CN115466055A

CN115466055A - Enamel composition, enamel liner and preparation method thereof, water heater and cooker

Info

Publication number: CN115466055A
Application number: CN202211268495.7A
Authority: CN
Inventors: 王奇; 谭德强; 陈昌中; 王成根; 范召卿; 柴国丰
Original assignee: Gree Electric Appliances Inc of Zhuhai
Current assignee: Gree Electric Appliances Inc of Zhuhai
Priority date: 2022-10-17
Filing date: 2022-10-17
Publication date: 2022-12-13

Abstract

The invention provides an enamel composition, an enamel liner and a preparation method thereof, a water heater and a cooker. The enamel composition has super-strong and lasting antibacterial effect and low manufacturing cost.

Description

Enamel composition, enamel liner and preparation method thereof, water heater and cooker

Technical Field

The invention relates to the field of enamel materials, in particular to an enamel composition, an enamel liner and a preparation method thereof, a water heater and a cooker.

Background

In the prior art, the enamel inner container is usually large because of more water storage, so that water is generally stored in the inner container of the water heater throughout the year. If the water heater is not used for a long time, water in the inner container becomes dead water, when the water is stored in the enamel inner container for a long time and is not used, escherichia coli, staphylococcus aureus and the like in the water can be bred, the quality of the water is affected, the health of a user can be possibly harmed, the inner container of the water heater is inconvenient to disassemble and difficult to clean, the vicious circle of pollution is easily caused, and the normal use of the user is affected. With the increasing emphasis on quality of life, people pay more and more attention to household environmental sanitation, and desire that living appliances have sterilization and disinfection functions. The problem of poor antibacterial and bacteriostatic activity commonly exists in related water heaters in the industry, and the water heaters hardly reach the national specified standard. Some water heater manufacturers perform antibacterial tests on enamel antibacterial templates for manufacturing enamel layers of enamel liners, and find that the antibacterial effect is only about 45-50% and the requirement that the antibacterial rate is more than or equal to 90% is not met (GB 21551.02-2010).

Currently, silver salts such as silver nitrate, titanium silver and the like are generally adopted as antibacterial agents used in the antibacterial enamel layer in the industry, and the aim of antibiosis is achieved by adjusting the addition amount of silver ions. Silver ions are easy to volatilize in the heating process, waste is easy to generate in the production process, and the antibacterial performance of the enamel is reduced. The existing antibacterial enamel cooker adopts an enamel layer of photocatalyst, the photocatalyst has an antibacterial effect under the action of light, and a water heater liner is in a closed environment, so that the photocatalyst is not antibacterial when being used for the water heater liner. The antibacterial agent adopts a nano silver, nano copper and nano silver phosphate antibacterial enamel coating, and the nano silver simple substance and the nano copper simple substance are not high temperature resistant, are easy to agglomerate and are easy to oxidize, so that the prepared antibacterial enamel layer has the problems of nonuniform antibiosis, poor antibacterial durability and the like.

The antibacterial low-temperature-resistant heat-insulating material has the advantages that the antibacterial performance is improved by adding the antibacterial agent comprising silver-loaded zirconium phosphate and the like, the antibacterial performance is good, the antibacterial durability is good, but a good antibacterial effect can be achieved only by adding a large amount of the antibacterial agent, and the cost is increased due to the high price of the antibacterial agent.

Disclosure of Invention

A first object of the present invention is to provide an enamel composition having an excellent and durable antibacterial effect and being manufactured at a low cost.

A second object of the invention is to provide an enamel liner with an enamel layer formed of the above enamel composition.

The third purpose of the invention is to provide a preparation method of the enamel liner.

The fourth purpose of the invention is to provide a water heater with the enamel liner.

A fifth object of the invention is to provide a cookware with an enamel layer formed of the enamel composition described above.

In order to achieve the first purpose, the invention provides an enamel composition which comprises enamel base glaze powder and a composite antibacterial agent, wherein the composite antibacterial agent comprises zirconium phosphate silver-zinc antibacterial powder and rare earth metal oxide.

According to the scheme, the silver-zinc silver-loaded zirconium phosphate antibacterial powder, the rare earth metal oxide and the enamel base glaze powder are combined, the rare earth element can activate metal silver ions, the surface activity of the silver-zinc silver-loaded zirconium phosphate antibacterial powder is increased due to the activation of the rare earth element, and the rare earth metal oxide is added, so that the superstrong and lasting antibacterial effect of an enamel inner container of the water heater can be realized by adding the silver-zinc silver phosphate antibacterial powder with lower content, the breeding of bacteria is reduced, and the production cost is greatly reduced.

One preferable scheme is that the zirconium phosphate silver-zinc-carrying antibacterial powder accounts for 0.1 to 10 percent by weight, and the rare earth metal oxide accounts for 0.1 to 1 percent by weight.

Therefore, the zirconium phosphate silver-zinc-loaded antibacterial powder with lower content can realize super-strong and lasting antibacterial effect, and the production cost is reduced.

The further proposal is that the content of the zirconium phosphate silver-zinc-carrying antibacterial powder is 2 percent to 4 percent.

In a further aspect, the rare earth metal oxide is present in an amount of 0.2% to 0.4%.

Therefore, the addition amount of the rare earth metal oxide is small, and the cost can be further reduced while the performance is ensured.

In a preferred embodiment, the silver-loading amount of the zirconium phosphate silver-loaded zinc antibacterial powder is 0.3wt% to 2.0wt%, and the zinc-loading amount is 6wt% to 35wt%.

The further proposal is that the silver-carrying amount in the zirconium phosphate silver-carrying zinc antibacterial powder is 0.4wt percent to 0.6wt percent, and the zinc-carrying amount is 26wt percent to 30wt percent.

In a preferred embodiment, the rare earth metal oxide includes at least one of cerium oxide, tungsten oxide, and lanthanum oxide.

Further, the specific surface area of cerium oxide is 50m ² G to 200m ² (iv) g; and/or the specific surface area of tungsten oxide is 50m ² G to 200m ² (iv) g; and/or lanthanum oxide having a specific surface area of 50m ² G to 200m ² /g。

In a preferred scheme, the zirconium phosphate silver-zinc-loaded antibacterial powder is cubic zirconium phosphate silver-zinc-loaded antibacterial powder.

In a preferred scheme, the enamel base glaze powder comprises the following raw materials in percentage by weight: 38% to 50% of silicon dioxide, 12% to 16% of sodium nitrate, 8% to 11% of potassium carbonate, 1% to 3% of lithium carbonate, 13% to 15% of boron oxide, 1% to 3% of cobalt oxide, 0.5% to 2% of nickel oxide, 3% to 5% of aluminum oxide, 7% to 12% of calcium fluoride and 1% to 2% of zirconium oxide.

In order to realize the second purpose, the invention provides an enamel liner, which comprises a liner substrate and an enamel antibacterial layer, wherein the enamel antibacterial layer is arranged on the inner wall of the liner substrate, and is prepared from the enamel composition.

In order to achieve the third object, the invention provides a preparation method of an enamel liner, wherein the enamel liner is the enamel liner, and the preparation method comprises the following steps: mixing the enamel base glaze powder with water to prepare enamel glaze slurry; mixing and stirring the enamel glaze slurry and the composite antibacterial agent, then carrying out ball milling, and standing and aging for a first preset time to obtain antibacterial enamel glaze slurry; the antibacterial enamel glaze slurry is coated on the inner wall of the liner base material by adopting an enamel process, and is sintered after being dried.

Therefore, the preparation method of the enamel liner is simple and the manufacturing cost is low. Meanwhile, the enamel layer and the liner base material are tightly combined through the control of the technological process, the stabilizing effect on antibacterial particles is good, and the antibacterial component is not easy to run off, so that the antibacterial effect of the enamel layer is exerted for a long time. When water is stored in the inner container of the water heater, the enamel layer with the strong antibacterial function has a good antibacterial function, can kill bacteria such as escherichia coli and staphylococcus aureus in water, inhibits the bacteria from breeding, and ensures the safety of water. The antibacterial enamel layer also avoids the pollution of bacteria breeding to the inner container of the water heater, reduces the cleaning process of the inner container and is more convenient to use; meanwhile, the manufacturing process is simple, the enamel is not needed for multiple times, and the production and manufacturing cost is reduced.

In a preferred scheme, in the step of preparing the enamel slip, the ratio of enamel base glaze powder to water is in a range of 100:35 to 100:40 in the range of.

In a preferred embodiment, in the step of preparing the antibacterial enamel slip, the stirring time is 4 hours to 6 hours, the ball milling time is 30 minutes to 50 minutes, and the first predetermined time is 4 hours to 5 hours.

In a preferred embodiment, the enamel process comprises adjusting the adsorption amount of the glaze slip to 18g to 22g.

In a preferable scheme, in the step of preparing the enamel antibacterial layer, the drying temperature is 140 ℃ to 160 ℃, the drying time is 30 minutes to 45 minutes, the sintering temperature is 820 ℃ to 850 ℃, and the sintering time is 7 minutes to 10 minutes.

In a preferred scheme, the thickness of the enamel antibacterial layer is in the range of 150 mu m to 500 mu m; and/or the thickness of the liner substrate is in the range of 1.8mm to 3 mm.

Further, the thickness of the enamel antibacterial layer is in the range of 200 μm to 350 μm.

Preferably, before the enamel process, the preparation method further comprises a sand blasting pretreatment of the liner base material, and after the sand blasting treatment, the enamel process is carried out within a second preset time.

In a further embodiment, the second predetermined time is 2 hours.

The further proposal is that the sand blasting pressure is 0.4Mpa to 0.6Mpa, the sand size of the sand blasting is 40 meshes to 60 meshes, the cleanness Sa of the sand blasting is more than or equal to 2.5, and the roughness is more than or equal to 20 mu m.

Therefore, through sand blasting, the surface of the liner substrate can be cleaned, the surface can be roughened, and the binding force between the enamel layer and the surface of the substrate can be increased.

In order to achieve the fourth purpose, the invention provides a water heater, which comprises an enamel inner container prepared by the preparation method of the enamel inner container.

In order to achieve the fifth object, the invention provides a cooker, which comprises a steel plate layer and an enamel antibacterial layer, wherein the enamel antibacterial layer is arranged on the inner wall of the steel plate layer, and the enamel antibacterial layer is made of the enamel composition.

Drawings

FIG. 1 is a cross-sectional view of an enamel liner embodiment of the present invention.

Fig. 2 is a partially enlarged view of a portion a in fig. 1.

The invention is further explained with reference to the drawings and the embodiments.

Detailed Description

The embodiment of the enamel composition, the enamel liner and the preparation method thereof comprises the following steps:

referring to fig. 1 and 2, the enamel liner 10 in the embodiment includes a liner substrate 1 and an enamel antibacterial layer 2, the enamel antibacterial layer 2 is disposed on an inner wall of the liner substrate 1, and the enamel antibacterial layer 2 is made of an enamel composition. The thickness of the liner substrate 1 is in the range of 1.8mm to 3mm, the thickness of the enamel antibacterial layer 2 is in the range of 150 μm to 500 μm, and preferably, the thickness of the enamel antibacterial layer 2 is in the range of 200 μm to 350 μm. The liner substrate 1 adopts a hot-rolled enameled steel plate.

The chemical composition of the hot-rolled enameled pressed steel meets the requirements of the following table, and the allowable deviation of the chemical composition meets the GB/T222 regulations.

TABLE 1 chemical composition requirements

The enamel composition consists of enamel base glaze powder and a composite antibacterial agent, wherein the composite antibacterial agent consists of zirconium phosphate silver-zinc antibacterial powder and rare earth metal oxide.

The enamel base glaze powder comprises the following raw materials in percentage by weight: 38% to 50% of silicon dioxide, 12% to 16% of sodium nitrate, 8% to 11% of potassium carbonate, 1% to 3% of lithium carbonate, 13% to 15% of boron oxide, 1% to 3% of cobalt oxide, 0.5% to 2% of nickel oxide, 3% to 5% of aluminum oxide, 7% to 12% of calcium fluoride and 1% to 2% of zirconium oxide. The proportion of the components is the proportion of the components in the enamel base glaze powder.

Preferably, the silver-zinc zirconium phosphate antibacterial powder is cubic silver-zinc zirconium phosphate antibacterial powder. The rare earth metal oxide includes at least one of cerium oxide, tungsten oxide, and lanthanum oxide. The specific surface areas of cerium oxide, tungsten oxide and lanthanum oxide were all 50m ² G to 200m ² /g。

According to the weight percentage, the content of the zirconium phosphate silver-zinc-carrying antibacterial powder is 0.1 percent to 10 percent, and the content of the rare earth metal oxide is 0.1 percent to 1 percent. Preferably, the content of the zirconium phosphate silver-zinc-carrying antibacterial powder is 2 to 4 percent, and the content of the rare earth metal oxide is 0.2 to 0.4 percent.

The silver-carrying amount (silver element content) in the zirconium phosphate silver-carrying zinc antibacterial powder is 0.3wt% to 2.0wt%, and the zinc-carrying amount (zinc element content) is 6wt% to 35wt%. Preferably, the silver-carrying amount in the zirconium phosphate silver-carrying zinc antibacterial powder is 0.4wt% to 0.6wt%, and the zinc-carrying amount is 26wt% to 30wt%. The grain diameter D50 of the zirconium-silver-zinc phosphate antibacterial powder is less than or equal to 10.0 mu m, and the zirconium-silver-zinc phosphate antibacterial powder is not decomposed when being heated at the temperature of 800-1300 ℃.

The preparation method of the enamel liner comprises the following steps:

firstly, mixing enamel base glaze powder and purified water according to the ratio of 100:35 to 100: mixing the components in the proportion within 40, and uniformly dispersing the components by a ball mill to prepare the enamel glaze slurry.

And then, mixing and stirring the enamel glaze slurry and the composite antibacterial agent for 4 to 6 hours, then carrying out ball milling for 30 to 50 minutes, and then standing and aging for a first preset time which is 4 to 5 hours to prepare the antibacterial enamel glaze slurry.

And then, carrying out sand blasting pretreatment on the liner base material by using a sand blasting machine, wherein the sand blasting pressure is 0.4-0.6 Mpa, the sand size of sand blasting is 40-60 meshes, the cleanliness Sa of sand blasting is more than or equal to 2.5, and the roughness is more than or equal to 20 microns. And carrying out an enamel process within second preset time after the sand blasting treatment, wherein the second preset time is 2 hours.

And finally, preparing an enamel antibacterial layer, coating antibacterial enamel glaze slurry on the inner wall of the liner base material by adopting an enamel process, wherein the adsorption quantity of the glaze slurry needs to be adjusted to 18-22 g in the enamel process. Then drying the glass liner at the temperature of 140-160 ℃ for 30-45 minutes, sintering the glass liner at the temperature of 820-850 ℃ for 7-10 minutes after drying, and obtaining the enamel liner with the enamel layer with the strong antibacterial function.

The enamel process preferably adopts a flow enamel process, and can also adopt wet enamel processes such as shaking enamel, dipping enamel, spraying enamel and the like.

The antibacterial performance test is carried out by preparing the antibacterial enamel test plate with the antibacterial enamel layer in the embodiment, the antibacterial enamel test plate is formed by forming the antibacterial enamel layer on a hot-rolled enamel steel plate, and the hot-rolled enamel steel plate is processed into a square with the length and the width of 50 mm by a laser cutting device. In the following embodiments, the components and the content of the enamel base glaze powder are the same, the rare earth metal oxide adopts the mixture of tungsten oxide and lanthanum oxide, the proportions of the components are the same, and the process method for preparing the antibacterial enamel test plate is the same as the preparation method of the enamel liner embodiment.

Example 1:

in this example, the content of the cubic silver zinc-loaded zirconium phosphate antibacterial powder in the enamel composition was 2%, the content of the rare earth metal oxide was 0.2%, and the content of the enamel base glaze powder was 97.8%.

Example 2:

in this example, the content of the cubic silver zinc-loaded zirconium phosphate antibacterial powder in the enamel composition was 4%, the content of the rare earth metal oxide was 0.2%, and the content of the enamel base glaze powder was 95.8%.

Comparative example 1:

in this comparative example, the enamel composition consisted of an enamel base glaze powder and a cubic silver-zinc-zirconium phosphate antimicrobial powder. The content of the zirconium phosphate silver-zinc antibacterial powder in the enamel composition is 2 percent, and the content of the enamel base glaze powder is 98 percent.

Comparative example 2:

in this comparative example, the enamel composition consisted of an enamel base glaze powder and a cubic silver zinc zirconium phosphate antimicrobial powder. The content of the zirconium phosphate silver-zinc antibacterial powder in the enamel composition is 4 percent, and the content of the enamel base glaze powder is 96 percent.

And (3) performance testing:

the antibacterial performance of the antibacterial enamel test plates prepared in the two examples and the two comparative examples is respectively detected, and the detection results are shown in table 2.

According to GB/T21551.2-2010 annex A antibacterial performance test method (pad pasting method) and effect evaluation, the materials of the examples are quantitatively tested for common infectious bacteria (such as escherichia coli and staphylococcus aureus).

Wherein the calculation formula of the antibacterial rate is as follows: antibacterial ratio (%) = [ (number of viable bacteria in control sample-number of viable bacteria in antibacterial enamel piece)/number of viable bacteria in control sample ] × 100%.

The hot water corrosion resistance of the antibacterial enamel test plates prepared in the two examples and the two comparative examples is respectively detected:

the resistance to hot water erosion is carried out for 504h for 2 times according to the regulation of 4.5 in QB/T2590-2021 enamel water heater parts.

TABLE 2 antibacterial Properties test results table

As can be seen from table 1, the enamel layers with strong antibacterial functions prepared in examples 1 and 2 of the present invention have strong antibacterial performance, the antibacterial rate to escherichia coli and staphylococcus aureus is all greater than 90%, and after a hot water corrosion resistance test for 42 days, the antibacterial performance is still maintained for a long time, which indicates that the antibacterial enamel layers have excellent antibacterial performance and good antibacterial durability.

The embodiment of the water heater comprises:

the water heater of the embodiment comprises the enamel composition, the enamel liner and the enamel liner in the preparation method embodiment.

Examples of cookware:

the cooker of the embodiment comprises a steel plate layer and an enamel antibacterial layer, wherein the enamel antibacterial layer is arranged on the inner wall of the steel plate layer, and the enamel antibacterial layer is made of the enamel composition in each enamel composition embodiment. The cooker may be a pot or the like, such as a steamer, stew pot or the like.

Therefore, the silver-zinc antibacterial powder with zirconium phosphate and the rare earth metal oxide are combined with the enamel basic glaze powder, the rare earth element can activate metal silver ions, the surface activity of the silver-zinc antibacterial powder with zirconium phosphate is increased due to the activation effect of the rare earth element, and the rare earth metal oxide is added, so that the superstrong and lasting antibacterial effect of the enamel inner container of the water heater can be realized by adding the silver-zinc antibacterial powder with lower content, the breeding of bacteria is reduced, and the production cost is greatly reduced.

Finally, it should be emphasized that the above-described preferred embodiments of the present invention are merely examples of implementations, and it should be understood that various changes and modifications may be made by those skilled in the art, and any changes, equivalents, improvements and the like, which fall within the spirit and principle of the present invention, should be included in the scope of the present invention.

Claims

1. The enamel composition consists of enamel base glaze powder and a composite antibacterial agent, and is characterized in that:

the composite antibacterial agent consists of zirconium phosphate silver-zinc-carrying antibacterial powder and rare earth metal oxide.

2. Enamel composition according to claim 1, characterized in that:

according to the weight percentage, the content of the zirconium phosphate silver-loaded zinc antibacterial powder is 0.1 to 10 percent, and the content of the rare earth metal oxide is 0.1 to 1 percent.

3. Enamel composition according to claim 2, characterized in that:

the content of the zirconium phosphate silver-zinc-carrying antibacterial powder is 2 to 4 percent.

4. Enamel composition according to claim 2, characterized in that:

the content of the rare earth metal oxide is 0.2 to 0.4 percent.

5. Enamel composition according to any one of claims 1 to 4, characterized in that:

the silver-carrying amount of the zirconium phosphate silver-carrying zinc antibacterial powder is 0.3wt% to 2.0wt%, and the zinc-carrying amount is 6wt% to 35wt%.

6. Enamel composition according to claim 5, characterized in that:

the silver-carrying amount of the zirconium phosphate silver-carrying zinc antibacterial powder is 0.4wt% to 0.6wt%, and the zinc-carrying amount is 26wt% to 30wt%.

7. Enamel composition according to any one of claims 1 to 4, characterized in that:

the rare earth metal oxide includes at least one of cerium oxide, tungsten oxide, and lanthanum oxide.

8. Enamel composition according to claim 7, characterized in that:

the specific surface area of the cerium oxide is 50m ² G to 200m ² (ii)/g; and/or

The specific surface area of the tungsten oxide is 50m ² G to 200m ² (ii)/g; and/or

The specific surface area of the lanthanum oxide is 50m ² G to 200m ² /g。

9. Enamel composition according to any one of claims 1 to 4, characterized in that:

the zirconium phosphate silver-zinc-loaded antibacterial powder is cubic zirconium phosphate silver-zinc-loaded antibacterial powder.

10. Enamel composition according to any one of claims 1 to 4, characterized in that:

the enamel base glaze powder comprises the following raw materials in percentage by weight: 38% to 50% of silicon dioxide, 12% to 16% of sodium nitrate, 8% to 11% of potassium carbonate, 1% to 3% of lithium carbonate, 13% to 15% of boron oxide, 1% to 3% of cobalt oxide, 0.5% to 2% of nickel oxide, 3% to 5% of aluminum oxide, 7% to 12% of calcium fluoride and 1% to 2% of zirconium oxide.

11. Enamel liner comprising a liner substrate and an enamel antibacterial layer provided on the inner wall of the liner substrate, characterized in that the enamel antibacterial layer is made of an enamel composition as claimed in any one of claims 1 to 10.

12. The preparation method of the enamel liner, wherein the enamel liner is the enamel liner as claimed in claim 11, and the preparation method comprises the following steps:

mixing the enamel base glaze powder with water to prepare enamel glaze slurry;

mixing and stirring the enamel glaze slurry and a composite antibacterial agent, then carrying out ball milling, and standing and aging for a first preset time to obtain antibacterial enamel glaze slurry;

and coating the antibacterial enamel glaze slurry on the inner wall of the liner base material by adopting an enamel process, and sintering after drying.

13. The method for producing as claimed in claim 12, characterized in that:

in the step of preparing the enamel slip, the ratio of the enamel base glaze powder to water is 100:35 to 100:40 in the range of.

14. The method for producing as claimed in claim 12, characterized in that:

in the step of preparing the antibacterial enamel slip, the stirring time is 4 to 6 hours, the ball milling time is 30 to 50 minutes, and the first preset time is 4 to 5 hours.

15. The production method according to any one of claims 12 to 14, characterized in that:

the enamel process comprises adjusting the adsorption quantity of the glaze slip to 18g to 22g.

16. The production method according to any one of claims 12 to 14, characterized in that:

in the step of preparing the enamel antibacterial layer, the drying temperature is 140 ℃ to 160 ℃, the drying time is 30 minutes to 45 minutes, the sintering temperature is 820 ℃ to 850 ℃, and the sintering time is 7 minutes to 10 minutes.

17. The production method according to any one of claims 12 to 14, characterized in that:

the thickness of the enamel antibacterial layer is in the range of 150-500 mu m; and/or

The thickness of the liner base material is in the range of 1.8mm to 3 mm.

18. The method of manufacturing according to claim 17, wherein:

the thickness of the enamel antibacterial layer is in the range of 200-350 μm.

19. The production method according to any one of claims 12 to 14, characterized in that:

before the enamel process, the preparation method also comprises the step of carrying out sand blasting pretreatment on the liner base material, and carrying out the enamel process within a second preset time after the sand blasting treatment.

20. The method of manufacturing according to claim 19, wherein:

the second preset time is 2 hours.

21. The method of claim 19, wherein:

the sand blasting pressure is 0.4Mpa to 0.6Mpa, the sand size of the sand blasting is 40 meshes to 60 meshes, the cleaning degree Sa of the sand blasting is more than or equal to 2.5, and the roughness is more than or equal to 20 mu m.

22. Water heater comprising an enamel liner obtained by a method for the production of an enamel liner according to any one of claims 12 to 20.

23. Cookware comprising a steel deck and an enamel antibacterial layer provided on the inner wall of said steel deck, characterized in that said enamel antibacterial layer is made with an enamel composition as claimed in any one of claims 1 to 10.