High-strength antibacterial glaze and preparation process thereof

Abstract

The application relates to high-strength antibacterial glaze and a preparation process, and belongs to the technical field of ceramics. The glaze comprises quartz, kaolin, mullite, calcite, europium nitrate, holmium nitrate, white resveratrol, sodium tripolyphosphate, sodium borate, diatomite, acetic acid, ethanol, ammonia water and deionized water. The sodium borate is used to increase the fluidity and wettability of the glaze, and the sodium tripolyphosphate is used to assist in control, so that the compatibility between the glaze and the ceramic substrate is improved, and the antibacterial performance of the glaze is further stabilized. In addition, the europium nitrate, the holmium nitrate and the white resveratrol are added, the three have a synergistic effect, from interfering with the normal physiological function of bacteria, to destroying the structure of bacteria, to inhibiting the defense system of bacteria, and gradually making the bacteria die; in addition, the europium nitrate and the holmium nitrate in the system can induce each other, so that the system achieves high-strength antibacterial effect; the diatomite is added, the antibacterial effect of the glaze is prolonged, and long-acting antibacterial effect is achieved.

Description

Technical Field

[0001] This invention belongs to the field of ceramic technology, specifically relating to a high-strength antibacterial glaze and its preparation process. Background Technology

[0002] Ceramics are various products made from natural clay and various natural minerals as the main raw materials through crushing, mixing, shaping, and firing. Ceramic art has always occupied an important position in various art and culture. For ceramic art, the glaze is an extremely crucial component. Generally speaking, ceramic glaze is a uniform, glassy thin layer covering the surface of the ceramic body. For ceramic products, ceramic glaze can improve performance and serve a decorative purpose.

[0003] The market offers a dazzling array of ceramic glazes, but as people's living standards improve, their demands for health also increase. Currently available ceramic glazes often lack sufficient antibacterial properties to meet these needs. This poor antibacterial effect is generally due to inadequate antibacterial components in the glaze, making it difficult to improve the glaze's structure and overall quality. Alternatively, poor compatibility between the glaze and the ceramic substrate can also hinder the antibacterial effect on the ceramic surface. Therefore, finding a high-strength antibacterial glaze to address these issues is of paramount importance. Summary of the Invention

[0004] The purpose of this invention is to provide a high-strength antibacterial glaze and its preparation process. This invention uses sodium borate to increase the glaze's fluidity and wettability, while sodium tripolyphosphate is used for auxiliary control. Both improve the compatibility between the glaze and the ceramic substrate, further stabilizing the glaze's antibacterial properties. Furthermore, this invention incorporates europium nitrate, holmium nitrate, and resveratrol. These three substances work synergistically, gradually leading to bacterial death by interfering with normal physiological functions, destroying bacterial structure, and inhibiting the bacterial defense system. In addition, europium nitrate and holmium nitrate in the system can mutually induce each other, increasing the release of europium and holmium ions, significantly enhancing the system's antibacterial performance and achieving a high-strength antibacterial effect. This invention also incorporates diatomaceous earth, fully utilizing its rich internal pore structure, large specific surface area, and strong adsorption properties to prolong the glaze's antibacterial effect, achieving long-lasting antibacterial action and solving the problem of poor antibacterial performance in existing glazes.

[0005] The objective of this invention can be achieved through the following technical solutions:

[0006] A high-strength antibacterial glaze, the glaze comprising the following raw materials in parts by weight:

[0007]

[0008] As a preferred embodiment of the present invention, the base material includes quartz, kaolin, mullite and calcite.

[0009] As a preferred embodiment of the present invention, the mass ratio of quartz, kaolin, mullite and calcite is 28-35:9-12:20-28:24-33.

[0010] As a preferred embodiment of the present invention, the preparation process of the glaze includes the following steps:

[0011] S1. Mix europium nitrate, holmium nitrate, resveratrol and ethanol evenly under controlled temperature to obtain mixture A, set aside; mix quartz, kaolin, mullite, calcite and deionized water evenly and ball mill to obtain basic mixture, set aside; mix diatomaceous earth and acetic acid, then add ammonia water and stir again to obtain mixture;

[0012] S2. Mix and stir the mixture A, the mixture, sodium tripolyphosphate and sodium borate. After stirring, let it stand to react, then centrifuge to separate the filtrate and filter material. Calcine the filter material at a controlled temperature to obtain the intermediate material.

[0013] S3. Ball mill the base mixture and intermediate material to obtain the glaze.

[0014] As a preferred embodiment of the present invention, the temperature at which the temperature is controlled and the mixture is homogenized in step S1 is 26-30°C.

[0015] As a preferred embodiment of the present invention, the mass of the ball in the ball mill in step S1 is 2-2.5 times the total mass of quartz, kaolin, mullite and calcite; the ball milling time is 20-30 minutes.

[0016] As a preferred embodiment of the present invention, the mixing and stirring time in step S1 is 15-25 min; the re-stirring time is 20-25 min.

[0017] As a preferred embodiment of the present invention, the mixing and stirring time in step S2 is 15-30 min; the standing reaction time is 3-5 h.

[0018] As a preferred embodiment of the present invention, the temperature of the temperature-controlled calcination in step S2 is 340-380℃ and the time is 10-15min.

[0019] As a preferred embodiment of the present invention, the ball milling time in step S3 is 25-35 minutes; the mass of the balls in the ball milling is twice the total mass of the base mixture and intermediate material.

[0020] The beneficial effects of this invention are:

[0021] (1) This invention incorporates sodium tripolyphosphate and sodium borate. The excellent solubility and compatibility of sodium borate interact with the components in the base material and promote the vitrification process of the glaze, thereby increasing the fluidity and wettability of the glaze and making it smoother and more uniform. On this basis, sodium tripolyphosphate interacts with the particles in the base material to form a strong chemical bond, which in turn controls the fluidity and wettability of the glaze and prevents the glaze from flowing or delaminating too quickly during the application or sintering process, thus improving the viscosity and stability of the glaze. In other words, sodium borate increases the fluidity and wettability of the glaze, while sodium tripolyphosphate is used for auxiliary control. Together, they improve the compatibility between the glaze and the ceramic substrate, thereby further stabilizing the antibacterial properties of the glaze.

[0022] (2) This invention incorporates europium nitrate, holmium nitrate, and resveratrol. The synergistic effect of these three compounds enhances the antibacterial properties of the prepared glaze. This is because holmium nitrate disrupts the acid-base balance within bacterial cells, interfering with their normal physiological functions; europium nitrate inhibits peptidoglycan synthesis and binds to hydrophobic hydroxyl groups in bacterial intracellular proteins, damaging the bacterial sheath and wall structure; and resveratrol inhibits bacterial stress responses and weakens their defense system. In other words, the synergistic effect of these three compounds gradually leads to bacterial death, from interfering with normal physiological functions to damaging bacterial structure and then inhibiting the bacterial defense system. Furthermore, the inventors have discovered that europium nitrate and holmium nitrate in the system can mutually induce each other, increasing the release of europium and holmium ions, significantly enhancing the antibacterial properties of the system and achieving a high level of antibacterial activity.

[0023] (3) This invention incorporates diatomaceous earth and fully utilizes the advantages of diatomaceous earth's rich internal pore structure, large specific surface area and strong adsorption, enabling it to effectively carry europium nitrate, holmium nitrate and resveratrol in the system and form an encapsulation structure to achieve slow release, thereby prolonging the antibacterial effect and achieving long-lasting antibacterial effect. Detailed Implementation

[0024] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0025] Example 1

[0026] A high-strength antibacterial glaze, the glaze comprising the following raw materials in parts by weight:

[0027]

[0028] The base material consists of quartz, kaolin, mullite and calcite in a mass ratio of 28:12:24:33.

[0029] The preparation process of the glaze includes the following steps:

[0030] S1. Mix europium nitrate, holmium nitrate, resveratrol and ethanol in the above weight proportions at a controlled temperature of 26°C until homogeneous to obtain mixture A, for later use; mix quartz, kaolin, mullite, calcite and deionized water until homogeneous and ball mill for 25 min to obtain basic mixture, for later use; mix diatomaceous earth and acetic acid and stir for 25 min, then add ammonia water and stir for another 20 min to obtain mixture;

[0031] The mass of the balls in the ball mill is 2.2 times the total mass of quartz, kaolin, mullite, and calcite;

[0032] S2. Mix the mixture A, the mixture, sodium tripolyphosphate and sodium borate for 30 min. After stirring, let it stand for 3 h to react. Then centrifuge to obtain the filtrate and filter material. Calcine the filter material at 340℃ for 13 min to obtain the intermediate material.

[0033] S3. Ball mill the base mixture and intermediate material to obtain the glaze;

[0034] The mass of the balls in the ball mill is twice the total mass of the base mixture and intermediate material.

[0035] Example 2

[0036] A high-strength antibacterial glaze, the glaze comprising the following raw materials in parts by weight:

[0037]

[0038]

[0039] The base material consists of quartz, kaolin, mullite and calcite in a mass ratio of 35:9:20:24.

[0040] The preparation process of the glaze includes the following steps:

[0041] S1. Mix europium nitrate, holmium nitrate, resveratrol and ethanol in the above weight proportions at a controlled temperature of 30°C to obtain mixture A, for later use; mix quartz, kaolin, mullite, calcite and deionized water evenly and ball mill for 20 min to obtain basic mixture, for later use; mix diatomaceous earth and acetic acid and stir for 15 min, then add ammonia water and stir for another 25 min to obtain mixture;

[0042] The mass of the balls in the ball mill is 2.5 times the total mass of quartz, kaolin, mullite, and calcite.

[0043] S2. Mix the mixture A, the mixture, sodium tripolyphosphate and sodium borate for 24 min. After stirring, let it stand for 5 h. Then centrifuge to obtain the filtrate and filter material. Calcine the filter material at 360℃ for 10 min to obtain the intermediate material.

[0044] S3. Ball mill the base mixture and intermediate material to obtain the glaze;

[0045] The mass of the balls in the ball mill is twice the total mass of the base mixture and intermediate material.

[0046] Example 3

[0047] A high-strength antibacterial glaze, the glaze comprising the following raw materials in parts by weight:

[0048]

[0049]

[0050] The base material consists of quartz, kaolin, mullite and calcite in a mass ratio of 31:10:28:29.

[0051] The preparation process of the glaze includes the following steps:

[0052] S1. Mix europium nitrate, holmium nitrate, resveratrol and ethanol in the above weight proportions at 28°C until homogeneous to obtain mixture A, for later use; mix quartz, kaolin, mullite, calcite and deionized water until homogeneous and ball mill for 30 min to obtain basic mixture, for later use; mix diatomaceous earth and acetic acid and stir for 20 min, then add ammonia water and stir for another 23 min to obtain mixture;

[0053] The mass of the balls in the ball mill is twice the total mass of quartz, kaolin, mullite, and calcite.

[0054] S2. Mix the mixture A, the mixture, sodium tripolyphosphate and sodium borate for 15 minutes. After stirring, let it stand for 4 hours. Then centrifuge to obtain the filtrate and the filter material. Calcine the filter material at 380℃ for 15 minutes to obtain the intermediate material.

[0055] S3. Ball mill the base mixture and intermediate material to obtain the glaze;

[0056] The mass of the balls in the ball mill is twice the total mass of the base mixture and intermediate material.

[0057] Comparative Example 1

[0058] Compared with Example 3, the difference is that sodium tripolyphosphate was not added in Comparative Example 1, while the other parameters and operating steps remained unchanged.

[0059] Comparative Example 2

[0060] Compared with Example 3, the difference is that sodium borate was not added in Comparative Example 2, while the other parameters and operating steps remained unchanged.

[0061] Comparative Examples 3-5

[0062] Compared with Example 3, the difference is that the weight parts of europium nitrate, holmium nitrate and resveratrol added in Comparative Examples 3-5 are shown in Table 1, while the other parameters and operating steps remain unchanged.

[0063] Table 1

[0064] Europium nitrate (parts by weight) Holmium nitrate (parts by weight) Resveratrol (parts by weight) Comparative Example 3 0 1 4.5 Comparative Example 4 1.3 0 4.2 Comparative Example 5 3 2.5 0

[0065] Comparative Example 6

[0066] Compared with Example 3, the difference is that no diatomaceous earth was added in Comparative Example 2, while the other parameters and operating steps remained unchanged.

[0067] Test Example 1

[0068] The glazes obtained in Examples 1-3 and Comparative Examples 1-6 were mixed with water to prepare 50wt% glaze slurries, which were then coated on the surface of ceramic blanks and fired at 1000℃ to obtain ceramic products (with an area of ​​90 square centimeters). The antibacterial rate of the ceramic products obtained in Examples 1-3 and Comparative Examples 1-5 was tested according to JC / T897-2014, and the antibacterial durability of Examples 1-3 and Comparative Example 6 was tested according to JC / T897-2014. The results are shown in Table 2.

[0069] Table 2

[0070]

[0071] As can be seen from Examples 1-3 and Comparative Examples 1-2 in Table 2, the glaze prepared by this invention has extremely strong antibacterial properties. The inventors speculate that this is due to the increased compatibility between the glaze and the ceramic substrate. Furthermore, this invention incorporates sodium tripolyphosphate and sodium borate. The excellent solubility and compatibility of sodium borate interact with the components in the base material, promoting the vitrification process of the glaze, thereby increasing its fluidity and wettability, making it smoother and more uniform. Based on this, sodium tripolyphosphate interacts with the particles in the base material, forming a strong chemical bond, which further controls the fluidity and wettability of the glaze, preventing excessively rapid flow or stratification during application or sintering, and improving the viscosity and stability of the glaze. In other words, sodium borate increases the fluidity and wettability of the glaze, while sodium tripolyphosphate provides auxiliary control; both work together to improve the compatibility between the glaze and the ceramic substrate, further stabilizing the antibacterial properties of the glaze.

[0072] As can be seen from Examples 1-3 and Comparative Examples 3-5 in Table 2, the glaze prepared by this invention has extremely strong antibacterial properties. This is because this invention incorporates europium nitrate, holmium nitrate, and resveratrol. Within the system, holmium nitrate disrupts the acid-base balance within bacterial cells, interfering with their normal physiological functions; europium nitrate inhibits the synthesis of peptidoglycan and combines with hydrophobic hydroxyl groups in bacterial intracellular proteins, destroying the bacterial sheath and wall structure; and resveratrol inhibits the bacterial stress response and weakens its defense system. In other words, the three work synergistically, from interfering with the normal physiological functions of bacteria, to destroying bacterial structure, and then to inhibiting the bacterial defense system, gradually leading to bacterial death. Furthermore, the inventors also discovered that europium nitrate and holmium nitrate in the system can mutually induce each other, increasing the release of europium and holmium ions, greatly enhancing the antibacterial properties of the system and achieving a high-strength antibacterial effect.

[0073] As can be seen from Examples 1-3 and Comparative Example 6 in Table 2, the glaze prepared by this invention has a long-lasting antibacterial effect. This is because this invention incorporates diatomaceous earth and fully utilizes the advantages of diatomaceous earth's rich internal pore structure, large specific surface area, and strong adsorption, enabling it to effectively carry europium nitrate, holmium nitrate, and resveratrol in the system and form an encapsulation structure, achieving slow release and thus prolonging the antibacterial effect, achieving long-lasting antibacterial action.

[0074] In the description of this specification, the references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0075] The above description is merely an example and illustration of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described, or use similar methods to replace them, as long as they do not deviate from the invention or exceed the scope defined in the claims, all of which should fall within the protection scope of the present invention.

Claims

1. A high-strength antibacterial glaze, characterized in that, The glaze comprises the following raw materials in parts by weight: 50-65 parts by weight of base material europium nitrate 0.7-1 parts by weight 0.5-0.8 parts by weight of holmium nitrate 3-4 parts by weight of resveratrol Sodium tripolyphosphate 0.1-0.4 parts by weight Sodium borate 0.2-0.3 parts by weight 6-10 parts by weight of diatomaceous earth Acetic acid 320-400 parts by weight 130-180 parts by weight of ethanol 15-18 parts by weight of ammonia water 23-28 parts by weight of deionized water; The base material includes quartz, kaolin, mullite and calcite; The high-strength antibacterial glaze is prepared by the following steps: S1. Mix europium nitrate, holmium nitrate, resveratrol and ethanol evenly under controlled temperature to obtain mixture A, set aside; mix quartz, kaolin, mullite, calcite and deionized water evenly and ball mill to obtain basic mixture, set aside; mix diatomaceous earth and acetic acid, then add ammonia water and stir again to obtain mixture; S2. Mix and stir the mixture A, the mixture, sodium tripolyphosphate and sodium borate. After stirring, let it stand to react, then centrifuge to separate the filtrate and filter material. Calcine the filter material at a controlled temperature to obtain the intermediate material. S3. Ball mill the base mixture and intermediate material to obtain the glaze.

2. The high-strength antibacterial glaze according to claim 1, characterized in that, The mass ratio of quartz, kaolin, mullite and calcite is 28-35:9-12:20-28:24-33.

3. The high-strength antibacterial glaze according to claim 1, characterized in that, The temperature at which the temperature is controlled and the mixture is homogenized in step S1 is 26-30℃.

4. The high-strength antibacterial glaze according to claim 1, characterized in that, In step S1, the mass of the balls used in the ball mill is 2-2.5 times the total mass of quartz, kaolin, mullite, and calcite; the ball milling time is 20-30 minutes.

5. The high-strength antibacterial glaze according to claim 1, characterized in that, The mixing and stirring time in step S1 is 15-25 minutes; the re-stirring time is 20-25 minutes.

6. The high-strength antibacterial glaze according to claim 1, characterized in that, The mixing and stirring time in step S2 is 15-30 min; the standing reaction time is 3-5 h.

7. The high-strength antibacterial glaze according to claim 1, characterized in that, The temperature for controlled calcination in step S2 is 340-380℃, and the time is 10-15 min.

8. The high-strength antibacterial glaze according to claim 1, characterized in that, The ball milling time in step S3 is 25-35 minutes; the mass of the balls used in the ball milling is twice the total mass of the base mixture and intermediate material.

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