Filler as well as preparation method and application thereof
By using fillers combined with LDHs sheets and iron tetraoxide nanoparticles in the marine environment, the corrosion problem of wave absorbing materials in high salt and high humidity environments is solved, and the excellent wave absorption and corrosion resistance of the coating is achieved, and the service life is extended.
Patent Information
- Application Number
- CN202510183545.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-02-19
- Publication Date
- 2025-06-17
AI Technical Summary
Existing absorbing materials are prone to corrosion in high-salt and high humidity marine environments, resulting in reduced functions and shortened service life, and polymer coatings have problems such as poor mechanical properties and easy destruction.
A filler with LDHs sheets combined with in-situ grown iron tetraoxide nanoparticles was prepared by adjusting the mass ratio of LDHs and iron tetraoxide to prepare a coating with excellent wave absorption and corrosion resistance.
The filler can be evenly dispersed in the resin, forming a multiple absorption structure, improving wave absorption performance, and at the same time, the complete sheet LDHs forms a barrier in the resin, significantly improving the corrosion resistance of the coating and meeting the dual requirements in the marine environment.
Smart Images
Figure CN120158129A_ABST
Abstract
Description
Technical Field
[0001] This application belongs to the technical field of fillers, and specifically relates to a filler and its preparation method and use. Background Art
[0002] Currently, microwave absorbing materials face serious corrosion problems in the high-salt and high-humidity marine environment. Corrosion will cause a sharp decline in the function of microwave absorbing materials and shorten their service life. Therefore, to protect the surfaces of electronic devices and other components in marine engineering equipment, a coating with excellent microwave absorption and anti-corrosion properties is needed.
[0003] Polymer coatings have been widely used in the anti-corrosion field due to their advantages such as low cost and easy construction. However, polymer coatings have tiny voids, poor mechanical properties, and are easily damaged. Once damaged, a large number of defects will be generated, and corrosive media such as oxygen, water molecules, and Cl - ions can easily reach the material surface through cracks and pores, thus accelerating corrosion. Summary of the Invention
[0004] The purpose of this application is to provide a filler and its preparation method and use to solve the problem of insufficient anti-corrosion ability of the filler.
[0005] According to the first aspect of the embodiments of this application, a method for preparing a filler is provided. The method may include: The filler includes LDHs sheets and magnetite nanoparticles grown in-situ on the LDHs sheets.
[0006] In some alternative embodiments of this application, the mass ratio of the LDHs sheets to the magnetite nanoparticles is 1:1, 1:2, and 1:3.
[0007] In some alternative embodiments of this application, it includes:
[0008] Dissolve LDHs powder in deionized water to obtain a first solution;
[0009] Pour ferric chloride and ferrous chloride with a mass ratio of 2:1 into the first solution of the first mass in sequence to obtain a first mixed solution;
[0010] Add excessive ammonia water to the first mixed solution to obtain a first filler through reaction;
[0011] Pour ferric chloride and ferrous chloride with a mass ratio of 2:1 into the first solution of the second mass in sequence to obtain a second mixed solution;
[0012] Add excessive ammonia water to the second mixed solution to obtain a second filler through reaction;
[0013] Pour ferric chloride and ferrous chloride with a mass ratio of 2:1 into the first solution of the third mass in sequence to obtain a third mixed solution;
[0014] Add excessive ammonia water to the third mixed solution to obtain a third filler through reaction;
[0015] Mix the first filler, the second filler and the third filler to obtain the filler.
[0016] In some alternative embodiments of the present application, dissolving the LDHs powder in deionized water to obtain the first solution includes:
[0017] Mix the LDHs powder and deionized water and then ultrasonicate for 10 min to obtain the first solution.
[0018] In some alternative embodiments of the present application, it further includes:
[0019] The reaction temperature is 80 °C and the reaction time is 2 h.
[0020] In some alternative embodiments of the present application, it further includes:
[0021] Ammonia gas is continuously introduced during the reaction process.
[0022] In some alternative embodiments of the present application, it further includes:
[0023] After the reaction, collect the first filler, the second filler and the third filler with a magnet and wash them multiple times with ethanol.
[0024] In some alternative embodiments of the present application, it further includes:
[0025] Put the washed first filler, second filler and third filler into a vacuum drying oven, dry at 60 °C for 12 h, and collect and grind them to obtain the filler.
[0026] In the second aspect of the present application, a method for preparing a coating is provided, including:
[0027] Mix the filler provided in any of the above embodiments with resin, add a curing agent, and then remove bubbles to obtain a mixed coating;
[0028] Spray or scrape the mixed coating on the surface of the target product with a thickness of 50 μm - 200 μm to obtain the coating.
[0029] In some alternative embodiments of the present application, the mass ratio of the filler to the resin is 0.5% - 5%;
[0030] The mass ratio of the resin to the curing agent is 3:1.
[0031] The above technical solution of the present application has the following beneficial technical effects:
[0032] In a filler provided by an embodiment of the present application, the magnetite nanoparticles obtained by in-situ growth of magnetite nanoparticles can be uniformly dispersed on the surface of LDHs. By utilizing the easy dispersibility of LDHs, the magnetite nanoparticles can be uniformly dispersed into the resin matrix. Moreover, the overlapping of the lamellar structures in the resin can perform multiple absorptions on microwaves, achieving the ability to enhance microwave absorption. On the other hand, the intact lamellar LDHs in the resin can form a barrier against corrosive media, thereby enhancing the corrosion resistance of the coating. The design of the above structure can well balance the dual requirements of microwave absorption and anti-corrosion. BRIEF DESCRIPTION OF THE DRAWINGS
[0033] Figure 1 is a schematic diagram of the filler in an exemplary embodiment of the present application;
[0034] Figure 2 is a schematic diagram of compounding iron oxide and LDHs by ball milling method in the related art
[0035] Figure 3 is a comparison chart of the microwave absorption performance of the filler provided by the present application, compounding iron oxide and LDHs by ball milling method
[0036] Figure 4 is a comparison experimental chart of the anti-corrosion performance of different fillers. DETAILED DESCRIPTION OF THE EMBODIMENTS
[0037] To make the objectives, technical solutions, and advantages of the present application clearer and more understandable, the present application will be further described in detail below in conjunction with specific embodiments and with reference to the accompanying drawings. It should be understood that these descriptions are merely exemplary and are not intended to limit the scope of the present application. In addition, in the following descriptions, the descriptions of well-known structures and technologies are omitted to avoid unnecessarily confusing the concepts of the present application.
[0038] The schematic diagram of the layer structure according to an embodiment of the present application is shown in the drawings. These drawings are not drawn to scale, where for the purpose of clarity, some details are enlarged and some details may be omitted. The various regions, shapes of the layers, and their relative sizes and positional relationships shown in the drawings are merely exemplary. In practice, there may be deviations due to manufacturing tolerances or technical limitations, and those skilled in the art can design regions / layers with different shapes, sizes, and relative positions according to actual needs.
[0039] Obviously, the described embodiments are some embodiments of the present application, rather than all embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments in the present application without creative efforts shall fall within the scope of protection of the present application.
[0040] In the description of the present application, it should be noted that the terms "first", "second", and "third" are only used for descriptive purposes and should not be construed as indicating or implying relative importance.
[0041] In addition, the technical features involved in different embodiments of the present application described below can be combined with each other as long as they do not conflict with each other.
[0042] Numerous studies have shown that adding nano-scale fillers to an organic coating system can specifically fill the fine voids inside it, block the penetration path of corrosive media through the coating, and thus significantly improve the corrosion resistance of the coating.
[0043] Nano-ferroferric oxide is a commonly used electromagnetic shielding and wave-absorbing material, but it is prone to agglomeration in resins and its corrosion resistance is insufficient. Therefore, it is necessary to prepare a filler that not only has good wave-absorbing ability but also good barrier ability to improve the anti-corrosion performance of the coating.
[0044] The following will combine the accompanying drawings to detail a filler provided by an embodiment of the present application, its preparation method and uses through specific examples and their application scenarios.
[0045] As Figure 1 shown, in the first embodiment of the first aspect of the present application, a filler is provided, including nano-ferroferric oxide and flaky LDHs; this filler is obtained by the in-situ reaction of lamellar LDHs, ferric chloride hydrate, ferrous chloride hydrate, and excessive ammonia water; among them, ferric chloride hydrate, ferrous chloride hydrate, and excessive ammonia water react to obtain nano-ferroferric oxide, and the nano-ferroferric oxide grows in-situ on the lamellar LDHs.
[0046] Furthermore, by adjusting the mass ratio of ferric chloride hydrate, ferrous chloride hydrate, ammonia water, and LDHs, fillers with different loadings of ferroferric oxide can be obtained. According to the mass ratio of ferroferric oxide to LDHs, several composite fillers with ratios of 3:1, 2:1, and 1:1 can be prepared.
[0047] The present invention provides a method for preparing a composite filler, including: ultrasonically dispersing lamellar LDHs, ferric chloride hydrate, and ferrous chloride hydrate in deionized water for 10 minutes, then heating to 80 °C, gradually adding ammonia water dropwise to the reaction system, detecting that the pH of the solution > 8, continuing to stir for 2 hours, and collecting the solid through a magnetic collector. Further, the solid is washed with ethanol multiple times and placed in a vacuum drying oven for drying for 12 hours to obtain the filler.
[0048] In some embodiments, the filler includes a first sub-filler, a second sub-filler, and a third sub-filler;
[0049] In the first sub-filler, the mass ratio of LDHs lamellae to iron oxide nanoparticles is 1:1. In the second sub-filler, the mass ratio of LDHs lamellae to iron oxide nanoparticles is 1:2. In the third sub-filler, the mass ratio of LDHs lamellae to iron oxide nanoparticles is 1:3. The first sub-filler, the second sub-filler and the third sub-filler are mixed according to a preset mass ratio to obtain the filler.
[0050] In this embodiment, the anti-corrosion performance of the first sub-filler is better than that of the second and third sub-fillers. The adsorption performance of the third sub-filler is better than that of the first and second sub-fillers. The anti-corrosion performance and adsorption performance of the second sub-filler are balanced. By mixing the first sub-filler, the second sub-filler and the third sub-filler according to a preset mass ratio, the obtained filler can simultaneously have high adsorption, anti-corrosion and stability.
[0051] As Figure 2 shown, compared with the composite filler prepared by blending iron oxide and LDHs by ball milling, the composite filler prepared by the in-situ growth method provided in this embodiment can maintain the original morphology of the particles and has the advantage of being more tightly combined, which helps to further improve the anti-corrosion performance of the filler.
[0052] In the second aspect of the present invention, a method for preparing an electromagnetic wave absorbing and anti-corrosion coating is provided, including: mixing the above composite filler with resin. Further, the mass fraction of the composite filler is 0.5-5% of the resin. Then, mechanical stirring is carried out for 1 hour and ultrasonic oscillation is carried out for 0.5 hour. Then, a curing agent is added, and the mass of the added curing agent is 30% of the resin. Further mechanical stirring is carried out until it is uniform to obtain a mixed slurry; the slurry is subjected to vacuum degassing and sprayed onto the surfaces of Q235 low-carbon steel plates, steel blocks, tinplate and 316L stainless steel blocks. All samples are placed in a drying oven and cured at 60°C for 24 hours to obtain a coating with both electromagnetic wave absorbing and anti-corrosion properties.
[0053] The nano-composite filler provided by the present invention includes nano iron oxide growing in-situ on the LDHs lamellae. On the one hand, it can improve the dispersion of iron oxide in the resin and play a better electromagnetic wave absorbing performance. Further, the nano iron oxide is fixed on the surface of the LDHs, and a multiple absorption structure can be constructed to further improve its electromagnetic wave absorbing ability in the resin. On the other hand, the LDHs lamellae can play a role in improving the anti-corrosion performance of the coating. Its physical barrier effect can extend the path and time for the corrosive medium to reach the surface of the metal substrate, thereby improving the corrosion resistance of the coating. Through the structural design of the filler, the dual requirements of electromagnetic wave absorption and anti-corrosion of the coating for marine ships can be met, and the scope of application is improved.
[0054] The present invention uses a hot solvent method to prepare three Fe3O4 and LDHs powder samples with different composite ratios. According to the in-situ growth method, first, 0.1 g of LDHs is weighed using a precision balance, dispersed in 60 ml of deionized water, and the mixture is stirred evenly and then poured into a 200-ml beaker. Then, it is ultrasonicated for 10 min to make the LDHs evenly dispersed in deionized water. Then, the mixture is poured into a 250-ml three-necked flask, and the experimental bench is set up through an oil bath and a condensing device. Keeping continuous stirring, 1.72 millimoles (mmol) of FeCl3·6H2O and 0.86 mmol of FeCl2·4H2O are weighed and poured into the reaction solution in sequence to ensure their full dissolution. Subsequently, an excessive amount of ammonia water is drawn using a 5-ml syringe and added dropwise to the reaction solution. Nitrogen is introduced for protection throughout the reaction process. The reaction temperature is 80 °C, and the reaction time is 2 h, denoted as Fe3O4@LDHs = 2:1. After the reaction, the sample is collected by magnetic force, washed repeatedly with ethanol, and finally placed in a vacuum drying oven and dried at 60 °C for 12 h, and then collected, ground, and reserved. The LDHs addition amount is changed to 0.067 g and 0.2 g, denoted as Fe3O4@S-LDHs = 3:1 and Fe3O4@LDHs = 1:1 respectively. Pure nano-Fe3O4 particles can be prepared by reacting without adding LDHs.
[0055] By adding 0.12 g of LDHs powder filler to 6 g of CYD-014 epoxy resin, followed by mechanical stirring for 1 h and ultrasonic oscillation for 0.5 h. To cure the coating, a certain proportion of curing agent is added to the above composite coating. The ratio of epoxy resin to curing agent is 3:1, and then it is mechanically stirred until uniform. Then, the bubbles generated in the coating are removed through a simple vacuum pumping device. Subsequently, the obtained coating is sprayed on the surfaces of Q235 low-carbon steel plates and blocks, tinplate, and 316L stainless steel blocks. All samples are placed in a drying oven and cured at 60 °C for 24 h.
[0056] Similarly, by adding 0.12 g of Fe3O4@LDHs and nano-Fe3O4 powder fillers with composite ratios of 1:1, 2:1, and 3:1 to 6 g of CYD-014 epoxy resin, followed by mechanical stirring for 1 h, and then placing it in an ultrasonic instrument for ultrasonic oscillation for 0.5 h. To cure the coating, a certain amount of curing agent is added to all the above composite coatings. The ratio of epoxy resin to curing agent is 3:1, and then it is mechanically stirred until uniform. Then, the bubbles generated in all the coatings are removed through a simple vacuum pumping device. Finally, the obtained coating is sprayed on the surfaces of Q235 low-carbon steel plates and blocks, tinplate, and 316L stainless steel blocks. All samples are placed in a forced-air drying oven, the curing temperature is 60 °C, and the curing time is 24 h.
[0057] As Figure 3As described above, compared with the iron tetroxide filler, the iron oxide prepared by ball milling, and the LDHs composite material, the filler provided by the present application has better wave absorption performance.
[0058] As Figure 4 shown, compared with the iron tetroxide filler, the iron oxide prepared by ball milling, and the LDHs composite material, the filler provided by the present application has better corrosion resistance.
[0059] The embodiments of the present application have been described above in conjunction with the accompanying drawings. However, the present application is not limited to the above specific embodiments. The above specific embodiments are merely illustrative and not restrictive. Under the inspiration of the present application, those of ordinary skill in the art can also make many forms without departing from the purpose of the present application and the scope protected by the claims, and all of them fall within the protection scope of the present application.
Claims
1. A filler, characterized in that: The filler comprises LDHs sheets and ferrosoferric oxide nanoparticles in-situ grown on the LDHs sheets.
2. A filler according to claim 1, characterized in that: The mass ratios of the LDHs sheet and the ferrosoferric oxide nanoparticles are 1:1, 1:2, and 1:
3.
3. A method for preparing a filler according to claim 1, characterized in that: include: Dissolving LDHs powder in deionized water to obtain a first solution; sequentially pouring ferric chloride and ferric chloride in a mass ratio of 2:1 into the first solution of the first mass to obtain a first mixed solution; Adding excess ammonia water to the first mixed solution to obtain a first filler through reaction; sequentially pouring ferric chloride and ferric chloride in a mass ratio of 2:1 into a second mass of the first solution to obtain a second mixed solution; Adding excess ammonia water to the second mixed solution to obtain a second filler through reaction; sequentially pouring ferric chloride and ferric chloride in a mass ratio of 2:1 into a third mass of the first solution to obtain a third mixed solution; Adding excess ammonia water to the third mixed solution to obtain a third filler through reaction; The filler is obtained by mixing the first filler, the second filler and the third filler.
4. A method for preparing a filler according to claim 3, characterized in that: Dissolving LDHs powder in deionized water to obtain a first solution comprises: The LDHs powder was mixed with deionized water and then ultrasonicated for 10 minutes to obtain the first solution.
5. A method for preparing a filler according to claim 3, characterized in that: Also includes: The reaction temperature was 80°C and the reaction time was 2h.
6. A method for preparing a filler according to claim 3, characterized in that: Also includes: Ammonia gas was continuously introduced during the reaction.
7. A method for preparing a filler according to claim 3, characterized in that: Also includes: After the reaction is completed, the first filler, the second filler and the third filler are collected by magnetic force and washed multiple times with ethanol.
8. A method for preparing a filler according to claim 7, characterized in that: Also includes: The washed first filler, the second filler and the third filler are placed in a vacuum drying oven, dried at 60° C. for 12 hours, and then collected and ground to obtain the filler.
9. A coating preparation method, characterized in that: include: The filler according to claim 1 is mixed with a resin, a curing agent is added, and bubbles are removed to obtain a mixed coating; The mixed coating is sprayed or scraped on the surface of the target product to obtain the coating with a thickness of 50 μm to 200 μm.
10. The coating preparation method according to claim 9, characterized in that: The mass ratio of the filler to the resin is 0.5%-5%; The mass ratio of the resin to the curing agent is 3:1.