High-entropy spherical microcontainers and methods of making the same

Abstract

This invention relates to the field of new materials, aiming to provide a high-entropy spherical microcontainer and its preparation method. The microcontainer has a particle size distribution ranging from 4 to 40 micrometers; it has a folded structure resembling brain gyri on its outer surface, and its inner surface is densely covered with several open-ended spherical microcavities, the diameter of which ranges from 1 to 4 micrometers; the wall material of the spherical microcontainer is a composite material with the molecular formula: (Al... 0.1 Ca 0.1 Co 0.1 Ni 0.1 ,Mn 0.1 ,Fe 0.1 ,La 0.1 V 0.1 Mo 0.1 W 0.1 OOH / TiO2. Applying the high-entropy spherical microcontainer of this invention to load corrosion resists can improve the corrosion resistance of anti-corrosion coatings, resins, or concrete mixed with the microcontainer due to its controllable slow-release characteristics. The densely distributed spherical microcavities on the inner surface of the microcontainer effectively increase the amount of corrosion resist loaded, while the brain-like folded structure on its outer surface allows the microcontainer to form a larger area of ​​connection with the substrate, thereby enabling the corrosion resist on the surface of the microcontainer to quickly reach the substrate and form an effective concentration.

Description

Technical Field

[0001] This invention relates to the field of new materials, specifically to a high-entropy spherical microcontainer and its preparation method. Background Technology

[0002] Microcapsules can protect the encapsulated material within their core, and their shell material can respond to changes in external conditions such as pH, ionic strength, and temperature, enabling the controlled release of the contents. Therefore, they have many potential applications and advantages in various fields. Particularly in the field of corrosion protection, microcapsules can be used to load corrosion inhibitors, leveraging their controlled, slow-release properties to enhance the corrosion resistance of coatings, resins, or concrete incorporating the microcapsules.

[0003] Although existing literature documents the large-scale production of microcontainers with a single internal cavity, the microcontainer products produced by current technologies typically have only a single internal cavity (e.g., Figure 3 on page 1550 of *Simultaneous dual pyrolysis synthesis of heterostructured FeCo / C porous hollow microspheres for highly efficient microwave absorption*, J. Mater. Chem. A. 2022. DOI: 10.1039 / D1TA09021F. 2022; Hollow metal oxide microspheres and their preparation methods and applications in drug sustained release, CN202010254334.7). Figure 1 (As shown). Once damaged by external forces such as mixing and stirring, the contents will leak out, and the micro-container will fail instantly.

[0004] Multi-cavity microcapsules, due to their relatively independent compartmentalized structure, exhibit better resistance to failure, making them a superior alternative to single-cavity microcapsules. Furthermore, the surface morphology of the microcapsules also influences resist release; microcapsules with numerous surface folds can form a larger bonding area with the substrate, allowing the resist on the microcapsule surface to rapidly reach the substrate and achieve an effective concentration. However, existing multi-cavity microcapsule fabrication techniques, when used for mass production, cannot simultaneously achieve both a multi-folded surface morphology and a multi-cavity internal structure. Therefore, there is an urgent need to develop a novel, highly controllable multi-cavity microcapsule fabrication technique. Summary of the Invention

[0005] The technical problem to be solved by the present invention is to overcome the shortcomings of the prior art and provide a high-entropy spherical microcontainer and its preparation method.

[0006] To solve the technical problem, the solution of the present invention is:

[0007] A high-entropy spherical microcontainer is provided, characterized in that...

[0008] The particle size distribution of this spherical microcontainer ranges from 4 to 40 micrometers;

[0009] The outer surface of the spherical microcontainer has a folded structure resembling the gyri of the brain; the inner surface of the spherical microcontainer is densely covered with several open spherical microcavities, the diameter of which ranges from 1 to 4 micrometers.

[0010] The wall material of this spherical microcontainer is a composite material, and the molecular formula of the composite material is: (Al 0.1 Ca 0.1 Co 0.1 Ni 0.1 ,Mn 0.1 ,Fe 0.1 ,La 0.1 V 0.1 Mo 0.1 W 0.1 )OOH / TiO2.

[0011] This invention further provides a method for preparing the aforementioned high-entropy spherical microcontainer, comprising the following steps:

[0012] (1) Take Al(NO3)3, CaCl2, Co(NO3)2, NiCl2, Mn(CH3COO)2, FeCl3 and LaCl3 as solutes in equimolar ratio; add the solutes to a mixed solvent of ethanol and n-propanol, with the total mass of solutes to the mass ratio of solvents being 30%, and stir until completely dissolved to obtain mixture one;

[0013] (2) Take dopamine hydrochloride, gluconic acid, NH4VO3, Na2MoO4 and Na2WO4 as solutes in a molar ratio of 0.1:0.3:1:1:1; add the solutes to a mixed solvent of deionized water and acetone, with the total mass of solutes being 10% of the mass of solvents, and stir until completely dissolved to obtain mixture II.

[0014] (3) Mix mixture one and mixture two at a mass ratio of 2:1 and stir until uniform to obtain mixture three;

[0015] In subsequent reactions, not all added metal ions will form wall material; some metal ions will be eluted after washing. Mixing the two solutions at a mass ratio of 2:1 ensures that the molar number of each metal ion is equal in the final product.

[0016] (4) Add tetrabutyl titanate to mixture three, the mass ratio of tetrabutyl titanate to mixture three is 0.3:1, stir until completely dissolved; then add ethyl acetoacetate accounting for 2% of the mass of tetrabutyl titanate, and continue stirring until completely homogeneous to obtain mixture four;

[0017] (5) Stir and cool the mixture four to 0°C, add hydrogen peroxide while stirring, the mass ratio of hydrogen peroxide to mixture four is 0.1:0.9; keep at 0°C and continue stirring to obtain mixture five;

[0018] (6) Add deionized water and mixture 5 to a hydrothermal reactor with stirring in a 1:1 ratio, turn on the stirring, keep the stirring speed at 1000 rpm, and stir for 10 to 20 minutes;

[0019] (7) Keep stirring, seal the hydrothermal reactor, raise the temperature to 110°C and keep it at that temperature for 3 to 5 hours; then raise the temperature to 130°C and keep it at that temperature for 1 to 3 hours; then raise the temperature to 160°C and keep it at that temperature for 30 minutes; after stopping the heating, cool to room temperature to obtain mixture one;

[0020] (8) Take the mixture out of the hydrothermal reactor, filter it and wash it three times with deionized water, and dry it to obtain a brown powdery high-entropy spherical microcontainer product.

[0021] As a preferred embodiment of the present invention, in the mixed solvent of step (1), the mass ratio of ethanol to n-propanol is 0.3:0.7; and the stirring time is 15 to 25 minutes.

[0022] As a preferred embodiment of the present invention, in the mixed solvent of step (2), the mass ratio of deionized water to acetone is 0.2:0.8; and the stirring time is 10 to 20 minutes.

[0023] As a preferred embodiment of the present invention, in step (3), the stirring time is 10 to 20 minutes.

[0024] As a preferred embodiment of the present invention, in step (4), the stirring time for the two stirring sessions is 3-5 minutes and 10-20 minutes respectively.

[0025] As a preferred embodiment of the present invention, in step (5), the stirring time is 24 hours.

[0026] As a preferred embodiment of the present invention, in step (6), the stirring rate is maintained at 1000 rpm and the stirring time is 10 to 20 minutes.

[0027] As a preferred embodiment of the present invention, in step (8), the drying temperature is 60°C and the drying time is 24 hours.

[0028] The present invention also provides a method for applying the aforementioned high-entropy spherical microcontainer in loading resist, comprising: immersing the high-entropy microcontainer in a saturated resist solution to allow resist molecules and solvent molecules to fully diffuse into the internal chamber of the high-entropy microcontainer; then rapidly cooling to 0°C to allow the solvent to precipitate out from the inside of the microcontainer, leaving only the resist in the internal chamber; and filtering and drying the high-entropy microcontainer powder at 0°C to obtain a high-entropy microcontainer loaded with resist.

[0029] Description of the invention principle:

[0030] First, the high entropy mentioned in this invention is a scientific definition, generally referring to compounds containing five or more elements located at the same chemical structural site. The definition of high entropy in this invention follows this general scientific definition. High-entropy materials exhibit better structural stability, and due to the multiple heterogeneous elements and structural distortions brought about by high entropy, the materials possess better designability; by adjusting the types of elements, desired material properties can be obtained.

[0031] Furthermore, this invention achieves precise control over the internal and external surface morphology of the high-entropy spherical microcontainer by controlling the nucleation rate of the cavity and the hydrolysis rate of the wall material. Specifically, the method involves: optimizing solvent solubility parameters through the combination of multiple solvents; stabilizing the structure by bridging dissimilar metal ions based on the types of anions and their competitive coordination relationships; and further, effectively regulating the hydrolysis rates of each metal precursor component through the combined action of ethyl acetoacetate, dopamine hydrochloride, and gluconic acid. This allows for controlled formation of the spherical microcontainer wall structure and the formation of micro-regions on the surface due to phase separation. On the other hand, this invention utilizes a polymerization-induced phase separation mechanism, combined with controlled polymerization of the container wall material (i.e., controlled hydrolysis of each metal precursor), to control the nucleation rate of the microcontainer cavity, ultimately obtaining a high-entropy microcontainer with unique internal and external surface morphologies.

[0032] In the spherical microcontainer prepared by this invention, its outer surface has a folded structure resembling the gyri of a brain, and its inner surface is densely covered (i.e., a high-density layout) with several spherical microcavities ranging in diameter from 1 to 4 micrometers. Although these microcavities all have openings facing the cavity, they are not interconnected or linked, each being a relatively independent "microcompartment" structure. Therefore, to a certain extent, the spherical microcontainer prepared by this invention is a "multi-cavity microcontainer." Due to its many compartment-like structures, the multi-cavity microcontainer has better resistance to failure, thus becoming a better alternative to single-cavity microcontainers. On the other hand, the outer surface morphology of the microcontainer also affects the release of the resist. Microcontainers with more surface folds can form a larger area of ​​connection with the substrate, thereby allowing the resist on the surface of the microcontainer to quickly reach the substrate and form an effective concentration.

[0033] Compared with the prior art, the present invention has the following beneficial effects:

[0034] 1. This invention optimizes the combination of solvent solubility parameters with dopamine hydrochloride, gluconic acid and ethyl acetoacetate, so that the hydrolysis process of each metal precursor is controlled. At the same time, through a composite process with strictly controlled parameters, a high-entropy spherical microcontainer with a brain-like sulcus and fold structure on the surface and a high-density cavity can be obtained.

[0035] 2. After performing microscopic analysis of the high-entropy spherical microcontainer product obtained by this invention, it can be observed that its outer surface has a folded structure resembling brain gyri, and the surface of the internal cavity has a high-density arrangement of spherical microchamber structures (such as...). Figure 1 , 2 However, products prepared using the one-pot method in existing technologies cannot produce microcapsules with the aforementioned structure.

[0036] 3. Applying the high-entropy spherical microcontainer of this invention to load corrosion resists can improve the corrosion resistance of anti-corrosion coatings, resins, or concrete mixed with the microcontainer due to its controllable slow-release characteristics. The densely distributed spherical microcavities on the inner surface of the microcontainer can effectively increase the amount of corrosion resist loaded, while the brain-like gyri and folded structure on its outer surface allows the microcontainer to form a larger area of ​​connection with the substrate, thereby enabling the corrosion resist on the surface of the microcontainer to quickly reach the substrate and form an effective concentration. Therefore, this invention brings obvious technical improvements compared to the prior art. Attached Figure Description

[0037] Figure 1 Electron micrograph of the high-entropy spherical microcontainer product prepared according to the present invention;

[0038] Figure 2 Electron micrograph of the internal pore structure of the high-entropy spherical microcontainer prepared in this invention. Detailed Implementation

[0039] The present invention will now be described in detail with reference to specific embodiments. These embodiments will help those skilled in the art to further understand the present invention, but do not limit the invention in any way. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention. These all fall within the scope of protection of the present invention.

[0040] In the following examples, Al(NO3)3, CaCl2, Co(NO3)2, NiCl2, Mn(CH3COO)2, FeCl3, LaCl3, NH4VO3, Na2MoO4, and Na2WO4 are all powdered solids. Ethanol, n-propanol, acetone, ethyl acetoacetate, and tetrabutyl titanate are all commercial reagents.

[0041] Example 1:

[0042] (1) Take Al(NO3)3, CaCl2, Co(NO3)2, NiCl2, Mn(CH3COO)2, FeCl3 and LaCl3 as solutes in a molar ratio of 1:1:1:1:1:1:1. Mix ethanol and n-propanol in a mass ratio of 0.3:0.7 to prepare a solvent. Add the solutes to the solvent, and the total mass of the solutes to the mass of the solvent is 30%. Stir for 15 minutes and after complete dissolution, a mixture is obtained.

[0043] (2) Take dopamine hydrochloride, gluconic acid, NH4VO3, Na2MoO4 and Na2WO4 as solutes in a molar ratio of 0.1:0.3:1:1:1, and mix deionized water and acetone in a mass ratio of 0.2:0.8 to prepare a solvent. Add the solutes to the solvent, and the total mass of the solutes to the mass of the solvent is 10%. Stir for 10 minutes and after complete dissolution, a mixture II is obtained.

[0044] (3) Mix mixture one and mixture two at a mass ratio of 2:1 and stir for 10 minutes to obtain mixture three.

[0045] (4) Add tetrabutyl titanate to mixture three. The mass ratio of tetrabutyl titanate to mixture three is 0.3:1. Stir for 3 minutes until completely dissolved. Then add ethyl acetoacetate accounting for 2% of the mass of tetrabutyl titanate and stir for 10 minutes until completely homogeneous to obtain mixture four.

[0046] (5) Stir the mixture four and cool it down to 0°C. Add hydrogen peroxide while stirring. The mass ratio of hydrogen peroxide to mixture four is 0.1:0.9. Keep it at 0°C and continue stirring for 24 hours to obtain mixture five.

[0047] (6) Add deionized water and mixture 5 to a hydrothermal reactor with a stirrer at a ratio of 1:1, turn on the stirrer, keep the stirring speed at 1000 rpm, and stir for 10 minutes.

[0048] (7) Keep stirring, seal the hydrothermal reactor, raise the temperature to 110°C and keep it at that temperature for 3 hours; then raise the temperature to 130°C and keep it at that temperature for 1 hour; then raise the temperature to 160°C and keep it at that temperature for 30 minutes, then stop heating and cool it to room temperature to obtain mixture one.

[0049] (8) Take the mixture out of the hydrothermal reactor, filter it, wash it three times with deionized water, and dry it at 60°C for 24 hours to obtain a brown powdery high-entropy spherical microcontainer product.

[0050] Electron microscopy revealed that the outer surface of the obtained high-entropy microcontainer has a brain-like sulcus and folded surface structure, and its inner surface is densely covered with several open spherical microcavities. The size of the microcontainer ranges from 4 to 22 micrometers, and the diameter of the spherical microcavities ranges from 1 to 3 micrometers.

[0051] The wall material of the spherical microcapsule product was confirmed to be (Al) by inductively coupled plasma optical emission spectrometry (ICP-OES). 0.1 Ca 0.1 Co 0.1 Ni 0.1 ,Mn 0.1 ,Fe 0.1 ,La 0.1 V 0.1 Mo 0.1 W 0.1 )OOH / TiO2 complex.

[0052] Example 2:

[0053] A method for preparing a high-entropy spherical microcontainer includes the following steps:

[0054] (1) Take Al(NO3)3, CaCl2, Co(NO3)2, NiCl2, Mn(CH3COO)2, FeCl3 and LaCl3 as solutes in a molar ratio of 1:1:1:1:1:1:1. Mix ethanol and n-propanol in a mass ratio of 0.3:0.7 to prepare a solvent. Add the solutes to the solvent, and the total mass of the solutes to the mass of the solvent is 30%. Stir for 25 minutes and after complete dissolution, a mixture is obtained.

[0055] (2) Take dopamine hydrochloride, gluconic acid, NH4VO3, Na2MoO4 and Na2WO4 as solutes in a molar ratio of 0.1:0.3:1:1:1, and mix deionized water and acetone in a mass ratio of 0.2:0.8 to prepare a solvent. Add the solutes to the solvent, and the total mass of the solutes to the mass of the solvent is 10%. Stir for 20 minutes and after complete dissolution, a mixture II is obtained.

[0056] (3) Mix mixture one and mixture two at a mass ratio of 2:1 and stir for 20 minutes to obtain mixture three.

[0057] (4) Add tetrabutyl titanate to mixture three. The mass ratio of tetrabutyl titanate to mixture three is 0.3:1. Stir for 5 minutes until completely dissolved. Then add ethyl acetoacetate accounting for 2% of the mass of tetrabutyl titanate and stir for 20 minutes until completely homogeneous to obtain mixture four.

[0058] (5) Stir the mixture four and cool it down to 0°C. Add hydrogen peroxide while stirring. The mass ratio of hydrogen peroxide to mixture four is 0.1:0.9. Keep it at 0°C and continue stirring for 24 hours to obtain mixture five.

[0059] (6) Add deionized water and mixture 5 to a hydrothermal reactor with a stirrer at a ratio of 1:1, turn on the stirrer, keep the stirring speed at 1000 rpm, and stir for 20 minutes.

[0060] (7) Keep stirring, seal the hydrothermal reactor, raise the temperature to 110°C and keep it at that temperature for 5 hours; then raise the temperature to 130°C and keep it at that temperature for 3 hours; then raise the temperature to 160°C and keep it at that temperature for 30 minutes, then stop heating and cool to room temperature to obtain mixture one.

[0061] (8) Take the mixture out of the hydrothermal reactor, filter it, wash it three times with deionized water, and dry it at 60°C for 24 hours to obtain a brown powdery high-entropy spherical microcontainer product.

[0062] Electron microscopy revealed that the outer surface of the obtained high-entropy microcontainer has a brain-like sulcus and folded surface structure, and its inner surface is densely covered with several open spherical microcavities. The size of the microcontainer ranges from 6 to 34 micrometers, and the diameter of the spherical microcavities ranges from 2 to 4 micrometers.

[0063] The wall material of the spherical microcapsule product was confirmed to be (Al) by inductively coupled plasma optical emission spectrometry (ICP-OES). 0.1 Ca 0.1 Co 0.1 Ni 0.1 ,Mn 0.1 ,Fe 0.1 ,La 0.1 V 0.1 Mo 0.1 W 0.1 )OOH / TiO2 complex.

[0064] Example 3:

[0065] A method for preparing a high-entropy spherical microcontainer includes the following steps:

[0066] (1) Take Al(NO3)3, CaCl2, Co(NO3)2, NiCl2, Mn(CH3COO)2, FeCl3 and LaCl3 as solutes in a molar ratio of 1:1:1:1:1:1:1. Mix ethanol and n-propanol in a mass ratio of 0.3:0.7 to prepare a solvent. Add the solutes to the solvent, and the total mass of the solutes to the mass of the solvent is 30%. Stir for 17 minutes and after complete dissolution, a mixture is obtained.

[0067] (2) Take dopamine hydrochloride, gluconic acid, NH4VO3, Na2MoO4 and Na2WO4 as solutes in a molar ratio of 0.1:0.3:1:1:1, and mix deionized water and acetone in a mass ratio of 0.2:0.8 to prepare a solvent. Add the solutes to the solvent, and the total mass of the solutes to the mass of the solvent is 10%. Stir for 15 minutes and after complete dissolution, a mixture II is obtained.

[0068] (3) Mix mixture one and mixture two at a mass ratio of 2:1 and stir for 15 minutes to obtain mixture three.

[0069] (4) Add tetrabutyl titanate to mixture three. The mass ratio of tetrabutyl titanate to mixture three is 0.3:1. Stir for 4 minutes until completely dissolved. Then add ethyl acetoacetate accounting for 2% of the mass of tetrabutyl titanate and stir for 15 minutes until completely homogeneous to obtain mixture four.

[0070] (5) Stir the mixture four and cool it down to 0°C. Add hydrogen peroxide while stirring. The mass ratio of hydrogen peroxide to mixture four is 0.1:0.9. Keep it at 0°C and continue stirring for 24 hours to obtain mixture five.

[0071] (6) Add deionized water and mixture 5 to a hydrothermal reactor with a stirrer at a ratio of 1:1, turn on the stirrer, keep the stirring speed at 1000 rpm, and stir for 15 minutes.

[0072] (7) Keep stirring, seal the hydrothermal reactor, raise the temperature to 110°C and keep it at that temperature for 4 hours; then raise the temperature to 130°C and keep it at that temperature for 2 hours; then raise the temperature to 160°C and keep it at that temperature for 30 minutes, then stop heating and cool it to room temperature to obtain mixture one.

[0073] (8) Take the mixture out of the hydrothermal reactor, filter it, wash it three times with deionized water, and dry it at 60°C for 24 hours to obtain a brown powdery high-entropy spherical microcontainer product.

[0074] Electron microscopy revealed that the outer surface of the obtained high-entropy microcontainer has a brain-like sulcus and folded surface structure, and its inner surface is densely covered with several open spherical microcavities. The size of the microcontainer ranges from 20 to 40 micrometers, and the diameter of the spherical microcavities ranges from 2 to 3 micrometers.

[0075] The wall material of the spherical microcapsule product was confirmed to be (Al) by inductively coupled plasma optical emission spectrometry (ICP-OES). 0.1 Ca 0.1 Co 0.1 Ni 0.1 ,Mn 0.1 ,Fe 0.1 ,La 0.1 V 0.1 Mo0.1 W 0.1 )OOH / TiO2 complex.

[0076] Example of how to use spherical microcontainers:

[0077] Example of a specific method for loading resist onto a product: Immerse a high-entropy microcontainer in a saturated resist solution to allow resist and solvent molecules to fully diffuse into the internal chamber of the high-entropy microcontainer; then rapidly cool to 0°C to allow the solvent to precipitate out from the inside of the microcontainer, leaving only the resist in the internal chamber; filter out and dry the high-entropy microcontainer powder at 0°C to obtain a high-entropy microcontainer loaded with resist.

[0078] Although the surface openings of the microcontainer product are not visible at the scanning electron microscope scale shown in the accompanying drawings, the surface of the spherical microcontainer of this invention actually contains a large number of smaller-scale pores. These pores allow molecular-scale corrosion inhibitors to gradually overflow through the microcontainer surface, thereby achieving a long-lasting corrosion inhibition effect.

[0079] Product effectiveness verification:

[0080] The high-entropy microcontainers prepared by this invention can be used in various industries such as corrosion prevention, catalysis, and electrical contact. The following example, demonstrating the corrosion resistance of the product in anti-corrosion coatings after loading with a corrosion inhibitor, illustrates the application effect of this invention's product in anti-corrosion coatings.

[0081] 1. The products in the three embodiments of the present invention are loaded with corrosion inhibitors according to the following steps to obtain anti-corrosion coatings:

[0082] (1) Micro-container loading of anticorrosive agent:

[0083] A suitable amount of spherical microcontainers was immersed in a 0.25% benzotriazole aqueous solution at 40°C and stirred for 15 minutes; then, an ice-water bath was placed, and stirring was continued for another 15 minutes. The spherical microcontainer powder was then separated and dried to obtain spherical microcontainer powder loaded with corrosion inhibitor.

[0084] (2) Premixing:

[0085] At a speed of 300 rpm, add 150 g of water, 1 g of sodium hexametaphosphate, 2 g of FX504 dispersant, and 0.5 g of defoamer (SEADAS 7005) at once; stir for 10 minutes, then add 1 g of hydroxyethyl cellulose, stir for 10 minutes, and stir at 1300 rpm for 20 minutes to obtain a mixture.

[0086] (3) Paint mixing:

[0087] At 300 rpm, 100g of silicone-acrylic emulsion, 0.5g of defoamer (SEADAS7005), 0.6g of ammonia, 0.3g of hydroxyethyl cellulose, 4g of alcohol ester-12, and 2g of propylene glycol were added to the above mixture in one step. After stirring for 10 minutes, 0.5g of micro-container powder containing corrosion inhibitor was added, and stirring was continued for 2 hours to obtain the anti-corrosion coating.

[0088] (4) Coating:

[0089] The paint film was applied using a frame-type end coater, with a wet film thickness of 500 μm, and dried at room temperature for 48 hours until dry. The dry film thickness was approximately 25 μm, and the substrate was a 50 mm × 120 mm × 0.3 mm tinplate (GB / T 2520).

[0090] 2. Comparative Example:

[0091] The microcapsule product was prepared according to the preparation method described in the published literature (RARE METAL MATERIALS AND ENGINEERING, 2016, 45(S11), 489). Then, the coating product was prepared according to the above-mentioned anti-corrosion coating preparation method, and the coating was applied according to the same operation.

[0092] 3. Comparison of test results:

[0093] According to the test method (drop method) specified in GB / T9274-1988 standard, a saturated NaOH ethanol solution was used as the test solution (23±2℃) to conduct various tests on the above-mentioned anti-corrosion coatings and coatings. The test results are shown in the table below:

[0094] sample Example 1 Example 2 Example 3 Comparative Example Base state No rust No rust No rust Obvious red rust

[0095] It can be seen that the high-entropy spherical micro-container obtained in the embodiments of the present invention has a good effect on improving the anti-corrosion performance of the anti-corrosion coating after loading the anti-corrosion agent.

[0096] Furthermore, because the high-entropy spherical microcapsule product of this invention possesses high specific surface area and good stability, it can also be used as a catalytic electrode material in the field of electrocatalytic water splitting. Because the high-entropy spherical microcapsule of this invention possesses high conductivity, it can also be used as a conductivity-enhancing phase in the field of electrical contacts for low-voltage electrical appliances.

[0097] The specific embodiments of the present invention have been described above. It should be understood that the present invention is not limited to the specific embodiments described above, and those skilled in the art can make various modifications or variations within the scope of the claims, which do not affect the essence of the present invention.

Claims

1. A high-entropy spherical microcontainer, characterized in that, The particle size distribution of this spherical microcontainer ranges from 4 to 40 micrometers; The outer surface of the spherical microcontainer has a folded structure resembling the gyri of the brain; the inner surface of the spherical microcontainer is densely covered with several open spherical microcavities, the diameter of which ranges from 1 to 4 micrometers. The wall material of this spherical microcontainer is a composite material, and the molecular formula of the composite material is: (Al 0.1 Ca 0.1 Co 0.1 Ni 0.1 ,Mn 0.1 ,Fe 0.1 ,La 0.1 V 0.1 Mo 0.1 W 0.1 )OOH / TiO2.

2. A method of producing high-entropy spherical microcontainers, characterized by Includes the following steps: (1) Take Al(NO3)3, CaCl2, Co(NO3)2, NiCl2, Mn(CH3COO)2, FeCl3, and LaCl3 as solutes in equimolar ratio; add the solutes to a mixed solvent of ethanol and n-propanol, and stir until completely dissolved to obtain a mixed solution; the mass ratio of ethanol to n-propanol in the mixed solvent is 0.3:0.7, and the total mass of the solute is 30% of the mass of the mixed solvent. (2) Take dopamine hydrochloride, gluconic acid, NH4VO3, Na2MoO4, and Na2WO4 as solutes in a molar ratio of 0.1:0.3:1:1:1; add the solutes to a mixed solvent of deionized water and acetone, and stir until completely dissolved to obtain a mixed solution. The mass ratio of deionized water to acetone in the mixed solvent is 0.2:0.8, and the total mass of the solute is 10% of the mass of the mixed solvent. (3) Mix mixture one and mixture two at a mass ratio of 2:1 and stir until homogeneous to obtain mixture three; (4) Add tetrabutyl titanate to mixture three, the mass ratio of tetrabutyl titanate to mixture three is 0.3:1, stir until completely dissolved; then add ethyl acetoacetate accounting for 2% of the mass of tetrabutyl titanate, and continue stirring until completely homogeneous to obtain mixture four; (5) Stir and cool the mixture four to 0°C, add hydrogen peroxide while stirring, the mass ratio of hydrogen peroxide to mixture four is 0.1:0.9; keep at 0°C and continue stirring to obtain mixture five; (6) Add deionized water and mixture 5 to a hydrothermal reactor with stirring in a 1:1 ratio, turn on the stirring and keep the stirring speed at 1000 rpm for 10-20 minutes; (7) Keep stirring, seal the hydrothermal reactor, raise the temperature to 110°C and keep it at that temperature for 3 to 5 hours; then raise the temperature to 130°C and keep it at that temperature for 1 to 3 hours; then raise the temperature to 160°C and keep it at that temperature for 30 minutes; after stopping the heating, cool it to room temperature to obtain mixture one; (8) Take the mixture out of the hydrothermal reactor, filter it and wash it three times with deionized water, and dry it to obtain a brown powdery high-entropy spherical microcontainer product.

3. The method of claim 2, wherein, In step (1), the stirring time is 15 to 25 minutes.

4. The method of claim 2, wherein, In step (2), the stirring time is 10 to 20 minutes.

5. The method of claim 2, wherein, In step (3), the stirring time is 10 to 20 minutes.

6. The method of claim 2, wherein, In step (4), the stirring time for the two stirring sessions is 3-5 minutes and 10-20 minutes respectively.

7. The method of claim 2, wherein, In step (5), the stirring time is 24 hours.

8. The method of claim 2, wherein, In step (6), the stirring rate is maintained at 1000 rpm and the stirring time is 10-20 minutes.

9. The method of claim 2, wherein, In step (8), the drying temperature is 60°C and the drying time is 24 hours.

10. The use of the high-entropy spherical microcontainers of claim 1 for loading of resists, characterized in that, include: The high-entropy microcontainer is immersed in a saturated resist solution, allowing resist and solvent molecules to diffuse fully into the internal chamber of the high-entropy microcontainer. Then, it is rapidly cooled to 0°C, causing the solvent to precipitate out of the microcontainer, leaving only the resist in the internal chamber. The high-entropy microcontainer powder is then filtered out and dried at 0°C to obtain the high-entropy microcontainer loaded with resist.

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