copper powder, and conduct mechanical stirring and ultrasonic vibration to obtain a uniformly mixed mud material of clay and copper powder;

[0087] Step 2. Vacuum filtration: Use a suction pump and a suction flask to conduct vacuum filtration on the mixed mud material. The vacuum degree for suction filtration is 0.01 MPa, and then peel it off from the microporous filter membrane to obtain a relatively dry thin slice of the mud material mixture;

[0088] Step 3. Atmospheric drying: Place the thin slice of the mud material mixture described in step (2) in an atmospheric drying oven for drying. Control the temperature at 60.0 °C and the time at 6.0 h;

[0089] Step 4. Mechanical grinding: Put the thin slice obtained by suction filtration, cemented carbide balls, and absolute ethanol into a nylon bottle, and conduct ball milling on a planetary ball mill. The ball-to-material ratio is between 5:1, the ball milling time is 48.0 h, and the ball milling speed is 150 rpm;

[0090] Step 5, Degreasing: Place the green compact in a vacuum sintering furnace for degreasing at a degreasing temperature of 300 °C and a holding time of 10.0 h;

[0091] Step 6, Sintering: Place the degreased blank in a vacuum hot pressing furnace for sintering. Heat the blank to 1100 °C at a heating rate of 2.0 °C / min and apply a pressure of 5.0 MPa, and hold for 1.5 h.

[0092] Sinter a high-strength and tough copper-Jianshui ceramic composite material with a Vickers hardness of 180 HV0.5, a cross-sectional shrinkage rate of 7.9%, and a 12-hour antibacterial rate of 96%. Example

[0093] The steps of a method for preparing an antibacterial high-strength and tough copper-modified Jianshui purple pottery are as follows:

[0094] Step 1, Molecular-level mixing: Put Jianshui clay and copper powder into a mixed solution, with 70 parts of clay and 30 parts of copper powder, and carry out mechanical stirring and ultrasonic vibration to obtain a uniformly mixed mud of clay and copper powder;

[0095] Step 2, Vacuum filtration: Use a suction filter pump and a suction filter flask to carry out vacuum filtration on the mixed mud, with a suction filtration vacuum degree of 0.1 MPa and peel it off from the microporous filter membrane to obtain a relatively dry thin slice of mud mixture;

[0096] Step 3, Atmospheric drying: Place the thin slice of the mud mixture described in step (2) in an atmospheric drying oven for drying, with the temperature controlled at 100 °C and the time of 5.9 h;

[0097] Step 4, Mechanical grinding: Put the thin slice obtained by suction filtration, cemented carbide balls, and absolute ethanol into a nylon bottle, and carry out ball milling on a planetary ball mill, with the ball-to-material ratio between 5:1, the ball milling time of 31.0 h, and the ball milling speed of 249 rpm;

[0098] Step 5, Degreasing: Place the green compact in a vacuum sintering furnace for degreasing at a degreasing temperature of 339 °C and a holding time of 4.0 h;

[0099] Step 6, Sintering: Place the degreased blank in a vacuum hot pressing furnace for sintering. Heat the blank to 983 °C at a heating rate of 7.0 °C / min and apply a pressure of 46.0 MPa, and hold for 1.0 h.

[0100] Sinter a high-strength and tough copper-Jianshui ceramic composite material with a Vickers hardness of 223 HV0.5, a cross-sectional shrinkage rate of 5.8%, and a 12-hour antibacterial rate of 94%. Example

[0101] The steps of a method for preparing an antibacterial high-strength and tough copper-modified Jianshui purple pottery are as follows:

[0102] Step 1. Molecular-level mixing: Put Jianshui clay and copper powder into the mixed solution, with 98 parts of clay and 2 parts of copper powder, and conduct mechanical stirring and ultrasonic vibration to obtain a uniformly mixed mud of clay and copper powder;

[0103] Step 2. Vacuum filtration: Use a suction pump and a suction flask to conduct vacuum filtration on the mixed mud, with a suction vacuum of 0.1 MPa and peel it off from the microporous filter membrane to obtain a relatively dry thin slice of mud mixture;

[0104] Step 3. Atmospheric drying: Place the thin slice of mud mixture described in step (2) in an atmospheric drying oven for drying, with the temperature controlled at 120 °C and the time of 3.0 h;

[0105] Step 4. Mechanical grinding: Put the thin slice obtained by suction filtration, tungsten carbide balls, and absolute ethanol into a nylon bottle, and conduct ball milling on a planetary ball mill, with the ball-to-material ratio between 15:1, the ball milling time of 2.0 h, and the ball milling speed of 300 rpm;

[0106] Step 5. Debinding: Place the green compact in a vacuum sintering furnace for debinding, with the debinding temperature of 400 °C and the holding time of 1.0 h;

[0107] Step 6. Sinter the debound blank in a vacuum hot press furnace, heat the blank to 800 °C at a heating rate of 10.0 °C / min, apply a pressure of 50.0 MPa, and hold for 0.8 h.

[0108] Sinter a high-strength and tough copper-Jianshui ceramic composite material, with a Vickers hardness of 303 HV0.5, a cross-sectional shrinkage rate of 5.0%, and an antibacterial rate of 86% for 12 hours. Example

[0109] The steps of an antibacterial high-strength and tough copper-modified Jianshui purple pottery and its preparation method are as follows:

[0110] Step 1. Molecular-level mixing: Put Jianshui clay and copper powder into the mixed solution, with 82 parts of clay and 18 parts of copper powder, and conduct mechanical stirring and ultrasonic vibration to obtain a uniformly mixed mud of clay and copper powder;

[0111] Step 2. Vacuum filtration: Use a suction pump and a suction flask to conduct vacuum filtration on the mixed mud, with a suction vacuum of 0.02 MPa and peel it off from the microporous filter membrane to obtain a relatively dry thin slice of mud mixture;

[0112] Step 3. Atmospheric drying: Place the thin slice of mud mixture described in step (2) in an atmospheric drying oven for drying, with the temperature controlled at 60 °C and the time of 3.4 h;

[0113] Step 4. Mechanical grinding: Put the thin slices obtained by suction filtration, cemented carbide balls and absolute ethanol into a nylon bottle, and carry out ball milling on a planetary ball mill. The ball-to-material ratio is between 7:1, the ball milling time is 32.0 h, and the ball milling speed is 169 rpm;

[0114] Step 5. Debinding: Place the green compact in a vacuum sintering furnace for debinding, with a debinding temperature of 374 °C and a holding time of 2.0 h;

[0115] Step 6. Sinter the debound blank in a vacuum hot press furnace. Heat the blank to 1017 °C at a heating rate of 4.0 °C / min, apply a pressure of 29.0 MPa, and hold for 0.9 h.

[0116] Sinter a high-strength and tough copper-Jianshui ceramic composite material with a Vickers hardness of 266 HV0.5, a cross-sectional shrinkage rate of 5.7%, and a bacteriostatic rate of 92% for 12 hours.

[0117] All the above embodiments are only a part of the embodiments of the present invention, rather than all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

Claims

1. A preparation method of antibacterial high-strength and tough copper-modified Jianshui purple pottery, characterized in that: (1) Molecular-level mixing: Put Jianshui clay and copper powder into a mixed solution, and perform mechanical stirring and ultrasonic vibration to obtain a uniformly mixed mud of clay and copper powder; (2) Vacuum filtration: Use a suction pump and a suction flask to perform vacuum filtration on the mixed mud, and peel it off from the microporous filter membrane to obtain a relatively dry thin slice of mud mixture; (3) Atmospheric drying: Place the thin slice of mud mixture described in step (2) in an atmospheric drying oven for drying, with the temperature controlled at 60.0-120.0 °C and the time of 3.0-6.0 h; (4) Mechanical grinding: Grind the mud to 600-1200 mesh by physical methods; (5) Degreasing: Place the green compact in a vacuum sintering furnace for degreasing, with the degreasing temperature of 300.0-400.0 °C and the holding time of 1.0-10.0 h; (6) Hot pressing and sintering: Place the degreased blank in a vacuum hot pressing furnace for sintering, and perform heating and pressure application treatments. The sintered shapes are tea sets, basins, bowls, and vats; The raw materials include the following components by mass fraction: 40-98 parts of Jianshui purple pottery clay; 2-60 parts of copper or copper alloy, totaling 100 parts, wherein the Jianshui purple pottery clay is a mixture of Yunnan Jianshui purple pottery clay and one or more of white clay, green clay, yellow clay, and variegated clay.

2. The preparation method of an antibacterial, high-strength and tough copper-modified Jianshui purple pottery according to claim 1, characterized in that, The raw materials include the following components: 70-98 parts of Jianshui purple pottery clay; 2-30 parts of copper or copper alloy, totaling 100 parts, wherein the Jianshui purple pottery clay is a mixture of Yunnan Jianshui purple pottery clay and one or more of white clay, green clay, yellow clay, and variegated clay.

3. The preparation method of an antibacterial, high-strength and tough copper-modified Jianshui purple pottery according to claim 1, characterized in that, The raw materials include the following components: 85-95 parts of Jianshui purple pottery clay; 5-15 parts of copper or copper alloy, totaling 100 parts, wherein the Jianshui purple pottery clay is a mixture of Yunnan Jianshui purple pottery clay and one or more of white clay, green clay, yellow clay, and variegated clay.

4. The preparation method of an antibacterial, high-strength and tough copper-modified Jianshui purple pottery according to claim 1, characterized in that, The copper in the raw materials is powdered pure copper, and the particle size of the selected powder can be micron-sized, nano-sized, or a mixture of both.

5. According to the preparation method of antibacterial high-strength and tough copper-modified Jianshui purple pottery described in claim 1, the special feature is that the copper alloy in the raw materials can be one or more of Cu-Cr alloy, aluminum bronze alloy, and iron bronze alloy.

6. The preparation method of an antibacterial, high-strength and tough copper-modified Jianshui purple pottery according to claim 1, wherein, It includes the following steps: (1) Molecular-level mixing: Put Jianshui clay and copper powder into a mixed solution, and perform mechanical stirring and ultrasonic vibration to obtain a uniformly mixed mud of clay and copper powder; (2) Vacuum filtration: Use a suction pump and a suction flask to perform vacuum filtration on the mixed mud, and peel it off from the microporous filter membrane to obtain a relatively dry thin slice of mud mixture; (3) Atmospheric drying: Place the thin slice of mud mixture described in step (2) in an atmospheric drying oven for drying, with the temperature controlled at 90.0-100.0 °C and the time of 3.0-5.0 h; (4) Mechanical grinding: Grind the mud to 600-1200 mesh by physical methods; (5) Degreasing: Place the green compact in a vacuum sintering furnace for degreasing, with the degreasing temperature of 350.0-400.0 °C and the holding time of 4.0-7.0 h; (6) Hot press sintering: Place the degreased blank in a vacuum hot press furnace for sintering, and perform heating and pressure application treatments. The sintered shapes are tea sets, basins, bowls, and vats.

7. The preparation method of an antibacterial, high-strength and tough copper-modified Jianshui purple pottery according to claim 1, wherein, In step (1), the mixed solution used for mixing and stirring is deionized water or absolute ethanol.

8. The preparation method of an antibacterial, high-strength and tough copper-modified Jianshui purple pottery according to claim 1, characterized in that, The device used for the vacuum filtration in step (2) includes a suction flask, a funnel, and a vacuum pump. The vacuum degree of the vacuum filtration is 0.01 - 0.1 MPa.

9. The preparation method of an antibacterial, high-strength and tough copper-modified Jianshui purple pottery according to claim 1, characterized in that, The pore size of the microporous filter membrane used for the vacuum filtration in step (2) is at the nanometer level. To ensure the filtration effect, the thickness of each thin sheet obtained by filtration does not exceed 3.0 mm.

10. The preparation method of an antibacterial, high-strength and tough copper-modified Jianshui purple pottery according to claim 1, characterized in that, In step (4), put the thin sheet obtained by filtration, cemented carbide balls, and absolute ethanol into a nylon bottle, and perform ball milling on a planetary ball mill. The ball-to-material ratio is between 5:1 and 15:1, the ball milling time is 2.0 - 48.0 h, and the ball milling speed is 150 - 300 rpm.

11. The preparation method of an antibacterial, high-strength and tough copper-modified Jianshui purple pottery according to claim 1, characterized in that, In the hot press sintering described in step (6), under vacuum conditions, heat the blank to 800 - 1100 °C at a heating rate of 2 - 10 °C / min, apply pressure to 5.0 - 50.0 MPa, and keep the temperature for 0.8 - 1.5 h.

12. The preparation method of an antibacterial, high-strength and tough copper-modified Jianshui purple pottery according to claim 1, characterized in that, The average particle size of the prepared modified Jianshui purple clay material is 10.0 - 30.0 μm.

13. The preparation method of an antibacterial, high-strength and tough copper-modified Jianshui purple pottery according to claim 1, characterized in that, The hardness of the prepared modified Jianshui purple clay material is 180 - 305 HV0.5, and the cross-sectional shrinkage rate is not less than 5.0%.

14. The preparation method of an antibacterial, high-strength and tough copper-modified Jianshui purple pottery according to claim 1, characterized in that The surface of the prepared modified Jianshui purple clay material has the metallic luster of copper, and the antibacterial rate after 12.0 hours exceeds 85.0%.

15. A preparation method of an antibacterial high-strength and tough copper-modified Jianshui purple pottery according to any one of claims 1-5, characterized in that, The prepared modified Jianshui purple clay material can be used for storage containers, components of water purification systems, and the four treasures of the study.

16. The preparation method of an antibacterial, high-strength and tough copper-modified Jianshui purple pottery according to claim 15, wherein: The storage containers include tea sets, basins, bowls, and vats.

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