Laser surface texturing processing method for stain-resistant and corrosion-resistant aluminum bronze

Abstract

The invention relates to a laser surface texturing processing method for stain-resistant and corrosion-resistant aluminum bronze, which comprises the following steps of: preparing an aluminum bronze workpiece, performing pretreatment of polishing and cleaning, etching the surface of the workpiece by adopting nanosecond laser to form a peak-shaped micro-nano surface structure, and performing heat treatment to obtain a stain-resistant and corrosion-resistant aluminum bronze surface. Chemical modification of the micro-nano surface structure is completed, and the stain-resistant and corrosion-resistant aluminum bronze is obtained. The purpose of improving the super-hydrophobicity, marine pollution resistance and marine corrosion resistance of the aluminum bronze is achieved.

Description

Technical Field

[0001] The present invention relates to the technical field of micro-nano processing, and particularly to a laser surface texturing processing method for stain- and corrosion-resistant aluminum bronze. Background Art

[0002] Due to its excellent mechanical properties and chemical stability, aluminum bronze materials play an important role in the shipbuilding industry and are commonly used in the manufacture of key components such as propellers, valves, and pump bodies. In the marine environment, due to the widespread presence of microorganisms, aluminum bronze components are prone to severe biocorrosion. The attachment and corrosion of microorganisms, as well as the deposition of marine mud, have become the main factors restricting the service life of marine equipment. Aluminum bronze with a superhydrophobic surface can significantly reduce the risk of microorganism attachment and corrosion. By constructing surface micro-nano structures or applying superhydrophobic coatings, aluminum bronze with excellent stain- and corrosion-resistant properties can be prepared. Currently, common preparation methods include electrochemical deposition, colloidal templating, and sol-gel methods, etc. However, these methods generally have problems such as complex processes, cumbersome operations, low processing efficiency, and environmental pollution.

[0003] Chinese Patent with Publication No. CN117210813A discloses a method for superhydrophobizing the surface of aluminum bronze and the obtained aluminum bronze. Using a hydrochloric acid solution of ferric chloride hexahydrate as an etching solution, the aluminum bronze is first pretreated to remove surface oil and grease. Subsequently, the pretreated aluminum bronze is chemically etched with the etching solution, and then blown dry with cold air to obtain a rough-structured aluminum bronze surface. Finally, it is modified with 1H,1H,2H,2H-perfluorodecyltriethoxysilane to self-assemble a superhydrophobic film on the rough surface of the aluminum bronze, thus obtaining the superhydrophobic surface of the aluminum bronze. Compared with the prior art, the present invention uses a chemical etching method to construct a rough structure on the surface of aluminum bronze, which is beneficial to the adsorption of 1H,1H,2H,2H-perfluorodecyltriethoxysilane. The preparation process is simple, the conditions are mild, the stability is relatively high, it is green and environmentally friendly. The superhydrophobic surface of the aluminum bronze obtained by the preparation has a contact angle of more than 160° and good corrosion resistance.

[0004] The above prior art solutions have the following defects: Although the preparation process of the chemical etching method is relatively simple, specific chemical reagents still need to be used, which may lead to the risk of environmental pollution, and the reaction conditions need to be strictly controlled during the treatment process to ensure the consistency of the etching effect. In addition, the superhydrophobic surface prepared by the chemical etching method may experience a decrease in hydrophobic performance due to the erosion of environmental factors during long-term use. Therefore, it is particularly important to explore a more efficient, environmentally friendly, and stable method for superhydrophobizing the surface of aluminum bronze.

[0005] As an advanced method for surface processing and modification of materials, laser etching technology has attracted much attention due to its advantages such as high precision, environmental friendliness, high processing efficiency, and strong process controllability. By optimizing the laser processing strategy, a textured structure with specific morphological characteristics is prepared on the surface of aluminum bronze, which can significantly improve the hydrophobic properties of the aluminum bronze surface, enhance its anti-fouling and corrosion resistance, and thus extend the service life of aluminum bronze components. Therefore, laser etching technology provides an innovative laser engineering solution for solving the anti-corrosion and anti-fouling problems of marine equipment. Summary of the Invention

[0006] The problem to be solved by the present invention is to provide a laser surface texturing processing method for anti-fouling and corrosion-resistant aluminum bronze in view of the above-mentioned deficiencies in the prior art, which achieves the purpose of improving the superhydrophobic, marine anti-fouling, and marine corrosion-resistant properties of aluminum bronze.

[0007] The above-mentioned invention purpose of the present invention is achieved through the following technical solutions: A laser surface texturing processing method for anti-fouling and corrosion-resistant aluminum bronze includes the following steps: preparing an aluminum bronze workpiece, first performing pre-treatment of grinding and cleaning, then using nanosecond laser to etch the surface of the workpiece to form a micro-nano surface structure in the shape of mountains, and then performing heat treatment to complete the chemical modification of the micro-nano surface structure, obtaining anti-fouling and corrosion-resistant aluminum bronze.

[0008] Further, during the grinding process, sandpapers with specifications of 80#, 500#, 800#, 1000#, 1500#, and 2000# are used to gradually grind the surface of the aluminum bronze workpiece until the surface roughness of the workpiece ≤ 0.55 µm.

[0009] Further, during the cleaning process, the workpiece is sequentially placed in acetone solution and deionized water, ultrasonically cleaned for 8 - 12 min, and then dried with compressed air.

[0010] Further, during the etching process, the wavelength of the nanosecond pulsed laser is controlled to be 1064 nm.

[0011] Still further, during the etching process, the laser frequency of the nanosecond pulsed laser is controlled to be 15 - 25 kHz, the spot diameter is 110 - 120 µm, and the maximum output power is 180 - 220 W.

[0012] Furthermore, during the etching process, the etching is carried out in an argon atmosphere.

[0013] Most further, during the etching process, the scanning pitch of the nanosecond pulsed laser is controlled to be 4 - 6 µm, the scanning speed is 1.5 - 2.0 m / s, and the laser power is 80 - 120 W.

[0014] Further, during the heat treatment process, an oven is used for heat treatment.

[0015] Still further, during the heat treatment process, the heating temperature of the heat treatment is controlled to be 150 - 170 °C, and the heating time is 1.5 - 2.5 h.

[0016] Even further, during the heat treatment process, the heat treatment is carried out in a vacuum environment.

[0017] In summary, the beneficial technical effects of the present invention are as follows: 1. For the preparation method involved in the present invention, its steps are designed very concisely and clearly, and are easy to operate, which significantly improves the efficiency of the entire processing process. At the same time, this method also embodies the concept of green chemistry during implementation, greatly reducing costs and meeting the requirements of sustainable development; 2. For the stain - and corrosion - resistant aluminum bronze material prepared by the present invention, its resistance to particulate pollutants and adhesive pollutants is significantly higher than that of the original surface of aluminum bronze without any treatment, demonstrating excellent stain - resistant performance. This enables the material to maintain the cleanliness of its surface and the integrity of its functions in various harsh environments; 3. The stain - and corrosion - resistant aluminum bronze material prepared by the present invention also has far higher resistance to microorganisms than the untreated original surface of aluminum bronze. This indicates that the material has excellent corrosion - resistant performance, can effectively prevent corrosion problems caused by microorganisms, thereby extending the service life of the material and ensuring its reliability in various application scenarios. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 is a schematic flow chart of the method provided in Embodiment 1 of the present invention; Figure 2 is a scanning electron microscope image of the workpiece obtained from S1 and S2 in Embodiment 2 of the present invention; Figure 3 is a static contact angle diagram of the workpiece obtained from S1 and S3 in Embodiment 2 of the present invention; Figure 4 is a diagram of the anti - fouling performance test of the stain - and corrosion - resistant aluminum bronze prepared in Embodiment 2 of the present invention against particulate pollutants; Figure 5 is a diagram of the anti - fouling performance test of the stain - and corrosion - resistant aluminum bronze prepared in Embodiment 2 of the present invention against adhesive pollutants; Figure 6 is a diagram of the surface anti - corrosion performance test of the stain - and corrosion - resistant aluminum bronze prepared in Embodiment 3 of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0019] In order to make the technical means, creative features, achieved objectives and functions of the present invention clearer and easier to understand, the present invention will be further described below in conjunction with the accompanying drawings and specific embodiments.

[0020] Example 1: Refer to Figure 1 , which is a laser surface texturing processing method for stain-resistant and corrosion-resistant aluminum bronze disclosed by the present invention, including the following steps: preparing an aluminum bronze workpiece, first performing pre-treatment of grinding and cleaning, and then using a nanosecond laser to etch the surface of the workpiece to form a micro-nano surface structure in the shape of mountains, and then performing heat treatment to complete the chemical modification of the micro-nano surface structure, thereby obtaining stain-resistant and corrosion-resistant aluminum bronze.

[0021] Example 2: It is a laser surface texturing processing method for stain-resistant and corrosion-resistant aluminum bronze disclosed by the present invention. The difference from Example 1 is that it includes the following steps: S1: Prepare an aluminum bronze workpiece, first successively polish the surface of the aluminum bronze workpiece with sandpapers of specifications 80#, 500#, 800#, 1000#, 1500#, and 2000# until the surface roughness of the workpiece ≤ 0.55 µm, then place the workpiece successively into acetone solution and deionized water, perform ultrasonic cleaning for 10 min, and then use compressed air to dry the workpiece to obtain a clean workpiece; S2: Under an argon atmosphere, use a nanosecond laser with a wavelength of 1064 nm to etch the surface of the workpiece obtained in S1. Control the laser frequency of the nanosecond pulsed laser to be 20 kHz, the spot diameter to be 115 µm, the maximum output power to be 200 W, the scanning pitch to be 5 µm, the scanning speed to be 1.7 m / s, and the laser power to be 115 W to form a micro-nano surface structure in the shape of mountains; S3: Transfer the workpiece obtained in S2 to a vacuum drying oven for heat treatment, control the heating temperature of the heat treatment to be 160 °C, and the heating time to be 2.0 h to obtain stain-resistant and corrosion-resistant aluminum bronze.

[0022] In order to verify the influence of the preparation method of the present invention on the improvement of the superhydrophobic, marine stain resistance, and marine corrosion resistance of stain-resistant and corrosion-resistant aluminum bronze, the following tests were carried out.

[0023] (1) Micro-nano surface structure: The workpieces obtained in S1 and S2 were respectively detected by a scanning electron microscope. The results are as Figure 2 shown. After the etching process was completed, a regular and periodic textured structure was formed on the surface of the aluminum bronze workpiece, that is, a periodic textured structure in the shape of mountains was formed on the surface of the aluminum bronze workpiece, distributed in the horizontal and vertical directions.

[0024] (2) Superhydrophobic performance: The static contact angle of the stain-resistant and corrosion-resistant aluminum bronze obtained in S3 was detected. The results are as Figure 3 shown. The contact angle with the water droplet is 151 ± 1 °, and the water droplet is 4 µL.

[0025] (3)Anti-particle contamination performance: To simulate particulate pollutants such as insoluble sediment in the ocean, an aqueous solution of chalk dust is used as the simulated pollutant. The specific experimental steps are as follows: Preparation of the simulated pollutant: Weigh 100 grams of chalk dust and dissolve it in 250 milliliters of deionized water. Stir well until the chalk dust is evenly dispersed to form an aqueous solution of chalk dust. Workpiece preparation: Take an untreated aluminum bronze workpiece and an aluminum bronze workpiece with superhydrophobic properties after laser etching. Clean the surfaces of the two workpieces with deionized water. Anti-fouling performance test: Use the untreated aluminum bronze workpiece and the aluminum bronze workpiece after laser etching as the control group and the experimental group. Immerse the two groups of workpieces in the aqueous solution of chalk dust at the same time. The results are as Figure 4 shown. Let the workpieces soak in the solution for 1 minute, then take them out at the same time for surface contamination evaluation. It is observed that a large amount of chalk dust particles remain on the original surface of the untreated aluminum bronze. In contrast, the surface of the superhydrophobic aluminum bronze after laser etching remains clean and dry, with no obvious chalk dust particles remaining.

[0026] (4)Anti-adhesion contamination performance: To simulate adhesive pollutants such as marine mud in the ocean, a starch solution is used as the simulated pollutant. The specific experimental steps are as follows: Preparation of the simulated pollutant: Weigh 150 grams of starch and dissolve it in 250 milliliters of deionized water. Stir well until the starch is evenly dispersed to form a thick starch solution. Workpiece preparation: Take an untreated aluminum bronze workpiece and an aluminum bronze workpiece with superhydrophobic properties after laser etching. Clean the surfaces of the two workpieces with deionized water. Anti-fouling performance test: Use the untreated aluminum bronze workpiece and the aluminum bronze workpiece after laser etching as the control group and the experimental group. Immerse the two groups of workpieces in the starch solution at the same time. The results are as Figure 5 shown. Let the workpieces soak in the solution for 1 minute, then take them out at the same time for surface contamination evaluation. It is observed that a large amount of starch solution adheres to the original surface of the untreated aluminum bronze, and the pollution situation is relatively serious. In contrast, the surface of the superhydrophobic aluminum bronze after laser etching has almost no obvious pollution, showing good resistance to adhesive pollutants.

[0027] From the 3rd to 4th tests, it can be clearly seen that the superhydrophobic aluminum bronze surface prepared by the present invention has significant advantages in terms of anti-adhesion and anti-particle pollutants, and its anti-fouling performance is much better than the original surface of untreated aluminum bronze. This result indicates that the superhydrophobic aluminum bronze surface of the present invention can effectively resist the adhesion of adhesive and particulate pollutants and has important practical application value.

[0028] (5)Marine corrosion resistance: To simulate a large number of microorganisms in the ocean, an Escherichia coli suspension is used as the simulated microorganism. The specific experimental steps are as follows: Preparation of Escherichia coli suspension: Put the Escherichia coli strain into an incubator at 37 °C for 12 h for activation. Use a measuring cylinder to measure 20 mL of the activated strain and pour it into a conical flask. Add sterilized culture medium to the conical flask up to the bottle mouth, ensuring that the liquid level is tangent to the bottom of the stopper to exclude the air in the bottle. Put the conical flask into the incubator at 37 °C again for 72 h to fully activate the Escherichia coli. Workpiece preparation: Take untreated aluminum bronze workpieces and aluminum bronze workpieces with superhydrophobic surfaces after laser etching. Put the workpieces into a culture flask to ensure that the microbial suspension completely covers the upper surface of the aluminum bronze workpieces. Corrosion resistance test: Use the original surface of untreated aluminum bronze as the control group and the superhydrophobic aluminum bronze surface as the experimental group. Put the culture flask containing the aluminum bronze workpieces in the microbial suspension into an incubator at 37 °C for 5 days to promote the attachment, growth, and reproduction of active microorganisms on the aluminum bronze surface. Take out the workpieces after 5 days, wash them twice with phosphate buffer solution and distilled water, and then place them in the air for 1 to 5 days for observation. The observation results show that the original surface of untreated aluminum bronze is severely corroded. In contrast, the superhydrophobic aluminum bronze surface after laser etching has only slight corrosion, and the results are as Figure 6 shown.

[0029] Through the 5th test, it can be clearly seen that the aluminum bronze surface with superhydrophobic characteristics prepared by the present invention has significant advantages in terms of corrosion resistance, and its corrosion resistance ability is far superior to the original surface of untreated aluminum bronze. This result indicates that the superhydrophobic aluminum bronze surface of the present invention can effectively resist corrosion caused by microorganisms and has important practical application value.

[0030] Example 3: A laser surface texturing processing method for stain-resistant and corrosion-resistant aluminum bronze disclosed in the present invention, which is different from Example 1 in that it includes the following steps, S1 Prepare an aluminum bronze workpiece. First, successively polish the surface of the aluminum bronze workpiece with sandpapers of specifications 80#, 500#, 800#, 1000#, 1500#, and 2000# until the surface roughness of the workpiece ≤ 0.55 µm. Then, put the workpiece into acetone solution and deionized water in turn, and ultrasonically clean it for 9 min. Then, use compressed air to dry the workpiece to obtain a clean workpiece; S2 Under an argon atmosphere, use a nanosecond laser with a wavelength of 1064 nm to etch the surface of the workpiece obtained in S1. Control the laser frequency of the nanosecond pulsed laser to be 24 kHz, the spot diameter to be 118 µm, the maximum output power to be 190 W, the scanning pitch to be 5 µm, the scanning speed to be 1.8 m / s, and the laser power to be 90 W to form a mountain-like micro-nano surface structure; S3 transfers the workpiece obtained in S2 to a vacuum drying oven for heat treatment, controlling the heating temperature of the heat treatment to be 165 °C and the heating time to be 2.0 h to obtain stain- and corrosion-resistant aluminum bronze.

[0031] Example 4: A laser surface texturing processing method for stain- and corrosion-resistant aluminum bronze disclosed by the present invention. The difference from Example 1 is that it includes the following steps. S1 Prepare an aluminum bronze workpiece. First, successively polish the surface of the aluminum bronze workpiece with sandpapers of specifications 80#, 500#, 800#, 1000#, 1500#, and 2000# until the surface roughness of the workpiece ≤ 0.55 µm. Then, place the workpiece successively in an acetone solution and deionized water, ultrasonically clean for 8 min, and then use compressed air to dry the workpiece to obtain a clean workpiece. S2 Under an argon atmosphere, use a nanosecond laser with a wavelength of 1064 nm to etch the surface of the workpiece obtained in S1, controlling the laser frequency of the nanosecond pulsed laser to be 15 kHz, the spot diameter to be 110 µm, the maximum output power to be 180 W, the scanning pitch to be 4 µm, the scanning speed to be 1.5 m / s, and the laser power to be 80 W to form a mountain-shaped micro-nano surface structure. S3 transfers the workpiece obtained in S2 to a vacuum drying oven for heat treatment, controlling the heating temperature of the heat treatment to be 150 °C and the heating time to be 1.5 h to obtain stain- and corrosion-resistant aluminum bronze.

[0032] Example 5: A laser surface texturing processing method for stain- and corrosion-resistant aluminum bronze disclosed by the present invention. The difference from Example 1 is that it includes the following steps. S1 Prepare an aluminum bronze workpiece. First, successively polish the surface of the aluminum bronze workpiece with sandpapers of specifications 80#, 500#, 800#, 1000#, 1500#, and 2000# until the surface roughness of the workpiece ≤ 0.55 µm. Then, place the workpiece successively in an acetone solution and deionized water, ultrasonically clean for 12 min, and then use compressed air to dry the workpiece to obtain a clean workpiece. S2 Under an argon atmosphere, use a nanosecond laser with a wavelength of 1064 nm to etch the surface of the workpiece obtained in S1, controlling the laser frequency of the nanosecond pulsed laser to be 25 kHz, the spot diameter to be 120 µm, the maximum output power to be 220 W, the scanning pitch to be 6 µm, the scanning speed to be 2.0 m / s, and the laser power to be 120 W to form a mountain-shaped micro-nano surface structure. S3 transfers the workpiece obtained in S2 to a vacuum drying oven for heat treatment, controlling the heating temperature of the heat treatment to be 170 °C and the heating time to be 2.5 h to obtain stain- and corrosion-resistant aluminum bronze.

[0033] 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. Although the present invention has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that the technical solutions of the present invention can be modified or equivalently replaced without departing from the spirit and scope of the technical solutions of the present invention, and they should all be covered within the scope of the claims of the present invention.

Claims

1. A laser surface texturing method for stain-resistant and corrosion-resistant aluminum bronze, characterized in that: The method comprises the following steps: preparing an aluminum bronze workpiece, pre-treating it by grinding and cleaning, etching the workpiece surface by nanosecond laser to form a peak-shaped micro-nano surface structure, and then performing heat treatment to complete the chemical modification of the micro-nano surface structure to obtain a stain-resistant and corrosion-resistant aluminum bronze.

2. The laser surface texturing method of stain-resistant and corrosion-resistant aluminum bronze according to claim 1, characterized in that: During the polishing process, the surface of the aluminum bronze workpiece is polished step by step using sandpapers of specifications 80#, 500#, 800#, 1000#, 1500#, and 2000# in sequence until the surface roughness of the workpiece is ≤0.55µm.

3. The laser surface texturing method of stain-resistant and corrosion-resistant aluminum bronze according to claim 1, characterized in that: During the cleaning process, the workpiece is placed in acetone solution and deionized water in turn, ultrasonically cleaned for 8 to 12 minutes, and then the workpiece is blown dry with compressed air.

4. The laser surface texturing method of stain-resistant and corrosion-resistant aluminum bronze according to claim 1, characterized in that: During the etching process, the wavelength of the nanosecond pulse laser is controlled to be 1064 nm.

5. The laser surface texturing method of stain-resistant and corrosion-resistant aluminum bronze according to claim 1, characterized in that: During the etching process, the laser frequency of the nanosecond pulse laser is controlled to be 15-25 kHz, the spot diameter is 110-120 µm, and the maximum output power is 180-220 W.

6. The laser surface texturing method of stain-resistant and corrosion-resistant aluminum bronze according to claim 1, characterized in that: In the etching process, the etching is performed under an argon atmosphere.

7. The laser surface texturing method of stain-resistant and corrosion-resistant aluminum bronze according to claim 1, characterized in that: During the etching process, the scanning interval of the nanosecond pulse laser is controlled to be 4-6 µm, the scanning speed is controlled to be 1.5-2.0 m / s, and the laser power is controlled to be 80-120 W.

8. The laser surface texturing method of stain-resistant and corrosion-resistant aluminum bronze according to claim 1, characterized in that: During the heat treatment process, a drying oven is used for heat treatment.

9. The laser surface texturing method of stain-resistant and corrosion-resistant aluminum bronze according to claim 1, characterized in that: During the heat treatment process, the heating temperature of the heat treatment is controlled to be 150-170° C., and the heating time is 1.5-2.5 hours.

10. The laser surface texturing processing method of stain-resistant and corrosion-resistant aluminum bronze according to claim 1, characterized in that: During the heat treatment process, the heat treatment is performed in a vacuum environment.

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