A high-performance antibacterial daily-use ceramic and its preparation method and application

Abstract

The present invention belongs to the technical field of daily-use ceramics, and specifically relates to a high-performance antibacterial daily-use ceramic and a preparation method and application thereof. 0.8 Ca 0.2 WO4 and nano zinc oxide, by utilizing the interaction between the components, have the characteristics of excellent antibacterial properties. At the same time, controlling the calcination conditions further improves the antibacterial properties of daily-use ceramics, and the antibacterial properties are excellent.

Description

Technical Field

[0001] The present invention belongs to the technical field of daily-use ceramics, and more specifically, relates to a high-performance antibacterial daily-use ceramic and a preparation method and application thereof. Background Art

[0002] With the rapid development of industry and the deteriorating environment, environmental protection issues have inevitably received more and more attention. Antibacterial materials are an important part of environmentally friendly materials. Daily-use ceramics, such as cups, bowls, plates, and trays, are often in contact with the human body, especially bathroom and kitchen ceramics, which are very susceptible to infection and breeding of pathogenic bacteria, such as Escherichia coli, Staphylococcus aureus, and Pseudomonas aeruginosa. The continuous proliferation of these bacteria makes commonly used ceramic products a medium for spreading harmful to human health. Antibacterial ceramics are a new functional material that protects the environment. It is prepared by adding inorganic antibacterial agents in the preparation process, especially in the ceramic glaze.

[0003] CN116751031A discloses an antibacterial daily-use ceramic cup and its preparation method. The antibacterial daily-use ceramic cup comprises a body layer, a bottom glaze layer and an antibacterial layer; the antibacterial layer is composed of the following raw materials: high-alumina bauxite, wollastonite, potassium feldspar, pyrophyllite, single-walled carbon nanotubes, nano-magnesium oxide, nano-zinc molybdate, and nano-titanium nitride. The antibacterial daily-use ceramic cup of the present invention first reduces the number of bacteria adhering to the ceramic cup by nano-titanium nitride, and then sterilizes through the interaction of single-walled carbon nanotubes, nano-magnesium oxide and nano-zinc molybdate. Among them: single-walled carbon nanotubes cause bacterial cell morphology to be distorted and cell membranes to be damaged to kill bacteria; nano-magnesium oxide generates peroxide ions by reacting with oxygen, and uses the strong oxidizing property of peroxide ions to kill bacteria; nano-zinc molybdate uses Zn 2+ The reaction with the thiol group causes the death of bacteria and sterilization; thus, the prepared ceramic cup has good antibacterial properties. Summary of the invention

[0004] The technical problem to be solved by the present invention is to overcome the defects and shortcomings of the prior art and provide a high-performance antibacterial daily-use ceramic and its preparation method and application. 0.8 Ca 0.2 WO4 and nano zinc oxide, by utilizing the interaction between the components, have the characteristics of excellent antibacterial properties. At the same time, controlling the calcination conditions further improves the antibacterial properties of daily-use ceramics, and the antibacterial properties are excellent.

[0005] The purpose of the present invention is to provide a method for preparing high-performance antibacterial daily-use ceramics.

[0006] Another object of the present invention is to provide a high-performance antibacterial daily-use ceramic.

[0007] Another object of the present invention is to provide a use of high-performance antibacterial daily-use ceramics.

[0008] The above-mentioned purpose of the present invention is achieved through the following technical solutions:

[0009] A method for preparing high-performance antibacterial daily-use ceramics, the preparation method comprising the following steps:

[0010] 1) Preparation of daily-use ceramic embryos:

[0011] 2) Weigh the following materials by weight: mullite, cordierite, vein quartz, spodumene and water, place them in a ball mill, and mill them at a speed of 200 to 300 r / min for 4 to 8 hours;

[0012] 3) Then ZIF-67(Ni);Co 0.8 Ca 0.2 WO4; nano zinc oxide and Tween-80 are added to the ball mill and ball milling is continued for 40 to 60 minutes to obtain a glaze;

[0013] 4) applying the glaze to the surface of the daily-use ceramic body in step 1), and drying naturally to obtain a glazed daily-use ceramic body;

[0014] 5) In a nitrogen atmosphere, the glazed daily-use ceramic body is heated from room temperature to 500-600°C at a rate of 3-7°C / min and kept warm for 4-8h, then the atmosphere is converted to air, and then the temperature is increased to 1200-1400°C at a rate of 9-11°C / min and kept warm for 2-6h, then the temperature is reduced to 600-800°C, kept warm for 1-3h, and then naturally cooled to room temperature to obtain high-performance antibacterial daily-use ceramics.

[0015] Further, by weight: 40 to 60 parts of mullite; 20 to 40 parts of cordierite; 20 to 40 parts of vein quartz; 10 to 20 parts of spodumene; 6 to 10 parts of ZIF-67 (Ni); Co 0.8 Ca 0.2 WO4 4-6 parts; nano zinc oxide 2-6 parts; Tween-80 5-9 parts; water 40-60 parts.

[0016] Further preferably, the zinc oxide is at least one of nano zinc oxide and zinc oxide nanofiber.

[0017] More preferably, the particle size of the nano zinc oxide is 40 to 120 nm; the length of the zinc oxide nanofiber is 100 to 200 nm, and the aspect ratio is 50 to 100:1.

[0018] Still more preferably, the zinc oxide is nano zinc oxide and zinc oxide nanofibers, and the mass ratio of the nano zinc oxide to the zinc oxide nanofibers is 3 to 5:1.

[0019] Furthermore, the nano-Co 0.8 Ca 0.2 The preparation method of WO4 comprises the following steps:

[0020] Cobalt nitrate, calcium nitrate and sodium tungstate were weighed in a molar ratio of 0.8:0.2:1; the above raw materials were then added to deionized water and magnetically stirred for 30 to 50 minutes; then transferred to a polytetrafluoroethylene reactor and hydrothermally reacted at 160 to 200°C for 20 to 30 hours; cooled to room temperature, washed, dried at 80 to 120°C for 10 to 20 hours, and ground into powder to obtain nano Co 0.8 Ca 0.2 WO4.

[0021] Furthermore, the preparation method of ZIF-67 (Ni) includes the following steps: ultrasonically dispersing nickel nitrate and 2-methylimidazole in ethanol water, wherein the volume ratio of ethanol to water is 4:1; then stirring the reaction at 40-80°C for 3-6 hours, standing for 18-22 hours, filtering, washing, and drying at 80-120°C for 10-18 hours to obtain ZIF-67 (Ni).

[0022] More preferably, the molar ratio of the nickel nitrate to 2-methylimidazole is 1:2-4.

[0023] A high-performance antibacterial daily-use ceramic is prepared based on the above-mentioned preparation method of a high-performance antibacterial daily-use ceramic.

[0024] Based on the above, a high-performance antibacterial daily-use ceramic is used in the field of daily-use ceramics.

[0025] The present invention has the following beneficial effects:

[0026] The present invention first performs calcination treatment in an inert atmosphere to achieve nitrogen self-doping, then converts the atmosphere into air, decomposes part of the carbon converted from MOF, and obtains nitrogen-doped nickel oxide, which is then combined with nano-Co 0.8 Ca 0.2 The interaction between WO4 and zinc oxide significantly improves the antibacterial properties of daily-use ceramics, and the antibacterial properties are excellent. DETAILED DESCRIPTION

[0027] The present invention is further described below with reference to specific examples, but the examples do not limit the present invention in any form. Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the art.

[0028] The nano Co used in the embodiment of the present invention 0.8 Ca 0.2 WO4 and ZIF-67(Ni) were prepared by the following method:

[0029] Among them, nano-Co 0.8 Ca 0.2 The preparation method of WO4 comprises the following steps:

[0030] 0.8 mol of cobalt nitrate, 0.2 mol of calcium nitrate and 1 mol of sodium tungstate were added to 200 mL of deionized water and stirred magnetically for 40 min. Then the mixture was transferred to a polytetrafluoroethylene reactor and subjected to hydrothermal reaction at 180 °C for 26 h. The mixture was cooled to room temperature, washed, dried at 100 °C for 18 h and ground into powder to obtain nano-Co. 0.8 Ca 0.2 WO4;

[0031] Among them, the preparation method of ZIF-67(Ni) includes the following steps: ultrasonically dispersing 1 mol of nickel nitrate and 3 mol of 2-methylimidazole into 150 mL of ethanol water, wherein the volume ratio of ethanol to water is 4:1; then stirring the reaction at 60°C for 5 hours, standing for 20 hours, filtering, washing, and drying at 100°C for 14 hours to obtain ZIF-67(Ni).

[0032] Unless otherwise specified, the reagents and materials used in the following examples are commercially available.

[0033] Example 1

[0034] A method for preparing high-performance antibacterial daily-use ceramics, the preparation method comprising the following steps:

[0035] 1) Preparation of daily-use ceramic embryos:

[0036] 2) Weigh the following materials by weight: mullite, cordierite, vein quartz, spodumene and water into a ball mill, and mill at a speed of 250 r / min for 6 h;

[0037] 3) Then ZIF-67(Ni);Co 0.8 Ca 0.2 WO4; nano zinc oxide and Tween-80 are added to the ball mill and ball milling is continued for 50 minutes to obtain a glaze;

[0038] 4) applying the glaze to the surface of the daily-use ceramic body in step 1), and drying naturally to obtain a glazed daily-use ceramic body;

[0039] 5) Under a nitrogen atmosphere, the glazed daily-use ceramic body is heated from room temperature to 550°C at a rate of 5°C / min and kept for 6 hours, then the atmosphere is converted to air, and then the temperature is increased to 1300°C at a rate of 10°C / min and kept for 4 hours, then the temperature is decreased to 700°C and kept for 2 hours, and then naturally cooled to room temperature to obtain high-performance antibacterial daily-use ceramics.

[0040] By weight: the glaze layer includes the following components: 50 parts of mullite; 30 parts of cordierite; 30 parts of vein quartz; 15 parts of spodumene; 8 parts of ZIF-67 (Ni); Co 0.8 Ca 0.2 WO4 5 parts; Nano zinc oxide 4 parts; Tween-80 7 parts; Water 50 parts;

[0041] The zinc oxide is nano zinc oxide;

[0042] The particle size of nano zinc oxide is 80nm.

[0043] Example 2

[0044] Except for the differences, the preparation method and conditions are the same as those of Example 1, and the differences from Example 1 are:

[0045] The zinc oxide is nano zinc oxide and zinc oxide nanofiber;

[0046] The particle size of nano zinc oxide is 80nm; the length of zinc oxide nanofiber is 150nm, and the aspect ratio is 75:1;

[0047] The mass ratio of nano zinc oxide to zinc oxide nanofibers is 4:1;

[0048] Example 3

[0049] Except for the differences, the preparation method and conditions are the same as those of Example 1, and the differences from Example 1 are:

[0050] By weight: the glaze layer includes the following components: 60 parts of mullite; 20 parts of cordierite; 40 parts of vein quartz; 10 parts of spodumene; 10 parts of ZIF-67 (Ni); Co 0.8 Ca 0.2 WO4 4 parts; nano zinc oxide 6 parts; Tween-80 5 parts; water 60 parts.

[0051] Example 4

[0052] Except for the differences, the preparation method and conditions are the same as those of Example 1, and the differences from Example 1 are:

[0053] By weight: 40 parts of mullite; 40 parts of cordierite; 20 parts of vein quartz; 20 parts of spodumene; 6 parts of ZIF-67 (Ni); Co 0.8 Ca 0.2 WO4 6 parts; nano zinc oxide 2 parts; Tween-80 9 parts; water 40 parts.

[0054] Comparative Example 1

[0055] The preparation method and conditions are the same as those in Example 1 except that 5 parts of CoWO4 are used instead of 5 parts of Co0.8 Ca 0.2 WO4.

[0056] Comparative Example 2

[0057] The preparation method and conditions are the same as those of Example 1 except that 13 parts of ZIF-67(Ni) are used to replace 8 parts of ZIF-67(Ni) and 5 parts of Co 0.8 Ca 0.2 WO4.

[0058] Comparative Example 3

[0059] The preparation method and conditions are the same as those of Example 1 except that 10 nanometers of zinc oxide is used to replace 4 parts of Co 0.8 Ca 0.2 WO4 and 6 parts of nano zinc oxide.

[0060] Comparative Example 4

[0061] Except for the differences, the preparation method and conditions are the same as those of Example 1, and the differences from Example 1 are:

[0062] 5) In an air atmosphere, the glazed daily-use ceramic body is heated from room temperature to 550°C at a rate of 5°C / min and kept for 6 hours, then heated to 1300°C at a rate of 10°C / min and kept for 4 hours, then cooled to 700°C and kept for 2 hours, and then naturally cooled to room temperature to obtain high-performance antibacterial daily-use ceramics.

[0063] According to JC / T897-2014 "Antibacterial Performance of Antibacterial Ceramic Products", the high-performance antibacterial daily-use ceramics prepared in Examples 1-4 and Comparative Examples 1-4 were tested for performance, and the results are shown in Table 1 below:

[0064] Table 1 Performance test results of antibacterial daily ceramic cups

[0065]

[0066] It can be seen from Table 1 that the high-performance antibacterial daily-use ceramics prepared in Examples 1-4 have excellent antibacterial properties. Comparing Example 1 with Comparative Examples 1-4, the ZIF-67 (Ni), Co 0.8 Ca 0.2 WO4 and nano zinc oxide have a synergistic effect, so that the prepared high-performance antibacterial daily-use ceramics have excellent antibacterial properties.

[0067] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.

Claims

1. A method for preparing high-performance antibacterial daily-use ceramics, characterized in that: The preparation method comprises the following steps: 1) Preparation of daily-use ceramic embryos: Weigh the following by weight: mullite, cordierite, vein quartz, spodumene and water, place them in a ball mill, and mill them at a speed of 200 to 300 r / min for 4 to 8 hours; 2) Then ZIF-67(Ni); nano-Co 0.8 Ca 0.2 WO4; nano zinc oxide and Tween-80 are added to the ball mill and ball milling is continued for 40 to 60 minutes to obtain a glaze; 3) applying the glaze to the surface of the daily-use ceramic body in step 1), and drying naturally to obtain a glazed daily-use ceramic body; 4) In a nitrogen atmosphere, the glazed daily-use ceramic body is heated from room temperature to 500-600° C. at a rate of 3-7° C. / min and kept warm for 4-8 hours, then the atmosphere is converted to air, and then the temperature is raised to 1200-1400° C. at a rate of 9-11° C. / min and kept warm for 2-6 hours, then the temperature is lowered to 600-800° C., kept warm for 1-3 hours, and then naturally cooled to room temperature to obtain a high-performance antibacterial daily-use ceramic; By weight, 40-60 parts of mullite, 20-40 parts of cordierite, 20-40 parts of vein quartz, 10-20 parts of spodumene, 6-10 parts of ZIF-67 (Ni), and nano-Co 0.8 Ca 0.2 WO4 4-6 parts, nano zinc oxide 2-6 parts, Tween-80 5-9 parts, water 40-60 parts; The nano-Co 0.8 Ca 0.2 The preparation method of WO4 comprises the following steps: Cobalt nitrate, calcium nitrate and sodium tungstate were weighed in a molar ratio of 0.8:0.2:1; the above raw materials were then added to deionized water and magnetically stirred for 30 to 50 minutes; then transferred to a polytetrafluoroethylene reactor and hydrothermally reacted at 160 to 200°C for 20 to 30 hours; cooled to room temperature, washed, dried at 80 to 120°C for 10 to 20 hours, and ground into powder to obtain nano Co 0.8 Ca 0.2 WO4; The preparation method of ZIF-67 (Ni) comprises the following steps: ultrasonically dispersing nickel nitrate and 2-methylimidazole into ethanol water, wherein the volume ratio of ethanol to water is 4:1; then stirring and reacting at 40-80°C for 3-6 hours, standing for 18-22 hours, filtering, washing, and drying at 80-120°C for 10-18 hours to obtain ZIF-67 (Ni); the molar ratio of nickel nitrate to 2-methylimidazole is 1:2-4.

2. The method for preparing a high-performance antibacterial daily-use ceramic according to claim 1, characterized in that: The zinc oxide is at least one of nano zinc oxide and zinc oxide nanofiber.

3. The method for preparing a high-performance antibacterial daily-use ceramic according to claim 2, characterized in that: The particle size of the nano zinc oxide is 40-120 nm; the length of the zinc oxide nanofiber is 100-200 nm, and the aspect ratio is 50-100:

1.

4. The method for preparing a high-performance antibacterial daily-use ceramic according to claim 3, characterized in that: The zinc oxide is nano zinc oxide and zinc oxide nanofibers, and the mass ratio of the nano zinc oxide to the zinc oxide nanofibers is 3-5:

1.

5. A high-performance antibacterial daily-use ceramic prepared according to the method for preparing a high-performance antibacterial daily-use ceramic according to any one of claims 1 to 4.

6. Application of the high-performance antibacterial daily-use ceramic according to claim 5 in the field of daily-use ceramics.

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