Nanometer tempering agent and preparation method thereof

Abstract

The application relates to the technical field of ceramicizing agents, in particular to a nano ceramicizing agent and a preparation method thereof. The nano ceramicizing agent is prepared from the following raw materials in parts by weight: 0.5-4 parts of a silane coupling agent, 0.4-4 parts of a titanate coupling agent, 1-10 parts of a zirconium salt, 3-5 parts of an alcohol solvent, 0.5-2 parts of nitric acid or a nitrate, 0.2-2 parts of modified nano clay, 0.01-0.03 parts of sodium hexametaphosphate, 1-5 parts of hydrogen peroxide, 0.1-0.5 parts of sodium lactate, and 60-80 parts of deionized water or tap water. The silane coupling agent and the titanate coupling agent are used as the basis of the ceramicizing agent, a protective film with good protection performance is formed on the metal surface, the zirconium salt chemically reacts with the metal base layer, so that a dense electrochemical protection passivation layer is formed on the metal surface, the adhesion of the film layer is improved, the use of fluorides is reduced through the addition of the modified nano clay, and the environmental protection performance of the product is further improved.

Description

Technical Field

[0001] This invention relates to the field of ceramic caustic agents, and more particularly to a nano-ceramic caustic agent and its preparation method. Background Technology

[0002] Traditional pretreatment processes for metal coating, especially steel, cast iron, and their alloys, include three parts: degreasing, rust removal, and phosphating, with phosphating being the central step. Phosphating is a process of chemical and electrochemical reactions to form a phosphate chemical conversion film, known as a phosphate film. The purpose of metal phosphating is primarily to provide protection for the base metal, preventing corrosion to a certain extent; it is also used as a pretreatment before painting to improve the adhesion and corrosion resistance of the paint film. However, phosphating solutions consist of phosphoric acid and phosphates, nitrates, heavy metal ions, and oxidants. Because they contain harmful substances such as heavy metal ions, they cause environmental pollution. Phosphates are classified as a Class II pollutant in China, with a Class I emission standard of less than 0.5 mg / L. Current research on metal coating pretreatment processes mainly focuses on improving quality, reducing environmental pollution, and saving energy.

[0003] In the applicant's earlier application, patent number 200910034639.0, entitled "Phosphorus-Free Film-Forming Agent and its Preparation Method," silane coupling agents and titanate coupling agents were used as the main organic components for film formation. The silane coupling agent undergoes hydrolysis in an aqueous system via its hydrolytic groups. The resulting active silanol groups are directionally aligned on the metal surface, forming Si-O-Me covalent bonds. Meanwhile, organic functional groups are orderly arranged on the outer side of the metal surface, undergoing cross-linking reactions with the organic polymers in the coating. The regular distribution of organic and inorganic functional groups on the metal surface forms a network structure, imparting excellent adhesion. In this invention, the titanate coupling agent undergoes hydrolysis in an aqueous system via its short-chain alkoxy groups. The resulting active silanol groups chemically bond with the metal surface to form a monolayer, achieving chemical coupling. This, combined with the effect of the silane coupling agent, creates a point-to-surface dual-linkage, resulting in strong adsorption. Simultaneously, under the action of the organic functional groups of the titanate coupling agent, it can chemically react with the organic materials of the subsequent coating to form a three-dimensional network structure with good adhesion. In particular, titanium has good anti-corrosion properties, so the monomolecular film formed by the titanate coupling agent has a special passivating chemical protection effect on the metal surface, providing corrosion and rust prevention. However, since this phosphorus-free film-forming agent contains a small amount of hydrofluoric acid and fluorine-containing compounds, fluoride ions are harmful to the human body. In order to further improve the environmental protection and safety performance of the product, we propose a nano-ceramic agent and its preparation method to solve the above problems. Summary of the Invention

[0004] The purpose of this invention is to address the shortcomings of existing technologies by proposing a nano-ceramic agent and its preparation method.

[0005] A nano-ceramic agent, the raw materials of which, by weight, include: 0.5-4 parts of silane coupling agent, 0.4-4 parts of titanate coupling agent, 1-10 parts of zirconium salt, 3-5 parts of alcohol solvent, 0.5-2 parts of nitric acid or nitrate, 0.2-2 parts of modified nano-clay, 0.01-0.03 parts of sodium hexametaphosphate, 1-5 parts of hydrogen peroxide, 0.1-0.5 parts of sodium lactate, and 60-80 parts of deionized water or tap water.

[0006] Preferably, the preparation method of modified nanoclay includes the following steps: adding nanoclay, glucose and deionized water into a hydrothermal reactor, and reacting hydrothermally at 180-200℃ for 4-12 hours. After the reaction is complete, the reaction solution is cooled to room temperature, filtered and washed, and the filter cake is collected and then dried. The dried filter cake is then activated, and the dried filter cake is placed in a crucible, phosphoric acid is added and mixed evenly. The crucible is then placed in a high-temperature furnace and calcined at 260-300℃ for 20-30 minutes. After cooling, the calcined product is washed and dried to obtain modified nanoclay.

[0007] Preferably, the mass ratio of nano-clay, glucose, and deionized water is 1:(0.05-0.2):(5-20); and the mass ratio of filter cake to phosphoric acid is 1:(1-2).

[0008] Preferably, the nano-clay is any one or a mixture of several of bentonite, lithium saponite, retto clay, zeolite powder and sepiolite powder.

[0009] Preferably, the reaction solution is stirred during the hydrothermal reaction process.

[0010] Preferably, after the hydrothermal reaction is complete, the filter cake is first washed 2-4 times with deionized water, and then washed 1-2 times with 95% ethanol solution.

[0011] Preferably, the zirconium salt is any one or a mixture of zirconium oxynitrate, zirconium chloride, zirconium nitrate and zirconium oxychloride.

[0012] Preferably, the alcohol solvent is any one or a mixture of several of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, and tripropylene glycol.

[0013] Preferably, a method for preparing a nano-ceramic agent includes the following steps: adding a silane coupling agent, a titanate coupling agent, modified nano-clay, sodium lactate, sodium hexametaphosphate, and an alcohol solvent to deionized water or tap water, mixing them evenly to obtain a semi-finished product A, wherein the amount of deionized water or tap water accounts for 55%-65% of the total water volume; adding zirconium salt and hydrogen peroxide to the remaining deionized water or tap water and stirring thoroughly until dissolved to obtain a semi-finished product B; when using, adding semi-finished product B to semi-finished product A and stirring thoroughly, adjusting the pH value of the mixed solution to between 4.5 and 6 with 0.5%-2% nitric acid or nitrate to obtain the nano-ceramic agent.

[0014] The beneficial effects of this invention are:

[0015] 1. This invention uses silane coupling agent and titanate coupling agent as the base of the passivating agent to form a protective film with good protective performance on the metal surface. Through the chemical reaction between zirconium salt and metal substrate, a dense electrochemical protective passivation layer can be formed on the metal surface, and the adhesion of the film layer can be improved.

[0016] 2. A small amount of modified nano-clay is added to this invention. The nano-clay can improve the mechanical strength of the protective film. During the preparation process, the modified nano-clay generates porous carbon and porous nano-clay. The porous carbon is uniformly attached to the porous nano-clay, which ultimately results in good adsorption of metal ions by the porous clay, reducing the corrosion of metal surfaces by free aluminum ions. The porous carbon has a good adsorption effect on organic components. During the application of the ceramic coating agent, after the water evaporates, a small amount of alcohol solvent can still be retained on the porous carbon, which improves the stability of the protective film around the modified nano-clay. The use of sodium hexametaphosphate improves the dispersion performance of the modified nano-clay, allowing the modified nano-clay to be uniformly distributed throughout the entire protective film, ensuring the stability of the entire protective film.

[0017] 3. In this invention, sodium lactate is added. Sodium lactate, in combination with water-based alcohol solvents such as ethylene glycol and propylene glycol, can further improve the stability of the protective film.

[0018] The nano-ceramic agent of this invention has good performance, reduces the use of fluorides, and further improves the environmental friendliness of the product. Detailed Implementation

[0019] The present invention will be further explained below with reference to specific embodiments.

[0020] In Example 1, a nano-ceramic agent is provided, and its raw materials include, by weight: 0.5 parts silane coupling agent, 0.4 parts titanate coupling agent, 1 part zirconium salt, 3 parts alcohol solvent, 0.5 parts nitric acid or nitrate, 0.2 parts modified nano-clay, 0.01 parts sodium hexametaphosphate, 1 part hydrogen peroxide, 0.1 parts sodium lactate, and 60 parts deionized water.

[0021] The preparation method of modified nanoclay includes the following steps: nanoclay, glucose and deionized water are added to a hydrothermal reactor and hydrothermally reacted at 180°C for 4 hours. After the reaction is completed, the reaction solution is cooled to room temperature, filtered and washed, and the filter cake is collected and then dried. The dried filter cake is activated and then placed in a crucible, phosphoric acid is added and mixed evenly. The crucible is then placed in a high-temperature furnace and calcined at 260°C for 20 minutes. After cooling, the calcined product is washed and dried to obtain modified nanoclay.

[0022] The mass ratio of nano-clay, glucose, and deionized water was 1:0.05:5; the mass ratio of filter cake to phosphoric acid was 1:1.

[0023] The nano-clay is bentonite.

[0024] During the hydrothermal reaction, the reaction solution is stirred.

[0025] After the hydrothermal reaction is complete, the filter cake is first washed twice with deionized water, and then washed once with 95% ethanol solution.

[0026] The zirconium salt is zirconium oxynitrate.

[0027] The alcohol solvent is ethylene glycol.

[0028] A method for preparing a nano-ceramic agent includes the following steps: adding a silane coupling agent, a titanate coupling agent, modified nano-clay, sodium lactate, sodium hexametaphosphate, and an alcohol solvent to deionized water and mixing them evenly to obtain a semi-finished product A, wherein the amount of deionized water accounts for 55% of the total water volume; adding zirconium salt and hydrogen peroxide to the remaining deionized water and stirring thoroughly until dissolved to obtain a semi-finished product B; when using, adding semi-finished product B to semi-finished product A and stirring thoroughly, adjusting the pH value of the mixed solution to between 4.5 and 6 with 0.5% nitric acid or nitrate to obtain the nano-ceramic agent.

[0029] In Example 2, a nano-ceramic agent is provided, and its raw materials by weight include: 4 parts silane coupling agent, 4 parts titanate coupling agent, 10 parts zirconium salt, 5 parts alcohol solvent, 2 parts nitric acid or nitrate, 2 parts modified nano-clay, 0.03 parts sodium hexametaphosphate, 5 parts hydrogen peroxide, 0.5 parts sodium lactate, and 80 parts tap water.

[0030] The preparation method of modified nanoclay includes the following steps: nanoclay, glucose and deionized water are added to a hydrothermal reactor and hydrothermally reacted at 200°C for 12 hours. After the reaction is completed, the reaction solution is cooled to room temperature, filtered and washed, and the filter cake is collected and then dried. The dried filter cake is then activated. The dried filter cake is placed in a crucible, phosphoric acid is added and mixed evenly. The crucible is then placed in a high-temperature furnace and calcined at 300°C for 30 minutes. After cooling, the calcined product is washed and dried to obtain modified nanoclay.

[0031] The mass ratio of nano-clay, glucose, and deionized water was 1:0.2:20; the mass ratio of filter cake to phosphoric acid was 1:2.

[0032] The nano-clay is lithium saponin.

[0033] During the hydrothermal reaction, the reaction solution is stirred.

[0034] After the hydrothermal reaction is complete, the filter cake is first washed four times with deionized water, and then washed twice with 95% ethanol solution.

[0035] The zirconium salt is zirconium chloride.

[0036] The alcohol solvent is a mixture of diethylene glycol and triethylene glycol in a volume ratio of 1:1.

[0037] A method for preparing a nano-ceramic agent includes the following steps: adding a silane coupling agent, a titanate coupling agent, modified nano-clay, sodium lactate, sodium hexametaphosphate, and an alcohol solvent to tap water and mixing them evenly to obtain a semi-finished product A, wherein the amount of tap water used accounts for 65% of the total water volume; adding zirconium salt and hydrogen peroxide to the remaining tap water and stirring thoroughly until dissolved to obtain a semi-finished product B; when using, adding semi-finished product B to semi-finished product A and stirring thoroughly, and adjusting the pH value of the mixed solution to between 4.5 and 6 with 2% nitric acid or nitrate to obtain the nano-ceramic agent.

[0038] In Example 3, a nano-ceramic agent is provided, and its raw materials include, by weight: 2 parts silane coupling agent, 2 parts titanate coupling agent, 6 parts zirconium salt, 4 parts alcohol solvent, 1.5 parts nitric acid or nitrate, 1.5 parts modified nano-clay, 0.02 parts sodium hexametaphosphate, 4 parts hydrogen peroxide, 0.4 parts sodium lactate, and 70 parts deionized water.

[0039] The preparation method of modified nanoclay includes the following steps: nanoclay, glucose and deionized water are added to a hydrothermal reactor and hydrothermally reacted at 190°C for 10 hours. After the reaction is completed, the reaction solution is cooled to room temperature, filtered and washed, and the filter cake is collected and then dried. The dried filter cake is activated and then placed in a crucible, phosphoric acid is added and mixed evenly. The crucible is then placed in a high-temperature furnace and calcined at 280°C for 25 minutes. After cooling, the calcined product is washed and dried to obtain modified nanoclay.

[0040] The mass ratio of nano-clay, glucose, and deionized water was 1:0.1:15; the mass ratio of filter cake to phosphoric acid was 1:1.5.

[0041] The nano-clay is a mixture of zeolite powder and sepiolite powder in a mass ratio of 1:1.

[0042] During the hydrothermal reaction, the reaction solution is stirred.

[0043] After the hydrothermal reaction is complete, the filter cake is first washed three times with deionized water, and then washed twice with 95% ethanol solution.

[0044] The zirconium salt is a mixture of zirconium chloride and zirconium nitrate in a mass ratio of 1:1.

[0045] The alcohol solvent is a mixture of propylene glycol, dipropylene glycol and tripropylene glycol in a volume ratio of 1:1:1.

[0046] A method for preparing a nano-ceramic agent includes the following steps: adding a silane coupling agent, a titanate coupling agent, modified nano-clay, sodium lactate, sodium hexametaphosphate, and an alcohol solvent to deionized water and mixing them evenly to obtain a semi-finished product A, wherein the amount of deionized water accounts for 60% of the total water volume; adding zirconium salt and hydrogen peroxide to the remaining deionized water and stirring thoroughly until dissolved to obtain a semi-finished product B; when using, adding semi-finished product B to semi-finished product A and stirring thoroughly, and adjusting the pH value of the mixed solution to between 4.5 and 6 with 1% nitric acid or nitrate to obtain the nano-ceramic agent.

[0047] In Example 4, a nano-ceramic agent is provided, and its raw materials by weight include: 2 parts silane coupling agent, 2 parts titanate coupling agent, 6 parts zirconium salt, 4 parts alcohol solvent, 1.5 parts nitric acid or nitrate, 1.5 parts modified nano-clay, 0.02 parts sodium hexametaphosphate, 4 parts hydrogen peroxide, 0.4 parts sodium lactate, and 70 parts deionized water.

[0048] The preparation method of modified nanoclay includes the following steps: nanoclay, glucose and deionized water are added to a hydrothermal reactor and hydrothermally reacted at 200°C for 12 hours. After the reaction is completed, the reaction solution is cooled to room temperature, filtered and washed, and the filter cake is collected and then dried. The dried filter cake is then activated. The dried filter cake is placed in a crucible, phosphoric acid is added and mixed evenly. The crucible is then placed in a high-temperature furnace and calcined at 300°C for 30 minutes. After cooling, the calcined product is washed and dried to obtain modified nanoclay.

[0049] The mass ratio of nano-clay, glucose, and deionized water was 1:0.1:15; the mass ratio of filter cake to phosphoric acid was 1:1.5.

[0050] The nano-clay is retto clay.

[0051] During the hydrothermal reaction, the reaction solution is stirred.

[0052] After the hydrothermal reaction is complete, the filter cake is first washed three times with deionized water, and then washed twice with 95% ethanol solution.

[0053] The zirconium salt is zirconium oxychloride.

[0054] The alcohol solvent is propylene glycol.

[0055] A method for preparing a nano-ceramic agent includes the following steps: adding a silane coupling agent, a titanate coupling agent, modified nano-clay, sodium lactate, sodium hexametaphosphate, and an alcohol solvent to deionized water and mixing them evenly to obtain a semi-finished product A, wherein the amount of deionized water accounts for 65% of the total water volume; adding zirconium salt and hydrogen peroxide to the remaining deionized water and stirring thoroughly until dissolved to obtain a semi-finished product B; when using, adding semi-finished product B to semi-finished product A and stirring thoroughly, and adjusting the pH value of the mixed solution to between 4.5 and 6 with 1% nitric acid or nitrate to obtain the nano-ceramic agent.

[0056] In Example 5, a nano-ceramic agent is provided, and its raw materials include, by weight: 2 parts silane coupling agent, 2 parts titanate coupling agent, 6 parts zirconium salt, 4 parts alcohol solvent, 1.5 parts nitric acid or nitrate, 1.5 parts modified nano-clay, 0.02 parts sodium hexametaphosphate, 4 parts hydrogen peroxide, 0.4 parts sodium lactate, and 70 parts deionized water.

[0057] The preparation method of modified nanoclay includes the following steps: nanoclay, glucose and deionized water are added to a hydrothermal reactor and hydrothermally reacted at 180°C for 4 hours. After the reaction is completed, the reaction solution is cooled to room temperature, filtered and washed, and the filter cake is collected and then dried. The dried filter cake is activated and then placed in a crucible, phosphoric acid is added and mixed evenly. The crucible is then placed in a high-temperature furnace and calcined at 260°C for 20 minutes. After cooling, the calcined product is washed and dried to obtain modified nanoclay.

[0058] The mass ratio of nano-clay, glucose, and deionized water was 1:0.1:15; the mass ratio of filter cake to phosphoric acid was 1:1.5.

[0059] The nano-clay is zeolite powder.

[0060] During the hydrothermal reaction, the reaction solution is stirred.

[0061] After the hydrothermal reaction is complete, the filter cake is first washed three times with deionized water, and then washed twice with 95% ethanol solution.

[0062] The zirconium salt is a mixture of zirconium chloride and zirconium oxychloride in a mass ratio of 1:1.

[0063] The alcohol solvent is a mixture of propylene glycol and dipropylene glycol in a volume ratio of 1:1.

[0064] A method for preparing a nano-ceramic agent includes the following steps: adding a silane coupling agent, a titanate coupling agent, modified nano-clay, sodium lactate, sodium hexametaphosphate, and an alcohol solvent to deionized water and mixing them evenly to obtain a semi-finished product A, wherein the amount of deionized water accounts for 55% of the total water volume; adding zirconium salt and hydrogen peroxide to the remaining deionized water and stirring thoroughly until dissolved to obtain a semi-finished product B; when using, adding semi-finished product B to semi-finished product A and stirring thoroughly, adjusting the pH value of the mixed solution to between 4.5 and 6 with 1% nitric acid or nitrate to obtain the nano-ceramic agent.

[0065] In Examples 1-5, this invention uses silane coupling agents and titanate coupling agents as the basis for coating agents. The silane coupling agent undergoes hydrolysis in an aqueous system through its hydrolytic groups. The resulting active silanol groups are directionally aligned on the metal surface, forming Si-O-Me covalent bonds with the metal surface. Meanwhile, the organic functional groups are orderly arranged on the outer side of the metal surface, undergoing a cross-linking reaction with the organic polymer in the coating. The regular distribution of organic and inorganic functional groups on the metal surface forms a network structure, imparting excellent adhesion. The titanate coupling agent of this invention undergoes hydrolysis in an aqueous system through its short-chain alkoxy groups. The resulting active silanol groups chemically bond with the metal surface to form a monolayer, achieving chemical coupling. This, combined with the effect of the silane coupling agent, creates a dual point-to-surface bonding, resulting in strong adsorption. Meanwhile, under the action of the organic functional groups of the titanate coupling agent, it can chemically react with the organic matter of the subsequent coating to form a three-dimensional network structure, which has good adhesion. In particular, titanium has good anti-corrosion properties, so the monomolecular film formed by the titanate coupling agent has a special passivation chemical protection effect on the metal surface, providing the film with anti-corrosion and anti-rust properties.

[0066] This invention utilizes the chemical reaction between zirconium salt and metal substrate to form a dense electrochemical protective passivation layer on the metal surface. The zirconium oxide composite film can fill the organic and inorganic network structure, thus further improving the anti-corrosion performance of the film. At the same time, due to the chemical bonding, the adhesion of the film is also greatly improved.

[0067] This invention incorporates a small amount of modified nanoclay, which enhances the mechanical strength of the protective film. During preparation, the modified nanoclay generates porous carbon and porous nanoclay, allowing the porous carbon to adhere uniformly to the porous nanoclay. During the hydrothermal reaction, glucose is carbonized and uniformly adhered to the surface of the nanoclay. During calcination, phosphoric acid expands the pores of both the carbon and nanoclay, improving their adsorption performance and generating porous carbon and porous nanoclay. Furthermore, phosphoric acid oxidizes the porous carbon, enhancing its adsorption capacity. The increased carbon oxide content enhances the adsorption performance of porous carbon for alcohol solvents, ultimately resulting in better adsorption of metal ions by porous clay and reducing the corrosion of metal surfaces by free aluminum ions. Porous carbon also exhibits good adsorption of organic components. During the application of the ceramic coating agent, even after the moisture evaporates, a small amount of alcohol solvent remains on the porous carbon, improving the stability of the protective film surrounding the modified nanoclay. The use of sodium hexametaphosphate improves the dispersion performance of the modified nanoclay, allowing it to be evenly distributed throughout the protective film, ensuring the overall stability of the protective film.

[0068] In this invention, sodium lactate is added. Sodium lactate, in combination with water-based alcohol solvents such as ethylene glycol and propylene glycol, can further improve the stability of the protective film.

[0069] The hydrogen peroxide-based oxidant of this invention can oxidize excess ferrous ions generated during solution use, converting them into precipitates, thus ensuring the performance stability of the membrane. In use, the pH of this invention is adjusted using nitric acid and nitrates, which stabilizes the acidity of the solution and also acts as an oxidant and passivating agent.

[0070] The nano-ceramic agent of this invention has good performance, reduces the use of fluorides, and further improves the environmental friendliness of the product.

[0071] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. A nano-ceramic agent, characterized in that, The raw materials, by weight, include: 0.5-4 parts silane coupling agent, 0.4-4 parts titanate coupling agent, 1-10 parts zirconium salt, 3-5 parts alcohol solvent, 0.5-2 parts nitric acid or nitrate, 0.2-2 parts modified nano-clay, 0.01-0.03 parts sodium hexametaphosphate, 1-5 parts hydrogen peroxide, 0.1-0.5 parts sodium lactate, and 60-80 parts deionized water or tap water; The preparation method of the modified nano-clay includes the following steps: adding nano-clay, glucose and deionized water into a hydrothermal reactor, and reacting hydrothermally at 180-200℃ for 4-12 hours. After the reaction is complete, the reaction solution is cooled to room temperature, filtered and washed, and the filter cake is collected and then dried. The dried filter cake is then activated by placing it in a crucible, adding phosphoric acid, mixing it evenly, and then placing the crucible in a high-temperature furnace and calcining it at 260-300℃ for 20-30 minutes. After cooling, the calcined product is washed and dried to obtain the modified nano-clay. The mass ratio of nano-clay, glucose, and deionized water is 1:(0.05-0.2):(5-20); the mass ratio of filter cake to phosphoric acid is 1:(1-2). The alcohol solvent is any one or a mixture of several of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, and tripropylene glycol.

2. The nano-ceramic agent according to claim 1, characterized in that, The nano-clay is any one or a mixture of several of bentonite, lithium saponite, retto clay, zeolite powder, and sepiolite powder.

3. The nano-ceramic agent according to claim 1, characterized in that, During the hydrothermal reaction, the reaction solution is stirred.

4. The nano-ceramic agent according to claim 1, characterized in that, After the hydrothermal reaction is complete, the filter cake is first washed 2-4 times with deionized water, and then washed 1-2 times with 95% ethanol solution.

5. A nano-ceramic agent according to any one of claims 2-4, characterized in that, The zirconium salt is any one or a mixture of zirconium oxynitrate, zirconium chloride, zirconium nitrate and zirconium oxychloride.

6. The method for preparing a nano-ceramic agent according to claim 5, characterized in that, The process includes the following steps: adding silane coupling agent, titanate coupling agent, modified nano-clay, sodium lactate, sodium hexametaphosphate, and alcohol solvent to deionized water or tap water, mixing thoroughly to obtain semi-finished product A, with deionized water or tap water accounting for 55%-65% of the total water volume; adding zirconium salt and hydrogen peroxide to the remaining deionized water or tap water and stirring thoroughly until dissolved to obtain semi-finished product B; when using, adding semi-finished product B to semi-finished product A and stirring thoroughly, adjusting the pH of the mixed solution to between 4.5 and 6 with 0.5%-2% nitric acid or nitrate to obtain the nano-ceramic agent.