Preparation method of copper alloy wire mesh for preventing marine organisms from adhering
The copper alloy wire mesh prepared through specific components and processes solves the problems of both antifouling performance, strength and corrosion resistance, and achieves long-term effective inhibition of marine biological adhesion in the marine environment, and improves the operating stability and economic benefits of marine aquaculture and nuclear power plants.
Patent Information
- Application Number
- CN202510649466.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-05-20
- Publication Date
- 2025-07-25
AI Technical Summary
The prior art is difficult to ensure the anti-fouling performance of copper alloy wire mesh while taking into account its strength, corrosion resistance and processing properties, resulting in serious problems in marine biological adhesion, affecting the normal operation of marine aquaculture and nuclear power plants.
Using copper alloy ingredients of specific components, copper alloy wire mesh with excellent antifouling performance, high strength and good corrosion resistance are prepared through vacuum induction furnace smelting, hot rolling, cold rolling, annealing treatment and surface pickling passivation treatment.
The prepared copper alloy wire mesh effectively inhibits marine organisms in the marine environment for a long time, improves the stability and service life of the wire mesh, reduces maintenance costs, and meets environmental protection requirements.
Smart Images
Figure CN120362377A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of protective materials for marine aquaculture cages and pollution-blocking nets for water intake channels of nuclear power plants, and in particular to a method for preparing a copper alloy wire mesh for preventing marine organisms from attaching. Background Art
[0002] In the complex marine environment where marine cage aquaculture and nuclear power plant water intake channel pollution nets are located, the problem of marine organism attachment has long been a major problem that has plagued the normal operation of the aquaculture industry and nuclear power plants. Various marine organisms, such as barnacles, oysters, seaweed, etc., are very easy to attach to the surface of the cage. The attachment of these marine organisms will bring many serious consequences: 1. Affecting water exchange: The attachment of marine organisms will block the mesh of the cage, making it difficult to exchange water in the cage. The water in the cage cannot be updated in time, and the dissolved oxygen content is reduced, causing the farmed fish to die due to lack of oxygen, seriously affecting the aquaculture output and economic benefits. The blockage of the mesh in the nuclear power plant water intake channel pollution net will seriously affect the operation of the nuclear power plant and even cause the reactor to shut down. 2. Increase the burden of the cage: The attached marine organisms will increase the weight of the cage. When the weight exceeds the carrying capacity of the cage, it will cause the cage to sink to the bottom in severe cases, causing a large number of farmed fish to be lost, bringing huge economic losses to the farmers.
[0003] At present, commonly used methods to prevent marine organisms from attaching include the use of antifouling paints, electrochemical antifouling, etc. However, these methods have obvious limitations: 1. Antifouling paints: Although antifouling paints can prevent marine organisms from attaching to a certain extent, they have a limited service life and need to be repainted regularly, which increases maintenance costs. Moreover, the harmful substances contained in some antifouling paints may cause pollution to the marine environment and do not meet the requirements of sustainable development. 2. Electrochemical antifouling: Electrochemical antifouling requires a lot of electricity and has high operating costs. In addition, the equipment of this method is complex and requires high maintenance and management of the equipment, which increases the difficulty and cost of actual operation.
[0004] Copper alloy has good antifouling performance, and the copper ions released by it can inhibit the growth and attachment of marine organisms. However, the existing copper alloy wire mesh preparation method is difficult to take into account the strength, corrosion resistance and processing performance of the wire mesh while ensuring the antifouling performance. Therefore, it is of great practical significance to develop a preparation method for copper alloy wire mesh that can produce high-performance and good antifouling effect. Summary of the invention
[0005] The purpose of the present invention is to solve the above-mentioned problems in the prior art and to provide a method for preparing a copper alloy wire mesh that prevents the attachment of marine organisms. The copper alloy wire mesh prepared by this method has excellent anti-fouling properties, can effectively inhibit the growth and attachment of marine organisms in the marine environment for a long time, and provide reliable protection for aquaculture cages and nuclear power plant water intake channel pollution control nets. Its high strength enables the wire mesh to withstand various external force impacts and pressures in the marine environment, is not easy to break, and ensures the stability and safety of the wire mesh. Good corrosion resistance ensures that the copper alloy wire mesh can be used for a long time in harsh marine environments, prolongs the service life of the wire mesh, and reduces the frequency and cost of replacing the wire mesh.
[0006] In order to achieve the above object, the present invention adopts the following technical scheme:
[0007] A method for preparing a copper alloy wire mesh for preventing marine organisms from attaching comprises the following steps:
[0008] 1) The ingredients are prepared according to the following mass percentages: 65% to 68% copper, 30% to 33.5% zinc, 0.5% to 1% tin, 0.5% to 1% aluminum, 0.005% to 0.01% nickel, and 0.05% to 0.1% rare earth elements; the rare earth elements are one or more of cerium, lanthanum, scandium, and yttrium;
[0009] 2) mixing the ingredients in step 1) and placing them in a vacuum induction furnace for melting under argon protection;
[0010] 3) Casting the smelted copper alloy liquid into a mold to make a copper alloy billet;
[0011] 4) hot rolling, cold rolling and annealing the copper alloy billet in sequence;
[0012] 5) The copper alloy sheet obtained in step 4) is processed into a wire, then pickled and passivated, and finally woven into a mesh.
[0013] In step 2), the smelting temperature is 1200-1300°C and the smelting time is 30-60 minutes; in step 3), the casting temperature is 1100-1200°C.
[0014] In step 4), the copper alloy billet is heated to 800-900° C. and hot rolled. The total deformation of the hot rolling is controlled at 60%-80%. The rolling is performed in multiple passes. The deformation of each pass is controlled at 10%-20%. After hot rolling, a copper alloy sheet with a thickness of 10-20 mm is obtained.
[0015] In step 4), the total deformation of cold rolling is controlled at 40% to 60%, which is carried out in multiple passes, and the deformation of each pass is controlled at 5% to 10%. After cold rolling, a copper alloy sheet with a thickness of 1 to 6 mm is obtained.
[0016] In step 5), the steps of processing the copper alloy thin plate into wire are as follows: the copper alloy thin plate is cut into strips and then undergoes rough stretching, annealing after rough stretching, and finally fine stretching. After fine stretching, copper alloy wire with a diameter of 0.5 mm to 4 mm is obtained.
[0017] In the present invention, the annealing temperature is 500 - 600 °C, and the heat preservation time is 1 - 2 hours.
[0018] In step 5), the pickling is to soak in a mixed solution containing 5% - 10% nitric acid and 1% - 3% hydrofluoric acid by mass concentration for 5 - 10 minutes, and then rinse with clean water; the passivation treatment is to put it into a passivation solution containing 2% - 5% potassium chromate and 1% - 2% sodium carbonate by mass concentration for 10 - 20 minutes, and finally rinse with clean water and dry.
[0019] In step 5), a copper alloy wire mesh with a mesh size of 5 mm to 50 mm is woven.
[0020] A copper alloy wire mesh for preventing marine organisms from attaching is prepared by the above - mentioned preparation method.
[0021] The application of the copper alloy wire mesh for preventing marine organisms from attaching is used as a protective material for marine aquaculture cages and a protective material for the trash rack in the water intake channel of nuclear power plants.
[0022] Compared with the prior art, the beneficial effects obtained by the technical solution of the present invention are as follows:
[0023] 1) Excellent anti - fouling performance: The copper alloy wire mesh prepared in the present invention contains appropriate amounts of elements such as copper, zinc, tin, aluminum, and rare earth elements. Copper ions can continuously release into the surrounding seawater, effectively inhibiting the growth and attachment of marine organisms; the addition of rare earth elements can improve the microstructure of the copper alloy, enhance the stability of its anti - fouling performance, and ensure good anti - fouling effects during long - term use.
[0024] 2) High strength and good corrosion resistance: Through reasonable composition design and processing technology, including hot rolling, cold rolling, and annealing treatment, etc., the copper alloy wire mesh has high strength and good corrosion resistance. In the marine environment, it can withstand external forces such as water flow impact and biological collision, and at the same time resist the corrosion of seawater, extend the service life of the cage, and reduce the cost of replacing the cage.
[0025] 3) Surface treatment further improves performance: During the surface treatment process, the mixed solution of nitric acid and hydrofluoric acid can remove the oxide layer and impurities on the surface of the wire mesh, making the surface of the copper alloy cleaner; the passivation treatment can form a dense passivation film on the surface of the wire mesh, further improving its corrosion resistance and anti - fouling performance. This surface treatment method not only improves the performance of the wire mesh but also reduces the pollution to the marine environment, meeting the environmental protection requirements. Description of the Drawings
[0026] Figure 1 The copper alloy wire mesh prepared for Example 1;
[0027] Figure 2 The biofouling map of the copper alloy wire mesh prepared for Example 1 after 6 months of exposure in the marine environment;
[0028] Figure 3 The biofouling map of the copper alloy wire mesh prepared for Comparative Example 1 after 6 months of exposure in the marine environment. Detailed Description of the Invention
[0029] In order to make the technical problems, technical solutions and beneficial effects to be solved by the present invention clearer and more understandable, the present invention will be further described in detail below with reference to the drawings and embodiments.
[0030] The preparation method of the copper alloy wire mesh for preventing marine biofouling according to the present invention includes the following steps:
[0031] 1) Raw material preparation
[0032] Copper, zinc, tin, and aluminum with a purity of not less than 99.9% are selected as the main raw materials, and the ingredients are prepared according to the following mass percentages: copper 65% - 68%, zinc 30% - 33.5%, tin 0.5% - 1%, aluminum 0.5% - 1%, nickel 0.005% - 0.01%, rare earth elements 0.05% - 0.1%, and the rare earth elements are one or more of cerium, lanthanum, scandium, and yttrium.
[0033] 2) Melting
[0034] The prepared raw materials are put into a vacuum induction furnace and melted under argon protection. The melting temperature is controlled at 1200 - 1300 °C, and the melting time is 30 - 60 minutes to ensure that the raw materials are fully melted and evenly mixed.
[0035] During the melting process, argon protection can prevent the raw materials from being oxidized at high temperatures and ensure the purity and quality of the alloy. Strictly controlling the melting temperature and time can enable various elements to be fully fused to form a uniform alloy structure.
[0036] 3) Casting and forming
[0037] The melted copper alloy liquid is cast into a pre-designed mold to make a copper alloy blank. The casting temperature is controlled at 1100 - 1200 °C, and the casting process should be kept stable to avoid defects such as pores and inclusions.
[0038] 4) Hot rolling
[0039] Heat the copper alloy blank to 800 - 900 °C and carry out hot rolling. Control the total deformation of hot rolling within 60% - 80%, and carry out rolling in multiple passes, with the deformation of each pass controlled within 10% - 20%. After hot rolling, a copper alloy sheet with a thickness of 10 - 20 mm is obtained.
[0040] 5) Cold rolling
[0041] Carry out cold rolling on the hot-rolled copper alloy sheet. Control the total deformation of cold rolling within 40% - 60%, and also carry out it in multiple passes, with the deformation of each pass controlled within 5% - 10%. After cold rolling, a copper alloy thin sheet with a thickness of 1 - 6 mm is obtained.
[0042] 6) Annealing treatment
[0043] Put the cold-rolled copper alloy thin sheet into an annealing furnace for annealing treatment. Control the annealing temperature within 500 - 600 °C, with a holding time of 1 - 2 hours, and then cool it in the furnace to room temperature. Annealing treatment can eliminate the internal stress generated during cold rolling and improve the plasticity and toughness of the copper alloy.
[0044] 7) Process into wire
[0045] Cut the strip: Use a shearing device to cut the copper alloy thin sheet into strips with appropriate widths. The shearing width should be determined according to the specifications of the final copper alloy wire, slightly wider than the diameter of the target copper alloy wire to leave a margin for the subsequent stretching process. Ensure that the shearing edge is neat and free of burrs to avoid stress concentration during subsequent processing and affect the quality of the copper alloy wire.
[0046] Rough stretching: Pass the cut copper alloy strip through a stretching machine for rough stretching. During the stretching process, the strip passes through a series of dies with gradually decreasing diameters and gradually becomes thinner and longer under the action of tensile force.
[0047] Annealing after rough stretching: After rough stretching, work hardening will occur inside the copper alloy, making the material hard and brittle, which is not conducive to further stretching. Therefore, annealing treatment is required. Put the copper alloy strip after rough stretching into an annealing furnace, control the annealing temperature within 500 - 600 °C, with a holding time of 1 - 2 hours, and then cool it in the furnace to room temperature. Annealing can eliminate the residual stress inside the material, restore the plasticity and toughness of the material, and prepare for the subsequent fine stretching.
[0048] Fine stretching: Pass the annealed copper alloy strip through a stretching machine for fine stretching again. The dies used for fine stretching have higher diameter precision, and the stretching process is more precise to gradually stretch the strip to the target diameter of 0.5 mm - 4 mm of the copper alloy wire. During the fine stretching process, strictly control the stretching speed and the magnitude of the tensile force to ensure that the diameter of the copper alloy wire is uniform and the surface is smooth.
[0049] 8) Surface treatment
[0050] The copper alloy wire is subjected to surface treatment to improve its anti-fouling performance and corrosion resistance. The surface treatment method is as follows:
[0051] Pickling: Immerse the copper alloy wire in a mixed solution containing 5% - 10% nitric acid and 1% - 3% hydrofluoric acid by mass concentration for 5 - 10 minutes, and then rinse it thoroughly with clean water. The mixed solution of nitric acid and hydrofluoric acid can remove the oxide layer and impurities on the surface of the copper alloy wire, making the surface of the copper alloy wire cleaner and facilitating the subsequent passivation treatment.
[0052] Passivation treatment: Put the pickled copper alloy wire into a passivation solution containing 2% - 5% potassium chromate and 1% - 2% sodium carbonate by mass concentration for passivation treatment for 10 - 20 minutes, and finally rinse it with clean water and dry it. The passivation treatment can form a dense passivation film on the surface of the copper alloy wire, further improving its corrosion resistance and anti-fouling performance.
[0053] 9) Weaving into a net
[0054] Use a weaving machine to process the copper alloy wire into a wire mesh. The weaving method can adopt diamond weaving, plain weaving, twill weaving or other suitable weaving methods. The mesh size of the wire mesh is adjusted according to the actual use requirements, generally 5 - 50 mm. Different weaving methods and mesh sizes can meet different use scenarios and requirements, such as the requirements for water body exchange and anti-biological attachment of different aquaculture varieties.
[0055] Example 1
[0056] The preparation method of a copper alloy wire mesh for preventing marine organisms from attaching in this Example 1 includes the following steps:
[0057] 1) Raw material preparation: Select copper, zinc, tin, aluminum, and nickel with a purity of 99.9% for batching. The mass percentage of copper is 65%, zinc is 33.5%, tin is 0.5%, aluminum is 0.945%, nickel is 0.005%, and rare earth elements are 0.05%. The rare earth elements include cerium, scandium, and yttrium.
[0058] 2) Melting: Put the batched raw materials into a vacuum induction furnace and melt them at a temperature of 1200°C for 60 minutes under argon protection to ensure that the raw materials are fully melted and evenly mixed.
[0059] 3) Casting and forming: Pour the melted copper alloy liquid into a pre-designed mold at a temperature of 1100°C to make a copper alloy blank. The casting process is stable without obvious pores and inclusions.
[0060] 4) Hot rolling: Heat the copper alloy billet to 800 °C and perform hot rolling. Control the total deformation amount at 60%, and carry out rolling in 6 passes, with a deformation amount of 10% for each pass. After hot rolling, a copper alloy plate with a thickness of 20 mm is obtained.
[0061] 5) Cold rolling: Perform cold rolling on the hot-rolled copper alloy plate. Control the total deformation amount at 40%, and carry out in 8 passes, with a deformation amount of 5% for each pass. After cold rolling, a copper alloy sheet with a thickness of 5 mm is obtained.
[0062] 6) Annealing treatment: Put the cold-rolled copper alloy sheet into an annealing furnace, keep it at 500 °C for 2 hours, and then cool it to room temperature with the furnace.
[0063] 7) Processing into wire: Cut the annealed copper alloy sheet into strips with appropriate widths, perform rough stretching, anneal at 500 °C for 2 hours after rough stretching, and then perform fine stretching to obtain a copper alloy wire with a diameter of 3 mm.
[0064] 8) Surface treatment: Immerse the copper alloy wire in a mixed solution containing 5% nitric acid and 1% hydrofluoric acid by mass concentration for 10 minutes. After rinsing it clean with water, put it into a passivation solution containing 2% potassium chromate and 1% sodium carbonate by mass concentration for 20 minutes of passivation, and finally rinse and dry it with water.
[0065] 9) Weaving into a mesh: Use a weaving machine to process the copper alloy wire into a wire mesh with a mesh size of 50 mm by diamond weaving. See the physical object in Figure 1 。
[0066] 10) Performance testing: Conduct tensile strength and elongation tests on the prepared copper alloy wire, and conduct corrosion resistance (corrosion rate after 1000 hours of salt spray test) and anti-fouling performance (biological attachment area after 6 months of exposure in the marine environment) tests on the copper alloy wire mesh. Figure 2 This is the biological attachment diagram of the copper alloy wire mesh prepared in this example after 6 months of exposure in the marine environment.
[0067] Example 2
[0068] The preparation method of a copper alloy wire mesh for preventing marine organism attachment in this Example 2 includes the following steps:
[0069] 1) Raw material preparation: Select copper, zinc, tin, aluminum, and nickel with a purity of 99.9% for batching. The mass percentage of copper is 68%, zinc is 30%, tin is 1%, aluminum is 0.89%, nickel is 0.01%, and rare earth elements are 0.1%. The rare earth elements include lanthanum, scandium, and yttrium.
[0070] 2) Melting: Put the batched raw materials into a vacuum induction furnace, and melt them at a temperature of 1300 °C for 30 minutes under argon protection to ensure that the raw materials are fully melted and evenly mixed.
[0071] 3) Casting molding: Pour the molten copper alloy liquid into a pre-designed mold at a temperature of 1200 °C to make a copper alloy blank. The casting process is stable, without obvious pores and inclusions.
[0072] 4) Hot rolling: Heat the copper alloy blank to 900 °C and carry out hot rolling. The total deformation is controlled at 80% and is carried out in 8 passes, with a deformation of 10% for each pass. After hot rolling, a copper alloy sheet with a thickness of 10 mm is obtained.
[0073] 5) Cold rolling: Carry out cold rolling on the hot-rolled copper alloy sheet. The total deformation is controlled at 60% and is carried out in 12 passes, with a deformation of 5% for each pass. After cold rolling, a copper alloy thin sheet with a thickness of 2 mm is obtained.
[0074] 6) Annealing treatment: Put the cold-rolled copper alloy thin sheet into an annealing furnace, keep it at 600 °C for 1 hour, and then cool it to room temperature with the furnace.
[0075] 7) Processing into wire: Cut the annealed copper alloy thin sheet into strips with appropriate width, carry out rough stretching, anneal at 600 °C for 1 hour after rough stretching, and then carry out fine stretching to obtain a copper alloy wire with a diameter of 1 mm.
[0076] 8) Surface treatment: Immerse the copper alloy wire in a mixed solution containing 10% nitric acid and 3% hydrofluoric acid by mass concentration for 5 minutes. After rinsing with clean water, put it into a passivation solution containing 5% potassium chromate and 2% sodium carbonate by mass concentration for 10 minutes, and finally rinse and dry with clean water.
[0077] 9) Weaving into a mesh: Use a weaving machine to process the copper alloy wire into a wire mesh with a mesh size of 5 mm by twill weaving.
[0078] Comparative Example 1
[0079] Use the same raw materials and process as in Example 1, only change the mass percentage of copper to 65.05% and do not add rare earth elements. Figure 3 It is a diagram of biofouling on the copper alloy wire mesh prepared in Comparative Example 1 after being exposed to the marine environment for 6 months.
[0080] Comparative Example 2
[0081] Use the same raw materials and process as in Example 1, only change the mass percentage of zinc to 33.55% and do not add rare earth elements.
[0082] Comparative Example 3
[0083] Use the same raw materials and process as in Example 2, only change the mass percentage of copper to 68.1% and do not add rare earth elements.
[0084] Comparative Example 4
[0085] The same raw materials and processes as in Example 2 are adopted, only changing the mass percentage of zinc to 30.1% and not adding rare earth elements.
[0086] Performance test
[0087] The copper alloy wire meshes prepared in the examples and comparative examples were subjected to performance tests, and the test results are shown in Table 1.
[0088] Table 1
[0089]
[0090] It can be seen from the test results that the copper alloy wire mesh prepared by the present invention has high strength, good plasticity, excellent anti-fouling performance and corrosion resistance, and can meet the actual needs of marine aquaculture cages. Different raw material ratios and process parameters will have a certain impact on the performance of the wire mesh, which can be adjusted according to specific usage requirements.
[0091] The above embodiments are only preferred embodiments of the present invention and cannot be considered as limiting the scope of implementation of the present invention. All equivalent changes and improvements made within the scope of the application of the present invention shall still fall within the scope covered by the patent of the present invention.
Claims
1. A method for preparing a copper alloy wire mesh for preventing marine organism attachment, characterized in that, It includes the following steps: 1) Mix ingredients according to the following mass percentages: copper 65% - 68%, zinc 30% - 33.5%, tin 0.5% - 1%, aluminum 0.5% - 1%, nickel 0.005% - 0.01%, rare earth elements 0.05% - 0.1%; the rare earth elements are one or more of cerium, lanthanum, scandium, and yttrium; 2) Put the ingredients in step 1) into a vacuum induction furnace and melt under argon protection; 3) Pour the melted copper alloy liquid into a mold to make a copper alloy blank; 4) Subject the copper alloy blank to hot rolling, cold rolling, and annealing in sequence; 5) Process the copper alloy thin plate obtained in step 4) into wire, then perform pickling and passivation treatments, and finally weave it into a net.
2. The preparation method of a copper alloy wire mesh for preventing marine organism attachment according to claim 1, characterized in that: In step 2), the melting temperature is 1200 - 1300 °C and the melting time is 30 - 60 minutes; in step 3), the casting temperature is 1100 - 1200 °C.
3. The preparation method of a copper alloy wire mesh for preventing marine organism attachment as described in claim 1, characterized in that: In step 4), heat the copper alloy blank to 800 - 900 °C for hot rolling. Control the total hot rolling deformation amount within 60% - 80%, and perform rolling in multiple passes. Control the deformation amount of each pass within 10% - 20%. After hot rolling, obtain a copper alloy plate with a thickness of 10 - 20 mm.
4. The preparation method of a copper alloy wire mesh for preventing marine organism attachment as described in claim 1, wherein: In step 4), control the total cold rolling deformation amount within 40% - 60%, and perform it in multiple passes. Control the deformation amount of each pass within 5% - 10%. After cold rolling, obtain a copper alloy thin plate with a thickness of 1 - 6 mm.
5. A method for preparing a copper alloy wire mesh for preventing marine organism attachment according to claim 1, characterized in that: In step 5), the steps of processing the copper alloy thin plate into wire are: cut the copper alloy thin plate into strips, perform rough stretching, anneal after rough stretching, and finally perform fine stretching. After fine stretching, obtain a copper alloy wire with a diameter of 0.5 mm - 4 mm.
6. The preparation method of a copper alloy wire mesh for preventing marine organism attachment as described in claim 1 or 5, characterized in that: The annealing temperature is 500 - 600 °C and the heat preservation time is 1 - 2 hours.
7. The preparation method of a copper alloy wire mesh for preventing marine organism attachment according to claim 1, characterized in that: In step 5), the pickling is to soak in a mixed solution containing 5% - 10% nitric acid and 1% - 3% hydrofluoric acid by mass concentration for 5 - 10 minutes, and then rinse with clean water; the passivation treatment is to put it into a passivation solution containing 2% - 5% potassium chromate and 1% - 2% sodium carbonate by mass concentration for 10 - 20 minutes, and finally rinse and dry with clean water.
8. The preparation method of a copper alloy wire mesh for preventing marine organism attachment according to claim 1, characterized in that: In step 5), weave it into a copper alloy wire mesh with a mesh size of 5 mm - 50 mm.
9. A copper alloy wire mesh for preventing marine organisms from attaching, characterized in that: Prepared by the preparation method according to any one of claims 1 - 8.
10. Use of a copper alloy wire mesh for preventing marine organism attachment according to claim 9, characterized in that: Used as a protective material for marine aquaculture cages and a protective material for the trash rack in the intake channel of a nuclear power plant.