Anticorrosive weather-resistant functional filler, preparation method thereof and anticorrosive weather-resistant coating

Abstract

The application discloses a functional filler for corrosion resistance and weather resistance, a preparation method thereof and a corrosion-resistant and weather-resistant coating. The functional filler for corrosion resistance and weather resistance comprises fly ash, a mesoporous oxide layer is coated on the fly ash, and a heteroatom-doped carbon quantum dot organic carbon layer is coated on the mesoporous oxide layer. The mesoporous oxide layer comprises a weather-resistant element and a passivation element. The weather-resistant element is one or both of titanium and zinc, and the passivation element is one or more of cerium and iron. The functional filler for corrosion resistance and weather resistance can effectively improve the corrosion resistance and weather resistance of the coating, and can reduce the possibility of degradation of the coating.

Description

Technical Field

[0001] This invention belongs to the field of coating technology, specifically relating to anti-corrosion and weather-resistant functional fillers, their preparation methods, and anti-corrosion and weather-resistant coatings. Background Technology

[0002] In the field of industrial engineering, the corrosion of metals causes significant economic losses and resource waste, and also poses major safety hazards. Surface coating protection technology is a simple and effective metal corrosion prevention measure. During the coating preparation process, microporous defects are formed, including gaps between polymer chains, micropores formed during solvent evaporation, and gaps between pigments / fillers and the resin matrix. These defects significantly affect the coating's performance. Weather resistance is an important durability indicator. Weather-resistant coatings often contain a large amount of weather-resistant fillers, which can fill the pores in the coating film, increase its density, and improve its corrosion and weather resistance.

[0003] Fly ash is a common solid waste from coal-fired power plants. It possesses stable physicochemical properties and holds great potential in the field of corrosion-resistant fillers, often used as a weather-resistant filler in anti-corrosion coatings. However, in practical applications, coatings containing fly ash are still insufficient to meet the corrosion and weather resistance requirements of enterprises, necessitating further improvements.

[0004] The information disclosed in this background section is intended only to enhance the understanding of the overall background of the invention and should not be construed as an admission or in any way implying that the information constitutes prior art known to those skilled in the art. Summary of the Invention

[0005] The purpose of this invention is to provide anti-corrosion and weather-resistant functional fillers, their preparation methods, and anti-corrosion and weather-resistant coatings. The anti-corrosion and weather-resistant functional fillers can improve the anti-corrosion and weather-resistant performance of the coatings.

[0006] To achieve the above objectives, a specific embodiment of the present invention provides the following technical solution:

[0007] Corrosion-resistant and weather-resistant filler, including fly ash, wherein the fly ash is coated with a mesoporous oxide layer, and the mesoporous oxide layer is coated with a heteroatom-doped carbon quantum dot organic carbon layer;

[0008] The mesoporous oxide layer includes weather-resistant elements and passivating elements. The weather-resistant elements are one or both of titanium and zinc, and the passivating elements are one or more of cerium and iron.

[0009] In one or more embodiments of the present invention, the raw materials, by weight, include: 200-400 parts of fly ash, 20-80 parts of pore-forming agent, 100-150 parts of oxide additive, 50-100 parts of carbon-based compound, 50-100 parts of carbon quantum dot dopant, 20-50 parts of chemical modifier, and 50-150 parts of glacial acetic acid; wherein, the oxide additive includes weather-resistant oxide additive and passivating oxide additive, the weather-resistant oxide additive being one or two of tetrabutyl titanate and zinc chloride; the passivating oxide additive being one or more of cerium nitrate hexahydrate, ferric chloride hexahydrate, and ferric nitrate nonahydrate.

[0010] In one or more embodiments of the present invention, the pore-forming agent is selected from one or more of polyoxyethylene polyoxypropylene ether, polyethyleneimine, and polyethylene glycol; and / or,

[0011] The carbon-based compound is selected from one or more of 4-aminosalicylic acid, citric acid, tartaric acid, ascorbic acid, succinic acid, and chitosan; and / or,

[0012] The carbon quantum dopant is selected from one or more of thiourea, ethylenediamine, p-phenylenediamine, o-phenylenediamine, and oleylamine; and / or,

[0013] The chemical modifier is selected from one or more of γ-aminopropyltriethoxysilane, trichlorovinylsilane, ethyl α-cyanoacrylate, and dopamine hydrochloride.

[0014] In one or more embodiments of the present invention, the weight ratio of weather-resistant oxide additive to passivating oxide additive is 1:(0.8-2).

[0015] Another specific embodiment of the present invention provides the following technical solution:

[0016] The preparation method of corrosion-resistant and weather-resistant functional filler includes the following steps:

[0017] Using fly ash, water, pore-forming agent, oxide additives, and glacial acetic acid as raw materials, a mesoporous oxide layer is coated on fly ash to obtain a mesoporous oxide-fly ash filler; wherein, the oxide additives include weather-resistant oxide additives and passivating oxide additives, the weather-resistant oxide additives make the mesoporous oxide layer include titanium and / or zinc elements, and the passivating oxide additives make the mesoporous oxide layer include cerium and / or iron elements;

[0018] Carbon-based mesoporous oxide-fly ash filler was obtained by loading carbon quantum dots onto the mesoporous oxide-fly ash filler using mesoporous oxide-fly ash filler, water, carbon-based compounds and carbon quantum dot dopants as raw materials.

[0019] Carbon-based mesoporous oxide-fly ash filler is reacted with a chemical modifier to obtain a corrosion-resistant and weather-resistant functional filler.

[0020] In one or more embodiments of the present invention, a one-pot calcination method is used to prepare mesoporous oxide-fly ash filler. Specifically, fly ash, water, pore-forming agent, oxide additive and glacial acetic acid are mixed and ground to form an adhesive mixture. Then, calcination, ultrasonication, hydrothermal reaction, alcohol washing and drying are performed to obtain the filler.

[0021] And / or, when preparing mesoporous oxide-fly ash filler, the weight ratio of fly ash, water, pore-forming agent, oxide additive and glacial acetic acid is (5-15):(0.5-3.5):(2-7):(3-10):(2-8);

[0022] And / or, when preparing carbon-based mesoporous oxide-fly ash filler, the weight ratio of mesoporous oxide-fly ash filler, carbon-based compound, water and carbon quantum dot dopant is (5-10):(2-3.5):(6-18):(1.2-3).

[0023] In one or more embodiments of the present invention, carbon-based mesoporous oxide-fly ash filler is prepared by hydrothermal reaction at a temperature of 130-220°C.

[0024] In one or more embodiments of the present invention, carbon-based mesoporous oxide-fly ash filler and chemical modifier are dispersed in an ethanol aqueous solution, stirred and mixed at 25-80°C, and then subjected to ultrasonication, filtration and drying to obtain corrosion-resistant and weather-resistant functional filler.

[0025] In one or more embodiments of the present invention, the weight ratio of the carbon-based mesoporous oxide-fly ash filler to the chemical modifier is (1-2):(0.5-1).

[0026] Another specific embodiment of the present invention provides the following technical solution:

[0027] Anti-corrosion and weather-resistant coatings, including the aforementioned anti-corrosion and weather-resistant functional fillers.

[0028] Compared with existing technologies, this invention applies solid waste fly ash, mesoporous oxides, carbon-based structures and carbon quantum dots to the coating system, thereby enhancing the anti-corrosion and weather resistance of the coating.

[0029] First, the microstructure and composition of fly ash were optimized, retaining the microsphere-shaped fly ash with excellent shielding performance, thus providing basic shielding properties for the coating.

[0030] A mesoporous oxide layer was then constructed on the surface of fly ash using a one-pot calcination method, giving the filler both corrosion resistance and weather resistance. The mesoporous structure helps improve the material's weather resistance and reduces the degradation damage of the weather-resistant filler to the coating.

[0031] Then, in a hydrothermal reaction, carbon-based compounds are polymerized on a mesoporous oxide layer to form an organic carbon layer containing carbon quantum dots. Nitrogen and phosphorus atoms are then doped into this layer, giving the composite filler excellent corrosion inhibition activity. During the composite process of carbon quantum dots and mesoporous functional fillers, the mesoporous structure exhibits a large specific surface area, allowing it to load a large number of carbon quantum dots, thereby enhancing the corrosion inhibition performance of the coating. Constructing a carbon-coated mesoporous structure on the fly ash surface enhances the interfacial behavior between the filler and the resin matrix.

[0032] Finally, a chemical modifier is used to modify the surface of the mesoporous anti-corrosion and weather-resistant filler, enhancing the interfacial bonding between the filler and the resin matrix. In particular, the double-layer coating method for treating the mesoporous oxide-fly ash filler significantly reduces the degradation effect of the weather-resistant filler on the coating. Attached Figure Description

[0033] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments recorded in the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0034] Figure 1 The above are the EIS test results of the coating samples of Examples 1, 2, Comparative Example 1 and Comparative Example 2 of the present invention at 60 days.

[0035] Figure 2 The following describes the variation trend of the water contact angle of the coating samples in Example 1, Comparative Example 1, and Comparative Example 2 of the present invention over time after a xenon lamp weathering test.

[0036] Figure 3 The microstructure of the mesoporous packing samples in Example 2 and Comparative Example 2 of this invention is shown. Detailed Implementation

[0037] To enable those skilled in the art to better understand the technical solutions of this invention, the technical solutions of the embodiments of this invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this invention, and not all embodiments. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort should fall within the scope of protection of this invention.

[0038] Fly ash is a mixture with uncertain composition and a loose, porous structure, which is unfavorable for preparing stable anti-corrosion coatings. Some oxides can provide coatings with novel properties, such as weather resistance and corrosion inhibition. Therefore, this invention explores the use of oxides to modify fly ash fillers to obtain stable anti-corrosion functional fillers.

[0039] Specifically, grinding, grading, and calcining industrial solid waste fly ash can enhance its shielding properties. Selecting fly ash with specific particle sizes as a base filler can provide basic anti-corrosion properties for coatings. Since fly ash fillers have limited properties, a one-pot calcination method can be used to construct an oxide outer layer with specific functions on the outer layer of fly ash, thus preparing a functional filler precursor with both anti-corrosion and weather-resistant properties.

[0040] However, the outer oxide layer of the corrosion-resistant and weather-resistant filler precursor primarily exhibits weather resistance, mainly by absorbing ultraviolet light from the environment. This process is often accompanied by a photocatalytic effect, which can lead to the degradation of the coating itself, hindering the maintenance of stable corrosion-resistant and weather-resistant properties. Therefore, constructing an organic carbon layer containing carbon quantum dots on the outer oxide layer, with the carbon quantum dots distributed within it, can provide certain corrosion inhibition and passivation properties to the metal substrate, while simultaneously reducing the degradation of the coating caused by the photocatalytic effect of the outer oxide layer. Furthermore, doping the carbon layer with heteroatomic elements can further enhance the complexation and passivation effect of carbon quantum dots on the metal substrate.

[0041] Meanwhile, introducing a pore-forming agent during the preparation of the oxide outer layer constructs an outer oxide with a mesoporous morphology, which not only increases the weather-resistant reaction sites but also increases the contact area between the filler and the coating film, thereby enhancing the anti-corrosion and weather-resistant properties of the carbon layer containing carbon quantum dots. This can appropriately reduce the degree of degradation of the coating system caused by the photocatalytic effect of the oxide outer layer.

[0042] Furthermore, in preparing the oxide outer layer, tetrabutyl titanate and zinc chloride, which are mainly weather-resistant, and cerium nitrate hexahydrate, ferric chloride hexahydrate, and ferric nitrate nonahydrate, which have passivating effects on the metal substrate, are selected to enable the oxide outer layer to exhibit weather resistance while reducing the negative impact of photocatalysis.

[0043] A specific embodiment of the present invention provides a corrosion-resistant and weather-resistant functional filler, comprising fly ash, wherein the fly ash is coated with a mesoporous oxide layer, and the mesoporous oxide layer is coated with a heteroatom-doped carbon quantum dot organic carbon layer; the mesoporous oxide layer comprises weather-resistant elements and passivating elements, wherein the weather-resistant elements are one or both of titanium and zinc, and the passivating elements are one or more of cerium and iron.

[0044] Specifically, fly ash itself possesses excellent shielding properties. A mesoporous oxide layer forms on the surface of the fly ash. This oxide layer is prepared using tetrabutyl titanate (primarily for weather resistance) and zinc chloride, and cerium nitrate hexahydrate, ferric chloride hexahydrate, and ferric nitrate nonahydrate (primarily for passivation). This allows the oxide layer to exhibit oxide doping or even atomic doping, effectively improving the overall weather resistance of the filler. Furthermore, carbon quantum dots, a carbon-based zero-dimensional material, contain numerous active groups such as hydroxyl, carboxyl, and amino groups, giving them excellent corrosion inhibition properties. Coating the oxide layer with an organic carbon layer containing carbon quantum dots enhances the interfacial bonding between the filler and the coating system through the affinity between the organic carbon layer and the coating system. Additionally, the coating effect of carbon quantum dots on the oxide layer appropriately reduces the decomposition effect of the oxide layer on the coating.

[0045] Furthermore, although the organic carbon layer appropriately reduces the photocatalytic effect by coating the oxide layer, the mesoporous morphology of the oxide layer provides channels for oxygen transport, allowing the filler to retain the weather resistance of the oxide layer in the coating. Therefore, through the combined use of the mesoporous oxide layer, weather-resistant oxide additives, and passivating oxide additives, along with the comprehensive effect of the organic carbon layer on fly ash, the resulting fly ash filler can simultaneously improve the weather resistance and corrosion resistance of the coating, and reduce the negative impact of photocatalytic effects on the coating.

[0046] In one specific embodiment, the raw materials, by weight, include: 200-400 parts fly ash, 20-80 parts pore-forming agent, 100-150 parts oxide additive, 50-100 parts carbon-based compound, 50-100 parts carbon quantum dot dopant, 20-50 parts chemical modifier, and 50-150 parts glacial acetic acid; wherein, the oxide additive includes weather-resistant oxide additive and passivating oxide additive, the weather-resistant oxide additive being one or both of tetrabutyl titanate and zinc chloride; the passivating oxide additive being one or more of cerium nitrate hexahydrate, ferric chloride hexahydrate, and ferric nitrate nonahydrate.

[0047] In one specific embodiment, the pore-forming agent is selected from one or more of polyoxyethylene polyoxypropylene ether, polyethyleneimine, and polyethylene glycol; the carbon-based compound is selected from one or more of 4-aminosalicylic acid, citric acid, tartaric acid, ascorbic acid, succinic acid, and chitosan; the carbon quantum dopant is selected from one or more of thiourea, ethylenediamine, p-phenylenediamine, o-phenylenediamine, and oleylamine; and the chemical modifier is selected from one or more of γ-aminopropyltriethoxysilane, trichlorovinylsilane, ethyl α-cyanoacrylate, and dopamine hydrochloride.

[0048] Specifically, pore-forming agents are used to create pores in the oxide layer, constructing a unique mesoporous structure and enhancing the reactive sites of the filler. Carbon quantum dot dopants can introduce N and S atoms into the carbon quantum dot layer. N and S atoms possess lone pairs of electrons or π bonds, making them readily adsorbed on metal surfaces and hindering contact between corrosive media and the metal, thereby enhancing the corrosion inhibition and protection effect of the organic carbon layer on the metal substrate. Chemical modifiers, after modifying the filler, can enhance the bonding between the filler and the coating system through interfacial modification of functional groups, thus promoting the dispersion of the filler in the coating, improving the mechanical properties of the coating, and also facilitating the filler's weather resistance in the coating.

[0049] In one specific embodiment, the weight ratio of weather-resistant oxide additive to passivating oxide additive is 1:(0.8-2).

[0050] Specifically, by compounding weather-resistant oxide additives and passivating oxide additives in a specific weight ratio, the resulting filler exhibits superior corrosion and weather resistance.

[0051] Another specific embodiment of the present invention provides a method for preparing anti-corrosion and weather-resistant functional fillers, including steps 1-3.

[0052] Step 1: Using fly ash, water, pore-forming agent, oxide additive and glacial acetic acid as raw materials, a mesoporous oxide layer is coated on fly ash by one-pot calcination to obtain mesoporous oxide-fly ash filler.

[0053] Specifically, in step 1, fly ash filler, water, pore-forming agent, oxide additive, and glacial acetic acid are mixed evenly in a container at a weight ratio of (5-15):(0.5-3.5):(2-7):(3-10):(2-8). The mixture is then ground to form a gel-like mixture, followed by calcination, ultrasonic treatment in ethanol, hydrothermal reaction, alcohol washing, and drying. The oxide additive includes weather-resistant oxide additives and passivating oxide additives. The weather-resistant oxide additive is selected from one or both of tetrabutyl titanate and zinc chloride, while the passivating oxide additive is one or more of cerium nitrate hexahydrate, ferric chloride hexahydrate, and ferric nitrate nonahydrate. Using a specific ratio of raw materials forms a mesoporous oxide layer on the fly ash, enabling the mesoporous oxide layer to possess superior weather resistance and passivation properties.

[0054] Step 2: Using mesoporous oxide-fly ash filler, water, carbon-based compounds and carbon quantum dot dopants as raw materials, carbon quantum dots are loaded onto the mesoporous oxide-fly ash filler through hydrothermal reaction to obtain carbon-based mesoporous oxide-fly ash filler.

[0055] Specifically, in step 2, mesoporous oxide-fly ash filler, carbon-based compounds, deionized water, and carbon quantum dot dopants are mixed in a ratio of (5-10):(2-3.5):(6-18):(1.2-3), placed in a reactor, and subjected to a hydrothermal reaction at 130-220℃. After filtration and drying, carbon-based mesoporous oxide-fly ash filler is obtained. Using a specific ratio of raw materials to load and coat a carbon quantum dot organic carbon layer onto the mesoporous oxide layer improves the bonding effect between the organic carbon layer and the mesoporous oxide layer, resulting in better corrosion resistance and weather resistance of the filler.

[0056] Step 3: React carbon-based mesoporous oxide-fly ash filler with chemical modifier to obtain corrosion-resistant and weather-resistant functional filler.

[0057] Specifically, the reaction between carbon-based mesoporous oxide-fly ash filler and chemical modifier is achieved through one or more of chemical grafting, chemical growth, and physical coating. Specifically, according to the weight ratio of carbon-based mesoporous oxide-fly ash filler and chemical modifier of (1-2):(0.5-1), carbon-based mesoporous oxide-fly ash filler and chemical modifier are dispersed in an ethanol aqueous solution, stirred and mixed at 25-80℃, and then subjected to ultrasonication, filtration and drying to obtain corrosion-resistant and weather-resistant functional filler.

[0058] Another specific embodiment of the present invention provides an anti-corrosion and weather-resistant coating, including the above-mentioned anti-corrosion and weather-resistant functional filler.

[0059] Specifically, adding anti-corrosion and weather-resistant fillers to coatings can simultaneously improve the coating's anti-corrosion performance and weather resistance.

[0060] The present invention will be further described in detail below with reference to specific embodiments.

[0061] Example 1

[0062] A corrosion-resistant and weather-resistant functional filler is prepared using the following method:

[0063] 500 parts by weight of solid waste fly ash were placed in a ball mill and ground for 12 hours. Then, the fly ash was placed in a cyclone separator and screened to obtain fly ash with a particle size of 5-20 μm. The fly ash was then calcined at 500℃ for 6 hours to obtain fly ash filler.

[0064] 200 parts by weight of fly ash filler, 50 parts by weight of glacial acetic acid, 30 parts by weight of water, 20 parts by weight of tetrabutyl titanate, 40 parts by weight of zinc chloride, 40 parts by weight of cerium nitrate hexahydrate, 10 parts by weight of polyethyleneimine, and 10 parts by weight of polyethylene glycol were placed in a mortar and ground thoroughly for 30 minutes to obtain a gel-like product. This product was then calcined in a muffle furnace at 300 degrees Celsius for 6 hours to obtain a mesoporous oxide-fly ash precursor. Subsequently, ultrasonic treatment and hydrothermal reaction were carried out stepwise in a mixed solution of water and ethanol to obtain the mesoporous oxide-fly ash filler.

[0065] 100 parts by weight of mesoporous oxide-fly ash filler were placed in a beaker, and 50 parts by weight of water, 15 parts by weight of 4-aminosalicylic acid, 20 parts by weight of tartaric acid, 5 parts by weight of chitosan, 10 parts by weight of succinic acid, 40 parts by weight of ethylenediamine, and 10 parts by weight of thiourea were added. After mechanical stirring for 20 minutes, the mixture was placed in a hydrothermal reactor and subjected to a hydrothermal reaction at 220°C for 12 hours. After filtration and drying, carbon-based mesoporous oxide-fly ash filler was obtained.

[0066] 50 parts by weight of carbon-based mesoporous oxide-fly ash packing were placed in a beaker, and 100 parts by weight of water, 50 parts by weight of anhydrous ethanol, 10 parts by weight of γ-aminopropyltriethoxysilane, and 10 parts by weight of dopamine hydrochloride were added. The mixture was mechanically stirred at 50°C for 12 hours, and the corrosion-resistant and weather-resistant packing was obtained after filtration.

[0067] Example 2

[0068] A corrosion-resistant and weather-resistant functional filler is prepared using the following method:

[0069] 300 parts by weight of solid waste fly ash were placed in a ball mill and ground for 12 hours. Then, the fly ash was placed in a cyclone separator and screened to obtain fly ash with a particle size of 0.1-15 μm. The fly ash was then calcined at 1000℃ for 6 hours to obtain fly ash filler.

[0070] 150 parts by weight of fly ash filler, 150 parts by weight of glacial acetic acid, 50 parts by weight of water, 100 parts by weight of cerium nitrate hexahydrate, 30 parts by weight of zinc chloride, 20 parts by weight of tetrabutyl titanate, and 80 parts by weight of polyoxyethylene polyoxypropylene ether were placed in a mortar and ground thoroughly for 60 minutes to obtain a gel-like product. This product was then placed in a muffle furnace at 500°C and calcined for 3 hours to obtain a mesoporous oxide-fly ash precursor. Subsequently, ultrasonic treatment and hydrothermal reaction were carried out stepwise in a mixed solution of water and ethanol to obtain the mesoporous oxide-fly ash filler.

[0071] 150 parts by weight of mesoporous oxide-fly ash packing were placed in a beaker, and 10 parts by weight of water, 40 parts by weight of anhydrous ethanol, 50 parts by weight of citric acid, 50 parts by weight of ascorbic acid, 40 parts by weight of p-phenylenediamine, 10 parts by weight of o-phenylenediamine, and 50 parts by weight of oleylamine were added. After mechanical stirring for 40 minutes, the mixture was placed in a hydrothermal reactor and subjected to a hydrothermal reaction at 130 degrees Celsius for 36 hours. After filtration and drying, carbon-based mesoporous oxide-fly ash packing was obtained.

[0072] 150 parts by weight of carbon-based mesoporous oxide-fly ash filler were placed in a beaker, and 300 parts by weight of water, 25 parts by weight of trichlorovinylsilane, and 25 parts by weight of ethyl α-cyanoacrylate were added. The mixture was mechanically stirred at 80°C for 12 hours, and the filler was obtained by filtration.

[0073] Example 3

[0074] A corrosion-resistant and weather-resistant functional filler is prepared using the following method:

[0075] 500 parts by weight of solid waste fly ash were placed in a ball mill and ground for 12 hours. Then, the fly ash was placed in a cyclone separator and screened to obtain fly ash with a particle size of 5-20 μm. The fly ash was then calcined at 500℃ for 6 hours to obtain fly ash filler.

[0076] 200 parts by weight of fly ash filler, 50 parts by weight of glacial acetic acid, 30 parts by weight of water, 20 parts by weight of tetrabutyl titanate, 20 parts by weight of ferric chloride hexahydrate, 40 parts by weight of zinc chloride, 20 parts by weight of ferric nitrate nonahydrate, 10 parts by weight of polyethyleneimine, and 10 parts by weight of polyethylene glycol were placed in a mortar and ground thoroughly for 30 minutes to obtain a gel-like product. This product was then calcined in a muffle furnace at 300 degrees Celsius for 6 hours to obtain a mesoporous oxide-fly ash precursor. Subsequently, ultrasonic treatment and hydrothermal reaction were carried out stepwise in a mixed solution of water and ethanol to obtain the mesoporous oxide-fly ash filler.

[0077] 100 parts by weight of mesoporous oxide-fly ash filler were placed in a beaker, and 50 parts by weight of water, 15 parts by weight of 4-aminosalicylic acid, 20 parts by weight of tartaric acid, 5 parts by weight of chitosan, 10 parts by weight of succinic acid, 40 parts by weight of ethylenediamine, and 10 parts by weight of thiourea were added. After mechanical stirring for 20 minutes, the mixture was placed in a hydrothermal reactor and subjected to a hydrothermal reaction at 220°C for 12 hours. After filtration and drying, carbon-based mesoporous oxide-fly ash filler was obtained.

[0078] 50 parts by weight of carbon-based mesoporous oxide-fly ash packing were placed in a beaker, and 100 parts by weight of water, 50 parts by weight of anhydrous ethanol, 10 parts by weight of γ-aminopropyltriethoxysilane, and 10 parts by weight of dopamine hydrochloride were added. The mixture was mechanically stirred at 50°C for 12 hours, and the corrosion-resistant and weather-resistant packing was obtained after filtration.

[0079] Example 4

[0080] The only difference between this embodiment and Embodiment 2 is that the amount of tetrabutyl titanate is 27 parts by weight, the amount of zinc chloride is 40 parts by weight, and the amount of cerium nitrate hexahydrate is 83 parts by weight.

[0081] Example 5

[0082] The only difference between this embodiment and Embodiment 2 is that the amount of tetrabutyl titanate is 35 parts by weight, the amount of zinc chloride is 40 parts by weight, and the amount of cerium nitrate hexahydrate is 75 parts by weight.

[0083] Example 6

[0084] The only difference between this embodiment and Embodiment 2 is that the amount of tetrabutyl titanate is 40 parts by weight, the amount of zinc chloride is 60 parts by weight, and the amount of cerium nitrate hexahydrate is 50 parts by weight.

[0085] Example 7

[0086] A corrosion-resistant and weather-resistant functional filler is prepared using the following method:

[0087] 300 parts by weight of solid waste fly ash were placed in a ball mill and ground for 12 hours. Then, the fly ash was placed in a cyclone separator and screened to obtain fly ash with a particle size of 0.1-15 μm. The fly ash was then calcined at 1000℃ for 6 hours to obtain fly ash filler.

[0088] 200 parts by weight of fly ash filler, 80 parts by weight of glacial acetic acid, 20 parts by weight of water, 80 parts by weight of cerium nitrate hexahydrate, 24 parts by weight of zinc chloride, 16 parts by weight of tetrabutyl titanate, and 80 parts by weight of polyoxyethylene polyoxypropylene ether were placed in a mortar and ground thoroughly for 60 minutes to obtain a gel-like product. This product was then placed in a muffle furnace at 500°C and calcined for 3 hours to obtain a mesoporous oxide-fly ash precursor. Subsequently, ultrasonic treatment and hydrothermal reaction were carried out stepwise in a mixed solution of water and ethanol to obtain the mesoporous oxide-fly ash filler.

[0089] 150 parts by weight of mesoporous oxide-fly ash packing were placed in a beaker, and 10 parts by weight of water, 40 parts by weight of anhydrous ethanol, 50 parts by weight of citric acid, 50 parts by weight of ascorbic acid, 40 parts by weight of p-phenylenediamine, 10 parts by weight of o-phenylenediamine, and 50 parts by weight of oleylamine were added. After mechanical stirring for 40 minutes, the mixture was placed in a hydrothermal reactor and subjected to a hydrothermal reaction at 130 degrees Celsius for 36 hours. After filtration and drying, carbon-based mesoporous oxide-fly ash packing was obtained.

[0090] 150 parts by weight of carbon-based mesoporous oxide-fly ash filler were placed in a beaker, and 300 parts by weight of water, 25 parts by weight of trichlorovinylsilane, and 25 parts by weight of ethyl α-cyanoacrylate were added. The mixture was mechanically stirred at 80°C for 12 hours, and the filler was obtained by filtration.

[0091] Example 8

[0092] A corrosion-resistant and weather-resistant functional filler is prepared using the following method:

[0093] 300 parts by weight of solid waste fly ash were placed in a ball mill and ground for 12 hours. Then, the fly ash was placed in a cyclone separator and screened to obtain fly ash with a particle size of 0.1-15 μm. The fly ash was then calcined at 1000℃ for 6 hours to obtain fly ash filler.

[0094] 150 parts by weight of fly ash filler, 150 parts by weight of glacial acetic acid, 50 parts by weight of water, 100 parts by weight of cerium nitrate hexahydrate, 30 parts by weight of zinc chloride, 20 parts by weight of tetrabutyl titanate, and 80 parts by weight of polyoxyethylene polyoxypropylene ether were placed in a mortar and ground thoroughly for 60 minutes to obtain a gel-like product. This product was then placed in a muffle furnace at 500°C and calcined for 3 hours to obtain a mesoporous oxide-fly ash precursor. Subsequently, ultrasonic treatment and hydrothermal reaction were carried out stepwise in a mixed solution of water and ethanol to obtain the mesoporous oxide-fly ash filler.

[0095] 250 parts by weight of the mesoporous oxide-fly ash filler prepared by the above method were placed in a beaker, and 300 parts by weight of water, 40 parts by weight of anhydrous ethanol, 50 parts by weight of citric acid, 50 parts by weight of ascorbic acid, 24 parts by weight of p-phenylenediamine, 6 parts by weight of o-phenylenediamine, and 30 parts by weight of oleylamine were added. After mechanical stirring for 40 minutes, the mixture was placed in a hydrothermal reactor and subjected to a hydrothermal reaction at 130 degrees Celsius for 36 hours. After filtration and drying, carbon-based mesoporous oxide-fly ash filler was obtained.

[0096] 150 parts by weight of carbon-based mesoporous oxide-fly ash filler were placed in a beaker, and 300 parts by weight of water, 25 parts by weight of trichlorovinylsilane, and 25 parts by weight of ethyl α-cyanoacrylate were added. The mixture was mechanically stirred at 80°C for 12 hours, and the filler was obtained by filtration.

[0097] Example 9

[0098] A corrosion-resistant and weather-resistant functional filler is prepared using the following method:

[0099] 300 parts by weight of solid waste fly ash were placed in a ball mill and ground for 12 hours. Then, the fly ash was placed in a cyclone separator and screened to obtain fly ash with a particle size of 0.1-15 μm. The fly ash was then calcined at 1000℃ for 6 hours to obtain fly ash filler.

[0100] 150 parts by weight of fly ash filler, 150 parts by weight of glacial acetic acid, 50 parts by weight of water, 100 parts by weight of cerium nitrate hexahydrate, 30 parts by weight of zinc chloride, 20 parts by weight of tetrabutyl titanate, and 80 parts by weight of polyoxyethylene polyoxypropylene ether were placed in a mortar and ground thoroughly for 60 minutes to obtain a gel-like product. This product was then placed in a muffle furnace at 500°C and calcined for 3 hours to obtain a mesoporous oxide-fly ash precursor. Subsequently, ultrasonic treatment and hydrothermal reaction were carried out stepwise in a mixed solution of water and ethanol to obtain the mesoporous oxide-fly ash filler.

[0101] 250 parts by weight of the mesoporous oxide-fly ash filler prepared by the above method were placed in a beaker, and 10 parts by weight of water, 40 parts by weight of anhydrous ethanol, 25 parts by weight of citric acid, 25 parts by weight of ascorbic acid, 37.5 parts by weight of p-phenylenediamine, 7.5 parts by weight of o-phenylenediamine, and 30 parts by weight of oleylamine were added. After mechanical stirring for 40 minutes, the mixture was placed in a hydrothermal reactor and subjected to a hydrothermal reaction at 130 degrees Celsius for 36 hours. After filtration and drying, carbon-based mesoporous oxide-fly ash filler was obtained.

[0102] 150 parts by weight of carbon-based mesoporous oxide-fly ash filler were placed in a beaker, and 300 parts by weight of water, 25 parts by weight of trichlorovinylsilane, and 25 parts by weight of ethyl α-cyanoacrylate were added. The mixture was mechanically stirred at 80°C for 12 hours, and the filler was obtained by filtration.

[0103] Example 10

[0104] A corrosion-resistant and weather-resistant functional filler is prepared using the following method:

[0105] 300 parts by weight of solid waste fly ash were placed in a ball mill and ground for 12 hours. Then, the fly ash was placed in a cyclone separator and screened to obtain fly ash with a particle size of 0.1-15 μm. The fly ash was then calcined at 1000℃ for 6 hours to obtain fly ash filler.

[0106] 150 parts by weight of fly ash filler, 150 parts by weight of glacial acetic acid, 50 parts by weight of water, 100 parts by weight of cerium nitrate hexahydrate, 50 parts by weight of tetrabutyl titanate, and 80 parts by weight of polyoxyethylene polyoxypropylene ether were placed in a mortar and ground thoroughly for 60 minutes to obtain a gel-like product. This product was then calcined in a muffle furnace at 500°C for 3 hours to obtain a mesoporous oxide-fly ash precursor. Subsequently, ultrasonic treatment and hydrothermal reaction were carried out stepwise in a mixed solution of water and ethanol to obtain the mesoporous oxide-fly ash filler.

[0107] 150 parts by weight of mesoporous oxide-fly ash packing were placed in a beaker, and 10 parts by weight of water, 40 parts by weight of anhydrous ethanol, 50 parts by weight of citric acid, 50 parts by weight of ascorbic acid, 40 parts by weight of p-phenylenediamine, 10 parts by weight of o-phenylenediamine, and 50 parts by weight of oleylamine were added. After mechanical stirring for 40 minutes, the mixture was placed in a hydrothermal reactor and subjected to a hydrothermal reaction at 130 degrees Celsius for 36 hours. After filtration and drying, carbon-based mesoporous oxide-fly ash packing was obtained.

[0108] 150 parts by weight of carbon-based mesoporous oxide-fly ash filler were placed in a beaker, and 300 parts by weight of water, 25 parts by weight of trichlorovinylsilane, and 25 parts by weight of ethyl α-cyanoacrylate were added. The mixture was mechanically stirred at 80°C for 12 hours, and the filler was obtained by filtration.

[0109] Example 11

[0110] A corrosion-resistant and weather-resistant functional filler is prepared using the following method:

[0111] 500 parts by weight of solid waste fly ash were placed in a ball mill and ground for 12 hours. Then, the fly ash was placed in a cyclone separator and screened to obtain fly ash with a particle size of 5-20 μm. The fly ash was then calcined at 500℃ for 6 hours to obtain fly ash filler.

[0112] 200 parts by weight of fly ash filler, 50 parts by weight of glacial acetic acid, 30 parts by weight of water, 20 parts by weight of tetrabutyl titanate, 40 parts by weight of zinc chloride, 40 parts by weight of cerium nitrate hexahydrate, 10 parts by weight of polyethyleneimine, and 10 parts by weight of polyethylene glycol were placed in a mortar and ground thoroughly for 30 minutes to obtain a gel-like product. This product was then placed in a muffle furnace at 300 degrees Celsius and calcined for 6 hours to obtain a mesoporous oxide-fly ash precursor. Subsequently, ultrasonic treatment and hydrothermal reaction were carried out stepwise in a mixed solution of water and ethanol to obtain the mesoporous oxide-fly ash filler.

[0113] 100 parts by weight of mesoporous oxide-fly ash filler were placed in a beaker, and 50 parts by weight of water, 15 parts by weight of 4-aminosalicylic acid, 20 parts by weight of tartaric acid, 5 parts by weight of chitosan, and 10 parts by weight of succinic acid were added. After mechanical stirring for 20 minutes, the mixture was placed in a hydrothermal reactor and subjected to a hydrothermal reaction at 220°C for 12 hours. After filtration and drying, carbon-based mesoporous oxide-fly ash filler precursor was obtained.

[0114] 100 parts by weight of carbon-based mesoporous oxide-fly ash packing precursor, 40 parts by weight of ethylenediamine, and 10 parts by weight of thiourea were placed in a beaker, and 50 parts by weight of water were added. After mechanical stirring for 30 minutes, the mixture was placed in a hydrothermal reactor and subjected to a hydrothermal reaction at 220°C for 6 hours. After filtration and drying, carbon-based mesoporous oxide-fly ash packing was obtained.

[0115] 50 parts by weight of carbon-based mesoporous oxide-fly ash packing were placed in a beaker, and 100 parts by weight of water, 50 parts by weight of anhydrous ethanol, 10 parts by weight of γ-aminopropyltriethoxysilane, and 10 parts by weight of dopamine hydrochloride were added. The mixture was mechanically stirred at 50°C for 12 hours, and the corrosion-resistant and weather-resistant packing was obtained after filtration.

[0116] Comparative Example 1

[0117] A corrosion-resistant and weather-resistant functional filler is prepared using the following method:

[0118] 500 parts by weight of solid waste fly ash were placed in a ball mill and ground for 12 hours. Then, the fly ash was placed in a cyclone separator and screened to obtain fly ash with a particle size of 5-20 μm. The fly ash was then calcined at 500℃ for 6 hours to obtain fly ash filler.

[0119] 100 parts by weight of fly ash filler were placed in a beaker, and 50 parts by weight of water, 15 parts by weight of 4-aminosalicylic acid, 20 parts by weight of tartaric acid, 5 parts by weight of chitosan, 10 parts by weight of succinic acid, 40 parts by weight of ethylenediamine, and 10 parts by weight of thiourea were added. After mechanical stirring for 20 minutes, the mixture was placed in a hydrothermal reactor and subjected to a hydrothermal reaction at 220°C for 12 hours. After filtration and drying, carbon-based fly ash filler was obtained.

[0120] 50 parts by weight of carbon-based fly ash filler were placed in a beaker, and 100 parts by weight of water, 50 parts by weight of anhydrous ethanol, 10 parts by weight of γ-aminopropyltriethoxysilane, and 10 parts by weight of dopamine hydrochloride were added. The mixture was mechanically stirred at 50°C for 12 hours, and the corrosion-resistant and weather-resistant filler was obtained after filtration.

[0121] Comparative Example 2

[0122] A corrosion-resistant and weather-resistant functional filler is prepared using the following method:

[0123] 500 parts by weight of solid waste fly ash were placed in a ball mill and ground for 12 hours. Then, the fly ash was placed in a cyclone separator and screened to obtain fly ash with a particle size of 5-20 μm. The fly ash was then calcined at 500℃ for 6 hours to obtain fly ash filler.

[0124] 200 parts by weight of fly ash filler, 50 parts by weight of glacial acetic acid, 30 parts by weight of water, 20 parts by weight of tetrabutyl titanate, 40 parts by weight of zinc chloride, 40 parts by weight of cerium nitrate hexahydrate, 10 parts by weight of polyethyleneimine, and 10 parts by weight of polyethylene glycol were placed in a mortar and ground thoroughly for 30 minutes to obtain a gel-like product. This product was then calcined in a muffle furnace at 300 degrees Celsius for 6 hours to obtain a mesoporous oxide-fly ash precursor. Subsequently, ultrasonic treatment and hydrothermal reaction were carried out stepwise in a mixed solution of water and ethanol to obtain the mesoporous oxide-fly ash filler.

[0125] 50 parts by weight of mesoporous oxide-fly ash packing were placed in a beaker, and 100 parts by weight of water, 50 parts by weight of anhydrous ethanol, 10 parts by weight of γ-aminopropyltriethoxysilane, and 10 parts by weight of dopamine hydrochloride were added. The mixture was mechanically stirred at 50°C for 12 hours, and the corrosion-resistant and weather-resistant packing was obtained after filtration.

[0126] Comparative Example 3

[0127] A corrosion-resistant and weather-resistant functional filler is prepared using the following method:

[0128] 300 parts by weight of solid waste fly ash were placed in a ball mill and ground for 12 hours. Then, the fly ash was placed in a cyclone separator and screened to obtain fly ash with a particle size of 0.1-15 μm. The fly ash was then calcined at 1000℃ for 6 hours to obtain fly ash filler.

[0129] 150 parts by weight of fly ash filler, 150 parts by weight of glacial acetic acid, 50 parts by weight of water, 100 parts by weight of cerium nitrate hexahydrate, 30 parts by weight of zinc chloride, and 20 parts by weight of tetrabutyl titanate were placed in a mortar and ground thoroughly for 60 minutes to obtain a mixture. This mixture was then placed in a muffle furnace at 500°C and calcined for 3 hours to obtain an oxide-fly ash precursor. Subsequently, ultrasonic treatment and hydrothermal reaction were carried out stepwise in a mixed solution of water and ethanol to obtain the oxide-fly ash filler.

[0130] 150 parts by weight of oxide-fly ash packing were placed in a beaker, and 10 parts by weight of water, 40 parts by weight of anhydrous ethanol, 50 parts by weight of citric acid, 50 parts by weight of ascorbic acid, 40 parts by weight of p-phenylenediamine, 10 parts by weight of o-phenylenediamine, and 50 parts by weight of oleylamine were added. After mechanical stirring for 40 minutes, the mixture was placed in a hydrothermal reactor and subjected to a hydrothermal reaction at 130 degrees Celsius for 36 hours. After filtration and drying, carbon-based oxide-fly ash packing was obtained.

[0131] 150 parts by weight of carbon-based oxide-fly ash filler were placed in a beaker, and 300 parts by weight of water, 25 parts by weight of trichlorovinylsilane, and 25 parts by weight of ethyl α-cyanoacrylate were added. The mixture was mechanically stirred at 80°C for 12 hours, and the filler was obtained by filtration.

[0132] Comparative Example 4

[0133] The only difference between this comparative example and Example 10 is that tetrabutyl titanate is replaced with an equal amount of cerium nitrate hexahydrate.

[0134] Comparative Example 5

[0135] The only difference between this comparative example and Example 10 is that cerium nitrate hexahydrate is replaced with an equal amount of tetrabutyl titanate.

[0136] In the preparation of anti-corrosion and weather-resistant coatings, the anti-corrosion and weather-resistant functional fillers in the above embodiments and comparative examples are all prepared using the following scheme: 50 parts by weight of epoxy resin, 30 parts by weight of polyamide, 15 parts by weight of xylene, and 15 parts by weight of acetone are mixed evenly using a high-speed disperser, and 20 parts by weight of anti-corrosion and weather-resistant functional filler are added and stirred evenly. The coating is then sprayed onto the surface of the metal substrate by air pump spraying and cured to form a coating layer.

[0137] Performance testing:

[0138] (1) Corrosion Resistance Test: The coating samples formed in each example and comparative example were placed in a 3.5% NaCl solution for electrochemical impedance spectroscopy (EIS) testing. A three-electrode system was used to perform EIS testing on the coatings, with a frequency range of 100 kHz to 0.01 Hz. A 20 mV sinusoidal perturbation signal was applied to the sample, and the test area of ​​the sample was 7.069 cm². 2 The main test data are shown in Table 1. The EIS test results after soaking in 3.5% NaCl solution for 60 days are as follows: Figure 1 As shown.

[0139] Table 1 EIS Test Data

[0140]

[0141] (2) Routine performance tests: The adhesion of the samples was tested using the pull-out test and the cross-cut test; the samples were subjected to weathering tests using a xenon lamp test chamber, in which the relative humidity inside the chamber was maintained at 50%, and the ultraviolet range of the xenon lamp was set to 340nm. The routine performance test data are shown in Table 2. The changes in the water contact angle of the samples after the xenon lamp weathering test are shown in Table 2. Figure 2 As shown.

[0142] Table 2. Standard Performance Test Data

[0143]

[0144] Referring to Tables 1 and 2, the following conclusions can be drawn:

[0145] (1) The samples of Example 1 and Example 2 exhibited high impedance moduli at low frequencies, with values ​​of 3.32 × 10⁻⁶ respectively. 11 Ω·cm 2 and 3.55×10 11 Ω·cm 2 The high impedance modulus indicates that the anti-corrosion coating has excellent shielding performance against corrosive media, and the functional composite filler with a specific structure effectively blocks corrosive media.

[0146] The samples in Comparative Example 1 and Comparative Example 2 exhibited relatively low impedance moduli at low frequencies, with values ​​of 2.76 × 10⁻⁶. 10 Ω·cm 2 and 2.04×10 11 Ω·cm 2 In comparison, the low-frequency impedance modulus of Comparative Example 1 is smaller, indicating that the mesoporous structure in Examples 1 and 2 contributes to the uniform distribution of carbon structures, which is beneficial to improving the corrosion resistance of the coating. For Comparative Example 2, although the sample exhibits a higher impedance modulus, it shows a significant upward trend in the high-frequency region of the Bode plot. Figure 1 (d) indicates that the sample exhibits two time constants, which suggests that stratification has occurred within the sample, which is highly detrimental to corrosion prevention.

[0147] In the EIS test results, there were also specific differences in the Nyquist plots of different samples, among which Comparative Example 1 had the smallest capacitive arc radius. Figure 1 (b) indicates that the coating exhibits some water absorption, which is highly detrimental to corrosion. This behavior also suggests poor internal dispersion of the material, indicating that the organic carbon layer can appropriately improve the bonding between the filler and the coating interface.

[0148] As shown in Table 2, Comparative Example 1 and Comparative Example 2 exhibited poor adhesion to the substrate, which was attributed to the uneven distribution of fillers within the coating. In Comparative Example 1, the absence of mesoporous structures in the functional filler reduced its dispersion, leading to decreased coating shielding performance and reduced neutral salt spray resistance and xenon lamp resistance test time. In Comparative Example 2, the lack of an organic carbon layer containing carbon quantum dots in the filler reduced the interfacial behavior between the filler and the resin matrix, resulting in poor compatibility between the mesoporous filler and the resin matrix. This significantly reduced the adhesion of the sample, achieving only 5.17 MPa in the pull-out adhesion strength test and a grade 3 in the cross-cut adhesion test. However, the xenon lamp resistance of Comparative Example 2 was not poor, withstanding 500 hours of xenon lamp testing, indicating that the mesoporous oxide layer imparted a certain degree of weather resistance to the coating.

[0149] (2) Xenon lamp aging tests were conducted on the coating samples of Example 1, Comparative Example 1 and Comparative Example 2. Subsequently, the contact angle of the coating surface was tested to analyze the degree of damage to the coating caused by the xenon lamp.

[0150] The initial water contact angle of the sample in Example 1 after the xenon lamp test was 84.68°. Figure 2 (a) As the settling time was extended to 100 seconds, the water contact angle decreased to 76.56°. Within 100 seconds, the water contact angle decreased by 8.12°. The initial water contact angle and water absorption rate of the sample were both moderate.

[0151] The initial water contact angle of the sample in Comparative Example 1 after the xenon lamp test was 63.24°. Figure 2 (b) The initial water contact angle was low. As the settling time increased to 100 seconds, the water contact angle decreased to 54.93°, a decrease of 8.31° within 100 seconds. The decrease in water contact angle of the Comparative Example 1 sample was similar to that of the Sample of Example 1, indicating that the water absorption rate of the coating was comparable. The low initial angle may be due to damage to the coating caused by the xenon lamp. The sample in Comparative Example 1 did not have a mesoporous oxide layer and showed no obvious resistance to the xenon lamp aging test.

[0152] The initial water contact angle of Comparative Example 2 sample after xenon lamp testing was 109.79°, a significant increase compared to other samples. This is likely due to the photocatalytic reaction of the mesoporous oxide components during the xenon lamp test. As the settling time increased to 100 seconds, the water contact angle decreased to 76.56°, a drop of 33.23° within 100 seconds. This indicates severe water absorption by the coating and significant surface defects. The filler in Comparative Example 2 lacked an organic carbon layer containing carbon quantum dots, and its poor performance may be due to poor interfacial crosslinking between the filler and resin.

[0153] (3) The mesoporous structure of the oxide layer is a key factor affecting the coating performance. Figure 3 The microstructures of the mesoporous oxides in Example 2 and Comparative Example 2 are shown. With the help of the carbon layer, the mesoporous morphology of the samples is more obvious, which is beneficial to the coating exhibiting better properties.

[0154] Oxides provide excellent weather resistance or corrosion resistance, and the mesoporous structure endows the filler with excellent transport channels and active sites. The low-frequency impedance modulus of the sample in Comparative Example 3, as measured by EIS, is only 2.48 × 10⁻⁶. 7 Ω·cm 2 This value is four orders of magnitude lower than that of the sample in Example 1, indicating severe porosity defects within the coating, which impairs the coating's corrosion resistance. Furthermore, the xenon lamp resistance time of the sample in Comparative Example 3 is 600 hours lower than that of the sample in Example 1, suggesting that the mesoporous morphology of the oxide layer facilitates the filler's functionality. The photocatalytic effect on the surface of weather-resistant fillers easily causes decomposition of the coating resin matrix, reducing the coating's corrosion resistance. Therefore, it is difficult to simultaneously improve both weather resistance and corrosion resistance in a system. This invention cleverly utilizes the mesoporous structure and the coating effect of an organic carbon layer containing carbon quantum dots to enhance the effect of the weather-resistant filler and reduce its destructive behavior on the coating.

[0155] (4) The mesoporous oxide layer structure does not contain only one type of oxide, nor is it a combination of multiple single oxides. Instead, it is a heterogeneous structure with a doped morphology, which has excellent oxygen transport capabilities. This oxygen transport performance enhances the weather-resistant unit function within the mesoporous structure, rapidly transporting oxygen from the sample surface into the mesoporous structure and improving the filler's weather resistance. The differences in this characteristic can be seen in Examples 10, 4, and 5. Comparative Example 4 is a carbon-based mesoporous CeO2-fly ash filler, which has not been doped with Ti atoms. Although the mesoporous CeO2 structure has a large pore structure, it lacks oxygen transport capabilities, which reduces the corrosion resistance and passivation performance of Ce on the metal substrate. The results show that the low-frequency impedance modulus in the EIS test of Comparative Example 4 is one order of magnitude lower than that of the sample in Example 10.

[0156] As can be seen from the xenon lamp resistance time of Example 10 and Comparative Example 5, the xenon lamp resistance time of the carbon-based mesoporous TiO2-fly ash coating without Ce atom doping is only 350 hours. This indicates that the lack of doping promotes the photocatalytic process on the filler surface, which has an adverse effect on the coating.

[0157] (5) The organic carbon layer coating is very beneficial to the interfacial bonding performance between the mesoporous oxide-fly ash filler and the resin matrix. The carbon layer prepared on the mesoporous oxide layer is enriched with N-atom doped carbon quantum dots, which have a strong affinity for the resin matrix interface. In addition, it is also very beneficial to the passivation behavior of the metal substrate.

[0158] In Example 1, the organic carbon layer and N-doped carbon quantum dots were synthesized in a one-step process into the mesoporous oxide-fly ash filler. The carbon quantum dots were mainly enriched in the outer layer of the filler, which effectively enhanced the bonding behavior between the carbon layer and the resin matrix, and also significantly reduced the decomposition effect of the weather-resistant filler on the interface. In Example 11, the organic carbon layer and carbon quantum dots were prepared stepwise into the functional filler. The carbon quantum dots were largely doped into the mesoporous structure, which hindered the release of the carbon quantum dots to the metal substrate and reduced the effectiveness of the weather-resistant filler. The results showed that Example 1 performed well in both the EIS test and the neutral salt spray test, which corroborated this effect. In addition, the pull-off adhesion strength of Examples 1 and 2 was higher than that of the sample in Example 11 (the adhesion strength of the sample in Comparative Example 6 was 7.15 MPa), which also indicates the difference in the interfacial bonding performance of the components inside the coating. Therefore, considering all factors, the one-step preparation of carbon-based mesoporous oxide-fly ash filler using hydrothermal reaction in Example 1 is more conducive to the filler's anti-corrosion and weather-resistant effects.

[0159] (6) The compounding ratio of weather-resistant oxide additives and passivating oxide additives affects the function of fillers. As can be seen from Examples 2 and 4-6, compounding weather-resistant oxide additives and passivating oxide additives at the weight ratio of 1:(0.8-2) disclosed in this invention helps fillers to enhance the anti-corrosion and weather-resistant properties of coatings, while reducing the adverse effects of photocatalysis.

[0160] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from its spirit or essential characteristics. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, all variations falling within the meaning and scope of equivalents of the claims are intended to be included within the present invention. No reference numerals in the claims should be construed as limiting the scope of the claims.

[0161] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A corrosion-resistant and weather-resistant filler, characterized in that, Includes fly ash, wherein the fly ash is coated with a mesoporous oxide layer, and the mesoporous oxide layer is coated with a heteroatom-doped carbon quantum dot organic carbon layer; The mesoporous oxide layer includes weather-resistant elements and passivating elements. The weather-resistant elements are one or both of titanium and zinc, and the passivating elements are one or more of cerium and iron. The preparation method of the corrosion-resistant and weather-resistant functional filler includes the following steps: Using fly ash, water, pore-forming agent, oxide additive and glacial acetic acid as raw materials, a mesoporous oxide layer is coated on fly ash to obtain mesoporous oxide-fly ash filler; The oxide additives include weather-resistant oxide additives and passivating oxide additives. The weather-resistant oxide additives make the mesoporous oxide layer include titanium and / or zinc elements, and the passivating oxide additives make the mesoporous oxide layer include cerium and / or iron elements. Using mesoporous oxide-fly ash filler, water, carbon-based compounds and carbon quantum dot dopants as raw materials, carbon quantum dots are loaded onto the mesoporous oxide-fly ash filler to obtain carbon-based mesoporous oxide-fly ash filler; in this step, carbon-based mesoporous oxide-fly ash filler is prepared by hydrothermal reaction at a temperature of 130-220℃. Carbon-based mesoporous oxide-fly ash filler is reacted with a chemical modifier to obtain a corrosion-resistant and weather-resistant filler. The oxide additives include weather-resistant oxide additives and passivating oxide additives. The weather-resistant oxide additives are one or two of tetrabutyl titanate and zinc chloride. The passivating oxide additives are one or more of cerium nitrate hexahydrate, ferric chloride hexahydrate, and ferric nitrate nonahydrate. The carbon-based compound is selected from one or more of 4-aminosalicylic acid, citric acid, tartaric acid, ascorbic acid, succinic acid, and chitosan; The carbon quantum dopant is selected from one or more of thiourea, ethylenediamine, p-phenylenediamine, o-phenylenediamine, and oleylamine.

2. The anti-corrosion and weather-resistant functional filler according to claim 1, characterized in that, The raw materials, by weight, include: 200-400 parts fly ash, 20-80 parts pore-forming agent, 100-150 parts oxide additive, 50-100 parts carbon-based compound, 50-100 parts carbon quantum dot dopant, 20-50 parts chemical modifier, and 50-150 parts glacial acetic acid.

3. The anti-corrosion and weather-resistant functional filler according to claim 2, characterized in that, The pore-forming agent is selected from one or more of polyoxyethylene polyoxypropylene ether, polyethyleneimine, and polyethylene glycol; And / or, the chemical modifier is selected from one or more of γ-aminopropyltriethoxysilane, trichlorovinylsilane, ethyl α-cyanoacrylate, and dopamine hydrochloride.

4. The anti-corrosion and weather-resistant functional filler according to claim 2, characterized in that, The weight ratio of the weather-resistant oxide additive to the passivating oxide additive is 1:(0.8-2).

5. The method for preparing the anti-corrosion and weather-resistant functional filler according to any one of claims 1-4, characterized in that, Includes the following steps: Using fly ash, water, pore-forming agent, oxide additive and glacial acetic acid as raw materials, a mesoporous oxide layer is coated on fly ash to obtain mesoporous oxide-fly ash filler; The oxide additives include weather-resistant oxide additives and passivating oxide additives. The weather-resistant oxide additives make the mesoporous oxide layer include titanium and / or zinc elements, and the passivating oxide additives make the mesoporous oxide layer include cerium and / or iron elements. Carbon-based mesoporous oxide-fly ash filler was obtained by loading carbon quantum dots onto the mesoporous oxide-fly ash filler using mesoporous oxide-fly ash filler, water, carbon-based compounds and carbon quantum dot dopants as raw materials. Carbon-based mesoporous oxide-fly ash filler is reacted with a chemical modifier to obtain a corrosion-resistant and weather-resistant filler.

6. The method for preparing the anti-corrosion and weather-resistant functional filler according to claim 5, characterized in that, Mesoporous oxide-fly ash filler was prepared by a one-pot calcination method. Specifically, fly ash, water, pore-forming agent, oxide additive and glacial acetic acid were mixed and ground to form a glue-like mixture. Then, calcination, ultrasonication, hydrothermal reaction, alcohol washing and drying were carried out to obtain the filler. And / or, when preparing mesoporous oxide-fly ash filler, the weight ratio of fly ash, water, pore-forming agent, oxide additive and glacial acetic acid is (5-15):(0.5-3.5):(2-7):(3-10):(2-8); And / or, when preparing carbon-based mesoporous oxide-fly ash filler, the weight ratio of mesoporous oxide-fly ash filler, carbon-based compound, water and carbon quantum dot dopant is (5-10):(2-3.5):(6-18):(1.2-3).

7. The method for preparing the anti-corrosion and weather-resistant functional filler according to claim 5, characterized in that, Carbon-based mesoporous oxide-fly ash filler was prepared by hydrothermal reaction at a temperature of 130-220℃.

8. The method for preparing the anti-corrosion and weather-resistant functional filler according to claim 5, characterized in that, Carbon-based mesoporous oxide-fly ash filler and chemical modifier are dispersed in an ethanol aqueous solution, stirred and mixed at 25-80℃, and then subjected to ultrasonication, filtration and drying to obtain corrosion-resistant and weather-resistant functional filler.

9. The method for preparing the anti-corrosion and weather-resistant functional filler according to claim 5, characterized in that, The weight ratio of the carbon-based mesoporous oxide-fly ash filler to the chemical modifier is (1-2):(0.5-1).

10. An anti-corrosion and weather-resistant coating, characterized in that, Includes the anti-corrosion and weather-resistant functional filler as described in any one of claims 1-4.

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