Aluminum alloy hole sealing agent, preparation method and application thereof

Abstract

The application discloses an aluminum alloy sealing agent and a preparation method and application thereof, and the aluminum alloy sealing agent comprises a gemini quaternary ammonium silane surfactant, a silane coupling agent, a dispersant, an inhibitor and deionized water; the gemini quaternary ammonium silane surfactant has a structure shown in the following formula A. The aluminum alloy sealing agent provided by the application takes the gemini quaternary ammonium silane surfactant as a main component, avoids the introduction of a nickel element, and based on excellent permeability and a synergistic effect formed between the gemini quaternary ammonium silane surfactant and the dispersant, can significantly improve the sealing effect of the sealing agent on the surface of the oxidized aluminum alloy, and then can effectively improve the corrosion resistance and wear resistance of the aluminum alloy, and can be widely applied in the technical field of aluminum alloy surface treatment.

Description

Technical Field

[0001] This invention relates to the field of aluminum alloy surface treatment technology, specifically to an aluminum alloy sealing agent, its preparation method, and its application. Background Technology

[0002] Aluminum is one of the six most widely distributed metals in nature, accounting for approximately 8.0% of the Earth's crust by mass. It has a low density and melting point, making it easy to process and mold into various profiles; however, pure aluminum has very low strength, making it unsuitable as a structural material. Through long-term production practice and scientific research, people have gradually strengthened aluminum by adding alloying elements and using heat treatment, resulting in a series of aluminum alloys. These alloys retain the advantages of pure aluminum, such as its light weight, while also possessing high strength, making them ideal structural materials.

[0003] Aluminum alloys are alloys made by adding a certain amount of other alloying elements to aluminum as the base material. They are one of the lightweight metal materials. Aluminum alloys have a specific strength close to that of high-alloy steel and a specific stiffness exceeding that of steel. They have good casting and plastic processing properties, good electrical and thermal conductivity, good corrosion resistance and weldability, and can be used as structural materials. They have a wide range of applications in aerospace, aviation, transportation, construction, electromechanical, light chemical and daily consumer goods.

[0004] However, aluminum alloys, as structural materials, suffer from drawbacks such as softness, poor wear resistance, poor corrosion resistance in special environments, and poor high-temperature resistance. Although aluminum alloys can spontaneously form an Al2O3 film on their surface in air, this film is very thin and has many defects, failing to effectively protect the substrate. Therefore, various methods are used to treat the surface of aluminum alloy profiles to improve their performance. To further enhance the performance of aluminum alloys, a series of surface oxidation treatment technologies have been developed, including anodizing, micro-arc oxidation, and the thermoelectric chemical oxidation proposed in recent years. After treatment, an oxide film ranging from a few micrometers to several hundred micrometers can be formed on the surface of the aluminum alloy. Compared with the natural oxide film of aluminum alloys, its corrosion resistance, wear resistance, and decorative properties are significantly improved.

[0005] Because the anodized film on aluminum parts has high porosity and adsorption capacity, it easily adsorbs contaminants, thus affecting its corrosion resistance. Sealing technology can fill the pores in the anodized film of aluminum alloys, playing an important role in improving the corrosion resistance and surface quality of aluminum alloys. However, the sealing agents used in existing sealing technologies contain a certain amount of nickel. When nickel-containing parts are in prolonged contact with human skin, Ni can be released under the influence of sweat. 2+ It causes skin itching and can trigger allergic contact dermatitis, so it is banned in many regions, and the sealing effect of sealing agents in existing technologies still needs to be improved.

[0006] Therefore, there is an urgent need for an aluminum alloy sealing agent that is nickel-free, has excellent sealing ability, and can effectively improve the corrosion resistance and wear resistance of aluminum alloys. Summary of the Invention

[0007] Purpose of the invention: In view of the deficiencies of the prior art, the purpose of this invention is to provide an aluminum alloy sealing agent that is nickel-free and has excellent sealing ability, which can effectively improve the corrosion resistance and wear resistance of aluminum alloys, as well as its preparation method and application.

[0008] Technical solution:

[0009] An aluminum alloy sealing agent comprises a gemini quaternary ammonium silane surfactant, a silane coupling agent, a dispersant, a corrosion inhibitor, and deionized water;

[0010] The gemini-type quaternary ammonium silane surfactant has the structure shown in Formula A:

[0011]

[0012] Further, the gemini-type quaternary ammonium silane surfactant is prepared by the following steps: in a reactor, hexadecyl dimethyl tertiary amine and solvent are added, stirred and mixed evenly, and under nitrogen protection, the temperature is raised to 70-80°C, 1,3-bis(3-chloropropyl)-1,1,3,3-tetramethyldisiloxane is added, and after reacting at this temperature for 2-3 hours, the solvent is removed, and the product is recrystallized to obtain the gemini-type quaternary ammonium silane surfactant.

[0013] In this invention, a gemini-type quaternary ammonium silane surfactant is used as the main component. On the one hand, its quaternary ammonium salt structure can not only improve the surface activity of the sealing agent, but also further improve the penetration effect of the sealing agent into the pores, thereby improving the sealing ability. On the other hand, its silane structure can form a network structure with a certain specification in the pores and surface of aluminum alloy, thereby playing a certain protective role and sealing the pores of the aluminum alloy, which can effectively improve the corrosion resistance and wear resistance of the treated aluminum alloy and improve its application value.

[0014] Furthermore, the solvent is selected from anhydrous ethanol or anhydrous isopropanol.

[0015] Further, the mass ratio of the hexadecyl dimethyl tertiary amine to 1,3-bis(3-chloropropyl)-1,1,3,3-tetramethyldisiloxane is 2-2.5:1.

[0016] Furthermore, the silane coupling agent is selected from one of γ-(2,3-epoxypropoxy)propyltrimethoxysilane, 3-aminopropyltriethoxysilane, or γ-methacryloyloxypropyltrimethoxysilane.

[0017] Furthermore, the dispersant is selected from sodium dodecyl sulfonate, sodium dodecylbenzene sulfonate, Tween 60, or Tween 80.

[0018] This invention combines a gemini-type quaternary ammonium silane surfactant with a dispersant, which has a certain synergistic effect and can improve the stability of the sealing agent, enabling it to maintain the stability and clarity of the tank solution during the treatment process, thereby improving the uniformity of the sealing effect.

[0019] Furthermore, the corrosion inhibitor is selected from one of dipentylamine, toluenethiourea, or ethylenediaminetetraacetic acid.

[0020] Furthermore, based on a total mass fraction of 100%, the mass percentage content of each component is as follows:

[0021]

[0022] The remainder is deionized water.

[0023] In this invention, a gemini-type quaternary ammonium silane surfactant is used as the main component. Its gemini structure with multiple polar and non-polar groups can endow it with excellent surface activity, which can not only improve the uniformity and stability of the sealing agent during the action process, but also improve its penetration effect on the pores of aluminum alloy surface, improve the coverage rate and coverage depth of the sealing agent on the pores of aluminum alloy surface, and thus improve the sealing effect.

[0024] The preparation method of any of the above aluminum alloy sealing agents includes the following steps: In a reactor, a gemini-type quaternary ammonium silane surfactant, a dispersant and a deionizer are added, heated to 40-50°C and stirred and mixed, then a silane coupling agent and a corrosion inhibitor are added, and the mixture is stirred at 100-150 rpm for 3-5 minutes and then cooled to obtain the aluminum alloy sealing agent.

[0025] The application of any of the above aluminum alloy sealing agents in the field of aluminum alloy surface treatment.

[0026] Beneficial effects:

[0027] (1) The aluminum alloy sealing agent provided by the present invention is prepared by mixing a gemini quaternary ammonium silane surfactant, a silane coupling agent, a dispersant, a corrosion inhibitor and deionized water. The gemini quaternary ammonium silane surfactant is used as the main component, which not only avoids the introduction of nickel, but also significantly improves the sealing effect of the sealing agent on the surface of oxidized aluminum alloy based on its excellent penetration ability and the synergistic effect formed with the dispersant. In this way, it can effectively improve the corrosion resistance and wear resistance of aluminum alloy and can be widely used in the field of aluminum alloy surface treatment technology.

[0028] (2) The aluminum alloy sealing agent provided by the present invention uses a twin-type quaternary ammonium silane surfactant as the main component. Its twin-type structure with multiple polar groups and multiple non-polar groups can endow it with excellent surface activity, which can not only improve the uniformity and stability of the sealing agent during the action process, but also improve its penetration effect on the pores of the aluminum alloy surface, improve the coverage rate and coverage depth of the sealing agent on the pores of the aluminum alloy surface, and thus improve the sealing effect.

[0029] (3) The aluminum alloy sealing agent provided by the present invention uses a gemini-type quaternary ammonium silane surfactant as the main component. On the one hand, its quaternary ammonium salt structure can not only improve the surface activity of the sealing agent, but also further improve the penetration effect of the sealing agent on the pores, thereby improving the sealing ability. On the other hand, its silane structure can form a network structure with a certain specification in the pores and surface of the aluminum alloy, thereby playing a certain protective role and sealing role for the aluminum alloy, thus effectively improving the corrosion resistance and wear resistance of the treated aluminum alloy and improving its application value.

[0030] (4) The aluminum alloy sealing agent provided by the present invention has a certain synergistic effect by combining the gemini quaternary ammonium silane surfactant with the dispersant, which can improve the stability of the sealing agent and enable it to maintain the stability and clarity of the tank liquid during the treatment process, thereby improving the uniformity of the sealing effect. Detailed Implementation

[0031] The present invention will be described below with reference to specific embodiments. It should be noted that the following embodiments are examples of the present invention and are used only to illustrate the invention, not to limit it. Other combinations and various modifications within the scope of the present invention can be made without departing from its spirit or scope.

[0032] The commercially available sealing agent was aluminum sealing agent LQ-A802 purchased from Huizhou Hanhuihe Environmental Technology Co., Ltd.; the other reagents and equipment were conventional reagents and equipment in this technical field.

[0033] Preparation of Gemini Quaternary Ammonium Silane Surfactants

[0034] Geminid quaternary ammonium silane surfactants were prepared using the following steps:

[0035] In a reactor, 5g of hexadecyl dimethyl tertiary amine and 100mL of anhydrous ethanol were added and stirred until homogeneous. Under nitrogen protection, the temperature was raised to 75°C, and 2g of 1,3-bis(3-chloropropyl)-1,1,3,3-tetramethyldisiloxane was added. After reacting at this temperature for 3 hours, the anhydrous ethanol was removed, and the product was recrystallized to obtain the Gemini quaternary ammonium silane surfactant.

[0036] Mass spectrometry data of the gemini quaternary ammonium silane surfactant: The products were analyzed by LC-MS, and the m / z values ​​of the products were 754.76 (100.0%), 755.46 (62.0%), 756.75 (42.4%), 757.52 (7.5%), and 758.26 (1.7%).

[0037] Example 1

[0038] Aluminum alloy sealing agent is prepared by the following steps:

[0039] In a reactor, a gemini-type quaternary ammonium silane surfactant, Tween 80, and deionized oil are added. After heating to 50°C and stirring, γ-(2,3-epoxypropoxy)propyltrimethoxysilane and dipentylamine are added. The mixture is stirred at 150 rpm for 3 minutes and then cooled to obtain the aluminum alloy sealing agent.

[0040] Based on a total mass fraction of 100%, the mass percentage of each component is as follows:

[0041] Gemini quaternary ammonium silane surfactant 10%

[0042] γ-(2,3-epoxypropoxy)propyltrimethoxysilane 5%

[0043] Tween 80 2%

[0044] Dipentylamine 1%

[0045] The remainder is deionized water.

[0046] Example 2

[0047] Basically the same as Example 1, except that, based on a total mass fraction of 100%, the components and their mass percentages are as follows:

[0048] Gemini quaternary ammonium silane surfactant 8%

[0049] 3-Aminopropyltriethoxysilane 3%

[0050] Sodium dodecyl sulfonate 3%

[0051] 2% ethylenediaminetetraacetic acid

[0052] The remainder is deionized water.

[0053] Example 3

[0054] Basically the same as Example 1, except that, based on a total mass fraction of 100%, the components and their mass percentages are as follows:

[0055] Gemini quaternary ammonium silane surfactant 9%

[0056] γ-Methacryloxypropyltrimethoxysilane 4%

[0057] Sodium dodecylbenzenesulfonate 3%

[0058] Toluenethionamide 2%

[0059] The remainder is deionized water.

[0060] Comparative Example 1

[0061] Commercially available sealing agents.

[0062] Comparative Example 2

[0063] The process is basically the same as in Example 1, except that the gemini quaternary ammonium silane surfactant is replaced with an equal amount of Tween 80.

[0064] Comparative Example 3

[0065] The process is basically the same as in Example 1, except that Tween 80 is replaced with an equal amount of Gemini quaternary ammonium silane surfactant.

[0066] Comparative Example 4

[0067] The process is basically the same as in Example 1, except that the gemini quaternary ammonium silane surfactant is replaced with an equal amount of hexadecyltrimethylammonium bromide.

[0068] Performance testing

[0069] Take aluminum alloys of the same specifications after oxidation treatment, and place them in the sealing agents prepared in Examples 1-3 and Comparative Examples 1-4 respectively. After heating to 75°C for 40 minutes, bake at 60°C for 15 minutes, and then test after standing.

[0070] Corrosion resistance test: The aluminum alloys of Examples 1-3 and Comparative Examples 1-4 after pore sealing treatment were tested under the standard of ISO9227-1990 to test their corrosion resistance to neutral salt spray.

[0071] Abrasion resistance test: The aluminum alloys of Examples 1-3 and Comparative Examples 1-4 after pore sealing were tested under the standard of ASTM F2357-04 to test their abrasion resistance.

[0072] Sealing effect test: The aluminum alloys treated with sealing in Examples 1-3 and Comparative Examples 1-4 were tested under the standard GB / T5237.2-2000 for aluminum alloy building profiles. The frost spots on the sample surface were wiped off with a dry cloth, and the samples were degreased with a suitable organic solvent at room temperature. After drying, the samples were weighed. Then, the samples were immersed in a phosphochromic acid solution at (38±1)℃ for 15 minutes. The samples were then removed, cleaned, dried, and weighed again. The weight loss was calculated to be 20 mg / dm³. 2 The following are considered qualified.

[0073] The test results are shown in the table below:

[0074] Corrosion resistance (h) Abrasion resistance (cycle) <![CDATA[Weight loss (mg / dm 2 )]]> Example 1 3200 1600 6.4 Example 2 3250 1700 6.2 Example 3 3200 1650 6.2 Comparative Example 1 2150 1010 19.7 Comparative Example 2 2230 1120 16.3 Comparative Example 3 2950 1500 8.6 Comparative Example 4 2670 1350 12.5

[0075] According to the comparison of the test results of Examples 1-3 and Comparative Example 1, the aluminum alloy sealing agent provided by the present invention has a better sealing ability than the aluminum alloy sealing agent in the prior art, which can effectively improve the corrosion resistance and wear resistance of aluminum alloys and can be widely used in the field of aluminum alloy surface treatment technology.

[0076] According to the comparison of the test results of Examples 1-3 and Comparative Examples 2-3, it can be seen that the aluminum alloy sealing agent provided by the present invention can significantly improve the sealing ability of the sealing agent by adding a gemini-type quaternary ammonium silane surfactant, thereby improving the corrosion resistance and wear resistance of the aluminum alloy. Furthermore, by combining it with a dispersant, it has a certain synergistic effect and can further improve its sealing ability.

[0077] According to the comparison of the test results of Examples 1-3 and Comparative Example 4, the gemini-type quaternary ammonium silane surfactant in the aluminum alloy sealing agent provided by the present invention not only has better surface activity than the quaternary ammonium salt surfactant in the prior art, but can also further improve the corrosion resistance and wear resistance of aluminum alloys.

[0078] The above embodiments are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the content of the present invention and implement it. They should not be used to limit the scope of protection of the present invention. All equivalent changes or modifications made in accordance with the spirit and essence of the present invention should be covered within the scope of protection of the present invention.

Claims

1. An aluminum alloy sealing agent, characterized in that, This includes gemini quaternary ammonium silane surfactants, silane coupling agents, dispersants, corrosion inhibitors, and deionized water; The gemini-type quaternary ammonium silane surfactant has the structure shown in Formula A: ； The silane coupling agent is selected from one of γ-(2,3-epoxypropoxy)propyltrimethoxysilane, 3-aminopropyltriethoxysilane or γ-methacryloxypropyltrimethoxysilane; The dispersant is selected from one of sodium dodecyl sulfonate, sodium dodecylbenzene sulfonate, Tween 60 or Tween 80; The corrosion inhibitor is selected from one of dipentylamine, toluenethiourea, or ethylenediaminetetraacetic acid.

2. The aluminum alloy sealing agent according to claim 1, characterized in that, The gemini-type quaternary ammonium silane surfactant is prepared by the following steps: In a reactor, hexadecyl dimethyl tertiary amine and solvent are added and stirred until homogeneous. Under nitrogen protection, the temperature is raised to 70-80°C, and 1,3-bis(3-chloropropyl)-1,1,3,3-tetramethyldisiloxane is added. After reacting at this temperature for 2-3 hours, the solvent is removed, and the product is recrystallized to obtain the gemini-type quaternary ammonium silane surfactant.

3. The aluminum alloy sealing agent according to claim 2, characterized in that, The solvent is selected from anhydrous ethanol or anhydrous isopropanol.

4. The aluminum alloy sealing agent according to claim 2, characterized in that, The mass ratio of the hexadecyl dimethyl tertiary amine to 1,3-bis(3-chloropropyl)-1,1,3,3-tetramethyldisiloxane is 2-2.5:

1.

5. The aluminum alloy sealing agent according to claim 1, characterized in that, Based on a total mass fraction of 100%, the mass percentage of each component is as follows: Gemini quaternary ammonium silane surfactants 8-10% Silane coupling agent 3-5% Dispersant 2-3% Corrosion inhibitor 1-2% The remainder is deionized water.

6. A method for preparing the aluminum alloy sealing agent according to any one of claims 1-5, characterized in that, The process includes the following steps: In a reactor, a gemini-type quaternary ammonium silane surfactant, a dispersant, and a deionizer are added. After heating to 40-50°C and stirring to mix, a silane coupling agent and a corrosion inhibitor are added. The mixture is stirred at 100-150 rpm for 3-5 minutes and then cooled to obtain the aluminum alloy sealing agent.

7. The application of the aluminum alloy sealing agent according to any one of claims 1-5 in the field of aluminum alloy surface treatment.

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