A high-strength decorative aluminum product metal material and its preparation method

Abstract

This invention belongs to the field of metal materials technology, specifically relating to a high-strength decorative aluminum product metal material and its preparation method. The preparation method of the high-strength decorative aluminum product metal material includes the following steps: (1) adding carbon nanoparticles, sulfuric acid, and oxalic acid to water to prepare a mixed acid solution, immersing an aluminum substrate in the mixed acid solution for anodizing, and then cleaning and drying to obtain a pretreated aluminum substrate; (2) adding polyoxymethylene fiber to a dispersion, heating and reacting to obtain a mixed solution, coating the mixed solution on the surface of the pretreated aluminum substrate, then performing heat treatment, aging at room temperature, cleaning, and drying to obtain the high-strength decorative aluminum product metal material. The preparation process of this invention is simple, the product performance is stable, and it has high strength, high hardness, wear resistance, superhydrophobicity, and self-cleaning properties.

Description

Technical Field

[0001] This invention belongs to the field of metal materials technology, specifically relating to a high-strength decorative aluminum product metal material and its preparation method. Background Technology

[0002] Aluminum, with its low density (only one-third that of steel), high specific strength, excellent electrical conductivity (approximately 60% of copper), and thermal conductivity, along with abundant reserves, has become the preferred material for lightweight applications in aerospace, transportation, building structures, power transmission, and electronic heat sinks. It has become an indispensable basic material in modern industry and daily life. Furthermore, the dense oxide film naturally forming on the aluminum surface provides excellent resistance to atmospheric corrosion. Combined with its good machinability (casting, extrusion, rolling, forging) and recyclability (recycling energy consumption is only 5% of that used in primary aluminum production), it is widely used in building curtain walls, doors and windows, food and beverage packaging, and durable consumer goods. However, the inherent weaknesses of aluminum limit its application in more demanding scenarios: for example, its relatively low strength and hardness, poor wear resistance, and limited corrosion resistance in certain environments restrict the use of aluminum products in more extreme environments.

[0003] To overcome the weaknesses of aluminum, modern surface treatment technology plays a crucial role, significantly improving its mechanical properties and greatly enriching its decorative possibilities. The main surface treatment technologies for aluminum alloys include anodizing, micro-arc oxidation, and surface laser treatment. By constructing high-performance ceramic or modified layers on their surfaces, these technologies have successfully overcome the bottlenecks in aluminum's strength, hardness, and wear resistance, enabling it to withstand more demanding engineering environments. Simultaneously, these technologies have opened the door to the decorative art of aluminum products, achieving a perfect unity of performance and aesthetics. With increasingly stringent environmental protection requirements, developing new surface treatment processes with lower energy consumption and less pollution will be a key direction for continuously enhancing the value of aluminum products in the future. Summary of the Invention

[0004] The primary objective of this invention is to provide a method for preparing high-strength decorative aluminum alloy materials. This method is relatively simple to operate, highly feasible, and helps to save production costs. This invention utilizes a special anodizing process to form an alumina composite film containing carbon nanotubes and a silicon dioxide-titanium dioxide coating on the surface of an aluminum alloy.

[0005] The second objective of this invention is to provide a high-strength decorative aluminum product metal material. This composite material has high hardness, wear resistance, and tensile strength. In addition, its surface silica-titanium dioxide coating also has good superhydrophobic properties and self-cleaning function.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0007] A method for preparing a high-strength decorative aluminum product metal material includes the following steps:

[0008] (1) Carbon nanoparticles, sulfuric acid and oxalic acid are added to water to prepare a mixed acid solution. The aluminum substrate is immersed in the mixed acid solution for anodizing. Then, after cleaning and drying, a pretreated aluminum substrate is obtained.

[0009] (2) Add polyoxymethylene fiber to the dispersion, heat to react and obtain a mixture, coat the mixture on the surface of the pretreated aluminum substrate, then heat treat, age at room temperature, clean and dry to obtain high-strength decorative aluminum product metal material.

[0010] Further, in step (1), the mass ratio of carbon nano-onion, sulfuric acid, and oxalic acid is (3-5):(100~200):(15~25), wherein the concentration of carbon nano-onion in water is 3~5 g / L.

[0011] Furthermore, the voltage for anodizing in step (1) is 20~50 V, and the current density is 2~5 A / dm³. 2 The time is 0.5 to 3 hours.

[0012] This invention employs an anodizing process, using aluminum alloy as the anode, and applies an electric current in an acidic electrolyte (sulfuric acid, oxalic acid, carbon nanotubes) to cause aluminum to lose electrons and generate Al. 3+ The carbon nanoparticles combine with oxygen to form a composite film containing carbon nanoparticles ("onion"). The electrolyte partially dissolves this film, forming an oxide layer, which effectively improves the material's hardness and wear resistance. Furthermore, the film and substrate are in-situ metallurgically bonded, exhibiting strong adhesion and good stability. Under the action of an electric arc, the carbon nanoparticles can fuse with the oxide film to form a carbon nanoparticle-alumina composite film. The addition of carbon nanoparticles alleviates coating brittleness, enhancing both the high hardness and tensile strength of the composite material.

[0013] Further, the dispersion in step (2) is prepared by mixing anhydrous ethanol, tetraethyl orthosilicate, tetrabutyl titanate, silane coupling agent KH550, dodecyltrimethylammonium chloride, and hexamethylenetetramine;

[0014] The ratio of anhydrous ethanol, tetraethyl orthosilicate, tetrabutyl titanate, silane coupling agent, dodecyltrimethylammonium chloride, and hexamethylenetetramine is 1000 mL: 40~50 mL: 40~50 mL: 5~30 g: 10~20 g: 2~5 g.

[0015] Further, the mass ratio of polyoxymethylene fiber, dispersion and aluminum matrix in step (2) is 1:(20~40):(40~80).

[0016] Furthermore, the heating reaction in step (2) is carried out at a temperature of 30~70℃ for 8~10h.

[0017] Further, the heat treatment in step (2) is performed at a temperature of 140~200℃ for 1~5h; the aging time is 15~25h.

[0018] Further, the aluminum matrix in step (1) is composed of the following components by weight percentage: Zn: 6.72-7.05 wt%, Mg: 1.62-1.94 wt%, Ti: 0.01-0.05 wt%, Zr: 0.12-0.19 wt%, Fe: <0.1 wt%, Si: <0.07 wt%, Mn: <0.05 wt%, Cr: <0.05 wt%, with the balance being Al.

[0019] A high-strength decorative aluminum product metal material is prepared using the above-mentioned preparation method.

[0020] Compared with the prior art, the main advantages of the present invention are as follows:

[0021] 1. This invention provides a high-strength decorative aluminum product metal material. This material is produced by introducing carbon nanotubes (CNOs) into the anodic oxidation electrolyte and using an electric arc to promote in-situ fusion with the grown alumina film, forming a "carbon nanotube onion-alumina composite film." This composite film not only improves the high hardness, high wear resistance, and strong adhesion to the substrate of the metal material, but also significantly improves the brittleness of the coating and greatly enhances the tensile strength of the material due to the addition of carbon nanotubes. Furthermore, CNOs have good dispersibility, further optimizing the filler-matrix interface polarization effect, inhibiting the initiation and propagation of microcracks, and reducing the risk of microcrack propagation.

[0022] 2. This invention involves immersing high-strength, high-modulus, and wear-resistant polyoxymethylene (POM) fibers in a solution containing tetrabutyl orthosilicate and tetrabutyl titanate, followed by heating. This process results in the simultaneous deposition of a SiO2 / TiO2 composite coating on both the POM fibers and the pretreated aluminum substrate. This improves the heat resistance of POM, preventing its degradation at high temperatures and enhancing the material's hardness. The resulting composite coating significantly increases the hardness of the POM. Furthermore, titanium dioxide possesses photocatalytic properties, synergistically degrading organic matter under light excitation. Its combination with silicon dioxide to form a micro / nano structure increases surface roughness and improves hydrophobicity, making it particularly suitable for decorative purposes while maintaining a clean appearance.

[0023] 3. This invention provides a method for preparing high-strength decorative aluminum metal materials. This method ensures a stable and durable bond between the POM fiber layer and the anodized aluminum matrix, synergistically achieving the unity of high strength, high hardness, excellent wear resistance, and self-cleaning function of the material. Attached Figure Description

[0024] Figure 1 This is a SEM image of the surface of the aluminum product in Example 1. Detailed Implementation

[0025] The technical solution of the present invention will be further described below with reference to specific embodiments. However, those skilled in the art should understand that the following embodiments are only for illustrating the present invention and should not be regarded as limiting the present invention. Specific conditions not specified in the embodiments are performed according to conventional conditions or conditions recommended by the manufacturer. Unless otherwise specified, the reagents or instruments used are all conventional products obtained through commercial channels.

[0026] Example 1

[0027] A method for preparing a high-strength decorative aluminum product metal material includes the following steps:

[0028] (1) Prepare a mixed acid solution containing 4g carbon nanoparticles, 150g 98% sulfuric acid, and 20g oxalic acid per 1L of water; polish the aluminum substrate to a smooth finish and clean off surface oil, then immerse it in the mixed acid solution for anodizing, wherein the voltage is 40V and the current density is 3A / dm³. 2 The process takes 2 hours, followed by cleaning and drying to obtain the pretreated aluminum substrate.

[0029] The aluminum matrix is ​​composed of the following components by weight percentage: Zn: 6.85 wt%, Mg: 1.78 wt%, Ti: 0.04 wt%, Zr: 0.15 wt%, Fe: 0.06 wt%, Si: 0.05 wt%, Mn: 0.02 wt%, Cr: 0.04 wt%, with the balance being Al;

[0030] (2) Preparation of dispersion: Each 1L of anhydrous ethanol contains 45 mL of tetraethyl orthosilicate, 45 mL of tetrabutyl titanate, 20 g of silane coupling agent KH550, 15 g of dodecyltrimethylammonium chloride, and 3 g of hexamethylenetetramine. After mixing evenly, polyoxymethylene fibers (diameter distribution of 2-5µm) are added to the dispersion and ultrasonically dispersed. The mixture is then reacted at 60℃ for 9 h. Subsequently, the mixture is coated onto the surface of a pretreated aluminum substrate, wherein the mass ratio of polyoxymethylene fibers, dispersion and aluminum substrate is 1:30:60. The mixture is then heat-treated at 180℃ for 3 h and aged for 20 h. After cleaning and drying, high-strength decorative aluminum product metal material is obtained.

[0031] This embodiment also provides a high-strength decorative aluminum product metal material, which is prepared using the above-described preparation method.

[0032] Example 2

[0033] A method for preparing a high-strength decorative aluminum product metal material includes the following steps:

[0034] (1) Prepare a mixed acid solution containing 3 g of carbon nanoparticles, 100 g of 98% sulfuric acid, and 15 g of oxalic acid per 1 L of water; polish the aluminum substrate to a smooth finish and clean off surface oil, then immerse it in the mixed acid solution for anodizing, wherein the voltage is 20 V and the current density is 2 A / dm. 2 The time is 1 hour, and the pretreated aluminum substrate is obtained by cleaning and drying.

[0035] The aluminum matrix is ​​composed of the following components by weight percentage: Zn: 6.85 wt%, Mg: 1.78 wt%, Ti: 0.04 wt%, Zr: 0.15 wt%, Fe: 0.06 wt%, Si: 0.05 wt%, Mn: 0.02 wt%, Cr: 0.04 wt%, with the balance being Al;

[0036] (2) Preparation of dispersion: Each 1L of anhydrous ethanol contains 40 mL of tetraethyl orthosilicate, 40 mL of tetrabutyl titanate, 5g of silane coupling agent KH550, 10g of dodecyltrimethylammonium chloride, and 2g of hexamethylenetetramine. Mix them evenly. Then, add polyoxymethylene fiber (diameter distribution of 2-5µm) to the dispersion and disperse it ultrasonically. React at 70 ℃ for 10h. Then coat it on the surface of the pretreated aluminum substrate. The mass ratio of polyoxymethylene fiber, dispersion and aluminum substrate is 1:20:40. Heat treat at 150 ℃ for 5h and age for 15h. Clean and dry to obtain high-strength decorative aluminum product metal material.

[0037] This embodiment also provides a high-strength decorative aluminum product metal material, which is prepared using the above-described preparation method.

[0038] Example 3

[0039] A method for preparing a high-strength decorative aluminum product metal material includes the following steps:

[0040] (1) Prepare a mixed acid solution containing 5 g of carbon nanoparticles, 200 g of 98% sulfuric acid, and 25 g of oxalic acid per 1 L of water; polish the aluminum substrate to a smooth surface and clean away surface oil, then immerse it in the mixed acid solution for anodizing, wherein the voltage is 50 V and the current density is 5 A / dm. 2 The time is 3 hours, and the pretreated aluminum substrate is obtained by cleaning and drying.

[0041] The aluminum matrix is ​​composed of the following components by weight percentage: Zn: 6.85 wt%, Mg: 1.78 wt%, Ti: 0.04 wt%, Zr: 0.15 wt%, Fe: 0.06 wt%, Si: 0.05 wt%, Mn: 0.02 wt%, Cr: 0.04 wt%, with the balance being Al;

[0042] (2) Preparation of dispersion: Each 1L of anhydrous ethanol contains 50 mL of tetraethyl orthosilicate, 50 mL of tetrabutyl titanate, 30 g of silane coupling agent KH550, 20 g of dodecyltrimethylammonium chloride, and 5 g of hexamethylenetetramine. After mixing evenly, polyoxymethylene fibers (diameter distribution of 2-5µm) are added to the dispersion and ultrasonically dispersed. The mixture is reacted at 40 ℃ for 10 h. Subsequently, it is coated on the surface of the pretreated aluminum substrate. The mass ratio of polyoxymethylene fibers, dispersion and aluminum substrate is 1:40:80. The mixture is then heat-treated at 200 ℃ for 1.5 h and aged for 15 h. After cleaning and drying, high-strength decorative aluminum product metal material is obtained.

[0043] This embodiment also provides a high-strength decorative aluminum product metal material, which is prepared using the above-described preparation method.

[0044] Comparative Example 1

[0045] This Comparative Example 1 is basically the same as Example 1, except that carbon nanoparticles are omitted in the mixed acid solution in step (1).

[0046] Comparative Example 2

[0047] Comparative Example 2 is basically the same as Example 1, except that tetrabutyl titanate is omitted from the dispersion in step (2).

[0048] Experimental Example 1

[0049] Figure 1 The image shows the electron microscope morphology of the aluminum product surface obtained in Example 1 of the present invention. As can be seen from the image, the uneven structure on the surface of the silicon dioxide and titanium dioxide composite coating of the aluminum product will generate more air gaps, effectively increasing the air content at the liquid-solid interface, thereby hindering the direct contact between the liquid and the solid surface and achieving a hydrophobic effect.

[0050] Experimental Example 2

[0051] 1. Superhydrophobic performance test: The water contact angle of the aluminum products obtained in Examples 1-3 and Comparative Examples 1-2 was measured using a contact angle measuring instrument. The results are shown in Table 1.

[0052] Table 1

[0053]

[0054] As shown in Table 1, the water contact angles of the products obtained in Examples 1-3 of the present invention are all greater than those in Comparative Examples 1 and 2, and the contact angles of Examples 1-3 are all higher than 150°. This indicates that the aluminum metal material obtained by the present invention has good superhydrophobic properties. When water comes into contact with the surface of the material, it is easy to roll off the surface and not easy to penetrate. During the rolling off process, the water droplets can carry away the contaminants, thus indicating that the material has excellent self-cleaning properties.

[0055] 2. Photocatalytic experiment: Take 50 mL of methylene blue solution with a concentration of 15 mg / L and place it in a petri dish. Take out the aluminum metal materials from Examples 1-3 and Comparative Examples 1-2 and put them into the methylene blue solution, completely covering the metal materials. Then place the above petri dish under a 300 W xenon lamp, with the distance between the petri dish and the xenon lamp being 20 cm. Then measure the absorbance of each group of methylene blue solutions at 6 h and 12 h after photocatalysis, respectively, with a test wavelength of 664 nm, and calculate the degradation rate of methylene blue.

[0056] Table 2

[0057]

[0058] As shown in Table 2, the degradation rate of methylene blue in Examples 1-3 of this invention is significantly higher than that in Comparative Example 2. Examples 1-3 all underwent titanium dioxide-silica composite coating treatment, while Comparative Example 2 omitted the addition of tetrabutyl titanate during sol preparation. This indicates that the titanium dioxide-silica composite coating in this invention can enhance the photocatalytic activity of the material and exhibit better superhydrophobicity.

[0059] Experimental Example 3

[0060] The tensile strength of the aluminum products obtained in Examples 1-3 and Comparative Examples 1-2 of this invention was tested according to GB / T228.1-2021.

[0061] A 1000# sandpaper was selected and a 50g weight was placed on the sandpaper as a load. The surface of the samples in Examples 1-3 and Comparative Examples 1-2 was rubbed 10 times with the 1000# sandpaper, and the wear amount per unit area of ​​the material was calculated.

[0062] The Vickers hardness of the aluminum products obtained in Examples 1-3 and Comparative Examples 1-2 of this invention was tested according to GB / T4340.1-2009. The results are shown in Table 3.

[0063] Table 3

[0064]

[0065] As shown in Table 3, the wear rate of the metal materials obtained in Examples 1-3 of this invention is maintained at around 0.69-0.75, the tensile strength can reach over 625 MPa, and the hardness can reach over 163 HB. Their wear resistance, tensile strength, and hardness are all superior to those of Comparative Examples 1 and 2. These results demonstrate that the aluminum metal materials obtained by this invention possess excellent wear resistance, strength, and hardness.

[0066] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them. The basic principles and main features of the present invention have been described above with specific implementation schemes. Based on the present invention, some modifications or substitutions can be made, but these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of protection claimed by the present invention.

Claims

1. A method for preparing a high-strength decorative aluminum product metal material, characterized in that, Includes the following steps: (1) Carbon nanoparticles, sulfuric acid and oxalic acid are added to water to prepare a mixed acid solution. The aluminum substrate is immersed in the mixed acid solution for anodizing. Then, after cleaning and drying, a pretreated aluminum substrate is obtained. (2) Add polyoxymethylene fiber to the dispersion, heat to react and obtain a mixture, coat the mixture on the surface of the pretreated aluminum substrate, then heat treat, age at room temperature, clean and dry to obtain high-strength decorative aluminum product metal material. The dispersion in step (2) is prepared by mixing anhydrous ethanol, tetraethyl orthosilicate, tetrabutyl titanate, silane coupling agent KH550, dodecyltrimethylammonium chloride and hexamethylenetetramine.

2. The method for preparing high-strength decorative aluminum product metal material according to claim 1, characterized in that, In step (1), the mass ratio of carbon nano-onion, sulfuric acid, and oxalic acid is (3-5):(100~200):(15~25), wherein the concentration of carbon nano-onion in water is 3~5 g / L.

3. The method for preparing high-strength decorative aluminum product metal material according to claim 1, characterized in that, The voltage for anodizing in step (1) is 20~50 V, and the current density is 2~5 A / dm³. 2 The time is 0.5 to 3 hours.

4. The method for preparing high-strength decorative aluminum product metal material according to claim 1, characterized in that, The ratio of anhydrous ethanol, tetraethyl orthosilicate, tetrabutyl titanate, silane coupling agent, dodecyltrimethylammonium chloride, and hexamethylenetetramine is 1000mL: 40~50mL: 40~50mL: 5~30g: 10~20g: 2~5g.

5. The method for preparing high-strength decorative aluminum product metal material according to claim 1, characterized in that, In step (2), the mass ratio of polyoxymethylene fiber, dispersion and aluminum matrix is ​​1:(20~40):(40~80).

6. The method for preparing high-strength decorative aluminum product metal material according to claim 1, characterized in that, The heating reaction in step (2) is carried out at a temperature of 30~70℃ for 8~10h.

7. The method for preparing high-strength decorative aluminum product metal material according to claim 1, characterized in that, The heat treatment in step (2) is carried out at a temperature of 140~200℃ for 1~5h; the aging time is 15~25h.

8. The method for preparing high-strength decorative aluminum product metal material according to claim 1, characterized in that, The aluminum matrix in step (1) consists of the following components by weight percentage. Composition: Zn: 6.72-7.05 wt%, Mg: 1.62-1.94 wt%, Ti: 0.01-0.05 wt%, Zr: 0.12-0.19 wt%, Fe: <0.1 wt%, Si: <0.07 wt%, Mn: <0.05 wt%, Cr: <0.05 wt%, balance Al.

9. A high-strength decorative aluminum product metal material, characterized in that, It is prepared by the preparation method according to any one of claims 1-8.

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