Composite enhanced antibacterial ceramic glaze and preparation method thereof

Abstract

The invention relates to the technical field of glazes, and discloses a composite enhanced antibacterial ceramic glaze and a preparation method thereof.The ceramic glaze is prepared from bentonite, potassium feldspar, kaolinite, calcite, quartz, lithium feldspar, mullite, a synergistic antibacterial agent and the like through grinding and mixing, and in the high-temperature ablation process of the glaze, the ceramic glaze is subjected to high-temperature ablation, so that the antibacterial ceramic glaze is obtained. A carrier of the synergistic antibacterial agent can be ablated to form zinc oxide and silica sol, so that silver can be protected, silver can continuously exist in a finally formed glaze layer to play an antibacterial role, meanwhile, zinc oxide has good performance, and silver and zinc oxide cooperate with each other to generate an enhanced antibacterial role, so that the purpose of improving the antibacterial effect by adding a small amount of silver and silica sol is achieved. The glaze layer can be endowed with excellent antibacterial performance. In addition, due to the existence of the silica sol, the surface of the glaze layer is super-hydrophobic, so that the glaze layer has self-cleaning performance.

Description

Technical Field

[0001] This invention relates to the field of glaze technology, specifically to a composite reinforced antibacterial ceramic glaze and its preparation method. Background Technology

[0002] Ceramic glaze refers to a thin layer of vitreous or glass-crystal mixture applied to the surface of a ceramic body. It is created by applying a specific formula of mineral raw material mixture to the surface of the body, melting it at high temperature, and then cooling and solidifying it to form a dense layer firmly bonded to the body. This glaze imparts a smooth, bright texture to the ceramic surface and can present a rich variety of colors, textures, and optical effects. It is not only an important means of decorating ceramic ware but also a key technology for improving the mechanical strength, chemical stability, airtightness, and ease of cleaning of ceramic products.

[0003] With the increasing application of ceramics, the functionality of glazes has gradually become a research hotspot, especially in the field of sanitary ware ceramics, where the antibacterial function of ceramic glazes is particularly important. Currently, it is common to use silver as an antibacterial additive to endow glazes with antibacterial properties. However, during the sintering process of the glaze, silver will undergo ablation and precipitation, resulting in the glaze layer having less than ideal antibacterial properties. Therefore, how to develop ceramic glazes with highly efficient and enhanced antibacterial properties is an urgent problem to be solved. Summary of the Invention

[0004] In order to solve the problems mentioned in the background art, the purpose of this invention is to provide a composite reinforced antibacterial ceramic glaze and its preparation method.

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

[0006] A composite reinforced antibacterial ceramic glaze, comprising the following raw materials by weight:

[0007] Bentonite 30-35 parts, potassium feldspar 30-35 parts, kaolinite 4-6 parts, calcite 5-10 parts, quartz 10-15 parts, lithium feldspar 1-2 parts, mullite 3-6 parts, calcium carbonate 2-4 parts, synergistic antibacterial agent 3-6.5 parts, 0.1-0.5 parts, binder 0.1-1 parts.

[0008] As a further aspect of the present invention, the synergistic antibacterial agent is prepared by the following method:

[0009] Step 1: Add the carrier to the silver nitrate solution and sonicate at an ultrasonic frequency of 100-120kHz for 1-3 hours. Then continue stirring for 4-8 hours to separate the material. After washing and vacuum drying, the silver-loaded carrier is obtained.

[0010] Step 2: Add the silver-loaded carrier to the reducing agent solution, stir evenly, control the temperature at 60-80℃, and separate the solid material after 12-24 hours. After washing and vacuum drying, the synergistic antibacterial agent is obtained.

[0011] As a further aspect of the present invention, in step one, the carrier is prepared by the following method:

[0012] Zinc salt and 5,5'-(dimethylsilyl)diisophthalic acid were added to an ethanol aqueous solution with a volume fraction of 60-70%. After the addition was complete, the mixture was mechanically stirred until homogeneous. Then, it was transferred to a reaction vessel for hydrothermal reaction. The mixture was cooled and discharged. The separated product was washed and vacuum dried to obtain the carrier.

[0013] As a further aspect of the present invention, the zinc salt is any one of zinc chloride, zinc sulfate, zinc nitrate, or zinc acetate.

[0014] As a further embodiment of the present invention, the hydrothermal reaction temperature is 120-130℃ and the time is 6-12h.

[0015] As a further aspect of the present invention, in step one, the concentration of the silver nitrate solution is 0.1-0.2 mol / L.

[0016] As a further embodiment of the present invention, the reducing agent solution is an aqueous solution of sodium borohydride with a mass fraction of 15-30%.

[0017] In the above technical solution, zinc salt and 5,5'-(dimethylsilanediyl)isophthalic acid are first used as raw materials. Through hydrothermal reaction, a metal framework carrier with a porous structure is formed. Then, through ultrasonic action, silver ions will break through the pore barrier of the carrier and enter the pores of the carrier. Then, by using a reducing agent, the silver ions are reduced to silver, thereby coating the silver in the pores of the carrier. This can effectively prevent the dissolution of silver and obtain a silver-loaded metal framework carrier, i.e., a synergistic antibacterial agent.

[0018] As a further aspect of the present invention, the dispersant is sodium polyacrylate.

[0019] As a further aspect of the present invention, the adhesive is any one of carboxymethyl cellulose, methyl cellulose, or polyvinyl alcohol.

[0020] A method for preparing a composite reinforced antibacterial ceramic glaze includes the following steps:

[0021] Step 1: Add bentonite, potassium feldspar, kaolinite, calcite, quartz, lithium feldspar, mullite and synergistic antibacterial agent into a grinder and grind through a 100-200 mesh sieve to form a premix.

[0022] The second step is to add the premix to the ball mill, and control the mass ratio of premix, balls and water to be 1:2-3:0.2-0.4. After wet ball milling for 6-8 hours, the material is discharged to form the precursor material.

[0023] The third step is to add water to the forward feed and adjust the slurry specific gravity to 1.6-1.65 g / cm³. 3 Then add the dispersant and binder, stir well, let stand to degas, and it's ready.

[0024] The beneficial effects of this invention are:

[0025] This invention prepares a synergistic antibacterial agent as a functional additive for glazes. During the high-temperature ablation process of the glaze, the carrier of the synergistic antibacterial agent ablates to form zinc oxide and silica sol. Due to the protective effect of the porous structure, silver does not ablate in the early stages of sintering. In the later stages of sintering, the zinc oxide and silica sol formed continue to coat the silver, protecting it. Thus, silver can remain in the final glaze layer, exerting its antibacterial effect. Simultaneously, zinc oxide itself possesses excellent properties. The two synergistically enhance each other's antibacterial effect, achieving the goal of imparting excellent antibacterial properties to the glaze layer with a small amount. Furthermore, the presence of silica sol makes the glaze surface superhydrophobic, thus providing self-cleaning properties.

[0026] Of course, any product implementing this invention does not necessarily need to achieve all of the advantages described above at the same time. Detailed Implementation

[0027] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments. 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 skilled in the art without creative effort are within the scope of protection of the present invention.

[0028] Preparation Example

[0029] Preparation of synergistic antibacterial agents:

[0030] Step A: Add 0.5g of zinc chloride and 1.4g of 5,5'-(dimethylsilanediyl)diisophthalic acid to a 70% (v / v) aqueous ethanol solution. After addition, mechanically stir until homogeneous, then transfer to a reaction vessel. Perform a hydrothermal reaction at 120°C for 9 hours. After cooling, discharge the material. Wash and vacuum dry the separated product to obtain the carrier.

[0031] Step B: Add 0.8g of the carrier to 100mL of 0.1mol / L silver nitrate solution, sonicate at 100kHz for 2h, then continue stirring for 6h, separate the material, wash and vacuum dry to obtain the silver-loaded carrier.

[0032] Step C: Add 0.6g of silver carrier to 10mL of 20% sodium borohydride aqueous solution, stir evenly, control the temperature at 70℃, and separate the solid material after 16h. After washing and vacuum drying, the synergistic antibacterial agent is obtained.

[0033] Example 1

[0034] A composite reinforced antibacterial ceramic glaze, comprising the following raw materials by weight:

[0035] 30 parts bentonite, 30 parts potassium feldspar, 4 parts kaolinite, 5 parts calcite, 10 parts quartz, 1 part lithium feldspar, 3 parts mullite, 2 parts calcium carbonate, 3 parts synergistic antibacterial agent, 0.1 parts sodium polyacrylate, and 0.1 parts carboxymethyl cellulose.

[0036] The method for preparing the ceramic glaze includes the following steps:

[0037] Step 1: Add bentonite, potassium feldspar, kaolinite, calcite, quartz, lithium feldspar, mullite and synergistic antibacterial agent into a grinder and grind through a 100-mesh sieve to form a premix.

[0038] The second step is to add the premix to the ball mill, control the mass ratio of premix, balls and water to be 1:2:0.3, and discharge the material after wet ball milling for 8 hours to form the precursor material.

[0039] Step 3: Add water to the forward feed and adjust the slurry specific gravity to 1.6 g / cm³. 3 Then add sodium polyacrylate and carboxymethyl cellulose, stir well, let stand to remove bubbles, and it's ready.

[0040] Example 2

[0041] A composite reinforced antibacterial ceramic glaze, comprising the following raw materials by weight:

[0042] 32 parts bentonite, 32 parts potassium feldspar, 5 parts kaolinite, 8 parts calcite, 12 parts quartz, 1.5 parts lithium feldspar, 4 parts mullite, 3 parts calcium carbonate, 6 parts synergistic antibacterial agent, 0.3 parts sodium polyacrylate, and 0.5 parts methylcellulose.

[0043] The method for preparing the ceramic glaze includes the following steps:

[0044] Step 1: Add bentonite, potassium feldspar, kaolinite, calcite, quartz, lithium feldspar, mullite and synergistic antibacterial agent into a grinder and grind through a 100-mesh sieve to form a premix.

[0045] The second step is to add the premix to the ball mill, control the mass ratio of premix, balls and water to be 1:2:0.3, and discharge the material after wet ball milling for 8 hours to form the precursor material.

[0046] Step 3: Add water to the forward feed and adjust the slurry specific gravity to 1.6 g / cm³. 3 Then add sodium polyacrylate and methylcellulose, stir well, let stand to remove bubbles, and it's ready.

[0047] Example 3

[0048] A composite reinforced antibacterial ceramic glaze, comprising the following raw materials by weight:

[0049] 35 parts bentonite, 35 parts potassium feldspar, 6 parts kaolinite, 10 parts calcite, 15 parts quartz, 2 parts lithium feldspar, 6 parts mullite, 4 parts calcium carbonate, 6.5 parts synergistic antibacterial agent, 0.5 parts sodium polyacrylate, and 1 part polyvinyl alcohol.

[0050] The method for preparing the ceramic glaze includes the following steps:

[0051] Step 1: Add bentonite, potassium feldspar, kaolinite, calcite, quartz, lithium feldspar, mullite and synergistic antibacterial agent into a grinder and grind through a 100-mesh sieve to form a premix.

[0052] The second step is to add the premix to the ball mill, control the mass ratio of premix, balls and water to be 1:2:0.3, and discharge the material after wet ball milling for 8 hours to form the precursor material.

[0053] Step 3: Add water to the forward feed and adjust the slurry specific gravity to 1.6 g / cm³. 3 Then add sodium polyacrylate and polyvinyl alcohol, stir well, let stand to remove bubbles, and it's ready.

[0054] Comparative Example 1

[0055] A composite reinforced antibacterial ceramic glaze, comprising the following raw materials by weight:

[0056] 32 parts bentonite, 32 parts potassium feldspar, 5 parts kaolinite, 8 parts calcite, 12 parts quartz, 1.5 parts lithium feldspar, 4 parts mullite, 3 parts calcium carbonate, 4 parts nano silver, 0.3 parts sodium polyacrylate, and 0.5 parts methylcellulose.

[0057] The method for preparing the ceramic glaze includes the following steps:

[0058] Step 1: Add bentonite, potassium feldspar, kaolinite, calcite, quartz, lithium feldspar, mullite and nano silver into a grinder and grind them through a 100-mesh sieve to form a premix.

[0059] The second step is to add the premix to the ball mill, control the mass ratio of premix, balls and water to be 1:2:0.3, and discharge the material after wet ball milling for 8 hours to form the precursor material.

[0060] Step 3: Add water to the forward feed and adjust the slurry specific gravity to 1.6 g / cm³. 3 Then add sodium polyacrylate and methylcellulose, stir well, let stand to remove bubbles, and it's ready.

[0061] Test case

[0062] A ceramic blank measuring 8cm×8cm×1cm was placed in a sintering furnace and sintered at 650℃ for 3 hours. The blank was then removed to form a ceramic slab. The ceramic slab was then immersed in the glazes used in the examples and comparative examples, three times for 5 seconds each time. After immersion, the slab was transferred to a kiln for firing at 1350℃ for 4 hours. After cooling, the slab was formed into a test sample.

[0063] (1) According to standard JC / T 897-2014, Staphylococcus aureus was used as the test strain to conduct antibacterial performance tests, and the results are recorded in the table below:

[0064] (2) The water contact angle of the glaze surface of the test sample was tested by using a contact angle measuring instrument;

[0065] The test results are recorded in the table below:

[0066] Analysis of the test results shows that the glaze layer formed after sintering the glaze prepared in this embodiment of the invention has good antibacterial properties and hydrophobic self-cleaning properties. When the synergistic antibacterial agent is replaced with nano-silver, the silver is ablated and precipitated during the ablation process, and the synergistic antibacterial effect of zinc oxide and the hydrophobic modification of silica sol are lost, resulting in a significant decrease in the performance of the glaze layer.

[0067] This document uses specific examples to illustrate the principles and implementation methods of the present invention. The descriptions of these embodiments are merely to aid in understanding the method and core ideas of the present invention, including the best mode, and to enable any person skilled in the art to practice the present invention, including manufacturing and using any device or system, and implementing any combined method. It should be noted that those skilled in the art can make various improvements and modifications to the present invention without departing from its principles, and these improvements and modifications also fall within the scope of protection of the claims. The scope of protection of this patent is defined by the claims and may include other embodiments that can be conceived by those skilled in the art. If these other embodiments have structural elements similar to those expressed in the claims, or if they include equivalent structural elements that are not substantially different from those expressed in the claims, then these other embodiments should also be included within the scope of the claims.

[0068] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. Such modifications or substitutions will not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A composite reinforced antibacterial ceramic glaze, characterized in that, By weight, it includes the following ingredients: Bentonite 30-35 parts, potassium feldspar 30-35 parts, kaolinite 4-6 parts, calcite 5-10 parts, quartz 10-15 parts, lithium feldspar 1-2 parts, mullite 3-6 parts, calcium carbonate 2-4 parts, synergistic antibacterial agent 3-6.5 parts, dispersant 0.1-0.5 parts, binder 0.1-1 parts.

2. The composite reinforced antibacterial ceramic glaze according to claim 1, characterized in that, The synergistic antibacterial agent is prepared using the following method: Step 1: Add the carrier to the silver nitrate solution and sonicate at an ultrasonic frequency of 100-120kHz for 1-3 hours. Then continue stirring for 4-8 hours to separate the material. After washing and vacuum drying, the silver-loaded carrier is obtained. Step 2: Add the silver-loaded carrier to the reducing agent solution, stir evenly, control the temperature at 60-80℃, and separate the solid material after 12-24 hours. After washing and vacuum drying, the synergistic antibacterial agent is obtained.

3. The composite reinforced antibacterial ceramic glaze according to claim 2, characterized in that, In step one, the carrier is prepared using the following method: Zinc salt and 5,5'-(dimethylsilyl)diisophthalic acid were added to an ethanol aqueous solution with a volume fraction of 60-70%. After the addition was complete, the mixture was mechanically stirred until homogeneous. Then, it was transferred to a reaction vessel for hydrothermal reaction. The mixture was cooled and discharged. The separated product was washed and vacuum dried to obtain the carrier.

4. The composite reinforced antibacterial ceramic glaze according to claim 3, characterized in that, The zinc salt is any one of zinc chloride, zinc sulfate, zinc nitrate, or zinc acetate.

5. The composite reinforced antibacterial ceramic glaze according to claim 3, characterized in that, The hydrothermal reaction is carried out at a temperature of 120-130℃ for 6-12 hours.

6. The composite reinforced antibacterial ceramic glaze according to claim 2, characterized in that, In step one, the concentration of the silver nitrate solution is 0.1-0.2 mol / L.

7. The composite reinforced antibacterial ceramic glaze according to claim 2, characterized in that, The reducing agent solution is an aqueous solution of sodium borohydride with a mass fraction of 15-30%.

8. The composite reinforced antibacterial ceramic glaze according to claim 1, characterized in that, The dispersant is sodium polyacrylate.

9. The composite reinforced antibacterial ceramic glaze according to claim 1, characterized in that, The binder is any one of carboxymethyl cellulose, methyl cellulose, or polyvinyl alcohol.

10. A method for preparing the composite reinforced antibacterial ceramic glaze as described in claim 1, characterized in that, Includes the following steps: Step 1: Add bentonite, potassium feldspar, kaolinite, calcite, quartz, lithium feldspar, mullite and synergistic antibacterial agent into a grinder and grind through a 100-200 mesh sieve to form a premix. The second step is to add the premix to the ball mill, and control the mass ratio of premix, balls and water to be 1:2-3:0.2-0.

4. After wet ball milling for 6-8 hours, the material is discharged to form the precursor material. The third step is to add water to the forward feed and adjust the slurry specific gravity to 1.6-1.65 g / cm³. 3 Then add the dispersant and binder, stir evenly, let stand to degas, and it's ready.

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