A high-performance corrosion-resistant aluminum bronze and its preparation process

Abstract

The present invention relates to the technical field of aluminum bronze, specifically to a high-performance corrosion-resistant aluminum bronze and a preparation process thereof. The present invention comprises the following steps: S1: putting raw materials into a vacuum medium-frequency induction furnace for smelting to obtain an alloy melt, and casting the alloy melt into an ingot; hot-extruding the ingot to obtain an extruded billet; stretching and annealing the extruded billet to obtain an aluminum bronze; step S2: uniformly mixing water-based epoxy resin, zinc phosphate, modified graphene oxide, a curing agent, a defoaming agent, a film-forming aid, a leveling agent, and deionized water to obtain a corrosion-resistant coating; step S3: coating the corrosion-resistant coating on the surface of the aluminum bronze, and curing to obtain a high-performance corrosion-resistant aluminum bronze. The high-performance corrosion-resistant aluminum bronze prepared by the present invention not only has excellent mechanical properties, but also has excellent corrosion resistance.

Description

Technical Field

[0001] The present invention relates to the technical field of aluminum bronze, in particular to a high-performance corrosion-resistant aluminum bronze and a preparation process thereof. Background Art

[0002] Aluminum bronze is an alloy primarily composed of copper, aluminum, and smaller amounts of other elements such as iron, nickel, and manganese. Its excellent corrosion resistance, wear resistance, and mechanical properties make it widely used in marine engineering, chemical equipment, and electrical contactors. This alloy excels in resisting seawater corrosion, mechanical friction, and high-strength requirements, making it suitable for a variety of harsh engineering applications.

[0003] However, with the continuous improvement of modern industry's requirements for material performance, especially for applications in extreme environments, the market demand for high-performance, corrosion-resistant aluminum bronze is increasing. Although aluminum bronze has relatively good corrosion resistance under general conditions, its corrosion resistance is still insufficient in certain special environments (such as high salt, high temperature or strong acid and alkali environments), and localized corrosion and pitting corrosion are prone to occur. These problems not only affect the service life of the material, but also limit its application in a wider range of fields. At the same time, due to insufficient hydrophobicity, water accumulates on the surface of aluminum bronze, which may cause localized corrosion or pitting corrosion. Especially in media containing salt or pollutants, these water accumulation areas often become the occurrence points of corrosion, further accelerating the spread of corrosion.

[0004] Therefore, we propose a high-performance corrosion-resistant aluminum bronze and its preparation process. Summary of the Invention

[0005] The purpose of the present invention is to provide a high-performance corrosion-resistant aluminum bronze and a preparation process thereof to solve the problems raised in the prior art.

[0006] To achieve the above object, the present invention provides the following technical solutions:

[0007] A preparation process for high-performance corrosion-resistant aluminum bronze comprises the following steps:

[0008] Step S1: placing raw materials into a vacuum medium frequency induction furnace for smelting to obtain an alloy melt, which is then cast into an ingot; hot extruding the ingot to obtain an extruded billet; and stretching and annealing the extruded billet to obtain aluminum bronze.

[0009] Step S2: uniformly mixing a waterborne epoxy resin, zinc phosphate, modified graphene oxide, a curing agent, a defoaming agent, a film-forming aid, a leveling agent, and deionized water to obtain a corrosion-resistant coating;

[0010] Step S3: coating the corrosion-resistant coating on the surface of the aluminum bronze, and curing the coating to obtain high-performance corrosion-resistant aluminum bronze.

[0011] Furthermore, the raw material includes the following components in percentage by mass: 8-12% aluminum, 2.5-5.0% nickel, 1-2% iron, 2-3% boron, 1-2% chromium, 1-2% manganese, 0.1-0.5% niobium, and the balance is copper.

[0012] Furthermore, the smelting temperature is 1200-1300° C., electromagnetic stirring is maintained during the smelting process, and the smelting time is 35-60 minutes.

[0013] Furthermore, the extrusion temperature is 700-800° C., and the extrusion ratio is 10-25.

[0014] Furthermore, the stretching speed is 4-12 m / min, and the stretching coefficient is 1.18-1.26.

[0015] Furthermore, the annealing process conditions are: annealing at 500-675° C. for 2-6 hours and then air cooling.

[0016] Furthermore, the corrosion-resistant coating includes the following components by weight: 50-60 parts of water-based epoxy resin, 4-8 parts of zinc phosphate, 6-12 parts of modified graphene oxide, 8-15 parts of curing agent, 0.5-1.2 parts of defoaming agent, 3-8 parts of film-forming aid, 0.3-0.8 parts of leveling agent, and 20-30 parts of deionized water.

[0017] Furthermore, the preparation method of the modified graphene oxide is as follows:

[0018] Step (1): polyvinyl pyrrolidone and anhydrous ethanol are mixed evenly, a graphene oxide aqueous solution is added, ultrasonic treatment is carried out for 30-60 minutes, ethyl orthosilicate, anhydrous ethanol and deionized water are added and mixed evenly, ammonia water is used to adjust the pH to 9-11, and the mixture is reacted at 40-50° C. for 10-12 hours, and then a mixed solution of γ-methacryloxypropyltrimethoxysilane and anhydrous ethanol is added, stirred for 3-5 hours, and after centrifugation, washing and drying, a single layer of coated graphene oxide is obtained;

[0019] Step (2): ultrasonically dispersing the monolayer coated graphene oxide in ethanol, adding methyl methacrylate, methacrylamide and 2-methyl-2-acrylic acid-2-hydroxyethyl ester phosphate, passing nitrogen, adding potassium persulfate, reacting at 70-80° C. for 10-12 hours, centrifuging, washing, and drying to obtain a double-layer coated graphene oxide;

[0020] Step (3): The double-layer coated graphene oxide, the fluorinated epoxy compound and tetrahydrofuran are mixed evenly, reacted at 40-50° C. for 8-10 hours, and then centrifuged, washed and dried to obtain modified graphene oxide.

[0021] Furthermore, in the step (1), the mass ratio of polyvinyl pyrrolidone, anhydrous ethanol and graphene oxide aqueous solution is 1: (50-60): (6-8).

[0022] Furthermore, the concentration of the graphene oxide aqueous solution is 10-20 mg / mL.

[0023] Furthermore, the amount of ethyl orthosilicate used is 0.3-0.5 times the mass of the graphene oxide aqueous solution.

[0024] Furthermore, in the step (1), the mass ratio of ethyl orthosilicate, anhydrous ethanol, deionized water, and γ-methacryloxypropyltrimethoxysilane is 1:(3-5):(0.6-1.0):(0.3-0.5).

[0025] Furthermore, the mass ratio of the γ-methacryloxypropyltrimethoxysilane to anhydrous ethanol is 1:(5-7).

[0026] Furthermore, the concentration of the ammonia water is 25-28 wt%.

[0027] Furthermore, in step (2), the mass ratio of the monolayer coated graphene oxide to ethanol is 1:(100-150).

[0028] Furthermore, in the step (2), the mass ratio of the monolayer coated graphene oxide, methyl methacrylate, methacrylamide and 2-methyl-2-acrylic acid-2-hydroxyethyl phosphate is 1:(1-2):(2-4):(0.5-1.5).

[0029] Furthermore, in the step (2), the amount of potassium persulfate used is 1-3% of the total mass of the monolayer coated graphene oxide, methyl methacrylate, methacrylamide and 2-methyl-2-acrylic acid-2-hydroxyethyl ester phosphate.

[0030] Furthermore, the mass ratio of the double-layer coated graphene oxide, the fluorinated epoxy compound and tetrahydrofuran is 1:(2-3):(4-6).

[0031] Furthermore, the preparation method of the fluorine-containing epoxy compound is as follows:

[0032] Trimethylolpropane triglycidyl ether, perfluoropolyether alcohol and tetrabutylammonium bromide are mixed evenly, reacted at 70-75°C for 3-5 hours, cooled to 50-55°C, sodium hydroxide is added, and the reaction is continued for 2-3 hours. After washing and vacuum distillation, a fluorine-containing epoxy compound is obtained.

[0033] Furthermore, the mass ratio of the trimethylolpropane triglycidyl ether, perfluoropolyether alcohol, tetrabutylammonium bromide and sodium hydroxide is 1:(3.5-5.0):(0.3-0.5):(1.5-2.0).

[0034] Furthermore, the coating thickness is 50-150 μm.

[0035] Compared with the prior art, the present invention has the following beneficial effects:

[0036] The present invention discloses a high-performance, corrosion-resistant aluminum bronze and a preparation process thereof. A sol-gel method is used with tetraethyl orthosilicate (TEOS) and γ-methacryloxypropyltrimethoxysilane (KH570) as binary modifiers to prepare high-performance silicon dioxide-coated graphene oxide (SiO2-GO) nanosheets, i.e., single-layer coated graphene oxide. This nanosheet can effectively reduce the number of pores on the coating surface, thereby reducing the possibility of corrosive medium intrusion and significantly improving the corrosion resistance of the aluminum bronze.

[0037] Then, under the action of an initiator, a polymer film is coated on the surface of the single-layer coated graphene oxide using methyl methacrylate, methacrylamide and 2-methyl-2-acrylate-2-hydroxyethyl phosphate as raw materials. The introduction of amino groups from the methacrylamide improves compatibility with the epoxy resin matrix. At the same time, the polymer film also contains phosphate groups, which can bind to the metal surface and produce a chelating effect, passivating the metal surface, thereby improving the metal's corrosion resistance and antioxidant properties. The double-layer coating structure achieves uniform dispersion of the nanofiller and the resin matrix through chemical bonding, reducing agglomeration.

[0038] In order to further improve the hydrophobic properties of the material, the scheme uses a ring-opening reaction between trimethylolpropane triglycidyl ether and perfluoropolyether alcohol to prepare a fluorinated epoxy compound; using the epoxy-amino ring-opening reaction, fluorinated groups are introduced on the surface of the double-layer coated graphene oxide, which can effectively reduce the attachment of surface water molecules and improve the material's ability to be used in humid environments, thereby realizing a gradient modified structure of "inorganic SiO2-organic polymer-fluorinated chain segment", which not only has excellent hydrophobicity, but also enhances corrosion resistance and long-term stability, so that the modified graphene oxide can jointly improve the corrosion resistance of the coating when compounded with zinc phosphate, thereby extending the service life of the material. DETAILED DESCRIPTION

[0039] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0040] In this embodiment, water-based epoxy resin: model CYDW-100, purchased from Guangzhou Hengjia Chemical Co., Ltd.; zinc phosphate: model ZP-55, purchased from Guangxi Kelifang New Materials Co., Ltd.; graphene oxide: thickness 1-3 nm, diameter 4-7 μm, number of layers 2-5 layers, purchased from Zhejiang Zhitianawei New Materials Co., Ltd.; perfluoropolyether alcohol: model P910026, purchased from Shanghai MacLean Biochemical Technology Co., Ltd.; curing agent: water-based epoxy resin curing agent CYDHD-220, Baling Petrochemical; leveling agent: model Keying KYC-615; defoaming agent: model BYK-028; film-forming aid: alcohol ester twelve.

[0041] In the following examples and comparative examples, 1 part is equal to 10 g.

[0042] Example 1: A process for preparing high-performance corrosion-resistant aluminum bronze, comprising the following steps:

[0043] Step S1: placing the raw materials into a vacuum medium frequency induction furnace for smelting at a smelting temperature of 1200° C., maintaining electromagnetic stirring during the smelting process, and smelting for 35 minutes to obtain an alloy melt, which is cast into an ingot; hot extruding the ingot at an extrusion temperature of 700° C. and an extrusion ratio of 10 to obtain an extruded billet; stretching the extruded billet at a stretching speed of 4 m / min and a stretching coefficient of 1.18, annealing at 500° C. for 2 hours, and then air cooling to obtain aluminum bronze;

[0044] Step S2: 50 parts of waterborne epoxy resin, 4 parts of zinc phosphate, 6 parts of modified graphene oxide, 8 parts of curing agent, 0.5 parts of defoaming agent, 3 parts of film-forming aid, 0.3 parts of leveling agent and 20 parts of deionized water are mixed to obtain a corrosion-resistant coating;

[0045] Step S3: applying a corrosion-resistant coating to the surface of the aluminum bronze (coating thickness is 100 μm), and after curing, obtaining a high-performance corrosion-resistant aluminum bronze;

[0046] The raw materials include the following components in percentage by mass: 8% aluminum, 2.5% nickel, 1% iron, 2% boron, 1% chromium, 1% manganese, 0.1% niobium, and the balance copper;

[0047] The preparation method of modified graphene oxide is as follows:

[0048] Step (1): 10 parts of polyvinyl pyrrolidone and 500 parts of anhydrous ethanol were mixed uniformly, 60 parts of a 10 mg / mL graphene oxide aqueous solution were added, and ultrasonic treatment was performed for 30 minutes. 18 parts of ethyl orthosilicate, 54 parts of anhydrous ethanol and 10.8 parts of deionized water were added and mixed uniformly. 25 wt% ammonia water was used to adjust the pH to 9. The mixture was reacted at 40° C. for 10 hours. A mixed solution of 5.4 parts of γ-methacryloxypropyltrimethoxysilane and 27 parts of anhydrous ethanol was added, and the mixture was stirred for 3 hours. After centrifugation, washing and drying, a monolayer of coated graphene oxide was obtained.

[0049] Step (2): ultrasonically dispersing 6 parts of the monolayer coated graphene oxide in 600 parts of ethanol, adding 6 parts of methyl methacrylate, 12 parts of methacrylamide and 3 parts of 2-methyl-2-acrylic acid-2-hydroxyethyl ester phosphate, passing nitrogen gas, adding 0.27 parts of potassium persulfate, reacting at 70°C for 10 hours, centrifuging, washing and drying to obtain a double-layer coated graphene oxide;

[0050] Step (3): 10 parts of trimethylolpropane triglycidyl ether, 35 parts of perfluoropolyether alcohol and 3 parts of tetrabutylammonium bromide were mixed uniformly, reacted at 70°C for 3 hours, cooled to 50°C, added with 15 parts of sodium hydroxide, and continued to react for 2 hours. After washing and vacuum distillation, a fluorine-containing epoxy compound was obtained;

[0051] 6 parts of double-layer coated graphene oxide, 12 parts of fluorine-containing epoxy compound and 24 parts of tetrahydrofuran were mixed evenly, reacted at 40° C. for 8 hours, and then centrifuged, washed and dried to obtain modified graphene oxide.

[0052] Example 2: A process for preparing high-performance corrosion-resistant aluminum bronze, comprising the following steps:

[0053] Step S1: placing the raw materials into a vacuum medium frequency induction furnace for smelting at a smelting temperature of 1250° C., maintaining electromagnetic stirring during the smelting process, and smelting for 40 minutes to obtain an alloy melt, which is cast into an ingot; hot extruding the ingot at an extrusion temperature of 750° C. and an extrusion ratio of 15 to obtain an extruded billet; stretching the extruded billet at a stretching speed of 8 m / min and a stretching coefficient of 1.2, annealing at 600° C. for 4 hours, and then air cooling to obtain aluminum bronze;

[0054] Step S2: 55 parts of waterborne epoxy resin, 5 parts of zinc phosphate, 8 parts of modified graphene oxide, 10 parts of curing agent, 1 part of defoaming agent, 5 parts of film-forming aid, 0.5 parts of leveling agent and 25 parts of deionized water are mixed to obtain a corrosion-resistant coating;

[0055] Step S3: applying a corrosion-resistant coating to the surface of the aluminum bronze (coating thickness is 100 μm), and after curing, obtaining a high-performance corrosion-resistant aluminum bronze;

[0056] The raw materials include the following components in percentage by mass: aluminum 10%, nickel 4%, iron 1.5%, boron 2.5%, chromium 1.5%, manganese 1.5%, niobium 0.3%, and the balance copper;

[0057] The preparation method of modified graphene oxide is as follows:

[0058] Step (1): 10 parts of polyvinyl pyrrolidone and 550 parts of anhydrous ethanol were mixed uniformly, 70 parts of a 15 mg / mL graphene oxide aqueous solution were added, and ultrasonic treatment was performed for 50 minutes. 28 parts of ethyl orthosilicate, 112 parts of anhydrous ethanol and 25 parts of deionized water were added and mixed uniformly. 27 wt% ammonia water was used to adjust the pH to 11. The mixture was reacted at 45° C. for 11 hours. A mixed solution of 12 parts of γ-methacryloxypropyltrimethoxysilane and 72 parts of anhydrous ethanol was added, and the mixture was stirred for 4 hours. After centrifugation, washing and drying, a monolayer of coated graphene oxide was obtained.

[0059] Step (2): 8 parts of the monolayer coated graphene oxide were ultrasonically dispersed in 960 parts of ethanol, 12 parts of methyl methacrylate, 24 parts of methacrylamide and 8 parts of 2-methyl-2-acrylic acid-2-hydroxyethyl ester phosphate were added, nitrogen was introduced, 1.2 parts of potassium persulfate were added, and the mixture was reacted at 75° C. for 11 hours. After centrifugation, washing and drying, a double-layer coated graphene oxide was obtained;

[0060] Step (3): 5 parts of trimethylolpropane triglycidyl ether, 20 parts of perfluoropolyether alcohol and 2 parts of tetrabutylammonium bromide were mixed uniformly, reacted at 72°C for 4 hours, cooled to 52°C, added with 7.5 parts of sodium hydroxide, and continued to react for 2.5 hours. After washing and distillation under reduced pressure, a fluorine-containing epoxy compound was obtained;

[0061] 8 parts of double-layer coated graphene oxide, 20 parts of fluorine-containing epoxy compound and 40 parts of tetrahydrofuran were mixed evenly, reacted at 45° C. for 9 hours, and then centrifuged, washed and dried to obtain modified graphene oxide.

[0062] Example 3: A process for preparing high-performance corrosion-resistant aluminum bronze, comprising the following steps:

[0063] Step S1: placing the raw materials into a vacuum medium frequency induction furnace for smelting at a smelting temperature of 1300° C., maintaining electromagnetic stirring during the smelting process, and smelting for 60 minutes to obtain an alloy melt, which is cast into an ingot; hot extruding the ingot at an extrusion temperature of 800° C. and an extrusion ratio of 25 to obtain an extruded billet; stretching the extruded billet at a stretching speed of 12 m / min and a stretching coefficient of 1.26, annealing at 675° C. for 6 hours, and then air cooling to obtain aluminum bronze;

[0064] Step S2: 60 parts of waterborne epoxy resin, 8 parts of zinc phosphate, 12 parts of modified graphene oxide, 15 parts of curing agent, 1.2 parts of defoaming agent, 8 parts of film-forming aid, 0.8 parts of leveling agent and 30 parts of deionized water are mixed to obtain a corrosion-resistant coating;

[0065] Step S3: applying a corrosion-resistant coating to the surface of the aluminum bronze (coating thickness is 100 μm), and after curing, obtaining a high-performance corrosion-resistant aluminum bronze;

[0066] The raw materials include the following components in percentage by mass: aluminum 12%, nickel 5.0%, iron 2%, boron 3%, chromium 2%, manganese 2%, niobium 0.5%, and the balance copper;

[0067] The preparation method of modified graphene oxide is as follows:

[0068] Step (1): 10 parts of polyvinyl pyrrolidone and 600 parts of anhydrous ethanol were mixed uniformly, 80 parts of 20 mg / mL graphene oxide aqueous solution were added, and ultrasonic treatment was performed for 60 minutes. 40 parts of ethyl orthosilicate, 200 parts of anhydrous ethanol and 40 parts of deionized water were added and mixed uniformly. 28 wt% ammonia water was used to adjust the pH to 11. The mixture was reacted at 50° C. for 12 hours. A mixed solution of 20 parts of γ-methacryloxypropyltrimethoxysilane and 140 parts of anhydrous ethanol was added and stirred for 5 hours. After centrifugation, washing and drying, a monolayer of coated graphene oxide was obtained.

[0069] Step (2): ultrasonically dispersing 12 parts of the monolayer coated graphene oxide in 1800 parts of ethanol, adding 24 parts of methyl methacrylate, 48 parts of methacrylamide and 18 parts of 2-methyl-2-acrylic acid-2-hydroxyethyl ester phosphate, passing nitrogen gas, adding 3.06 parts of potassium persulfate, reacting at 80° C. for 12 hours, centrifuging, washing and drying to obtain a double-layer coated graphene oxide;

[0070] Step (3): 7.2 parts of trimethylolpropane triglycidyl ether, 36 parts of perfluoropolyether alcohol and 3.6 parts of tetrabutylammonium bromide were mixed uniformly, reacted at 75°C for 5 hours, cooled to 55°C, added with 14.4 parts of sodium hydroxide, and continued to react for 3 hours. After washing and distillation under reduced pressure, a fluorine-containing epoxy compound was obtained;

[0071] 12 parts of double-layer coated graphene oxide, 36 parts of fluorine-containing epoxy compound and 72 parts of tetrahydrofuran were mixed evenly, reacted at 50° C. for 10 hours, and then centrifuged, washed and dried to obtain modified graphene oxide.

[0072] Comparative Example 1: A process for preparing high-performance corrosion-resistant aluminum bronze, comprising the following processes:

[0073] The raw materials include the following components in percentage by mass: 10% aluminum, 4% nickel, 2.5% boron, 1.5% chromium, 1.5% manganese, 0.3% niobium, and the balance is copper. Compared with Example 2, Comparative Example 1 removes the iron element from the raw materials, and the other steps are the same as Example 2.

[0074] Comparative Example 2: A process for preparing high-performance corrosion-resistant aluminum bronze, comprising the following processes:

[0075] Compared with Example 2, Comparative Example 2 replaces the modified graphene oxide with a single-layer coated graphene oxide of the same mass, and the other steps are the same as those of Example 2.

[0076] Comparative Example 3: A process for preparing high-performance corrosion-resistant aluminum bronze, comprising the following processes:

[0077] Compared with Example 2, Comparative Example 3 removed 2-methyl-2-acrylic acid-2-hydroxyethyl ester phosphate in step (2), and the other steps were the same as those in Example 2.

[0078] Comparative Example 4: A process for preparing high-performance corrosion-resistant aluminum bronze, comprising the following processes:

[0079] The preparation method of modified graphene oxide is as follows:

[0080] Step (1): 10 parts of polyvinyl pyrrolidone and 550 parts of anhydrous ethanol were mixed uniformly, 70 parts of a 15 mg / mL graphene oxide aqueous solution were added, and ultrasonic treatment was performed for 50 minutes. 28 parts of ethyl orthosilicate, 112 parts of anhydrous ethanol and 25 parts of deionized water were added and mixed uniformly. 27 wt% ammonia water was used to adjust the pH to 11. The mixture was reacted at 45° C. for 11 hours. A mixed solution of 12 parts of γ-methacryloxypropyltrimethoxysilane and 72 parts of anhydrous ethanol was added, and the mixture was stirred for 4 hours. After centrifugation, washing and drying, a monolayer of coated graphene oxide was obtained.

[0081] Step (2): 8 parts of the monolayer coated graphene oxide were ultrasonically dispersed in 960 parts of ethanol, 12 parts of methyl methacrylate, 24 parts of methacrylamide and 8 parts of 2-methyl-2-acrylic acid-2-hydroxyethyl ester phosphate were added, nitrogen was introduced, 1.2 parts of potassium persulfate were added, and the mixture was reacted at 75° C. for 11 hours. After centrifugation, washing and drying, a double-layer coated graphene oxide was obtained;

[0082] Step (3): 5 parts of trimethylolpropane triglycidyl ether, 20 parts of perfluoropolyether alcohol and 2 parts of tetrabutylammonium bromide were mixed uniformly, reacted at 72°C for 4 hours, cooled to 52°C, added with 7.5 parts of sodium hydroxide, and continued to react for 2.5 hours. After washing and distillation under reduced pressure, a fluorine-containing epoxy compound was obtained;

[0083] 8 parts of double-layer coated graphene oxide, 4 parts of fluorinated epoxy compound and 40 parts of tetrahydrofuran were mixed evenly, reacted at 45°C for 9 hours, centrifuged, washed and dried to obtain modified graphene oxide;

[0084] Compared with Example 2, in step (3) of Comparative Example 4, the mass ratio of the double-layer coated graphene oxide and the fluorine-containing epoxy compound is 1:0.5, and the other steps are the same as those in Example 2.

[0085] Experiment: Take the high-performance corrosion-resistant aluminum bronze obtained in Examples 1-3 and Comparative Examples 1-4, prepare samples, test their properties respectively and record the test results:

[0086] Hardness test: An RTC TH700 digital Vickers hardness tester was used, with an indenter diameter of 5 mm and a loading force of 294 N. Each specimen was tested at five different points, and the average value was taken. During the test, the specimen was required to be perpendicular to the indenter and evenly contact the specimen surface. After indentation, the diagonal dimension of the indentation was measured, and the corresponding hardness value was then calculated based on the measured dimension.

[0087] Electrochemical test: A three-electrode test system was used, with 3.5 wt% NaCl aqueous solution as the test solution, a platinum electrode as the auxiliary electrode, a saturated calomel electrode (SCE) as the reference electrode, and the coating sample as the working electrode. The test was performed using a Shanghai Chenhua CHI660E electrochemical workstation. The test area of ​​the working electrode was 1 cm 2 , the test temperature is 25℃; the EIS test frequency range is 10 -2 Hz-10 5 Hz, amplitude of 10 mV, soak for 20 days, and record the data.

[0088] Hydrophilicity test: The contact angle was measured using an SDC-100 contact angle meter with a volume of 3 μL of deionized water.

[0089] The test results are as follows:

[0090] Hardness (HV) <![CDATA[Electrochemical impedance (Ω·cm 2 )]]> Contact angle (°) Example 1 472 <![CDATA[7.95×10 8 ]]> 122.4 Example 2 484 <![CDATA[9.87×10 8 ]]> 126.5 Example 3 480 <![CDATA[8.26×10 8 ]]> 125.2 Comparative Example 1 398 <![CDATA[7.64×10 8 ]]> 121.7 Comparative Example 2 447 <![CDATA[3.42×10 8 ]]> 97.5 Comparative Example 3 459 <![CDATA[6.59×10 8 ]]> 112.3 Comparative Example 4 468 <![CDATA[7.01×10 8 ]]> 104.6

[0091] According to the data in the above table, we can clearly draw the following conclusions:

[0092] 1. Compared with Examples 1-3, the hardness and electrochemical impedance of the product obtained in Comparative Example 1 are both reduced, indicating that the added iron element improves the hardness and corrosion resistance of the bronze alloy.

[0093] 2. Compared with Examples 1-3, the electrochemical impedance and contact angle of the products obtained in Comparative Examples 2-4 decreased. It can be seen that in Comparative Example 2, the modified graphene oxide prepared by the present invention has better hydrophobicity and corrosion resistance than the single-layer coated graphene oxide; in Comparative Example 3, 2-methyl-2-acrylic acid-2-hydroxyethyl phosphate was not introduced, resulting in a decrease in corrosion resistance; in Comparative Example 4, the amount of fluorinated epoxy compound added was reduced, so the hydrophobicity decreased.

[0094] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the invention can be embodied in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as illustrative and non-restrictive, and the scope of the invention is defined by the appended claims rather than the foregoing description, and it is intended that all variations that come within the meaning and range of equivalents of the claims be embraced therein.

Claims

1. A process for preparing high-performance corrosion-resistant aluminum bronze, characterized by: The steps include: Step S1: placing raw materials into a vacuum medium frequency induction furnace for smelting to obtain an alloy melt, which is then cast into an ingot; hot extruding the ingot to obtain an extruded billet; and stretching and annealing the extruded billet to obtain aluminum bronze. Step S2: uniformly mixing a waterborne epoxy resin, zinc phosphate, modified graphene oxide, a curing agent, a defoaming agent, a film-forming aid, a leveling agent, and deionized water to obtain a corrosion-resistant coating; Step S3: applying the corrosion-resistant coating on the surface of the aluminum bronze, and curing the coating to obtain high-performance corrosion-resistant aluminum bronze; The preparation method of the modified graphene oxide is as follows: Step (1): polyvinyl pyrrolidone and anhydrous ethanol are mixed evenly, graphene oxide aqueous solution is added, ultrasonic treatment is carried out for 30-60 minutes, ethyl orthosilicate, anhydrous ethanol and deionized water are added and mixed evenly, ammonia water is used to adjust the pH to 9-11, the reaction is carried out at 40-50°C for 10-12 hours, and then a mixed solution of γ-methacryloxypropyltrimethoxysilane and anhydrous ethanol is added, stirred for 3-5 hours, and after centrifugation, washing and drying, a single layer of coated graphene oxide is obtained; Step (2): ultrasonically dispersing the monolayer coated graphene oxide in ethanol, adding methyl methacrylate, methacrylamide and 2-methyl-2-acrylic acid-2-hydroxyethyl ester phosphate, passing nitrogen, adding potassium persulfate, reacting at 70-80°C for 10-12h, centrifuging, washing and drying to obtain a double-layer coated graphene oxide; Step (3): uniformly mixing the double-layer coated graphene oxide, the fluorinated epoxy compound and tetrahydrofuran, reacting at 40-50° C. for 8-10 hours, and obtaining modified graphene oxide after centrifugation, washing and drying; The preparation method of the fluorine-containing epoxy compound is as follows: Trimethylolpropane triglycidyl ether, perfluoropolyether alcohol and tetrabutylammonium bromide are mixed evenly, reacted at 70-75°C for 3-5 hours, cooled to 50-55°C, sodium hydroxide is added, and the reaction is continued for 2-3 hours. After washing and vacuum distillation, a fluorine-containing epoxy compound is obtained.

2. The process for preparing high-performance corrosion-resistant aluminum bronze according to claim 1, characterized in that: The raw materials include the following components in percentage by mass: 8-12% aluminum, 2.5-5.0% nickel, 1-2% iron, 2-3% boron, 1-2% chromium, 1-2% manganese, 0.1-0.5% niobium, and the balance is copper.

3. The process for preparing high-performance corrosion-resistant aluminum bronze according to claim 1, characterized in that: The smelting temperature is 1200-1300° C., electromagnetic stirring is maintained during the smelting process, and the smelting time is 35-60 minutes.

4. The process for preparing high-performance corrosion-resistant aluminum bronze according to claim 1, characterized in that: The corrosion-resistant coating comprises the following components by weight: 50-60 parts of waterborne epoxy resin, 4-8 parts of zinc phosphate, 6-12 parts of modified graphene oxide, 8-15 parts of curing agent, 0.5-1.2 parts of defoaming agent, 3-8 parts of film-forming aid, 0.3-0.8 parts of leveling agent, and 20-30 parts of deionized water.

5. The process for preparing high-performance corrosion-resistant aluminum bronze according to claim 1, characterized in that: In the step (1), the mass ratio of tetraethyl orthosilicate, anhydrous ethanol, deionized water, and γ-methacryloxypropyltrimethoxysilane is 1: (3-5): (0.6-1.0): (0.3-0.5).

6. The process for preparing high-performance corrosion-resistant aluminum bronze according to claim 1, characterized in that: In the step (2), the mass ratio of the monolayer coated graphene oxide, methyl methacrylate, methacrylamide and 2-methyl-2-acrylic acid-2-hydroxyethyl phosphate is 1: (1-2): (2-4): (0.5-1.5).

7. The process for preparing high-performance corrosion-resistant aluminum bronze according to claim 1, characterized in that: In the step (3), the mass ratio of the double-layer coated graphene oxide, the fluorinated epoxy compound and tetrahydrofuran is 1: (2-3): (4-6).

8. A high-performance, corrosion-resistant aluminum bronze prepared according to the preparation process according to any one of claims 1 to 7.