A metal silane composite ceramicizing agent and its preparation method

Abstract

The present invention relates to the technical field of metal surface treatment, and discloses a metal silane composite ceramic and a preparation method thereof. The composite ceramic comprises the following components by mass fraction: 2-10% of a fluorozirconate compound, 0.5-2% of a complexing agent, 1-5% of a silane coupling agent, 0.1-0.5% of a hydrolysis stabilizer, 5-8% of a film-forming aid A, 0.01-0.5% of a film-forming aid B, 3-10% of anhydrous alcohol, and the balance being water. The fluorozirconate crystals and Si-O-Si film formed by hydrolysis in the composite ceramic of the present invention can increase the density of the surface film, thereby effectively improving the corrosion resistance of the metal; the added film-forming aid A can not only facilitate adhesion and film formation, better filling the gaps between the fluorozirconate crystals, but also improve the electron transfer rate, greatly increasing the timeliness of corrosion resistance. The surface film formed by the film-forming aid A and the film-forming aid B after cooperation has better density and better corrosion resistance.

Description

Technical Field

[0001] The present invention relates to the technical field of metal surface treatment, in particular to a metal silane composite ceramic agent and a preparation method thereof. Background Art

[0002] Metals typically undergo pretreatment before painting. After degreasing and rust removal, a chemical conversion film is formed on the surface. This conversion film has a certain degree of corrosion resistance, preventing rust from forming in the short period before spraying. It also increases the roughness of the metal surface and strengthens the adhesion between the paint and the substrate. Most of the pretreatment processes used are phosphating, but with the continuous advancement of energy conservation and emission reduction, ceramic coating is gradually replacing phosphating.

[0003] The ceramics used in the ceramic process typically include zirconium and zirconium-titanium based agents. Through reaction, they form a corrosion-resistant zirconium oxide film on the surface of the metal workpiece, thereby passivating the metal workpiece surface. Zirconium-based treatment agents not only offer irreplaceable advantages over phosphating technology, such as environmental protection, energy saving, ease of operation, and low cost, but also easily integrate well with various subsequent treatment methods such as powder coating, electrophoresis, and painting, and can simultaneously treat multiple substrates on a single workpiece. For example, patent application WO2017214992A1 discloses a ceramic, a metal part, and a ceramic treatment method. The ceramic is used for surface pretreatment of metal parts and comprises, per 1000 parts by weight, the following components in parts by weight: 10-40 parts fluorozirconic acid, 3-10 parts ammonium fluorotitanate, 5-20 parts sodium molybdate, 1-4 parts fluoroboric acid, 2-10 parts nitric acid solution, and the balance water. However, the surface film formed on the metal typically has poor corrosion resistance and adhesion, resulting in rapid rust recurrence and a short-lived corrosion resistance. Summary of the Invention

[0004] In order to solve the above technical problems, the present invention provides a metal silane composite ceramic agent and a preparation method thereof. By introducing a fluorozirconic acid or fluorozirconate system and a silane film, the density of the surface film is increased, thereby effectively improving the corrosion resistance of the metal and effectively extending the corrosion resistance time.

[0005] The purpose of the present invention is achieved through the following technical solutions:

[0006] In a first aspect, the present invention provides a metal silane composite ceramic agent, wherein the composite ceramic agent comprises the following components by mass fraction:

[0007]

[0008]

[0009] The present invention introduces fluorozirconic acid or fluorozirconate system, and the fluorozirconate ion is hydrolyzed to produce ZrF6- At the same time, the introduction of hydrogen ions continuously corrodes the metal surface, producing metal ions; the fluorozirconate ions combine with the metal ions and continuously accumulate on the metal surface to form fluorozirconate precipitates, thereby forming a ceramic film. Silane is hydrolyzed to produce silanols, and the condensation reaction between the silanol groups forms a silane film with a Si-O-Si three-dimensional network structure on the metal surface. Fluorozirconate crystals have a prismatic structure, and the Si-O-Si film has a spherical structure, which effectively fills the gaps between the fluorozirconate crystals and increases the density of the surface film, thereby effectively improving the corrosion resistance of the metal. In addition, the addition of film-forming aids A and B helps to enhance the film-forming effect of the ceramic. The surface film formed by the cooperation of the two has a better density and better corrosion resistance.

[0010] Preferably, the preparation method of the film-forming aid A comprises the following steps:

[0011] (1) mixing ferric sulfate, manganese sulfate, triethanolamine borate, triethanolamine oleate, sodium hydroxide, and water, ball-milling the mixture, and then sieving the mixture to obtain modified ferromanganese sulfate;

[0012] (2) adding modified manganese iron sulfate and naringin to a mixed solution of ethanol and acetone, adding 3-hexenal, dicumyl peroxide and glacial acetic acid while heating and stirring under nitrogen, and heating and refluxing to react;

[0013] (3) After the reaction is completed, the product is rotary evaporated and dried, and guar gum powder and water are added to the mixture and ball milled to obtain film-forming aid A.

[0014] Guar gum has good water solubility and can be fully hydrated in aqueous solution to form a viscous liquid. Therefore, it can be used as a thickener in the ceramic process. It can not only maintain good fluidity, but also help to form adhesion films and fix the fluorozirconate precipitation on the metal surface. It can also better fill the gaps between fluorozirconate crystals, increase the density of the ceramic film, and thus enhance the corrosion resistance.

[0015] Furthermore, the addition of ferromanganese sulfate as a metallic element improves the electron transfer rate and interacts with the metallic elements in film-forming aid B, significantly enhancing the long-term corrosion resistance. Modification of the ferromanganese sulfate surface with triethanolamine borate and triethanolamine oleate enhances its dispersibility and binding within the film-forming aid components. Furthermore, triethanolamine borate and triethanolamine oleate are also excellent rust and corrosion inhibitors, further enhancing corrosion resistance. Their combination allows for a more effective film formation on the ferromanganese sulfate surface. Triethanolamine oleate is grafted onto naringin via a 3-hexenal reaction. Naringin, rich in phenolic hydroxyl and carbonyl groups, forms strong hydrogen bonds with macromolecular components of guar gum, such as polysaccharides and proteins. These interactions enhance stability and binding, and also improve the dispersion of ferromanganese sulfate in the ceramic. Furthermore, naringin is weakly acidic, and the lowered pH upon hydrolysis helps maintain the guar gum in an acidic microenvironment, reducing viscosity and increasing fluidity, thereby enhancing film formation.

[0016] Preferably, in step (1), the mass ratio of the ferric sulfate, manganese sulfate, triethanolamine borate, triethanolamine oleate, sodium hydroxide and water is 7-8:2-4:2-3:6-7:0.05-0.1:10; in step (3), the mass ratio of the product, guar gum powder and water is 1:0.3-0.4:10; the rotation speed of the mixing ball mill is 200-300 r / min, and the time is 30-40 min.

[0017] Preferably, in step (2), the mass volume ratio of the modified manganese iron sulfate, naringin and the mixed solution is 3-5 g:8-10 g:50 mL; the volume ratio of ethanol and acetone is 1:1-2; the mass volume ratio of 3-hexenal, dicumyl peroxide, glacial acetic acid and the mixed solution is 1.5-2 g:0.2-0.4 g:10 mL:50 mL; and the heating reflux reaction time is 1-3 h.

[0018] Preferably, the fluorozirconate compound is one or more of fluorozirconic acid, ammonium fluorozirconate, potassium fluorozirconate, and sodium fluorozirconate; and the silane coupling agent is one or more of KH550 (γ-aminopropyltriethoxysilane), KH560 (3-(2,3-epoxypropyl)propyltrimethoxysilane), and KH792 (γ-aminopropyltrimethoxysilane).

[0019] Preferably, the complexing agent is one or more of glycine, oxalic acid, acetic acid, and tartaric acid; the hydrolysis stabilizer is one or more of glycerol and ethylene glycol; and the film-forming aid B is one or more of zirconium nitrate, zirconyl nitrate, and zirconium oxychloride.

[0020] Preferably, the composite ceramic further comprises 0.5-2% of a sealing agent by mass; the sealing agent is one or more of monoethanolamine borate, diethanolamine borate, triethanolamine borate, triethanolamine, and thiourea.

[0021] Preferably, the composite ceramic agent further comprises 0.5-2% of a buffer by mass; the buffer is one or more of ammonium acetate, ammonium carbonate, and ammonium bicarbonate.

[0022] Preferably, the composite ceramic agent further comprises 0.01-0.5% of a penetrant by mass; the penetrant is one or more of JFC and OP-10.

[0023] In a second aspect, the present invention further provides a method for preparing a metal silane composite ceramic agent, comprising the following steps:

[0024] Step 1: Add a silane coupling agent, anhydrous alcohol, and a hydrolysis stabilizer to water, and continue stirring for 4 to 20 hours to obtain a first solution;

[0025] Step 2: Add the fluorozirconate compound into water and stir until dissolved to obtain a second solution;

[0026] Step 3: Add film-forming aid A to water, adjust the pH to 4-4.5, add film-forming aid B and stir evenly to obtain a third solution;

[0027] Step 4: Mix the third solution and the second solution and stir evenly, then add the complexing agent, blocking agent, buffer, first solution, and penetrant in sequence and stir evenly, and add the balance of water to obtain a metal silane composite ceramic agent.

[0028] The preparation method of the present invention first hydrolyzes the silane coupling agent to generate silanol groups to prepare a first solution for standby use, and then hydrolyzes the fluorozirconate ions to generate ZrF6 - , to obtain a second solution. Subsequently, film-forming aids A and B are mixed to obtain a third solution. The guar gum in film-forming aid A can form a viscous solution in an aqueous solution. By adjusting the appropriate pH value, the appropriate viscosity can be adjusted, so that while maintaining good fluidity, it can also maintain a good thickening effect, achieving better fixation and filling of fluorozirconate crystals, and improving the fixation and density of the surface film. The third solution and the second solution are then mixed and stirred evenly, and then a complexing agent, a sealing agent, a buffer, the first solution, and a penetrant are added in sequence and stirred evenly, and the balance of water is supplemented to obtain a metal silane composite ceramic. The order of adding ingredients in the preparation method of the present invention will affect the final film-forming effect and the timeliness of the anti-corrosion.

[0029] Preferably, the ratio of the amount of water added in step one, the amount of water added in step two, the amount of water added in step three and the remaining water in step four to the total mass of water is 10-15%:50%:20-25%:10-20%.

[0030] Compared with the prior art, the present invention has the following beneficial effects:

[0031] (1) The fluorozirconate crystals formed by the hydrolysis of the fluorozirconate compound have a prismatic structure, and the Si-O-Si film formed by the hydrolysis of silane has a spherical structure, which fills the gaps between the fluorozirconate crystals and increases the density of the surface film, thereby effectively improving the corrosion resistance of the metal;

[0032] (2) Film-forming aid A not only acts as a thickener, maintaining good fluidity while facilitating adhesion film formation and fixation of fluorozirconate precipitation on the metal surface, but also better fills the gaps between fluorozirconate crystals, increases the density of the ceramic film, and thus enhances corrosion resistance. Moreover, the added metal elements can improve the electron transfer rate, greatly increasing the timeliness of corrosion resistance.

[0033] (3) The addition of film-forming aids A and B helps to improve the film-forming effect of the ceramic agent. The surface film formed by the two agents working together has better density and better corrosion resistance.

[0034] (4) The sequence of steps and condition parameters in the ceramic preparation method help to achieve better film-forming effects and further improve the timeliness of corrosion protection. DETAILED DESCRIPTION

[0035] The technical solutions of the present invention are described below with specific embodiments, but the protection scope of the present invention is not limited thereto:

[0036] Overall embodiment

[0037] A metal silane composite ceramic agent, comprising the following components by mass fraction: (as shown in Table 1)

[0038] Table 1

[0039]

[0040] The fluorozirconate compound is one or more of fluorozirconic acid, ammonium fluorozirconate, potassium fluorozirconate, and sodium fluorozirconate. The silane coupling agent is one or more of KH550, KH560, and KH792. The complexing agent is one or more of glycine, oxalic acid, acetic acid, and tartaric acid. The hydrolysis stabilizer is one or more of glycerol and ethylene glycol. The film-forming aid B is one or more of zirconium nitrate, zirconyl nitrate, and zirconium oxychloride. The blocking agent is one or more of monoethanolamine borate, diethanolamine borate, triethanolamine borate, triethanolamine, and thiourea. The buffer is one or more of ammonium acetate, ammonium carbonate, and ammonium bicarbonate. The penetrant is one or more of JFC and OP-10.

[0041] The preparation method of film-forming aid A comprises the following steps:

[0042] (1) mixing ferric sulfate, manganese sulfate, triethanolamine borate, triethanolamine oleate, sodium hydroxide, and water, and then ball milling the mixture, wherein the mass ratio of ferric sulfate, manganese sulfate, triethanolamine borate, triethanolamine oleate, sodium hydroxide, and water is 7-8:2-4:2-3:6-7:0.05-0.1:10, and then sieving to obtain modified ferromanganese sulfate, wherein the mesh size of the obtained modified ferromanganese sulfate is 100-300 mesh;

[0043] (2) adding modified ferromanganese sulfate and naringin to a mixed solution of ethanol and acetone, wherein the mass volume ratio of modified ferromanganese sulfate, naringin and the mixed solution is 3-5 g:8-10 g:50 mL; the volume ratio of ethanol and acetone is 1:1-2, heating to 40-45°C under nitrogen and stirring, while adding 3-hexenal, diisopropylbenzene peroxide and glacial acetic acid, wherein the mass volume ratio of 3-hexenal, diisopropylbenzene peroxide, glacial acetic acid and the mixed solution is 1.5-2 g:0.2-0.4 g:10 mL:50 mL, heating and reflux for 1-3 hours;

[0044] (3) After the reaction is completed, the product is rotary evaporated and dried, and guar gum powder and water are added to the obtained product and mixed and ball-milled. The mass ratio of the product, guar gum powder and water is 1:0.3-0.4:10, and the speed of the mixed ball mill is 200-300 r / min, and the time is 30-40 min to obtain film-forming aid A.

[0045] The preparation method of the metal silane composite ceramic agent comprises the following steps:

[0046] Step 1: Add a silane coupling agent, anhydrous alcohol, and a hydrolysis stabilizer to water, and continue stirring for 4 to 20 hours to obtain a first solution;

[0047] Step 2: Add the fluorozirconate compound into water and stir until dissolved to obtain a second solution;

[0048] Step 3: Add film-forming aid A to water, adjust the pH to 4-4.5, add film-forming aid B and stir evenly to obtain a third solution;

[0049] Step 4: Mix the third solution and the second solution and stir evenly, then add the complexing agent, blocking agent, buffer, first solution, and penetrant in sequence and stir evenly, and add the balance of water to obtain a metal silane composite ceramic agent.

[0050] The ratio of the amount of water added in step 1, the amount of water added in step 2, the amount of water added in step 3 and the remaining water in step 4 to the total mass of water is 10-15%: 50%: 20-25%: 10-20%.

[0051] Example 1

[0052] A metal silane composite ceramic agent, comprising the following components by mass fraction: (as shown in Table 2)

[0053] Table 2

[0054]

[0055]

[0056] The preparation method of film-forming aid A comprises the following steps:

[0057] (1) Iron sulfate, manganese sulfate, triethanolamine borate, triethanolamine oleate, sodium hydroxide, and water in a mass ratio of 7:3:2:7:0.07:10 were mixed and ball-milled, and then sieved to obtain modified manganese ferrosulfate, wherein the mesh size of the obtained modified manganese ferrosulfate was 100-300 mesh;

[0058] (2) Modified manganese ferrosulfate and naringin were added to a mixed solution of ethanol and acetone in a volume ratio of 1:2, wherein the mass volume ratio of modified manganese ferrosulfate, naringin and the mixed solution was 5 g:10 g:50 mL, and 3-hexenal, diisopropylbenzene peroxide and glacial acetic acid were added while heating to 45°C under nitrogen and stirring, wherein the mass volume ratio of 3-hexenal, diisopropylbenzene peroxide, glacial acetic acid and the mixed solution was 1.5 g:0.3 g:10 mL:50 mL, and the temperature was raised to reflux for 3 h;

[0059] (3) After the reaction is completed, the mixture is rotary evaporated and dried, and the obtained product, guar gum powder, and water are mixed and ball-milled in a mass ratio of 1:0.4:10 at a speed of 300 r / min for 35 min to obtain film-forming aid A.

[0060] The preparation method of the metal silane composite ceramic agent comprises the following steps:

[0061] Step 1: Add a silane coupling agent, anhydrous alcohol, and a hydrolysis stabilizer to water (accounting for 15% of the total mass of water) and continue stirring for 14 hours to obtain a first solution;

[0062] Step 2: Add the fluorozirconate compound to water (accounting for 50% of the total mass of water) and stir until dissolved to obtain a second solution;

[0063] Step 3: Add film-forming aid A to water (accounting for 25% of the total mass of water), adjust the pH to 4, add film-forming aid B and stir evenly to obtain a third solution;

[0064] Step 4: Mix the third solution and the second solution and stir evenly, then add the complexing agent, blocking agent, buffer, first solution, and penetrant in sequence and stir evenly, and add the balance water (accounting for 10% of the total mass of water) to obtain a metal silane composite ceramic agent.

[0065] Example 2

[0066] A metal silane composite ceramic agent, comprising the following components by mass fraction: (as shown in Table 3)

[0067] Table 3

[0068]

[0069] The preparation method of film-forming aid A comprises the following steps:

[0070] (1) Iron sulfate, manganese sulfate, triethanolamine borate, triethanolamine oleate, sodium hydroxide, and water in a mass ratio of 7:4:3:7:0.05:10 were mixed and ball-milled, and then sieved to obtain modified manganese ferrosulfate, wherein the mesh size of the modified manganese ferrosulfate was 100 to 300 meshes;

[0071] (2) Modified manganese ferrosulfate and naringin were added to a mixed solution of ethanol and acetone in a volume ratio of 1:2, wherein the mass volume ratio of modified manganese ferrosulfate, naringin and the mixed solution was 3 g:8 g:50 mL, and while heating to 40 ° C under nitrogen and stirring, 3-hexenal, diisopropylbenzene peroxide and glacial acetic acid were added, wherein the mass volume ratio of 3-hexenal, diisopropylbenzene peroxide, glacial acetic acid and the mixed solution was 2 g:0.3 g:10 mL:50 mL, and the temperature was raised to reflux for 2 h;

[0072] (3) After the reaction is completed, the product is rotary evaporated and dried, and the obtained product, guar gum powder, and water are mixed and ball-milled in a mass ratio of 1:0.35:10 at a speed of 250 r / min for 40 min to obtain film-forming aid A.

[0073] The preparation method of the metal silane composite ceramic agent comprises the following steps:

[0074] Step 1: Add a silane coupling agent, anhydrous alcohol, and a hydrolysis stabilizer to water (accounting for 15% of the total mass of water) and continue stirring for 18 hours to obtain a first solution;

[0075] Step 2: Add the fluorozirconate compound to water (accounting for 50% of the total mass of water) and stir until dissolved to obtain a second solution;

[0076] Step 3: Add film-forming aid A to water (accounting for 22% of the total mass of water), adjust the pH to 4.5, add film-forming aid B and stir evenly to obtain a third solution;

[0077] Step 4: Mix the third solution and the second solution and stir evenly, then add the complexing agent, blocking agent, buffer, first solution, and penetrant in sequence and stir evenly, and add the balance water (accounting for 13% of the total mass of water) to obtain a metal silane composite ceramic agent.

[0078] Example 3

[0079] A metal silane composite ceramic agent, comprising the following components by mass fraction: (as shown in Table 4)

[0080] Table 4

[0081]

[0082] The preparation method of film-forming aid A comprises the following steps:

[0083] (1) Iron sulfate, manganese sulfate, triethanolamine borate, triethanolamine oleate, sodium hydroxide, and water in a mass ratio of 8:3:3:6:0.05:10 were mixed and ball-milled, and then sieved to obtain modified manganese ferrosulfate, wherein the mesh size of the obtained modified manganese ferrosulfate was 100-300 mesh;

[0084] (2) adding modified ferromanganese sulfate and naringin to a mixed solution of ethanol and acetone in a volume ratio of 1:1, wherein the mass volume ratio of modified ferromanganese sulfate, naringin and the mixed solution is 4 g:10 g:50 mL, heating to 45 ° C under nitrogen conditions and stirring, while adding 3-hexenal, diisopropylbenzene peroxide and glacial acetic acid, wherein the mass volume ratio of 3-hexenal, diisopropylbenzene peroxide, glacial acetic acid and the mixed solution is 1.7 g:0.3 g:10 mL:50 mL, and heating and reflux for 3 hours;

[0085] (3) After the reaction is completed, the mixture is rotary evaporated and dried, and the obtained product, guar gum powder, and water are mixed and ball-milled in a mass ratio of 1:0.4:10 at a speed of 200 / min for 40 min to obtain film-forming aid A.

[0086] The preparation method of the metal silane composite ceramic agent comprises the following steps:

[0087] Step 1: Add a silane coupling agent, anhydrous alcohol, and a hydrolysis stabilizer to water (accounting for 15% of the total mass of water) and continue stirring for 20 hours to obtain a first solution;

[0088] Step 2: Add the fluorozirconate compound to water (accounting for 50% of the total mass of water) and stir until dissolved to obtain a second solution;

[0089] Step 3: Add film-forming aid A to water (accounting for 20% of the total mass of water), adjust the pH to 4.5, add film-forming aid B and stir evenly to obtain a third solution;

[0090] Step 4: Mix the third solution and the second solution and stir evenly, then add the complexing agent, blocking agent, buffer, first solution, and penetrant in sequence and stir evenly, and add the balance water (accounting for 15% of the total mass of water) to obtain a metal silane composite ceramic agent.

[0091] Comparative Example 1

[0092] The difference from Example 1 is that no film-forming aid A is added.

[0093] A metal silane composite ceramic agent, comprising the following components by mass fraction: (as shown in Table 5)

[0094] Table 5

[0095]

[0096] The preparation method of the metal silane composite ceramic agent comprises the following steps:

[0097] Step 1: Add a silane coupling agent, anhydrous alcohol, and a hydrolysis stabilizer to water (accounting for 15% of the total mass of water) and continue stirring for 14 hours to obtain a first solution;

[0098] Step 2: Add the fluorozirconate compound to water (accounting for 50% of the total mass of water) and stir until dissolved to obtain a second solution;

[0099] Step 3: Add film-forming agent B, complexing agent, blocking agent, buffer, first solution, and penetrant to the second solution in sequence and stir evenly, and make up the balance with water (accounting for 35% of the total mass of water) to obtain a metal silane composite ceramic agent.

[0100] Comparative Example 2

[0101] The difference from Example 1 is that modified manganese ferrosulfate is not added to the film-forming aid A.

[0102] The preparation method of film-forming aid A comprises the following steps:

[0103] (1) Naringin was added to a mixed solution of ethanol and acetone in a volume ratio of 1:2, wherein the mass volume ratio of naringin to the mixed solution was 5 g:10 g:50 mL, and 3-hexenal, dicumyl peroxide, and glacial acetic acid were added while being heated to 45°C and stirred under nitrogen, wherein the mass volume ratio of 3-hexenal, dicumyl peroxide, glacial acetic acid, and the mixed solution was 1.5 g:0.3 g:10 mL:50 mL, and the mixture was heated and refluxed for 3 h;

[0104] (2) After the reaction is completed, the mixture is rotary evaporated and dried, and the obtained product, guar gum powder, and water are mixed and ball-milled in a mass ratio of 1:0.4:10 at a speed of 300 r / min for 35 min to obtain film-forming aid A.

[0105] Comparative Example 3

[0106] The difference from Example 1 is that no naringin is added to the film-forming aid A.

[0107] The preparation method of film-forming aid A comprises the following steps:

[0108] (1) Iron sulfate, manganese sulfate, triethanolamine borate, triethanolamine oleate, sodium hydroxide, and water in a mass ratio of 7:3:2:7:0.07:10 were mixed and ball-milled, and then sieved to obtain modified manganese ferrosulfate, wherein the mesh size of the obtained modified manganese ferrosulfate was 100-300 mesh;

[0109] (2) adding the modified ferromanganese sulfate to a mixed solution of ethanol and acetone in a volume ratio of 1:2, wherein the mass volume ratio of the modified ferromanganese sulfate to the mixed solution is 5 g:50 mL, heating to 45°C under nitrogen and stirring, adding 3-hexenal, diisopropylbenzene peroxide and glacial acetic acid, wherein the mass volume ratio of 3-hexenal, diisopropylbenzene peroxide, glacial acetic acid and the mixed solution is 1.5 g:0.3 g:10 mL:50 mL, and heating and reflux for 3 h;

[0110] (3) After the reaction is completed, the mixture is rotary evaporated and dried, and the obtained product, guar gum powder, and water are mixed and ball-milled in a mass ratio of 1:0.4:10 at a speed of 300 r / min for 35 min to obtain film-forming aid A.

[0111] Comparative Example 4

[0112] The difference from Example 1 is that 3-hexenal is not added to the film-forming aid A.

[0113] The preparation method of film-forming aid A comprises the following steps:

[0114] (1) Iron sulfate, manganese sulfate, triethanolamine borate, triethanolamine oleate, sodium hydroxide, and water in a mass ratio of 7:3:2:7:0.07:10 were mixed and ball-milled, and then sieved to obtain modified manganese ferrosulfate, wherein the mesh size of the obtained modified manganese ferrosulfate was 100-300 mesh;

[0115] (2) adding the modified ferromanganese sulfate and naringin into a mixed solution of ethanol and acetone in a volume ratio of 1:2, wherein the mass volume ratio of the modified ferromanganese sulfate, naringin and the mixed solution is 5 g:10 g:50 mL, and heating and refluxing for 3 h;

[0116] (3) After the reaction is completed, the mixture is rotary evaporated and dried, and the obtained product, guar gum powder, and water are mixed and ball-milled in a mass ratio of 1:0.4:10 at a speed of 300 r / min for 35 min to obtain film-forming aid A.

[0117] Comparative Example 5

[0118] The difference from Example 1 is that the order of steps in the preparation method of the metal silane composite ceramic agent is different.

[0119] The preparation method of the metal silane composite ceramic agent comprises the following steps:

[0120] Step 1: Add a silane coupling agent, anhydrous alcohol, and a hydrolysis stabilizer to water (accounting for 15% of the total mass of water) and continue stirring for 14 hours to obtain a first solution;

[0121] Step 2: Add the fluorozirconate compound to water (accounting for 50% of the total mass of water) and stir until dissolved to obtain a second solution;

[0122] Step 3: adding film-forming aid A to water (accounting for 25% of the total mass of water) without adjusting the pH to obtain a third solution;

[0123] Step 4: Mix the third solution and the second solution and stir evenly, then add the blocking agent, buffer, first solution, penetrant, film-forming aid B, and complexing agent in sequence and stir evenly, and add the balance water (accounting for 10% of the total mass of water) to obtain a metal silane composite ceramic.

[0124] The metal workpiece is degreased with a degreasing agent to remove oil stains from the metal surface; the degreased metal workpiece is washed with water in multiple steps; the metal workpiece is immersed in the ceramic agent of the embodiment and the comparative example to ceramicize; the ceramicized workpiece is washed with clean water and then dried for spraying.

[0125] Salt spray resistance test: Conduct a neutral salt spray test in accordance with GB / T10125-1997. Prepare a 5% sodium chloride solution by mass and adjust the pH to 6.8±0.2 with hydrochloric acid or sodium hydroxide solution. Heat the salt solution to maintain the temperature of 35°C. Place the test sample in a salt spray tester and spray it continuously until red rust, powdering, flaking, blistering, etc. appear on the surface of the test sample. The duration of the test is calculated.

[0126] Adhesion test: After the workpiece is ceramicized and dried, it is sprayed with polyurethane plastic powder or epoxy plastic powder by electrostatic adsorption and baked at 180℃ to obtain the finished product. The finished product is tested for adhesion according to the standard of GB / T9286-1998. A 1mm square is scratched on the surface of the workpiece with a grid knife. 2 100 small grids are scratched, with the scratch depth required to penetrate the surface coating and reach the sample substrate. Then, firmly adhere the small grid to be tested with a 5mm wide pressure-sensitive tape with an adhesion of (10±1)N / 25mm. Rub the tape vigorously with an eraser. Grab one end of the tape and pull it off at a 90-degree angle. Perform the same test twice at the same location. After the test, observe the surface coating of the grid and rate it against the standard.

[0127] Table 6

[0128]

[0129] As shown in Table 6, workpieces treated with the composite ceramic agent of the present invention form a dense film on their surfaces, exhibiting excellent corrosion and impact resistance, and enhancing adhesion between metal coatings. Comparative Example 1 demonstrates that film-forming aid A contributes to improved film density and adhesion, as well as improved corrosion resistance over time. Comparative Examples 2-4 demonstrate that the components of film-forming aid A contribute to improved material bonding and stability, promoting better film adhesion, enhancing complexation with metal workpieces, and improving corrosion resistance over time. Comparative Example 5 demonstrates that the order of steps in the ceramic preparation method can affect the final ceramicization process results.

[0130] The above are only preferred embodiments of the present invention and are not intended to limit the patent scope of the present invention. Any equivalent structure or equivalent process transformation made using the description of the present invention, or directly or indirectly applied in other related technical fields, are also included in the patent protection scope of the present invention.

Claims

1. A metal silane composite ceramic agent, characterized in that: The composite ceramic agent comprises, by mass fraction, 2-10% of a fluorozirconate compound, 0.5-2% of a complexing agent, 1-5% of a silane coupling agent, 0.1-0.5% of a hydrolysis stabilizer, 5-8% of a film-forming aid A, 0.5-1% of a film-forming aid B, 3-10% of anhydrous alcohol, and the balance being water; Film-forming aid A is prepared by adding modified ferromanganese sulfate and naringin to a mixed solution of ethanol and acetone, heating and stirring under nitrogen, then adding 3-hexenal, dicumyl peroxide, and glacial acetic acid. The mixture is heated under reflux for reaction, followed by rotary evaporation and drying. The resulting product is then added to guar gum powder and water, mixed, and ball-milled. The modified ferromanganese sulfate is prepared by mixing ferric sulfate, manganese sulfate, triethanolamine borate, triethanolamine oleate, sodium hydroxide, and water, ball-milled, and then sieved. The film-forming aid B is one or more of zirconium nitrate, zirconium oxynitrate and zirconium oxychloride.

2. The metal silane composite ceramic agent according to claim 1, characterized in that: The mass ratio of the ferric sulfate, manganese sulfate, triethanolamine borate, triethanolamine oleate, sodium hydroxide and water is 7-8:2-4:2-3:6-7:0.05-0.1:10; the mass ratio of the product, guar gum powder and water is 1:0.3-0.4:10; The obtained product is added with guar gum powder and water, and the mixture is ball-milled. The rotation speed of the mixing ball-milling is 200-300 r / min, and the time is 30-40 min.

3. The metal silane composite ceramic agent according to claim 1, characterized in that: The mass volume ratio of the modified manganese iron sulfate, naringin and the mixed solution is 3-5 g:8-10 g:50 mL; the volume ratio of ethanol and acetone is 1:1-2; the mass volume ratio of 3-hexenal, dicumyl peroxide, glacial acetic acid and the mixed solution is 1.5-2 g:0.2-0.4 g:10 mL:50 mL; and the heating reflux reaction time is 1-3 h.

4. The metal silane composite ceramic agent according to claim 1, wherein: The fluorozirconate compound is one or more of fluorozirconic acid, ammonium fluorozirconate, potassium fluorozirconate, and sodium fluorozirconate; and the silane coupling agent is one or more of KH550, KH560, and KH792.

5. The metal silane composite ceramic agent according to claim 1, characterized in that: The complexing agent is one or more of glycine, oxalic acid, acetic acid, and tartaric acid; and the hydrolysis stabilizer is one or more of glycerol and ethylene glycol.

6. The metal silane composite ceramic agent according to claim 1, characterized in that: The composite ceramic agent further comprises 0.5-2% of a sealing agent by mass fraction; the sealing agent is one or more of monoethanolamine borate, diethanolamine borate, triethanolamine borate, triethanolamine, and thiourea.

7. The metal silane composite ceramic agent according to claim 1, characterized in that: The composite ceramic agent further comprises 0.5-2% of a buffer by mass; the buffer is one or more of ammonium acetate, ammonium carbonate, and ammonium bicarbonate.

8. The metal silane composite ceramic agent according to claim 1, characterized in that: The composite ceramic agent further comprises 0.01-0.5% of a penetrant by mass; the penetrant is one or more of JFC and OP-10.

9. A method for preparing the metal silane composite ceramic agent according to any one of claims 1 to 8, characterized in that: The steps include: Step 1: Add a silane coupling agent, anhydrous alcohol, and a hydrolysis stabilizer to water, and continue stirring for 4 to 20 hours to obtain a first solution; Step 2: Add the fluorozirconate compound into water and stir until dissolved to obtain a second solution; Step 3: Add film-forming aid A to water, adjust the pH to 4-4.5, add film-forming aid B and stir evenly to obtain a third solution; Step 4: Mix the third solution and the second solution and stir evenly, then add the complexing agent, blocking agent, buffer, first solution, and penetrant in sequence and stir evenly, and add the balance of water to obtain a metal silane composite ceramic agent.

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