A high-strength antibacterial ceramic glaze and its processing method

Abstract

This invention relates to the field of ceramic glaze technology, and discloses a high-strength antibacterial ceramic glaze and its processing method. This ceramic glaze is formed by mixing potassium feldspar, calcite, and other materials as base materials, and loaded attapulgite antibacterial materials as additives. During the sintering process, the copper ions in the loaded attapulgite antibacterial material are ablated to form copper oxide. Because the copper oxide is loaded with attapulgite, it avoids agglomeration, thus better exerting its antibacterial properties. Furthermore, the silicon-oxygen bonds contained in the organic modification of the attapulgite form silica sol during sintering. The presence of silica sol significantly improves the hydrophobicity of the glaze layer, thereby effectively improving its cleaning effect. In addition, the copper oxide loaded on the attapulgite surface acts as anchor points. When external force is applied to the glaze layer, these anchor points prevent direct slippage of the lamellae, causing cracks to bypass the anchor points, thereby extending the crack propagation path and achieving a reinforcing effect.

Description

Technical Field

[0001] This invention relates to the field of ceramic glaze technology, specifically to a high-strength antibacterial ceramic glaze and its processing method. Background Technology

[0002] Ceramic glaze is a thin, glassy layer applied to the surface of a ceramic body. After being fired at high temperatures, it bonds firmly to the body. Its main functions include: decoration: giving ceramics rich colors, luster, textures, and special artistic effects; protection: improving the mechanical strength, hardness, and wear resistance of the body, and isolating it from moisture and chemical corrosion; and practicality: improving surface cleanliness and meeting food hygiene requirements.

[0003] The limitation of traditional glazes lies in their poor antibacterial properties. In humid environments, biofilms easily form on the surface of everyday ceramics, leading to a high detection rate of pathogens such as Escherichia coli and Staphylococcus aureus, which can easily cause cross-infection risks.

[0004] Currently, adding antibacterial agents to impart antibacterial properties to glazes is a common technique. For example, inorganic antibacterial agents such as silver can be added. However, silver antibacterial agents inevitably suffer from ablation during high-temperature sintering, making it difficult to guarantee good antibacterial performance. Other nanoscale antibacterial agents, on the other hand, tend to be unevenly dispersed, making it difficult to effectively exert their antibacterial properties. Based on this, the present invention provides a ceramic glaze that can solve the problems existing in the prior art. Summary of the Invention

[0005] In order to solve the problems mentioned in the background art, the purpose of this invention is to provide a high-strength antibacterial ceramic glaze and a processing method thereof.

[0006] The objective of this invention can be achieved through the following technical solutions:

[0007] A high-strength antibacterial ceramic glaze, comprising the following raw materials by weight:

[0008] Potassium feldspar 38-45 parts, calcite 15-22 parts, dolomite 5-9 parts, wollastonite 2-4 parts, bauxite 6-10 parts, spodumene 1-2 parts, alumina 4-8 parts, borax 1-2 parts, talc 5-12 parts, zircon 1-3 parts, supported attapulgite antibacterial material 1.5-3.6 parts, sodium hexametaphosphate 3-5 parts, water 100-150 parts;

[0009] The loaded attapulgite antibacterial material is attapulgite loaded with copper ions.

[0010] As a further aspect of the present invention, the loaded attapulgite antibacterial material is prepared by the following method:

[0011] Organically modified attapulgite was added to purified water, and the ultrasonic frequency was controlled at 100-120kHz for 30-40 minutes. Then, copper salt was added to the formed uniform dispersion. After the addition was complete, the pH was adjusted to 10-11, the heating was turned on, and the temperature was controlled at 60-80℃. The mixture was kept warm and stirred for 4-8 hours. The heating was stopped, the material was cooled and discharged, the solid was collected by centrifugation, and then washed and vacuum dried to obtain the loaded attapulgite antibacterial material.

[0012] As a further aspect of the present invention, the method for preparing the organically modified attapulgite includes the following steps:

[0013] Step A: Add attapulgite to N,N-dimethylformamide and disperse it evenly by ultrasonication. Then, add (3-glycidyl ether propyl)-1,1,3,3-tetramethyldisiloxane and catalyst to the dispersion. After the addition is complete, turn on the heater and raise the temperature to 120-140℃. Keep the temperature and stir for 6-12 hours. Stop the heating, cool down and discharge the material. Collect the solid material by centrifugation, and then wash and vacuum dry it to obtain functionalized attapulgite.

[0014] Step B: Add functionalized attapulgite to toluene, sonicate until a uniform dispersion is formed, then add hexadiene tartrate diamine and platinum catalyst. After the addition is complete, turn on the heater and heat to 80-90℃. Keep the temperature for 6-9 hours, then stop the heating, cool down and discharge the material. After washing and vacuum drying, organic modified attapulgite is obtained.

[0015] As a further aspect of the present invention, in step A, the mass ratio of the attapulgite clay and (3-glycidyl ether propyl)-1,1,3,3-tetramethyldisiloxane is 1:0.1-0.15.

[0016] As a further aspect of the present invention, in step A, the catalyst is stannous chloride.

[0017] As a further aspect of the present invention, in step B, the platinum catalyst is a chloroplatinic acid-isopropanol solution with a mass fraction of 1-2%.

[0018] As a further aspect of the present invention, the mass ratio of the organically modified attapulgite to the copper salt is 1:0.1-0.2.

[0019] As a further embodiment of the present invention, the copper salt is copper nitrate or copper chloride.

[0020] A processing method for a high-strength antibacterial ceramic glaze includes the following steps:

[0021] Step 1: Place potassium feldspar, calcite, dolomite, wollastonite, bauxite, spodumene, alumina, borax, talc, zircon, and loaded attapulgite antibacterial material into a ball mill and ball mill until it passes through a 100-120 mesh sieve to form a fine mixture.

[0022] Step 2: Mix sodium hexametaphosphate and water thoroughly, then mix with the fine mixture and continue stirring until well combined.

[0023] The beneficial effects of this invention are:

[0024] This invention first uses (3-glycidyl etherpropyl)-1,1,3,3-tetramethyldisiloxane as a modifier to perform ring-opening with the hydroxyl groups on the surface of attapulgite under the action of a catalyst, thus obtaining attapulgite with surface-modified hydroxyl bonds. Then, under the action of a platinum catalyst, the hydroxyl bonds further undergo an addition reaction with the unsaturated alkenyl substituents in the structure of hexadiene tartrate diamine, thereby achieving the organic modification of attapulgite and obtaining organically modified attapulgite. Then, the organic amide functional groups modified on the surface of attapulgite can adsorb a large number of copper ions generated by the ionization of copper salt, thereby loading a large number of copper ions on the surface of attapulgite to obtain a supported attapulgite antibacterial material.

[0025] During the sintering process of the glaze, copper ions are ablated to form copper oxide. Because the copper oxide is loaded with attapulgite, it avoids agglomeration, and this dispersion allows the loaded attapulgite antibacterial material to be more evenly distributed in the glaze layer, thus better exerting its antibacterial properties. Furthermore, the silicon and oxygen elements contained in the organic modification of the attapulgite form silica sol during sintering. The presence of silica sol significantly improves the hydrophobicity of the glaze layer, thereby effectively improving its cleaning effect. In addition, the copper oxide loaded on the attapulgite surface acts as anchor points. When external force is applied to the glaze layer, these anchor points prevent direct slippage of the lamellae, causing cracks to bypass the anchor points, thereby extending the crack propagation path and thus providing a reinforcing effect.

[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 load-bearing attapulgite antibacterial material:

[0030] Step 1: Add 2.4g of attapulgite to N,N-dimethylformamide and disperse it evenly by ultrasonication. Then add 0.3g of (3-glycidyl ether propyl)-1,1,3,3-tetramethyldisiloxane and 0.01g of stannous chloride to the dispersion. After the addition is complete, turn on the heater and raise the temperature to 130℃. Keep the temperature and stir for 92h. Then stop the heating, cool down and discharge the material. Collect the solid material by centrifugation, and then wash and vacuum dry it to obtain functionalized attapulgite.

[0031] The second step involves adding 2g of functionalized attapulgite to toluene and sonicating it until a uniform dispersion is formed. Then, 0.4g of hexadiene tartrate diamine and 0.1mL of 1% chloroplatinic acid-isopropanol solution are added. After the addition is complete, heating is turned on and the temperature is raised to 85℃. After holding at this temperature for 8 hours, heating is stopped, the material is cooled and discharged. After washing and vacuum drying, organically modified attapulgite is obtained.

[0032] Third step: Add 1.8g of organically modified attapulgite to purified water, control the ultrasonic frequency at 100kHz, and ultrasonically treat for 30min. Then add 0.3g of copper chloride to the formed uniform dispersion. After the addition is complete, adjust the pH to 11, turn on the heating, control the temperature at 70℃, and keep it warm and stirring for 6h. Stop the heating, cool down and discharge the material, collect the solid by centrifugation, and perform washing and vacuum drying to obtain the loaded attapulgite antibacterial material.

[0033] Example 1

[0034] A high-strength antibacterial ceramic glaze, comprising the following raw materials by weight:

[0035] Potassium feldspar 38 parts, calcite 15 parts, dolomite 5 parts, wollastonite 2 parts, bauxite 6 parts, spodumene 1 part, alumina 4 parts, borax 1 part, talc 5 parts, zircon 1 part, supported attapulgite antibacterial material 1.5 parts, sodium hexametaphosphate 3 parts, water 100 parts.

[0036] The processing method of the ceramic glaze includes the following steps:

[0037] Step 1: Place potassium feldspar, calcite, dolomite, wollastonite, bauxite, spodumene, alumina, borax, talc, zircon, and loaded attapulgite antibacterial material into a ball mill and ball mill until it passes through a 100-mesh sieve to form a fine mixture.

[0038] Step 2: Mix sodium hexametaphosphate and water thoroughly, then mix with the fine mixture and continue stirring until well combined.

[0039] The preparation method of the loaded attapulgite antibacterial material is shown in the preparation example, and the same applies to the following.

[0040] Example 2

[0041] A high-strength antibacterial ceramic glaze, comprising the following raw materials by weight:

[0042] Potassium feldspar 40 parts, calcite 18 parts, dolomite 6 parts, wollastonite 3 parts, bauxite 8 parts, spodumene 1.5 parts, alumina 6 parts, borax 1.5 parts, talc 6 parts, zircon 2 parts, supported attapulgite antibacterial material 3.2 parts, sodium hexametaphosphate 4 parts, water 120 parts.

[0043] The processing method of the ceramic glaze includes the following steps:

[0044] Step 1: Place potassium feldspar, calcite, dolomite, wollastonite, bauxite, spodumene, alumina, borax, talc, zircon, and loaded attapulgite antibacterial material into a ball mill and ball mill until it passes through a 100-mesh sieve to form a fine mixture.

[0045] Step 2: Mix sodium hexametaphosphate and water thoroughly, then mix with the fine mixture and continue stirring until well combined.

[0046] Example 3

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

[0048] Potassium feldspar 45 parts, calcite 22 parts, dolomite 9 parts, wollastonite 4 parts, bauxite 10 parts, spodumene 2 parts, alumina 8 parts, borax 2 parts, talc 12 parts, zircon 3 parts, supported attapulgite antibacterial material 3.6 parts, sodium hexametaphosphate 5 parts, water 150 parts.

[0049] The processing method of the ceramic glaze includes the following steps:

[0050] Step 1: Place potassium feldspar, calcite, dolomite, wollastonite, bauxite, spodumene, alumina, borax, talc, zircon, and loaded attapulgite antibacterial material into a ball mill and ball mill until it passes through a 100-mesh sieve to form a fine mixture.

[0051] Step 2: Mix sodium hexametaphosphate and water thoroughly, then mix with the fine mixture and continue stirring until well combined.

[0052] Comparative Example 1

[0053] A high-strength antibacterial ceramic glaze differs from Example 2 in that the load-bearing attapulgite antibacterial material is replaced with attapulgite, while the rest are the same.

[0054] Comparative Example 2

[0055] A high-strength antibacterial ceramic glaze differs from Example 2 in that the loaded attapulgite antibacterial material is removed, while the rest are the same.

[0056] Test case

[0057] A 10cm×10cm×81cm porcelain blank was immersed in the ceramic glazes of Examples 1-3 and Comparative Examples 1-2, respectively. The glaze thickness was controlled to be 0.1mm through multiple immersions. The blanks were then transferred to a firing furnace and fired at 1250℃ for 8 hours. After natural cooling, they were removed and used as test samples for the following performance tests:

[0058] According to standard JC / T 897-2014, antibacterial properties were tested, and Staphylococcus aureus was selected as the bacterial strain.

[0059] A water contact angle measuring instrument was used to test the water contact angle.

[0060] A 0.5kg steel ball was dropped vertically onto the sample surface from above. The drop height of the steel ball was recorded when phenomena such as cracking and chipping of the glaze appeared. The strength of the glaze layer was evaluated. Generally speaking, the higher the drop height, the better the strength, and vice versa.

[0061] The test results are recorded in the table below:

[0062]

[0063] Analysis of the test results shows that the ceramics formed after sintering the glaze prepared in the embodiments of the present invention have excellent properties.

[0064] 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.

[0065] 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 high-strength antibacterial ceramic glaze, characterized in that, By weight, it includes the following ingredients: Potassium feldspar 38-45 parts, calcite 15-22 parts, dolomite 5-9 parts, wollastonite 2-4 parts, bauxite 6-10 parts, spodumene 1-2 parts, alumina 4-8 parts, borax 1-2 parts, talc 5-12 parts, zircon 1-3 parts, supported attapulgite antibacterial material 1.5-3.6 parts, sodium hexametaphosphate 3-5 parts, water 100-150 parts; The loaded attapulgite antibacterial material is attapulgite loaded with copper ions.

2. The high-strength antibacterial ceramic glaze according to claim 1, characterized in that, The loaded attapulgite antibacterial material is prepared using the following method: Organically modified attapulgite was added to purified water, and the ultrasonic frequency was controlled at 100-120kHz for 30-40 minutes. Then, copper salt was added to the formed uniform dispersion. After the addition was complete, the pH was adjusted to 10-11, the heating was turned on, and the temperature was controlled at 60-80℃. The mixture was kept warm and stirred for 4-8 hours. The heating was stopped, the material was cooled and discharged, the solid was collected by centrifugation, and then washed and vacuum dried to obtain the loaded attapulgite antibacterial material.

3. The high-strength antibacterial ceramic glaze according to claim 2, characterized in that, The method for preparing the organically modified attapulgite includes the following steps: Step A: Add attapulgite to N,N-dimethylformamide and disperse it evenly by ultrasonication. Then, add (3-glycidyl ether propyl)-1,1,3,3-tetramethyldisiloxane and catalyst to the dispersion. After the addition is complete, turn on the heater and raise the temperature to 120-140℃. Keep the temperature and stir for 6-12 hours. Stop the heating, cool down and discharge the material. Collect the solid material by centrifugation, and then wash and vacuum dry it to obtain functionalized attapulgite. Step B: Add functionalized attapulgite to toluene, sonicate until a uniform dispersion is formed, then add hexadiene tartrate diamine and platinum catalyst. After the addition is complete, turn on the heater and heat to 80-90℃. Keep the temperature for 6-9 hours, then stop the heating, cool down and discharge the material. After washing and vacuum drying, organic modified attapulgite is obtained.

4. The high-strength antibacterial ceramic glaze according to claim 3, characterized in that, In step A, the mass ratio of the attapulgite clay to (3-glycidyl ether propyl)-1,1,3,3-tetramethyldisiloxane is 1:0.1-0.

15.

5. The high-strength antibacterial ceramic glaze according to claim 3, characterized in that, In step A, the catalyst is stannous chloride.

6. The high-strength antibacterial ceramic glaze according to claim 3, characterized in that, In step B, the platinum catalyst is a chloroplatinic acid-isopropanol solution with a mass fraction of 1-2%.

7. The high-strength antibacterial ceramic glaze according to claim 2, characterized in that, The mass ratio of the organically modified attapulgite to copper salt is 1:0.1-0.

2.

8. The high-strength antibacterial ceramic glaze according to claim 2, characterized in that, The copper salt is copper nitrate or copper chloride.

9. A processing method for the high-strength antibacterial ceramic glaze as described in claim 1, characterized in that, Includes the following steps: Step 1: Place potassium feldspar, calcite, dolomite, wollastonite, bauxite, spodumene, alumina, borax, talc, zircon, and loaded attapulgite antibacterial material into a ball mill and ball mill until it passes through a 100-120 mesh sieve to form a fine mixture. Step 2: Mix sodium hexametaphosphate and water thoroughly, then mix with the fine mixture and continue stirring until well combined.

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