A lanthanum-containing antibacterial glaze and its application on ceramic cups

Abstract

The present invention provides a lanthanum-containing antibacterial glaze and its application on a ceramic cup. The lanthanum-containing antibacterial glaze is coated on the ceramic cup and eventually forms an antibacterial film layer on the ceramic surface. The antibacterial film layer can catalyze active oxygen and destroy the cell structure of bacteria by strong oxidizing property to prevent their reproduction, thereby effectively inhibiting the growth of bacteria on the surface of the cup. At the same time, these antibacterial materials are harmless to the human body, safe and reliable. Compared with traditional ceramic cups, antibacterial ceramic cups have significant advantages in health protection, service life and environmental protection performance.

Description

Technical Field

[0001] The invention relates to the technical field of ceramic glazes, in particular to a lanthanum-containing antibacterial glaze and application thereof on ceramic cups. Background Art

[0002] In today's social context of increasing emphasis on health and environmental protection, the research and development of antibacterial ceramic cups is particularly important. In recent years, with the improvement of people's living standards and the improvement of quality of life, the requirements for the hygiene, health and environmental performance of daily necessities have also been continuously improved. As a new type of ceramic product with antibacterial function, the research and application of antibacterial ceramic cups are based on such an era background. First of all, the problem of bacterial breeding has received increasing attention. In daily life, people frequently come into contact with various bacteria, especially in the process of drinking water, the inner wall of the cup is prone to breed bacteria, which poses a potential threat to people's health. Therefore, the development of ceramic cups with antibacterial function is crucial to ensure the safety and health of people's drinking water. Secondly, ceramic products are widely used in daily life. As a traditional material with excellent performance, ceramics are widely used in catering, home, medical and other fields. However, traditional ceramic products have major defects in antibacterial performance and cannot meet the requirements of modern people for healthy life. Therefore, the development of antibacterial glazes and antibacterial ceramic cups is not only to improve the performance of ceramic materials, but also to expand the application field of ceramic products. Summary of the invention

[0003] In view of this, the present invention aims to propose a lanthanum-containing antibacterial glaze and its application on a ceramic cup. The lanthanum-containing antibacterial glaze is coated on the ceramic cup and will eventually form an antibacterial film layer on the ceramic surface. The antibacterial film layer can catalyze active oxygen to destroy the cell structure of bacteria and prevent their reproduction, thereby effectively inhibiting the growth of bacteria on the surface of the cup.

[0004] To achieve the above object, the technical solution of the present invention is achieved as follows:

[0005] A lanthanum-containing antibacterial glaze comprises, by weight, 2-10 parts of feldspar, 2-10 parts of lanthanum-containing rare earth material LYS and 80-96 parts of water; wherein the lanthanum-containing rare earth material LYS comprises raw materials Co(NO3)3, Fe(NO3)3, La(NO3)3 and urea, and the raw materials are mixed and calcined in a muffle furnace to obtain the lanthanum-containing rare earth material LYS.

[0006] Furthermore, the weight ratio of Co(NO3)3, Fe(NO3)3, La(NO3)3 and urea is 5-15:15-25:1-10:1-10.

[0007] Furthermore, the calcination temperature is 500-1500° C., and the calcination time is 1-5 h.

[0008] Further, the feldspar includes magnesia feldspar and / or chalcedony.

[0009] Furthermore, the particle size of the lanthanum-containing rare earth material LYS is between 100-900 nm.

[0010] Furthermore, the lanthanum-containing rare earth material LYS needs to be prepared into a lanthanum-containing rare earth material LYS slurry before use, that is, the lanthanum-containing rare earth material LYS needs to be mixed with a dispersant and sand-milled to form a uniformly dispersed liquid.

[0011] Furthermore, the dispersant is 2800 aqueous dispersant and / or PVP solid dispersant.

[0012] The present invention also provides an application of the lanthanum-containing antibacterial glaze as described above on a ceramic cup. In the glazing step of the ceramic making process, a layer of lanthanum-containing antibacterial glaze is coated on the inner and outer surfaces of the ceramic cup body to form an antibacterial film layer on the ceramic surface.

[0013] Furthermore, the thickness of the antibacterial film layer is between 0.01 mm and 0.2 mm.

[0014] Furthermore, the calcination temperature after glazing is 800°C-1500°C and the calcination time is 5-25 hours. This calcination temperature can ensure the quality of the fired ceramics. If the calcination is not within this range, the obtained ceramics are relatively brittle and have irregular surfaces.

[0015] Compared with the prior art, the lanthanum-containing antibacterial glaze of the present invention and its application in ceramic cups have the following advantages:

[0016] (1) The lanthanum-containing rare earth material LYS in the lanthanum-containing antibacterial glaze of the present invention is obtained by high-temperature calcination and is resistant to high temperatures. It can withstand high-temperature heating during the porcelain-making process without losing its antibacterial function.

[0017] (2) The effects of the lanthanum-containing antibacterial glaze described in the present invention are as follows: first, the glaze contains feldspar glazes containing magnesia feldspar and / or chalcite. After calcination, the surface of the porcelain is dense and smooth, with high hardness, and is very suitable for ceramic products such as ceramic cups that have high requirements for hardness and aesthetics; second, the lanthanum rare earth material LYS is selected as an additional supplementary component in the glaze. The lanthanum rare earth material LYS can catalyze the production of active oxygen, which has strong oxidizing properties and can cause oxidative stress to microorganisms in the environment, thereby achieving an antibacterial effect. At the same time, the lanthanum rare earth material LYS is originally calcined at high temperature, so it has a strong high temperature resistance and can withstand high temperature calcination in the preparation process of ceramic products. Mixing the lanthanum rare earth material LYS into the feldspar glaze for the production of ceramic cups can produce a layer of antibacterial glaze on the surface of the ceramic cup, thereby obtaining an antibacterial ceramic cup and improving people's drinking water environment.

[0018] (3) The lanthanum-containing antibacterial glaze of the present invention is coated on the ceramic cup body during the glazing step of the porcelain making process. After firing, it adheres to the surface of the glaze layer and will not fall off, be washed or dissolved. It can kill bacteria by contact or by catalyzing the strong oxidizing properties of active oxygen, thereby achieving a safe and lasting antibacterial effect. The antibacterial film layer attached to the surface of the cup body can achieve excellent antibacterial effects and increase the strength, durability and elasticity of the ceramic cup.

[0019] (4) It has been repeatedly confirmed that the ceramic cup of the present invention has the characteristics of high activity, good chemical stability and thermal stability, no secondary pollution, no irritation, safety and non-toxicity. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] The accompanying drawings constituting a part of the present invention are used to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation of the present invention. In the accompanying drawings:

[0021] Figure 1 This is a SEM scanning electron microscope of the lanthanum-containing rare earth material LYS1;

[0022] Figure 2 To detect the particle size of LYS1, a rare earth material containing lanthanum;

[0023] Figure 3 The antibacterial effect of each lanthanum-containing rare earth material LYS;

[0024] Figure 4 It is the active oxygen content of the water in the antibacterial ceramic cup;

[0025] Figure 5 This is the antibacterial effect diagram of the antibacterial ceramic cup. DETAILED DESCRIPTION

[0026] It should be noted that, in the absence of conflict, the embodiments of the present invention and the features in the embodiments may be combined with each other.

[0027] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0028] Example 1 Preparation of lanthanum-containing antibacterial glaze

[0029] The weight ratio of Co(NO3)3, Fe(NO3)3, La(NO3)3 and urea is 5-15:15-25:1-10:1-10.

[0030] 1. Preparation of LYS1:

[0031] Weigh 100g Co(NO3)3, 200g Fe(NO3)3, 50g La(NO3)3 and 50g urea, mix well, add 3000mL water, stir at room temperature for 30min, dry at 70℃, and then calcine at 1200℃ in a muffle furnace for 3h.

[0032] 2. Preparation of LYS2:

[0033] Weigh 55g Co(NO3)3, 125g Fe(NO3)3, 20g La(NO3)3 and 20g urea, mix well, add 3000mL water, stir at room temperature for 30min, dry at 70℃, and then calcine in a muffle furnace at 1200℃ for 3h.

[0034] 3. Preparation of LYS3:

[0035] Weigh 140 g Co(NO3)3, 250 g Fe(NO3)3, 90 g La (NO3)3 and 90 g urea, mix well, add 3000 mL water, stir at room temperature for 30 min, dry at 70 °C, and then calcine in a muffle furnace at 1200 °C for 3 h.

[0036] 4. Preparation of LYS4:

[0037] Weigh 250g Co(NO3)3, 140g Fe(NO3)3, 50g La (NO3)3 and 50g urea, mix well, add 3000mL water, stir at room temperature for 30min, dry at 70℃, and then calcine in a muffle furnace at 1200℃ for 3h.

[0038] 5. Preparation of LYS5:

[0039] Weigh 200 g Co(NO3)3, 300 g Fe(NO3)3, 50 g La (NO3)3 and 50 g urea, mix well, add 3000 mL water, stir at room temperature for 30 min, dry at 70 °C, and then calcine in a muffle furnace at 1200 °C for 3 h.

[0040] 6. Preparation of LYS6:

[0041] Weigh 50g Co(NO3)3, 50g Fe(NO3)3, 50g La (NO3)3 and 50g urea, mix well, add 3000mL water, stir at room temperature for 30 min, dry at 70℃, and then calcine in a muffle furnace at 1200℃ for 3 h.

[0042] 7. Preparation of LYS7-LYS10:

[0043] According to the following table, lanthanum-containing rare earth materials LYS7-LYS10 were prepared according to the proportions of the raw materials of lanthanum-containing rare earth material LYS1, and the rest were the same as LYS1, where "-" represents no addition and "+" represents addition.

[0044] Table 1 Comparison of LYS4-LYS7 regimens

[0045]

[0046] 8. Preparation of LYS11:

[0047] Weigh 100g Co(NO3)3, 200g Fe(NO3)3, 50g La(NO3)3 and 50g urea, mix well, add 3000mL water, stir at room temperature for 10min, and do not calcine.

[0048] 9. Preparation of 10% lanthanum rare earth material slurry:

[0049] Take 50g of each LYS1-LYS11 rare earth material, add it to 450mL of water, then add 5g of aqueous 2800 dispersant, stir evenly and place it in a sand mill for sand grinding. The total sand grinding time is 6 hours. After sand grinding, a uniformly dispersed lanthanide rare earth material LYS series slurry is obtained, and the LYS1 slurry is subjected to SEM scanning and particle size detection. The SEM scanning results are shown in Figure 1 , the particle size test results are shown in Figure 2 The particle size is about 500nm. The slurry has a small particle size and is evenly dispersed. It will not cause other side effects when added to the glaze water component in the glazing process. The final porcelain product has smooth inner and outer surfaces.

[0050] 10. Glaze preparation:

[0051] Weigh 2 g of magnesia feldspar, 4 g of orthoclase and 2 g of lanthanum rare earth material LYS1-11 slurry, add 92 mL of water and mix well to obtain a lanthanum-containing antibacterial glaze.

[0052] 11. Antibacterial test

[0053] First, 10 mg of lanthanum-containing antibacterial glaze containing LYS1-LYS11 was weighed, 1 mL of PBS buffer was added, and ultrasonic-assisted dispersion was used. Then, 100 uL of the prepared LYS solution of each lanthanum-containing rare earth material was aspirated and mixed with 800 uL PBS buffer in the clean bench as experimental groups 1-11. At the same time, 900 uL PBS buffer was directly aspirated for the control group and placed at room temperature for use.

[0054] Then, the E. coli that had been activated twice was diluted 10 times in a 10-fold dilution gradient using PBS in an ultra-clean workbench. 4times, and the strain concentration was controlled at 1×10 5 -1×10 6 cfu / mL, take 100uL of the diluted E. coli solution and add it to the control group and experimental groups 1-11 respectively, set up three groups in parallel, and finally put it in a constant temperature shaker at 180rpm, incubate at 37℃ for 18 h, then spread it on the LB plate, and then put the coated LB plate in a constant temperature incubator for overnight culture, and observe the experimental results after the colonies grow on the plate.

[0055] The experimental results are as follows Figure 3 As shown, the control group plate was full of E. coli (250-360 cfu), while the rare earth material LYS1 experimental group 1 plate had fewer E. coli colonies (40-60 cfu), the rare earth material LYS2 experimental group 2 plate had fewer E. coli colonies (40-60 cfu); the rare earth material LYS3 experimental group 3 plate had fewer E. coli colonies (40-60 cfu); the rare earth material LYS4 experimental group 4 plate had more E. coli colonies (200-300 cfu); the rare earth material LYS5 experimental group 5 plate had more E. coli colonies (200-300 cfu); the rare earth material LYS6 experimental group 6 plate had more E. coli colonies (200-300 cfu); the rare earth material LYS7 experimental group 7 plate had more E. coli colonies (200-300 cfu); the rare earth material LYS8 experimental group 8 plate had more E. coli colonies (200-300 cfu); There are more E. coli colonies on the plate 9 of the soil material LYS9 experimental group; there are more E. coli colonies on the plate 10 of the rare earth material LYS10 experimental group; there are more E. coli colonies on the plate 11 of the rare earth material LYS11 experimental group; it can be seen from the above results that, as in experimental groups 4-6, the rare earth material LYS did not add the raw materials according to the proportion of the present invention, and its effect of inhibiting and killing E. coli was greatly reduced. For example, in experimental groups 7-10, the rare earth material LYS obtained by lacking any raw material also had a poor effect of inhibiting and killing E. coli. For example, in experimental groups 1-3, the rare earth material LYS prepared according to the specific components and specific proportions of the present invention can effectively inhibit and kill E. coli. This is because the carbon quantum dots on the surface of the urea molecule are exposed after high-temperature calcination, and the carbon quantum dots contain a large number of hydroxyl, carboxyl and epoxy functional groups, which can be modified to obtain multifunctional nanomaterials. However, single carbon quantum dots have certain limitations and poor antibacterial function. Therefore, carbon quantum dots are combined with Co, Fe and La elements to form highly antibacterial rare earth functional materials. Since the exposed carbon quantum dots need to be completely filled and modified, specific chemical elements that can be modified and a specific ratio are required to exert an antibacterial effect.

[0056] Example 2 Safety of lanthanum-containing rare earth material LYS

[0057] LYS1 was used as an example to detect animal toxicity.

[0058] Twenty healthy mice weighing 18-22g were selected and randomly divided into two groups, with 10 mice in each group. There was a blank control group (0.2ml / mouse of physiological saline) and three lanthanum-containing rare earth material LYS groups (0.2ml / mouse of 5% rare earth material LYS slurry). The mice were weighed on a FA1004 electronic analytical balance before the experiment, and the original weight of each mouse was recorded. During the experiment, the blank control group was fed with 0.2mL of physiological saline every day while feeding the mice, and the lanthanide rare earth material LYS group was fed with 0.2mL of 5% rare earth material LYS slurry every day while feeding the mice. The administration was continued for 7 days, and then fed normally for 7 days. Finally, the mice were weighed on a FA1004 electronic analytical balance, and the toxicity of the wash solution was determined based on the weight changes of the mice before and after the experiment. The results are shown in Table 2.

[0059] Table 2 Toxicity test of rare earth material LYS

[0060]

[0061] The experimental results showed that there was no death among mice and no significant weight loss, indicating that the rare earth material LYS has no acute toxicity to animals.

[0062] Example 3 Preparation of antibacterial ceramic cup

[0063] First of all, we need to choose the right raw materials for porcelain making, mainly clay and glaze. The clay should be high-quality with fine texture, no impurities and low sand content. The glaze should be selected according to the required color and texture. The treated clay is made into the embryo of the ceramic cup by hand. The formed embryo needs to be placed in a ventilated and dry place for natural drying to enhance its strength and durability. The stabilized embryo enters the low-temperature pre-firing stage, and the low-temperature firing makes the embryo initially solidified to form a semi-finished product, laying the foundation for subsequent glazing and high-temperature firing. After the semi-finished product is polished and cleaned, it is glazed.

[0064] Take the glaze prepared by LYS1 and apply it on the surface of the embryo in the form of a brush. After the application, an unsintered glaze layer is formed. The glazed ceramic cup enters the high-temperature firing stage. After being fired at 1100℃ for 18 hours, the lanthanum-containing rare earth material LYS, the glaze and the embryo are closely combined. The glaze layer and the antibacterial film layer are formed on the surface of the porcelain body in turn. The thickness of the antibacterial film layer is about 0.46mm, and finally a strong, durable, and antibacterial ceramic cup with excellent antibacterial effect is obtained.

[0065] Example 4 Active oxygen catalytic effect of antibacterial ceramic cup

[0066] In this example, 2',7'-dichlorofluorescein diacetate (DCFH-DA) fluorescent probe is used to detect the catalytic active oxygen generation effect of the antibacterial ceramic cup. DCFH-DA can be oxidized by active oxygen to 2'-7' dichlorofluorescein (DCF). DCF is a fluorescent compound that can be detected by a fluorescence spectrophotometer. Its excitation spectrum and emission spectrum are 495 nm and 529 nm, respectively.

[0067] In this example, 2',7'-dichlorofluorescein diacetate (DCFH-DA) fluorescent probe is used to detect the catalytic active oxygen generation effect of the antibacterial ceramic cup. DCFH-DA can be oxidized by active oxygen to 2'-7' dichlorofluorescein (DCF). DCF is a fluorescent compound that can be detected by a fluorescence spectrophotometer. Its excitation spectrum and emission spectrum are 495 nm and 529 nm, respectively.

[0068] The specific detection process is as follows: 0.146g of DCFH-DA (300μM) is added to a 2mL centrifuge tube, and then 1mL of dimethyl sulfoxide is added to the centrifuge tube to prepare a mother solution, mixed and dissolved, and placed in a -20°C refrigerator for use. 5mL of sodium acetate buffer is added to the ceramic cup prepared in Example 3, and then 5mL of peroxidizing solution is added, and finally 10μL of DCFH-DA probe mother solution is added. 1mL of the mixed solution in the ceramic cup is taken at regular intervals, and the fluorescence intensity at 525nm is detected by a fluorescence spectrophotometer when the excitation wavelength is 488, and the catalytic generation effect of active oxygen in the ceramic cup is judged according to the fluorescence intensity.

[0069] The experimental results are as follows Figure 4 As shown in the figure, as time goes by, the fluorescence signal of the mixed liquid in the ceramic cup continues to increase, indicating that over time, a large amount of active oxygen is generated in the ceramic cup, and the active oxygen oxidizes DCFH-DA into DCF, thereby showing a strong fluorescence signal. Active oxygen has strong oxidizing ability, which can cause oxidative stress in microbial cells and destroy the microbial cell membrane to achieve a bactericidal effect. At the same time, active oxygen can also oxidize some organic matter, thereby achieving the effect of purifying water quality.

[0070] Example 5 Antibacterial effect of antibacterial ceramic cup

[0071] The experiment uses the milk colonization method to detect the antibacterial effect of the antibacterial ceramic cup in practical application. The specific detection process is: take an ordinary ceramic cup and an antibacterial ceramic cup prepared in Example 3, add 100mL of milk within the shelf life to the two ceramic cups respectively, and then place the two cups containing milk together in any corner of the laboratory, open the cup mouth, without any protective measures, and place for 12 hours. After 12 hours, take 1mL of the milk in the cup from the ordinary ceramic cup and the lanthanum rare earth antibacterial ceramic cup to the sterile LB plate, and spread the plate on the clean workbench. After the coating is completed, place it in a constant temperature incubator and culture it at 37°C for 48 hours. The experiment sets up 3 parallel groups, and the antibacterial effect is judged by comparing the colony counts in the ordinary ceramic cup and the antibacterial ceramic cup.

[0072] The experimental results are as follows Figure 5 As shown, after 12 hours of storage, the milk in the ordinary ceramic cup probably bred 20-30 cfu of bacteria, while in the three parallel groups of milk in the antibacterial ceramic cup, only one group produced 1 cfu of bacteria. This can clearly show the antibacterial effect of the lanthanum rare earth antibacterial ceramic cup in actual use.

[0073] The research and development significance of the lanthanum-containing antibacterial glaze described in the present invention lies in meeting people's growing demand for healthy living, while promoting technological progress and industrial upgrading in the ceramic industry. The antibacterial ceramic cup prepared by the present invention not only has good strength, durability and elasticity of the ceramic cup body, but is also safe and non-toxic, has high stability, and has stable and long-lasting antibacterial properties, and has excellent antibacterial effects during daily use. With the continuous innovation of technology and the continuous expansion of the market, antibacterial ceramic cups will play a more important role in the future and make greater contributions to people's healthy lives and environmental protection.

[0074] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A lanthanum-containing antibacterial glaze, characterized in that: The glaze comprises 2-10 parts of feldspar, 2-10 parts of lanthanum-containing rare earth material LYS and 80-96 parts of water by weight; wherein the lanthanum-containing rare earth material LYS comprises raw materials Co(NO3)3, Fe(NO3)3, La(NO3)3 and urea, and the weight ratio of Co(NO3)3, Fe(NO3)3, La(NO3)3 and urea is 8:16:4:4 or 11:25:4:4 or 14:25:9:

9. After mixing, the raw materials are placed in a muffle furnace and calcined to obtain the lanthanum-containing rare earth material LYS.

2. The lanthanum-containing antibacterial glaze according to claim 1, characterized in that: The calcination temperature is 500-1500°C, and the calcination time is 1-5 h.

3. The lanthanum-containing antibacterial glaze according to claim 1, characterized in that: The feldspar includes magnesia feldspar and / or chalcedony.

4. The lanthanum-containing antibacterial glaze according to claim 1, characterized in that: The particle size of the lanthanum-containing rare earth material LYS is between 100-900 nm.

5. The lanthanum-containing antibacterial glaze according to claim 1, characterized in that: The lanthanum-containing rare earth material LYS needs to be prepared into a lanthanum-containing rare earth material LYS slurry before use, that is, the lanthanum-containing rare earth material LYS needs to be mixed with a dispersant and sand-milled to form a uniformly dispersed liquid.

6. The lanthanum-containing antibacterial glaze according to claim 5, characterized in that: The dispersant used is 2800 aqueous dispersant and / or PVP solid dispersant.

7. The use of the lanthanum-containing antibacterial glaze according to any one of claims 1 to 6 on a ceramic cup, characterized in that: In the glazing step of the porcelain making process, a layer of lanthanum-containing antibacterial glaze is coated on the inner and outer surfaces of the ceramic cup body to form an antibacterial film layer on the ceramic surface.

8. The use of the lanthanum-containing antibacterial glaze on a ceramic cup according to claim 7, characterized in that: The thickness of the antibacterial film layer is between 0.1mm and 0.8mm.

9. The use of the lanthanum-containing antibacterial glaze on a ceramic cup according to claim 7, characterized in that: The calcination temperature after glazing is 800°C-1500°C, and the calcination time is 5-25 hours.

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