Preparation method of antibacterial Jianshui purple pottery product

Abstract

A preparation method of an antibacterial Jianshui purple pottery product comprises the following steps: weighing 100 parts of diatomite, adding 200 parts of ethanol and 500 parts of deionized water, and uniformly stirring to obtain a primary mixture; mixing 10-30 parts of cerium nitrate or cerium acetate, 50-300 parts of manganese nitrate or manganese acetate and 10-50 parts of zinc nitrate or zinc acetate to obtain a mixed solution, adding the mixed solution into the primary mixture, and uniformly stirring to obtain a mixture; the mixture is dried and fired, and the antibacterial agent is obtained; adding the antibacterial agent into the Jianshui purple pottery pug, then adding water, and stirring to prepare slurry; carrying out filter pressing dehydration on the slurry, and carrying out vacuum pugging on the filter-pressed pug to obtain antibacterial pug; the antibacterial pug is subjected to compaction forming or throwing forming, fettling and drying are performed, then high-temperature firing is performed, and the antibacterial Jianshui purple pottery product is obtained. The method adapts to the characteristics and preparation technology of the Jianshui purple pottery pug, and the prepared Jianshui purple pottery product is good in antibacterial property.

Description

Technical Field

[0001] This invention belongs to the technical field of antibacterial ceramic preparation methods, specifically relating to the preparation method of antibacterial Jianshui purple pottery products. Background Technology

[0002] Antibacterial technology can effectively prevent the growth of bacteria, viruses, and other microorganisms in daily-use products, ensuring the health and safety of users. As people's attention to health and safety continues to increase, antibacterial ceramics are becoming increasingly popular. Jianshui purple pottery, with its long history and widespread appeal, has gained increasing favor due to the rise of tea culture consumption and the improvement of general consumer spending power. However, in the traditional unglazed polishing process, a small amount of organic oil is used to enhance the gloss of Jianshui purple pottery. If not cleaned thoroughly, there is a risk of organic matter mold and deterioration, affecting the usability of the Jianshui purple pottery. Therefore, it is necessary to research a method for preparing antibacterial Jianshui purple pottery.

[0003] There are two main existing methods for producing antibacterial ceramic products. One method involves adding inorganic antibacterial agents that dissolve metal ions, such as silver, to the ceramic glaze. Through glazing and high-temperature firing, the antibacterial agent is evenly dispersed in the glaze layer on the ceramic surface, achieving sterilization through the dissolution of the silver ions. However, once the silver antibacterial ions are made into a glaze, their structure is very dense, resulting in poor ion release and affecting the antibacterial effect. It can also affect the color of the glaze to some extent. The other method involves coating the ceramic glaze with a TiO2-based antibacterial agent with photocatalytic antibacterial capabilities using a coating process. Then, heat treatment is typically carried out at temperatures below 800°C to obtain antibacterial ceramics. This method achieves antibacterial properties through the photocatalytic reaction of TiO2. This method requires ultraviolet light to activate the catalytic action, and TiO2 transforms from anatase to rutile at high temperatures, thus losing its photocatalytic activity, limiting its application conditions. Existing technologies, such as the antibacterial and environmentally friendly daily-use ceramics and their preparation methods disclosed in CN110015884A, the long-lasting antibacterial daily-use ceramics and their preparation methods disclosed in CN116730707A, and the long-lasting antibacterial daily-use ceramics preparation methods disclosed in CN115925388A, either have low firing temperatures that cannot meet the requirements of high-temperature firing of Jianshui purple pottery, or cannot meet the characteristics of Jianshui purple pottery clay, or have overly complex preparation methods. Summary of the Invention

[0004] The purpose of this invention is to fill the gap in the prior art and provide a method for preparing Jianshui purple pottery products with antibacterial properties that is adapted to the characteristics of Jianshui purple pottery clay and the preparation process.

[0005] The technical solution adopted in this invention is as follows: A method for preparing an antibacterial Jianshui purple pottery product includes the following steps: (1) Weigh 100 parts of diatomaceous earth by mass, add 200 parts of ethanol and 500 parts of deionized water, stir evenly to obtain the initial mixture; (2) Take 10-30 parts of cerium nitrate or cerium acetate, 50-300 parts of manganese nitrate or manganese acetate, and 10-50 parts of zinc nitrate or zinc acetate by mass, mix them and stir evenly to obtain a mixed solution, add the mixed solution to the initial mixture prepared in step (1), stir evenly to obtain a mixture; (3) Pour the mixture into a tray and place it in an oven to dry. The drying temperature is 60-70℃ and the drying time is 12-24h. Stir the material every 60 minutes when drying begins, and stir every 30 minutes when crystals begin to precipitate, until the material is dried. (4) After placing the dried material into the drying tray, put it into the atmosphere furnace, open the vacuum valve, evacuate to a pressure of -0.2MPa and then close the vacuum valve; then open the vent valve, fill with nitrogen until the pressure gauge shows 5MPa and then close the vent valve to start firing the antibacterial agent. After firing, close the vent valve and wait for the material in the furnace to cool to room temperature before taking it out to obtain the antibacterial agent. (5) Add antibacterial agent to Jianshui purple pottery clay material at a ratio of 3-15% of the mass of Jianshui purple pottery clay material, then add water and stir evenly to make a mud slurry with a mass concentration of 30%-50%. (6) The mud is dewatered by filter pressing, and the filtered mud is then vacuum-kneaded to obtain antibacterial mud. (7) Press or pull the antibacterial mud into blanks; (8) After trimming and drying the shaped blank, it is fired at 1000℃-1250℃ to prepare antibacterial Jianshui purple pottery products.

[0006] Furthermore, in step (2) above, the method of adding the mixed solution to the initial mixture and stirring is to stir for 30-60 minutes, then stop stirring, let it stand for 5-10 minutes, and then continue stirring for 30-60 minutes.

[0007] Furthermore, in step (4) above, the atmosphere furnace program for the process of sending the dried material into the atmosphere furnace for firing is set as follows: heat up to 200℃ and hold for 30 minutes, then heat up to 300℃-400℃ and hold for 2 hours, and then automatically cool down to room temperature.

[0008] Furthermore, the Jianshui purple pottery clay material mentioned in step (5) above is Jianshui purple pottery red clay material and Jianshui purple pottery white clay material.

[0009] The present invention has the following beneficial effects: 1. In this invention, the manganese nitrate or manganese acetate, and zinc nitrate or zinc acetate used to prepare the antibacterial agent undergo thermal decomposition at 300-400℃ to generate new oxides, namely manganese dioxide and zinc oxide. On the one hand, Mn... 2 Zn 2+ These are broad-spectrum, highly effective antibacterial ions, their mechanism of action being the disruption of bacterial cell membranes, interference with enzyme systems, and protein synthesis. On the other hand, nascent manganese dioxide and zinc oxide have catalytic activity, converting oxygen or dissolved oxygen in water into reactive oxygen species. These reactive oxygen species can disrupt microbial cell membranes, exhibiting antibacterial effects. However, manganese nitrate or manganese acetate readily decomposes at high temperatures to form manganese trioxide or manganese tetroxide, losing their catalytic activity. Introducing cerium nitrate or cerium acetate into the pyrolysis at high temperatures... 3+ / Ce 4+ Redox pairs can inhibit excessive reduction of manganese oxides (such as MnO2→Mn2O3), stabilize the valence state of manganese, and maintain high valence manganese (Mn). 4+ Ce exhibits antibacterial activity. 3+ It possesses inherent antibacterial properties, capable of disrupting the outer membrane of Gram-negative bacteria (through phospholipid binding), and synergistically with manganese and zinc to cover a wider range of bacterial species. The combination of these three antibacterial agents produces a complex effect, resulting in a stable and long-lasting antibacterial effect with low risk of drug resistance.

[0010] 2. This invention uses diatomaceous earth as a carrier. Diatomaceous earth has a huge specific surface area and strong adsorption capacity. Its essence is hydrated amorphous SiO2. Diatomaceous earth is widely available and inexpensive. In particular, it has a unique original pore structure of diatoms, which can easily adsorb the above-mentioned antibacterial agents into the pore structure. When added to the Jianshui purple pottery body, the specific surface area can be increased, which is conducive to the slow dissolution of manganese and zinc ions.

[0011] 3. In this invention, ethanol and water are added as solvents, and the product is dried at a low temperature of 60-70°C. This effectively disperses the antibacterial agent, and the final antibacterial agent particles are fine, uniform, and not prone to agglomeration.

[0012] 4. Traditional antibacterial agents are generally made into glaze layers. Glaze is a very dense glassy state with a very dense structure. Its ion release and catalytic generation of active oxygen are poor, which affects the antibacterial effect. The antibacterial agent of this invention is introduced into the body of Jianshui purple pottery as a body material, which has a good antibacterial effect.

[0013] 5. The method of this invention is well adapted to the characteristics of purple clay and the traditional preparation process of Jianshui purple pottery. While improving the antibacterial effect of Jianshui purple pottery, it does not need to change the process of shaping, carving, firing and unglazed polishing of Jianshui purple pottery, and can well maintain the traditional techniques of Jianshui purple pottery preparation. Detailed Implementation

[0014] The present invention will be further described below with reference to the embodiments. Example 1

[0015] A method for preparing an antibacterial Jianshui purple pottery product includes the following steps: (1) Weigh 100 parts of -300 mesh diatomaceous earth by mass, add 200 parts of ethanol and 500 parts of deionized water, stir evenly to obtain the initial mixture; (2) Take 20 parts cerium acetate, 100 parts manganese nitrate, and 30 parts zinc nitrate by mass, mix them, stir evenly, and then add them to the initial mixture prepared in step (1). Stir evenly. The stirring method is to stir for 45 minutes, then stop stirring, let it stand for 10 minutes, and then continue stirring for 40 minutes to obtain the mixture. (3) Pour the mixture into a tray and place it in an oven to dry. The drying temperature is 70℃ and the drying time is 12h. Stir the material every 60 minutes when drying begins. When crystals begin to precipitate (the concentration of nitrate or acetate solution increases after water evaporates to produce crystals), stir every 30 minutes until the material is dried. (4) After placing the dried material into the drying tray, load it into the atmosphere furnace, open the vacuum valve, evacuate to a pressure of -0.2 MPa, and then close the vacuum valve; then open the vent valve, fill with nitrogen until the pressure gauge shows 5 MPa, and then close the vent valve to start firing the antibacterial agent. After firing, close the vent valve and wait for the material in the furnace to cool to room temperature before taking it out to obtain the antibacterial agent. The atmosphere furnace program for the firing process of sending the dried material into the atmosphere furnace is set as follows: heat up to 200℃ and hold for 30 minutes, then heat up to 350℃ and hold for 2 hours, and then automatically cool down to room temperature. During the firing process, a large amount of gas will be generated as the temperature rises. It is necessary to pay attention to the atmosphere furnace pressure gauge at all times. When the pressure is greater than 0.2 MPa, the exhaust valve needs to be opened; when the furnace starts to cool down, the exhaust valve is closed; after firing, wait for the furnace temperature to drop to room temperature before opening the valve to take out the material. (5) Add the antibacterial agent to the Jianshui purple pottery red clay material at a ratio of 10% of the mass of the Jianshui purple pottery red clay material, then add water and stir evenly to prepare a mud slurry with a mass concentration of 50%. The traditional formula of Jianshui purple pottery red clay material has the following mass proportions: white clay 10-20 parts, purple clay 10-20 parts, yellow clay 10-30 parts, green clay 10-30 parts, and five-colored clay 10-40 parts. In this embodiment, the proportions are: white clay 15 parts, purple clay 15 parts, yellow clay 20 parts, green clay 15 parts, and five-colored clay 30 parts. (6) The mud is dewatered by filter pressing, and the filtered mud is then vacuum-kneaded to obtain antibacterial mud. (7) Press or pull the antibacterial mud into blanks; (8) After the molded body is trimmed and dried, it is fired at a high temperature of about 1200℃ to prepare antibacterial Jianshui purple pottery products. Example 2

[0016] A method for preparing an antibacterial Jianshui purple pottery product includes the following steps: (1) Weigh 100 parts of -300 mesh diatomaceous earth by mass, add 200 parts of ethanol and 500 parts of deionized water, stir evenly to obtain the initial mixture; (2) Take 10 parts by mass of cerium nitrate, 50 parts by mass of manganese acetate, and 50 parts by mass of zinc acetate. Mix them thoroughly and then add them to the initial mixture prepared in step (1). Stir thoroughly. The stirring method is to stir for 30 minutes, then stop stirring, let it stand for 5 minutes, and then continue stirring for 60 minutes to obtain the mixture. (3) Pour the mixture into a tray and place it in an oven to dry. The drying temperature is 65℃ and the drying time is 20h. Stir the material every 60 minutes when drying begins, and stir every 30 minutes when crystals begin to precipitate, until the material is dried. (4) After placing the dried material into the drying tray, load it into the atmosphere furnace, open the vacuum valve, evacuate to a pressure of -0.2 MPa, and then close the vacuum valve; then open the vent valve, fill with nitrogen until the pressure gauge shows 5 MPa, and then close the vent valve to start firing the antibacterial agent. After firing, close the vent valve and wait for the material in the furnace to cool to room temperature before taking it out to obtain the antibacterial agent. The atmosphere furnace program for the firing process is set as follows: heat up to 200℃ and hold for 30 min, then heat up to 400℃ and hold for 2 h, and then automatically cool down to room temperature; (5) Add the antibacterial agent to the Jianshui purple pottery white clay material at a ratio of 15% of the mass of the Jianshui purple pottery white clay material, then add water and stir evenly to prepare a slurry with a mass concentration of 45%. The traditional formula of Jianshui purple pottery white clay material is 30-60 parts white clay and 40-70 parts green clay. In this embodiment, it is 50 parts white clay and 50 parts green clay. (6) The mud is dewatered by filter pressing, and the filtered mud is then vacuum-kneaded to obtain antibacterial mud. (7) Press or pull the antibacterial mud into blanks; (8) After the molded body is trimmed and dried, it is fired at a high temperature of about 1250℃ to prepare antibacterial Jianshui purple pottery products. Example 3

[0017] A method for preparing an antibacterial Jianshui purple pottery product includes the following steps: (1) Weigh 100 parts of -300 mesh diatomaceous earth by mass, add 200 parts of ethanol and 500 parts of deionized water, stir evenly to obtain the initial mixture; (2) Take 30 parts cerium acetate, 300 parts manganese acetate, and 10 parts zinc acetate by mass, mix them thoroughly, and then add them to the initial mixture prepared in step (1). Stir thoroughly. The stirring method is to stir for 60 minutes, then stop stirring, let it stand for 5 minutes, and then continue stirring for 30 minutes to obtain the mixture. (3) Pour the mixture into a tray and place it in an oven to dry. The drying temperature is 60℃ and the drying time is 24h. Stir the material every 60 minutes when drying begins, and stir every 30 minutes when crystals begin to precipitate, until the material is dried. (4) After placing the dried material into the drying tray, load it into the atmosphere furnace, open the vacuum valve, evacuate to a pressure of -0.2 MPa, and then close the vacuum valve; then open the vent valve, fill with nitrogen until the pressure gauge shows 5 MPa, and then close the vent valve to start firing the antibacterial agent. After firing, close the vent valve and wait for the material in the furnace to cool to room temperature before taking it out to obtain the antibacterial agent. The atmosphere furnace program for the firing process is set as follows: heat up to 200℃ and hold for 30 min, then heat up to 350℃ and hold for 2 h, and then automatically cool down to room temperature; (5) Add the antibacterial agent to the Jianshui purple pottery white clay material at a ratio of 3% of the mass of the Jianshui purple pottery white clay material, then add water and stir evenly to prepare a slurry with a mass concentration of 30%. The formula of Jianshui purple pottery white clay material is 30 parts white clay and 40 parts green clay; (6) The mud is dewatered by filter pressing, and the filtered mud is then vacuum-kneaded to obtain antibacterial mud. (7) Press or pull the antibacterial mud into blanks; (8) After the shaped blank is trimmed and dried, it is fired at a high temperature of about 1100℃ to prepare antibacterial Jianshui purple pottery products.

[0018] The Jianshui purple pottery products prepared by the method of this invention were subjected to a film covering method. Escherichia coli and Staphylococcus aureus bacterial solutions were dropped onto the surface of the products and covered with a film to ensure full contact. After culturing for 24 hours, the samples were recovered and counted. The antibacterial rate against both bacteria reached more than 90%, proving that the products have good antibacterial properties.

[0019] In the method of this invention, vacuum kneading, pressing or pulling, trimming, drying, and firing are all existing technologies. The atmosphere furnace and filter press equipment used are also existing technologies.

Claims

1. A method for preparing an antibacterial Jianshui purple pottery product, characterized in that, Includes the following steps: (1) Weigh 100 parts of diatomaceous earth by mass, add 200 parts of ethanol and 500 parts of deionized water, stir evenly to obtain the initial mixture; (2) Take 10-30 parts of cerium nitrate or cerium acetate, 50-300 parts of manganese nitrate or manganese acetate, and 10-50 parts of zinc nitrate or zinc acetate by mass, mix them and stir evenly to obtain a mixed solution, add the mixed solution to the initial mixture prepared in step (1), stir evenly to obtain a mixture; (3) Pour the mixture into a tray and place it in an oven to dry. The drying temperature is 60-70℃ and the drying time is 12-24h. Stir the material every 60 minutes when drying begins, and stir every 30 minutes when crystals begin to precipitate, until the material is dried. (4) After placing the dried material into the drying tray, put it into the atmosphere furnace, open the vacuum valve, evacuate to a pressure of -0.2MPa and then close the vacuum valve; then open the vent valve, fill with nitrogen until the pressure gauge shows 5MPa and then close the vent valve to start firing the antibacterial agent. After firing, close the vent valve and wait for the material in the furnace to cool to room temperature before taking it out to obtain the antibacterial agent. (5) Add antibacterial agent to Jianshui purple pottery clay material at a ratio of 3-15% of the mass of Jianshui purple pottery clay material, then add water and stir evenly to make a mud slurry with a mass concentration of 30%-50%. (6) The mud is dewatered by filter pressing, and the filtered mud is then vacuum-kneaded to obtain antibacterial mud. (7) Press or pull the antibacterial mud into blanks; (8) After trimming and drying the shaped blank, it is fired at 1000℃-1250℃ to prepare antibacterial Jianshui purple pottery products.

2. The preparation method of an antibacterial Jianshui purple pottery product according to claim 1, characterized in that, In step (2) above, the method for adding the mixed solution to the initial mixture and stirring is to stir for 30 min-60 min, then stop stirring, let it stand for 5-10 min, and then continue stirring for 30-60 min.

3. The method for preparing an antibacterial Jianshui purple pottery product according to claim 1, characterized in that, In step (4) above, the atmosphere furnace program for the process of sending the dried material into the atmosphere furnace for firing is set as follows: heat up to 200℃ and hold for 30 minutes, then heat up to 300℃-400℃ and hold for 2 hours, and then automatically cool down to room temperature.

4. The method for preparing an antibacterial Jianshui purple pottery product according to claim 1, characterized in that, The Jianshui purple pottery clay material mentioned in step (5) above is Jianshui purple pottery red clay material and Jianshui purple pottery white clay material.