Copper-based elastic alloy and preparation method thereof

Abstract

The invention relates to the technical field of metallurgy, and provides a copper-based elastic alloy and a preparation method thereof.The preparation raw materials of the copper-based elastic alloy comprise 18-25 wt% of Zn, 20-30 wt% of Cu and the balance Cu; 1 to 5 wt% of Al; 1 to 6 wt% of Ni; ce, 0.02 wt% to 0.12 wt%; and the balance of Cu. The copper-based elastic alloy prepared from Zn, Al, Ni, Cu and Ce realizes excellent combination of high strength, high elasticity and excellent corrosion resistance.

Description

Technical Field

[0001] This application belongs to the field of metallurgical technology, and particularly relates to a copper-based elastic alloy and a preparation method thereof. Background Art

[0002] Copper-based elastic alloys refer to a class of alloys that mainly consist of copper and add specific alloying elements to significantly improve their elasticity and other mechanical properties. These alloys usually have a high elastic limit, good fatigue resistance, and stable dimensions, making them very valuable in applications that require high precision and stability.

[0003] Brass is an important alloy in copper alloys. It not only inherits the good electrical and thermal conductivity of copper metal but also has good corrosion resistance, excellent mechanical properties, and good hot and cold working properties. It is an alloy material that can be widely used in the field of non-ferrous metals. Due to its excellent physical and mechanical properties, brass alloy has become one of the most common alloy materials in the field of non-ferrous metal applications. The characteristics of this alloy adapting to working environments such as high-speed heavy loads and low lubrication make it show extremely obvious advantages when preparing high-speed hydraulic rotors, connecting rod bushings, automotive synchronizer gear rings, bearings, and precision parts.

[0004] In related technologies, aluminum brass is often used as a corrosion-resistant part to make condenser tubes. However, the environment where condenser tubes are located is usually relatively harsh. It has good corrosion resistance in the atmosphere, but dezincification will occur and corrosion cracking will occur after a long time in seawater or coolant environments. The oxide film on the pipe surface will be damaged by various components in the condensate water. For example, some acidic, chlorine-containing, and ammonia-containing liquids will cause the corrosion failure of the material. A large amount of chloride ions will accumulate on the surface of the pure copper area to form a chloride film. This film has little impact resistance and is extremely easy to be damaged and cannot protect the material. Summary of the Invention

[0005] The purpose of this application is to provide a copper-based elastic alloy and a preparation method thereof, which can improve the problems of poor corrosion resistance, low mechanical properties, and low electrical conductivity of copper-based alloys.

[0006] To achieve the above application purpose, the technical solutions adopted in this application are as follows:

[0007] In the first aspect, this application provides a copper-based elastic alloy, and the preparation raw materials of the copper-based elastic alloy include the following components:

[0008] Zn, 18 - 25 wt%;

[0009] Al, 1 - 5 wt%;

[0010] Ni, 1 - 6 wt%;

[0011] Ce, 0.02 - 0.12 wt%;

[0012] The rest is Cu.

[0013] In the copper-based elastic alloy provided by the present application, 18-25 wt% of Zn combines with Cu to form the basic structure of α and β phases, which can improve the mechanical properties and processing properties of the copper-based elastic alloy; 1-5 wt% of Al can play a role in solid solution strengthening. The zinc equivalent coefficient of Al is high, which can significantly narrow the α phase region and shift it towards the copper corner, and has a great tendency to form the β phase, thereby improving the hardness and strength of the copper-based elastic alloy; at the same time, Al can also improve the corrosion resistance of the copper-based elastic alloy, that is, the ionization tendency of Al is greater than that of Zn, and it can preferentially combine with oxygen in the corrosive medium and react to form a dense and hard Al 2 O 3 film, preventing the alloy from being further corroded. 1-6 wt% of Ni can be infinitely dissolved into the Cu matrix to play a role in solid solution strengthening, and also refine the grains, increasing the strength and hardness of the copper-based elastic alloy. With the dissolution of Ni atoms, a Cottrell atmosphere will be formed. Ni atoms have a pinning effect on the dislocations with Cottrell atmosphere, which hinders the movement of dislocations, thereby strengthening the copper-based elastic alloy. At the same time, AlNi 3 and AlNi intermetallic compounds formed by Ni and Al play a role in precipitation strengthening. Therefore, the resistance to dislocation movement is further increased, and the tensile strength and hardness are improved. The addition of 0.02-0.12 wt% of Ce can purify the matrix, refine the grains, degas and remove impurities, and can also greatly increase its polarization resistance, reduce the corrosion current, and slow down the corrosion process; moreover, it can preferably prevent Zn from diffusing from the matrix surface to the medium through the corrosion product, and to a certain extent inhibit dezincification. Therefore, the copper-based elastic alloy prepared by Zn, Al, Ni, Cu and Ce realizes an excellent combination of high strength, high elasticity and excellent corrosion resistance.

[0014] In some embodiments, the raw materials for preparing the copper-based elastic alloy include the following components:

[0015] Zn, 19-22 wt%;

[0016] Al, 2-4 wt%;

[0017] Ni, 1-5 wt%;

[0018] Ce, 0.02-0.10 wt%;

[0019] The rest is Cu.

[0020] In a second aspect, the present application provides a preparation method of a base elastic alloy. The preparation method of the copper-based elastic alloy includes:

[0021] Providing the components of the copper-based elastic alloy according to any one of the first aspect, melting each component to obtain an alloy ingot;

[0022] Anneal and roll the alloy ingot to obtain a copper-based elastic alloy.

[0023] The method for preparing a copper-based elastic alloy provided by this application can uniformly mix each component after melting, and the annealing and rolling treatment can effectively improve the microstructure of the alloy, including refining grains and uniformly distributing second-phase particles, etc. These changes in the microstructure directly enhance the mechanical properties of the material, such as strength, elasticity, and corrosion resistance.

[0024] In some embodiments, melting each component to obtain an alloy ingot includes:

[0025] Put each component into a melting device for melting to obtain an alloy melt;

[0026] Draw the alloy melt to obtain an alloy ingot.

[0027] In some embodiments, putting each component into a melting device for melting to obtain an alloy melt includes:

[0028] Put Cu and Ni into a melting device for melting to obtain a semi-alloy melt;

[0029] Add a Cu-Ce master alloy, Zn, and Al to the semi-alloy melt for melting to obtain an alloy melt.

[0030] In some embodiments, putting Cu and Ni into a melting device for melting to obtain a semi-alloy melt includes:

[0031] Put Cu and Ni into a melting device, evacuate to 10 -1 Pa or less;

[0032] Fill with argon to atmospheric pressure, evacuate to 10 -1 Pa or less;

[0033] Fill with argon to a pressure of 6×10 4 Pa to 8×10 4 Pa and then heat and melt to obtain a semi-alloy melt; wherein, the heating temperature is 1250 °C.

[0034] In some embodiments, adding a Cu-Ce master alloy, Zn, and Al to the semi-alloy melt for melting to obtain an alloy melt includes:

[0035] Add a Cu-Ce master alloy, Zn, and Al to the semi-alloy melt, keep warm for 5 - 10 min after melting to obtain a primary alloy melt;

[0036] Transfer the initial-state alloy melt to a heat preservation device, and perform heat preservation at a heat preservation temperature of 1050-1100 °C to obtain an alloy melt;

[0037] And / or, when pulling the alloy melt to obtain an alloy ingot, the pulling speed is 0.20-0.30 m / min, the pulling stop time is 100-300 ms, the reverse push stroke is 0.05-0.5 mm, and the pulling frequency is 20-40 Hz.

[0038] In some embodiments, annealing and rolling the alloy ingot to obtain a copper-based elastic alloy includes:

[0039] Put the alloy ingot into an annealing device for heat preservation, and then perform water quenching treatment to obtain a solution-treated alloy ingot;

[0040] Put the solution-treated alloy ingot into an annealing device for heat preservation, and then perform rolling to obtain an alloy casting;

[0041] Perform annealing and cold rolling on the alloy casting to obtain a semi-finished copper-based elastic alloy;

[0042] Put the semi-finished copper-based elastic alloy into an annealing device for heat preservation treatment, and then perform pickling to obtain a copper-based elastic alloy.

[0043] In some embodiments, putting the alloy ingot into an annealing device for heat preservation and then performing water quenching treatment to obtain a solution-treated alloy ingot includes:

[0044] Put the alloy ingot into an annealing device at a temperature of 800-950 °C, after heat preservation for 30-90 min, quench the alloy ingot to room temperature to obtain a solution-treated alloy ingot;

[0045] And / or, putting the solution-treated alloy ingot into an annealing device for heat preservation and then performing rolling to obtain an alloy casting includes:

[0046] Put the solution-treated alloy ingot into an annealing device at a temperature of 800-950 °C, after heat preservation for 20-30 min, perform hot rolling at a temperature of 700 °C-950 °C to obtain an alloy casting; wherein, the deformation amount of the alloy casting is controlled at 80%-90%.

[0047] In some embodiments, performing annealing and cold rolling on the alloy casting to obtain a semi-finished copper-based elastic alloy includes:

[0048] Put the alloy casting into an annealing device at a temperature of 400-500 °C for heat preservation for 1-2 h, and then air-cool the alloy casting to room temperature;

[0049] The alloy cast is pickled with 15 - 25 wt% dilute phosphoric acid, and then cold-rolled to obtain a first annealed cold-rolled alloy; wherein, the deformation amount of the first annealed cold-rolled alloy is controlled at 55 - 65%;

[0050] After putting the first annealed cold-rolled alloy into an annealing device at a temperature of 400 - 500 °C and holding for 1 - 2 h, the first annealed cold-rolled alloy is air-cooled to room temperature;

[0051] The first annealed cold-rolled alloy is pickled with 15 - 25 wt% dilute phosphoric acid, and then cold-rolled to obtain a second annealed cold-rolled alloy; wherein, the deformation amount of the second annealed cold-rolled alloy is controlled at 45 - 55%;

[0052] After putting the second annealed cold-rolled alloy into an annealing device at a temperature of 400 - 500 °C and holding for 1 - 2 h, the second annealed cold-rolled alloy is air-cooled to room temperature;

[0053] The second annealed cold-rolled alloy is pickled with 15 - 25 wt% dilute phosphoric acid, and then cold-rolled to obtain a semi-finished copper-based elastic alloy; wherein, the deformation amount of the second annealed cold-rolled alloy is controlled at 75 - 85%;

[0054] And / or, after putting the semi-finished copper-based elastic alloy into an annealing device for heat preservation treatment, pickling is carried out to obtain a copper-based elastic alloy, including:

[0055] After putting the semi-finished copper-based elastic alloy into an annealing device at a temperature of 300 - 500 °C and holding for 0.5 - 8 h, the semi-finished copper-based elastic alloy is air-cooled to room temperature;

[0056] The semi-finished copper-based elastic alloy is pickled with 15 - 25 wt% dilute phosphoric acid to obtain a copper-based elastic alloy.

[0057] The above description is only an overview of the technical solution of this application. In order to be able to understand the technical means of this application more clearly, it can be implemented according to the content of the specification. And in order to make the above and other purposes, features and advantages of this application more obvious and understandable, the following specific embodiments of this application are specifically given. Brief Description of the Drawings

[0058] In order to more clearly illustrate the technical solutions in the embodiments of this application, the following will briefly introduce the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings in the following description are only some embodiments of this application. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without creative efforts.

[0059] Figure 1It is a schematic flow chart of the method for preparing a copper-based elastic alloy provided by an embodiment of the present application;

[0060] Figure 2 It is a schematic flow chart of step S200 of the method for preparing a copper-based elastic alloy provided by an embodiment of the present application;

[0061] Figure 3 It is a schematic flow chart of step S230 of the method for preparing a copper-based elastic alloy provided by an embodiment of the present application. Detailed implementation manners

[0062] In order to make the technical problems to be solved, technical solutions and beneficial effects of the present application clearer, the present application will be further described in detail below in conjunction with embodiments. It should be understood that the specific embodiments described herein are only used to explain the present application and are not used to limit the present application.

[0063] In the present application, the term "and / or" describes the association relationship of associated objects and indicates that three relationships may exist. For example, A and / or B may represent: A exists alone, A and B exist simultaneously, and B exists alone. Where A and B may be singular or plural. The character " / " generally represents an "or" relationship between the associated objects before and after.

[0064] In the present application, "at least one" means one or more, and "a plurality" means two or more. "At least one (item)" or similar expressions thereof refer to any combination of these items, including any combination of single item (item) or plural items (items). For example, "at least one (item) of a, b, or c", or, "at least one (item) of a, b, and c" can both represent: a, b, c, a - b (i.e., a and b), a - c, b - c, or a - b - c, where a, b, and c can be single or multiple respectively.

[0065] It should be understood that in various embodiments of the present application, the magnitude of the serial numbers of the above processes does not mean the order of execution. Some or all steps may be executed in parallel or sequentially. The execution order of each process should be determined by its function and internal logic, and should not constitute any limitation to the implementation process of the embodiments of the present application.

[0066] The terms used in the embodiments of the present application are only for the purpose of describing specific embodiments and are not intended to limit the present application. The singular forms of "a", "the" and "said" used in the embodiments of the present application and the appended claims are also intended to include the plural forms unless the context clearly indicates otherwise.

[0067] In the description of the embodiments of the present application, the weight of the relevant components mentioned not only can refer to the specific content of each component, but also can represent the proportional relationship between the weights of each component. Therefore, as long as the content of the relevant components in the description of the embodiments of the present application is enlarged or reduced in proportion, it is within the scope disclosed in the description of the embodiments of the present application. Specifically, the mass described in the description of the embodiments of the present application can be mass units well-known in the chemical industry such as μg, mg, g, kg, etc.

[0068] The terms "first" and "second" are only used for descriptive purposes to distinguish objects such as substances from each other, and cannot be understood as indicating or implying relative importance or implicitly specifying the quantity of the indicated technical features. For example, without departing from the scope of the embodiments of the present application, the first XX can also be referred to as the second XX, and similarly, the second XX can also be referred to as the first XX. Thus, the features defined with "first" and "second" can explicitly or implicitly include one or more of such features.

[0069] Copper-based elastic alloys refer to a class of alloys with copper as the main component and specific alloying elements added to significantly improve their elasticity and other mechanical properties. Such alloys usually have a high elastic limit, good fatigue resistance, and stable dimensions, making them very valuable in applications that require high precision and stability.

[0070] Brass is an important alloy in copper alloys. It not only inherits the good electrical and thermal conductivity of copper metal, but also has good corrosion resistance, excellent mechanical properties, and good hot and cold working properties, etc. It is an alloy material that can be widely used in the field of non-ferrous metal applications. Due to its excellent physical and mechanical properties, brass alloy has become one of the most common alloy materials in the field of non-ferrous metal applications. The characteristics of this alloy to adapt to working environments such as high-speed heavy loads and low lubrication make it show extremely obvious advantages when preparing high-speed hydraulic rotors, connecting rod bushings, automotive synchronizer gear rings, bearings, and precision parts.

[0071] In the related art, aluminum brass, as a corrosion-resistant part, is often used to make condenser tubes. However, the environment where the condenser tubes are located is usually relatively harsh. It has good corrosion resistance in the atmosphere, but dezincification will occur and corrosion cracking will occur after a long time in the environment of seawater or coolant. The oxide film on the surface of the pipeline will be damaged by various components in the condensate water. For example, some acidic, chlorine-containing, and ammonia-containing liquids will cause the corrosion failure of the material. A large amount of chloride ions will accumulate on the surface of the pure copper area to form a chloride film. This film has little impact resistance and is extremely easy to be damaged and cannot protect the material.

[0072] Based on this, to improve the problems of poor corrosion resistance, low mechanical properties, and low electrical conductivity of copper-based alloys in the related art, the embodiments of the present application provide the following solutions.

[0073] In the first aspect of the embodiments of the present application, a copper-based elastic alloy is provided. The raw materials for preparing the copper-based elastic alloy include the following components: Zn 18-25 wt%; Al 1-5 wt%; Ni 1-6 wt%; Ce 0.02-0.12 wt%; and the balance is Cu.

[0074] It can be understood that Zn refers to zinc, and Zn 18-25 wt% means that when the total weight of the raw materials is 100, Zn is 18-25, for example, it can be 18, 20, 22, 25, etc. Al refers to aluminum, and Al 1-5 wt% means that when the total weight of the raw materials is 100, Zn is 1-5, for example, it can be 1, 2, 3, 5, etc. Ni refers to nickel, and Ni 1-6 wt% means that when the total weight of the raw materials is 100, Ni is 1-6, for example, it can be 1, 2, 4, 6, etc. Ce refers to cerium, and Ce 0.02-0.12 wt% means that when the total weight of the raw materials is 100, Ce is 0.02-0.12, for example, it can be 0.02, 0.08, 0.10, 0.12, etc. Cu refers to copper, and the balance being Cu means that after determining the component ratios of Zn, Al, Ni, and Ce, the remaining part is entirely composed of Cu. For example, when the total of the component ratios of Zn, Al, Ni, and Ce is 21 wt%, the component ratio of Cu is 79 wt%, that is, when the total weight of the raw materials is 100 and the total weight of Zn, Al, Ni, and Ce is 21, the weight of Cu is 79. When the total of the component ratios of Zn, Al, Ni, and Ce is 36 wt%, the component ratio of Cu is 64 wt%, that is, when the total weight of the raw materials is 100 and the total weight of Zn, Al, Ni, and Ce is 36, the weight of Cu is 64, and so on.

[0075] As can be seen from the above, for the copper-based elastic alloy provided by the embodiments of the present application, 18-25 wt% of Zn combines with Cu to form the basic structure of the α and β phases, which can improve the mechanical properties and processing performance of the copper-based elastic alloy; 1-5 wt% of Al can play a role in solution strengthening. The zinc equivalent coefficient of Al is high, which can significantly narrow the α phase region and shift it towards the copper corner, and has a greater tendency to form the β phase, thereby improving the hardness and strength of the copper-based elastic alloy; at the same time, Al can also improve the corrosion resistance of the copper-based elastic alloy, that is, the ionization tendency of Al is greater than that of Zn, and it can preferentially combine with oxygen in the corrosive medium and react to form a dense and hard Al 2 O 3 film to prevent further corrosion of the alloy. 1-6 wt% of Ni can infinitely dissolve into the Cu matrix to play a role in solution strengthening, and also refine the grains, increasing the strength and hardness of the copper-based elastic alloy. And with the dissolution of Ni atoms, a Cottrell atmosphere will be formed. Ni atoms have a pinning effect on the dislocations with Cottrell atmospheres, which hinders dislocation movement, thereby strengthening the copper-based elastic alloy. At the same time, Ni and Al will form AlNi 3, The AlNi intermetallic compound plays a precipitation strengthening role, thus further increasing the dislocation movement resistance and improving the tensile strength and hardness. The addition of 0.02 - 0.12 wt% of Ce can purify the matrix, refine the grains, degas and remove impurities, and can also greatly increase its polarization resistance, reduce the corrosion current, and slow down the corrosion process; Ce can also form a protective layer around the Zn phase, enhancing the overall corrosion resistance of the copper-based elastic alloy, especially in a chlorine-containing environment; moreover, during the high-temperature melting process, Zn is prone to evaporation loss, and Ce can reduce the evaporation of zinc by forming stable compounds to keep the proportion of Zn in the final copper-based elastic alloy stable, that is, it can better prevent Zn from diffusing from the surface of the copper matrix through the corrosion products into the medium, and to a certain extent inhibit the dezincification phenomenon. Therefore, the copper-based elastic alloy prepared from Zn, Al, Ni, Cu, and Ce achieves an excellent combination of high strength, high elasticity, and excellent corrosion resistance.

[0076] In some embodiments, the raw materials for preparing the copper-based elastic alloy include the following components: Zn 19 - 22 wt%; Al 2 - 4 wt%; Ni 1 - 5 wt%; Ce 0.02 - 0.10 wt%; the balance is Cu.

[0077] With such settings, using Zn 19 - 22 wt%; Al 2 - 4 wt%; Ni 1 - 5 wt%; Ce 0.02 - 0.10 wt%; the balance is Cu, can further optimize the elastic modulus and strength of the copper-based elastic alloy, achieve the balance among hardness, tensile strength, and elongation, thereby obtaining more excellent mechanical properties, and at the same time can further improve the corrosion resistance of the copper-based elastic alloy.

[0078] The second aspect of the embodiments of the present application provides a method for preparing a copper-based elastic alloy, and the method for preparing the copper-based elastic alloy includes:

[0079] S100, providing the components of the copper-based elastic alloy as described in any of the above embodiments, melting the components to obtain an alloy ingot.

[0080] S200, performing annealing rolling treatment on the alloy ingot to obtain a copper-based elastic alloy.

[0081] As can be seen from the above, the method for preparing a copper-based elastic alloy provided by the embodiments of the present application can make the components uniformly mixed after melting, and the annealing rolling treatment can effectively improve the microstructure of the alloy, including refining grains, uniformly distributing second-phase particles, etc. These changes in the microstructure directly enhance the mechanical properties of the material, such as strength, elasticity, and corrosion resistance.

[0082] In some embodiments, in step S100, melting the components to obtain an alloy ingot includes:

[0083] S110. Put each component into a melting device for smelting to obtain an alloy molten liquid.

[0084] S120. Draw the alloy molten liquid to obtain an alloy ingot.

[0085] It can be understood that the smelting device can be a crucible furnace, an induction furnace or other smelting equipment. The equipment for drawing can be a continuous casting machine, a drawing machine, etc., but is not limited thereto.

[0086] With such a setting, during the smelting process, all components can be fully mixed to form a uniform alloy molten liquid, which is crucial for obtaining consistent material properties; the drawing process can control the formation of the grain structure inside the alloy ingot, effectively improve the quality of the alloy ingot, and endow it with good mechanical properties and physical characteristics.

[0087] In some embodiments, in step S110, putting each component into a melting device for smelting to obtain an alloy molten liquid includes:

[0088] S111. Put Cu and Ni into a melting device for smelting to obtain a semi-alloy molten liquid.

[0089] S112. Add a Cu-Ce master alloy, Zn and Al into the semi-alloy molten liquid for melting to obtain an alloy molten liquid.

[0090] It can be understood that the Cu-Ce master alloy refers to a pre-prepared mixed alloy containing a specific proportion of Cu and Ce. Rare earth elements are prone to oxidation, and adding them in a pure state may cause partial loss. Adding them in the form of a master alloy can reduce this loss.

[0091] With such a setting, first melt Cu and Ni. On the one hand, Cu and Ni have similar melting points; on the other hand, Ni can dissolve into the Cu matrix to play a solid solution strengthening role, and also refine the grains to increase the strength and hardness of the alloy. The dissolution of Ni atoms will form a Cottrell atmosphere. Ni atoms have a pinning effect on the dislocations with Cottrell atmospheres, which hinders the movement of dislocations. Adding them earlier helps to form a stable matrix and provides good conditions for the addition of subsequent elements. Then add the Cu-Ce master alloy, Zn and Al into the semi-alloy molten liquid, which can make the subsequently added elements melt and mix evenly, and further enhance the performance of the copper-based elastic alloy.

[0092] In some embodiments, in step S111, putting Cu and Ni into a melting device for smelting to obtain a semi-alloy molten liquid includes:

[0093] S1111. Put Cu and Ni into a melting device and evacuate to 10 -1 Pa or less.

[0094] S1112, Fill the argon gas until the pressure reaches atmospheric pressure, and then evacuate the air to 10 -1 Pa or lower.

[0095] S1113, Fill the argon gas until the pressure reaches 6×10 4 Pa~8×10 4 Pa, and then heat and melt to obtain a semi-alloy molten liquid; wherein, the heating temperature is 1250 °C.

[0096] With such settings, evacuating the air and other possible gases (such as oxygen, nitrogen, etc.) in the melting device by vacuum pumping can reduce the possibility of metal oxidation. After filling the inert gas (argon), evacuating the air again can further ensure the purity of the environment and prepare an oxygen-free atmosphere for subsequent operations; setting a specific range of argon gas pressure (6×10 4 Pa~8×10 4 Pa) helps to maintain a stable melting environment, prevent the infiltration of external air, and set the heating temperature at 1250 °C. At a temperature that satisfies the complete melting of Cu and Ni, it will not be too high to cause unnecessary element evaporation or material loss. Under controlled temperature and atmosphere conditions, Cu and Ni can be fully mixed to form a uniform molten liquid, preparing for adding other components in the next step.

[0097] In some embodiments, in step S112, add the Cu-Ce intermediate master alloy, Zn, and Al to the semi-alloy molten liquid for melting to obtain an alloy molten liquid, including:

[0098] S1121, Add the Cu-Ce intermediate master alloy, Zn, and Al to the semi-alloy molten liquid, keep it warm for 5 - 10 minutes after melting to obtain a primary alloy molten liquid.

[0099] S1122, Transfer the primary alloy molten liquid to a heat preservation device, and keep it warm at a heat preservation temperature of 1050 - 1100 °C to obtain an alloy molten liquid.

[0100] It can be understood that when adding the Cu-Ce intermediate master alloy, Zn, and Al to the semi-alloy molten liquid, heating is not required, and the temperature of the semi-alloy molten liquid can be used to melt these added components. The heat preservation device can be a heat preservation furnace, a resistance heating furnace, or other heat preservation equipment.

[0101] With such a setting, since the semi-alloy molten liquid is already in a high-temperature state, its heat can be directly utilized to melt the added Cu-Ce master alloy, Zn, and Al. This not only simplifies the process flow but also reduces energy consumption. After adding these components, the molten liquid will maintain a certain temperature within 5 - 10 minutes to enable all new components to be completely dissolved and fully mixed with the semi-alloy molten liquid to form the initial alloy molten liquid. After transferring the initial alloy molten liquid to the heat preservation device, heat preservation treatment at 1050 - 1100 °C can ensure the fluidity of the molten liquid without being too high to cause unnecessary element evaporation or material loss. Through appropriate heat preservation time and temperature control, all components are evenly distributed in the molten liquid, reducing microstructural inconsistencies and potential defects. The uniform composition distribution and stable microstructure contribute to improving the mechanical properties, elasticity, and corrosion resistance of the material.

[0102] In some embodiments, in step S120, when the alloy molten liquid is drawn to obtain an alloy ingot, the drawing speed is 0.20 - 0.30 m / min, the drawing stop time is 100 - 300 ms, the reverse push stroke is 0.05 - 0.5 mm, and the drawing frequency is 20 - 40 Hz.

[0103] It can be understood that the drawing speed is 0.20 - 0.30 m / min, for example, it can be 0.20 m / min, 0.25 m / min, 0.30 m / min, etc., but not limited thereto. The drawing stop time is 100 - 300 ms, the reverse push stroke is 0.05 - 0.5 mm, and the drawing frequency is 20 - 40 Hz. The same applies and will not be elaborated here.

[0104] With such a setting, a drawing speed of 0.20 - 0.30 m / min helps reduce the thermal stress inside the casting and the generation of cracks and other defects. The drawing stop time of 100 - 300 ms helps improve the local cooling conditions, promote a more uniform temperature distribution, and at the same time can induce more nucleation sites, thereby refining the grains and improving the strength and toughness of the material. The reverse push stroke of 0.05 - 0.5 mm can further improve the material density. The drawing frequency of 20 - 40 Hz can better adapt to the changes in the fluidity of the molten liquid and the cooling conditions, enabling each drawing to achieve the desired effect. At the same time, through precise control of the drawing parameters, it helps improve the quality of the alloy ingot and obtain a high-quality alloy ingot with a uniform Zn phase distribution.

[0105] In some embodiments, in step S200, the alloy ingot is subjected to annealing rolling treatment to obtain a copper-based elastic alloy, including:

[0106] S210, after placing the alloy ingot in an annealing device for heat preservation, it is subjected to water quenching treatment to obtain a solution-treated alloy ingot.

[0107] S220. After putting the solution-treated alloy ingot into an annealing device for heat preservation, perform rolling to obtain an alloy casting.

[0108] S230. Perform annealing cold rolling on the alloy casting to obtain a semi-finished copper-based elastic alloy.

[0109] S240. After putting the semi-finished copper-based elastic alloy into an annealing device for heat preservation treatment, perform pickling to obtain a copper-based elastic alloy.

[0110] It can be understood that the annealing device can be a box-type resistance furnace, a pit furnace, etc., but is not limited thereto. Pickling refers to the process of using pickling solution to remove scale, rust, residues, and other impurities on the metal surface.

[0111] With such a setting, after putting the alloy ingot into an annealing device for heat preservation and then performing water quenching treatment, a fine and uniform grain structure can be formed inside the solution-treated alloy ingot; after putting the solution-treated alloy ingot into an annealing device for heat preservation and then performing rolling, pores, shrinkage cavities, etc. in the solution-treated alloy ingot can be eliminated, improving the density of the alloy casting; performing annealing cold rolling on the alloy casting to obtain a semi-finished copper-based elastic alloy increases the strength and hardness of the material, while maintaining a certain ductility and helping to restore some elastic properties; after putting the semi-finished copper-based elastic alloy into an annealing device for heat preservation treatment and then performing pickling, the microstructure of the material is stabilized. The treatments in each stage refine and evenly distribute the grain structure inside the material, improving the quality consistency of the copper-based elastic alloy.

[0112] In some embodiments, in step S210, after putting the alloy ingot into an annealing device for heat preservation and then performing water quenching treatment to obtain a solution-treated alloy ingot, it includes: putting the alloy ingot into an annealing device at a temperature of 800 - 950 °C, after heat preservation for 30 - 90 min, water quench the alloy ingot to room temperature to obtain a solution-treated alloy ingot.

[0113] It can be understood that the temperature of 800 - 950 °C can be, for example, 800 °C, 900 °C, 950 °C, etc., but is not limited thereto. The same applies to the heat preservation time of 30 - 90 min, which will not be elaborated here.

[0114] With such a setting, the heat preservation temperature is 800 - 950 °C and the heat preservation time is 30 - 90 min, which helps to inhibit the formation of coarse grains, maintain a fine and uniform grain size, and can also release some internal stresses generated during the casting process, reducing the possibility of cracks and other defects; water quenching to room temperature can quickly freeze the microstructure at high temperature, prevent the re-precipitation of alloying elements or the formation of unfavorable phases, and can significantly improve the hardness and strength of the material while maintaining a certain ductility.

[0115] In some embodiments, in step S220, after putting the solution-treated alloy ingot into an annealing device for heat preservation and then performing rolling, an alloy casting is obtained, including: putting the solution-treated alloy ingot into an annealing device at a temperature of 800 - 950 °C, heat-preserving for 20 - 30 min, and then performing hot rolling at a temperature of 700 °C - 950 °C to obtain the alloy casting; wherein, the deformation amount of the alloy casting is controlled at 80% - 90%.

[0116] It can be understood that controlling the deformation amount of the alloy casting at 80% - 90% means the proportion of the reduction in the cross-sectional area size after rolling. The deformation amount controlled at 80% - 90% can be, for example, 80%, 85%, 90%, etc., but is not limited thereto. The same applies to the temperature of 800 - 950 °C, heat preservation for 20 - 30 min, and the temperature of 700 °C - 950 °C, which will not be elaborated here.

[0117] With such a setting, putting the solution-treated alloy ingot into an annealing device at a temperature of 800 - 950 °C and heat-preserving for 20 - 30 min can soften the material, reduce the hardness, improve the plasticity, and prepare for the subsequent hot rolling; performing hot rolling at a temperature of 700 °C - 950 °C with the deformation amount controlled at 80% - 90%, through hot rolling with a large deformation amount, further refines the grain structure, improves the strength and toughness of the material, and at the same time endows the material with the required shape and size, promotes dislocation movement and recrystallization, and helps to form a favorable microstructure, such as a fibrous structure, which can improve the fatigue resistance of the material.

[0118] In some embodiments, in step S230, the alloy casting is subjected to annealing and cold rolling treatment to obtain a semi-finished copper-based elastic alloy, including:

[0119] S231, putting the alloy casting into an annealing device at a temperature of 400 - 500 °C, heat-preserving for 1 - 2 h, and then air-cooling the alloy casting to room temperature.

[0120] S232, pickling the alloy casting with 15 - 25 wt% dilute phosphoric acid, and then performing cold rolling to obtain a first annealed and cold-rolled alloy; wherein, the deformation amount of the first annealed and cold-rolled alloy is controlled at 55 - 65%.

[0121] S233, putting the first annealed and cold-rolled alloy into an annealing device at a temperature of 400 - 500 °C, heat-preserving for 1 - 2 h, and then air-cooling the first annealed and cold-rolled alloy to room temperature.

[0122] S234, pickling the first annealed and cold-rolled alloy with 15 - 25 wt% dilute phosphoric acid, and then performing cold rolling to obtain a second annealed and cold-rolled alloy; wherein, the deformation amount of the second annealed and cold-rolled alloy is controlled at 45 - 55%.

[0123] For S235, after placing the second annealed cold-rolled alloy in an annealing device at a temperature of 400 - 500 °C and holding for 1 - 2 h, the second annealed cold-rolled alloy is air-cooled to room temperature.

[0124] For S236, the second annealed cold-rolled alloy is pickled with 15 - 25 wt% dilute phosphoric acid and then cold-rolled to obtain a semi-finished copper-based elastic alloy; wherein, the deformation amount of the second annealed cold-rolled alloy is controlled at 75 - 85%.

[0125] It can be understood that the 15 - 25 wt% dilute phosphoric acid can be 15 wt%, 20 wt%, 25 wt%, etc., but not limited thereto. The same applies to a temperature of 400 - 500 °C, a holding time of 1 - 2 h, a deformation amount controlled at 55 - 65%, a deformation amount controlled at 45 - 55%, and a deformation amount controlled at 75 - 85%, and will not be elaborated herein.

[0126] With such settings, through multiple cold-rollings and control of the deformation amount, the grain size of the alloy is gradually refined, improving the overall strength and toughness of the material. The annealing treatment after each cold-rolling helps to release internal stress, restore some elastic properties, and reduce the increase in brittleness caused by cold work hardening. The repeated heat treatment and cold work promote dislocation movement and recrystallization, forming a favorable microstructure and enhancing the fatigue resistance. The pickling step removes surface oxides and other impurities, making the alloy surface smooth and bright, improving the appearance quality and corrosion resistance. This multi-stage annealing, pickling, and cold-rolling treatment process not only refines the microstructure of the copper-based elastic alloy but also significantly improves its comprehensive mechanical properties and surface quality, providing a solid foundation for the high quality and high performance of the final product.

[0127] In some embodiments, in step S240, after placing the semi-finished copper-based elastic alloy in an annealing device for heat preservation treatment, pickling is carried out to obtain a copper-based elastic alloy, including:

[0128] For S241, after placing the semi-finished copper-based elastic alloy in an annealing device at a temperature of 300 - 500 °C and holding for 0.5 - 8 h, the semi-finished copper-based elastic alloy is air-cooled to room temperature.

[0129] For S242, the semi-finished copper-based elastic alloy is pickled with 15 - 25 wt% dilute phosphoric acid to obtain a copper-based elastic alloy.

[0130] It can be understood that the temperature of 300 - 500 °C can be, for example, 300, 400, 500, etc., but not limited thereto. The same applies to a holding time of 0.5 - 8 h and 15 - 25 wt% dilute phosphoric acid, and will not be elaborated herein.

[0131] With such settings, the final annealing treatment helps to eliminate any remaining internal stress, stabilize the grain structure, and ensure the reliability and consistency of the material during long-term use. By adjusting the annealing temperature and holding time, the elasticity and ductility of the material can be further optimized without sacrificing strength. The final pickling treatment not only removes surface oxides and other impurities, but also makes the surface of the copper-based elastic alloy smooth and bright, improving the appearance quality and corrosion resistance.

[0132] The following is an illustration with specific embodiments.

[0133] Embodiment 1

[0134] 1) Prepare 22 wt% Zn, 4 wt% Al, 5 wt% Ni, 0.1 wt% Ce according to the group ratio, with the balance being Cu. Put the prepared Cu and Ni into a melting crucible, evacuate to 10 -1 Pa, fill with argon to atmospheric pressure, then evacuate to 10 -1 Pa, fill with argon until the pressure reaches 8×10 4 Pa, and then heat and melt at a heating temperature of 1250 °C to obtain a semi-alloy molten liquid.

[0135] 2) Then add the prepared Cu-Ce master alloy, Zn, and Al to the semi-alloy molten liquid, hold for 10 min after melting to obtain a primary alloy molten liquid. Transfer the primary alloy molten liquid to a holding furnace and hold at a holding temperature of 1100 °C to obtain an alloy molten liquid. Draw the alloy molten liquid, control the drawing speed of the drawing machine to be 0.30 m / min, the drawing stop time to be 300 ms, the reverse push stroke to be 0.5 mm, and the drawing frequency to be 40 Hz to obtain an alloy ingot.

[0136] 3) Put the alloy ingot into an annealing furnace at 950 °C and hold for 90 min, then water-quench the alloy ingot to room temperature to obtain a solution-treated alloy ingot. Then put the solution-treated alloy ingot into an annealing furnace at 950 °C and hold for 90 min, and then perform hot rolling at 950 °C, and control the deformation amount of the alloy casting to be 90% to obtain an alloy casting.

[0137] 4) First, place the alloy ingot in an annealing furnace at a temperature of 500 °C and hold it for 2 h. Then, air-cool the alloy ingot to room temperature. Next, pickle the alloy ingot with 25 wt% dilute phosphoric acid, followed by cold rolling. Control the deformation amount to 65% to obtain the first annealed cold-rolled alloy. Then, place the first annealed cold-rolled alloy in an annealing furnace at a temperature of 500 °C and hold it for 2 h. After that, air-cool the first annealed cold-rolled alloy to room temperature. Then, pickle the first annealed cold-rolled alloy with 25 wt% dilute phosphoric acid, followed by cold rolling. Control the deformation amount to 55% to obtain the second annealed cold-rolled alloy. Then, place the second annealed cold-rolled alloy in an annealing furnace at a temperature of 500 °C and hold it for 2 h. After that, air-cool the second annealed cold-rolled alloy to room temperature; pickle the second annealed cold-rolled alloy with 25 wt% dilute phosphoric acid, followed by cold rolling. Control the deformation amount to 85% to obtain the semi-finished copper-based elastic alloy.

[0138] 5) Finally, place the semi-finished copper-based elastic alloy in an annealing furnace at a temperature of 500 °C and hold it for 8 h. Then, air-cool the semi-finished copper-based elastic alloy to room temperature; then pickle the semi-finished copper-based elastic alloy with 25 wt% dilute phosphoric acid to obtain the copper-based elastic alloy.

[0139] Example 2

[0140] 1) Prepare 20 wt% Zn, 3 wt% Al, 3 wt% Ni, 0.07 wt% Ce according to the component ratio, with the balance being Cu. Put the prepared Cu and Ni into a melting crucible, evacuate to 10 -1 Pa, fill with argon to atmospheric pressure, then evacuate to 10 -1 Pa, fill with argon until the pressure is 7×10 4 Pa, and then heat and melt at a heating temperature of 1250 °C to obtain the semi-alloy molten liquid.

[0141] 2) Then, add the prepared Cu-Ce master alloy, Zn, and Al to the semi-alloy molten liquid. After melting, hold for 8 min to obtain the initial alloy molten liquid; transfer the initial alloy molten liquid to a holding furnace and hold it at a holding temperature of 1100 °C to obtain the alloy molten liquid. Pull the alloy molten liquid, control the pulling speed of the pulling machine to 0.25 m / min, the pulling stop time to 200 ms, the reverse push stroke to 0.3 mm, and the pulling frequency to 30 Hz to obtain the alloy ingot.

[0142] 3) Place the alloy ingot in an annealing furnace at a temperature of 900 °C and hold it for 60 min. Then, water-quench the alloy ingot to room temperature to obtain the solution-treated alloy ingot. Then, place the solution-treated alloy ingot in an annealing furnace at a temperature of 900 °C and hold it for 60 min. Then, perform hot rolling at a temperature of 900 °C and control the deformation amount of the alloy ingot to 85% to obtain the alloy ingot.

[0143] 4) First, put the alloy ingot into an annealing furnace at 450 °C and keep it for 1.5 h, then air-cool the alloy ingot to room temperature. Then, pickle the alloy ingot with 20 wt% dilute phosphoric acid, followed by cold rolling, and control the deformation amount to 60% to obtain the first annealed cold-rolled alloy. Next, put the first annealed cold-rolled alloy into an annealing furnace at 450 °C and keep it for 1.5 h, then air-cool the first annealed cold-rolled alloy to room temperature. Then, pickle the first annealed cold-rolled alloy with 20 wt% dilute phosphoric acid, followed by cold rolling, and control the deformation amount to 50% to obtain the second annealed cold-rolled alloy. Then, put the second annealed cold-rolled alloy into an annealing furnace at 450 °C and keep it for 1.5 h, then air-cool the second annealed cold-rolled alloy to room temperature; pickle the second annealed cold-rolled alloy with 20 wt% dilute phosphoric acid, followed by cold rolling, and control the deformation amount to 80% to obtain the semi-finished copper-based elastic alloy.

[0144] 5) Finally, put the semi-finished copper-based elastic alloy into an annealing furnace at 400 °C and keep it for 4 h, then air-cool the semi-finished copper-based elastic alloy to room temperature; then pickle the semi-finished copper-based elastic alloy with 20 wt% dilute phosphoric acid to obtain the copper-based elastic alloy.

[0145] Example 3

[0146] 1) Prepare 19 wt% Zn, 2 wt% Al, 1 wt% Ni, 0.04 wt% Ce according to the component ratio, and the balance is Cu. Put the prepared Cu and Ni into a melting crucible, evacuate to 10 -1 Pa, fill with argon to normal pressure, then evacuate to 10 -1 Pa, fill with argon until the pressure is 6×10 4 Pa, and then heat and melt at a heating temperature of 1250 °C to obtain a semi-alloy molten liquid.

[0147] 2) Then add the prepared Cu-Ce master alloy, Zn and Al to the semi-alloy molten liquid, keep it for 5 min after melting to obtain the initial alloy molten liquid; transfer the initial alloy molten liquid to a holding furnace and hold it at a holding temperature of 1050 °C to obtain the alloy molten liquid. Draw the alloy molten liquid, control the drawing speed of the drawing machine to 0.20 m / min, the drawing stop time to 100 ms, the reverse push stroke to 0.05 mm, and the drawing frequency to 20 Hz to obtain the alloy ingot.

[0148] 3) Put the alloy ingot into an annealing furnace at 800 °C and keep it for 30 min, then water-quench the alloy ingot to room temperature to obtain a solution-treated alloy ingot. Then put the solution-treated alloy ingot into an annealing furnace at 800 °C and keep it for 30 min, then perform hot rolling at 700 °C and control the deformation amount of the alloy ingot to 80% to obtain the alloy ingot.

[0149] 4) First, put the alloy ingot into an annealing furnace at 400 °C and hold for 1 h, then air-cool the alloy ingot to room temperature. Then, pickle the alloy ingot with 15 wt% dilute phosphoric acid, and then perform cold rolling, and control the deformation amount to 55% to obtain the first annealed and cold-rolled alloy. Then, put the first annealed and cold-rolled alloy into an annealing furnace at 400 °C and hold for 1 h, then air-cool the first annealed and cold-rolled alloy to room temperature. Then, pickle the first annealed and cold-rolled alloy with 15 wt% dilute phosphoric acid, and then perform cold rolling, and control the deformation amount to 45% to obtain the second annealed and cold-rolled alloy. Then, put the second annealed and cold-rolled alloy into an annealing furnace at 400 °C and hold for 1 h, then air-cool the second annealed and cold-rolled alloy to room temperature; pickle the second annealed and cold-rolled alloy with 15 wt% dilute phosphoric acid, and then perform cold rolling, and control the deformation amount to 75% to obtain the semi-finished copper-based elastic alloy.

[0150] 5) Finally, put the semi-finished copper-based elastic alloy into an annealing furnace at 300 °C and hold for 0.5 h, then air-cool the semi-finished copper-based elastic alloy to room temperature; then pickle the semi-finished copper-based elastic alloy with 15 wt% dilute phosphoric acid to obtain the copper-based elastic alloy.

[0151] Comparative Example 1

[0152] 1) Prepare 22 wt% Zn according to the component ratio, and the balance is Cu. Put Cu into the melting crucible, evacuate to 10 -1 Pa, fill with argon to normal pressure, then evacuate to 10 -1 Pa, fill with argon to a pressure of 8×10 4 Pa, and then heat and melt at a heating temperature of 1250 °C to obtain the Cu molten liquid.

[0153] 2) Then add Zn to the Cu molten liquid, keep it molten for 10 min after melting to obtain the Cu-Zn alloy molten liquid; transfer the Cu-Zn alloy molten liquid to the holding furnace and hold it at a holding temperature of 1100 °C to obtain the alloy molten liquid. Perform traction on the alloy molten liquid, control the traction speed of the traction machine to 0.30 m / min, the traction stop time to 300 ms, the reverse push stroke to 0.5 mm, and the traction frequency to 40 Hz to obtain the alloy ingot.

[0154] 3) Put the alloy ingot into an annealing furnace at 950 °C and hold for 90 min, then water-quench the alloy ingot to room temperature to obtain the solution-treated alloy ingot. Then, put the solution-treated alloy ingot into an annealing furnace at 950 °C and hold for 90 min, and then perform hot rolling at 950 °C, and control the deformation amount of the alloy ingot to 90% to obtain the alloy ingot.

[0155] 4) First, place the alloy ingot in an annealing furnace at a temperature of 500 °C and hold for 2 h. Then, air-cool the alloy ingot to room temperature. Next, pickle the alloy ingot with 25 wt% dilute phosphoric acid, followed by cold rolling, and control the deformation amount to 65% to obtain the first annealed cold-rolled alloy. Then, place the first annealed cold-rolled alloy in an annealing furnace at a temperature of 500 °C and hold for 2 h. After that, air-cool the first annealed cold-rolled alloy to room temperature. Then, pickle the first annealed cold-rolled alloy with 25 wt% dilute phosphoric acid, followed by cold rolling, and control the deformation amount to 55% to obtain the second annealed cold-rolled alloy. Then, place the second annealed cold-rolled alloy in an annealing furnace at a temperature of 500 °C and hold for 2 h. Then, air-cool the second annealed cold-rolled alloy to room temperature; pickle the second annealed cold-rolled alloy with 25 wt% dilute phosphoric acid, followed by cold rolling, and control the deformation amount to 85% to obtain the semi-finished copper-based elastic alloy.

[0156] 5) Finally, place the semi-finished copper-based elastic alloy in an annealing furnace at a temperature of 500 °C and hold for 8 h. Then, air-cool the semi-finished copper-based elastic alloy to room temperature; then, pickle the semi-finished copper-based elastic alloy with 25 wt% dilute phosphoric acid to obtain the copper-based elastic alloy.

[0157] Comparative Example 2

[0158] 1) Prepare 22 wt% Zn, 4 wt% Al, and the balance Cu according to the component ratio. Place Cu in a melting crucible, evacuate to 10 -1 Pa, fill with argon to atmospheric pressure, then evacuate to 10 -1 Pa, fill with argon to a pressure of 6×10 4 Pa, and then heat and melt at a heating temperature of 1250 °C to obtain a semi-alloy molten liquid.

[0159] 2) Then, add Zn and Al to the semi-alloy molten liquid, hold for 5 min after melting to obtain the initial alloy molten liquid; transfer the initial alloy molten liquid to a holding furnace and hold at a holding temperature of 1050 °C to obtain the alloy molten liquid. Pull the alloy molten liquid, control the pulling speed of the pulling machine to 0.20 m / min, the pulling stop time to 100 ms, the reverse push stroke to 0.05 mm, and the pulling frequency to 20 Hz to obtain the alloy ingot.

[0160] 3) Place the alloy ingot in an annealing furnace at a temperature of 800 °C and hold for 30 min. Then, water-quench the alloy ingot to room temperature to obtain the solution-treated alloy ingot. Then, place the solution-treated alloy ingot in an annealing furnace at a temperature of 800 °C and hold for 30 min. Then, perform hot rolling at a temperature of 800 °C and control the deformation amount of the alloy ingot to 80% to obtain the alloy ingot.

[0161] 4) First, place the alloy ingot in an annealing furnace at a temperature of 400 °C and hold for 1 h, then air-cool the alloy ingot to room temperature. Then, pickle the alloy ingot with 15 wt% dilute phosphoric acid, followed by cold rolling, and control the deformation amount to 55% to obtain the first annealed and cold-rolled alloy. Next, place the first annealed and cold-rolled alloy in an annealing furnace at a temperature of 400 °C and hold for 1 h, then air-cool the first annealed and cold-rolled alloy to room temperature. Then, pickle the first annealed and cold-rolled alloy with 15 wt% dilute phosphoric acid, followed by cold rolling, and control the deformation amount to 45% to obtain the second annealed and cold-rolled alloy. Then, place the second annealed and cold-rolled alloy in an annealing furnace at a temperature of 400 °C and hold for 1 h, then air-cool the second annealed and cold-rolled alloy to room temperature; pickle the second annealed and cold-rolled alloy with 15 wt% dilute phosphoric acid, followed by cold rolling, and control the deformation amount to 75% to obtain the semi-finished copper-based elastic alloy.

[0162] 5) Finally, place the semi-finished copper-based elastic alloy in an annealing furnace at a temperature of 300 °C and hold for 0.5 h, then air-cool the semi-finished copper-based elastic alloy to room temperature; then pickle the semi-finished copper-based elastic alloy with 15 wt% dilute phosphoric acid to obtain the copper-based elastic alloy.

[0163] Comparative Example 3

[0164] 1) Prepare 22 wt% Zn, 4 wt% Al, 5 wt% Ni, and the balance is Cu according to the component ratio. Put the prepared Cu and Ni into a melting crucible, evacuate to 10 -1 Pa, fill with argon to normal pressure, then evacuate to 10 -1 Pa, fill with argon to a pressure of 7×10 4 Pa, and then heat and melt at a heating temperature of 1250 °C to obtain a semi-alloy molten liquid.

[0165] 2) Then add Zn and Al to the semi-alloy molten liquid, keep it molten and hold for 8 min to obtain the initial alloy molten liquid; transfer the initial alloy molten liquid to a holding furnace and hold at a holding temperature of 1100 °C to obtain the alloy molten liquid. Perform traction on the alloy molten liquid, control the traction speed of the traction machine to 0.25 m / min, the traction stop time to 200 ms, the reverse push stroke to 0.3 mm, and the traction frequency to 30 Hz to obtain the alloy ingot.

[0166] 3) Place the alloy ingot in an annealing furnace at a temperature of 900 °C and hold for 60 min, then water-quench the alloy ingot to room temperature to obtain the solution-treated alloy ingot. Then place the solution-treated alloy ingot in an annealing furnace at a temperature of 900 °C and hold for 60 min, then perform hot rolling at a temperature of 900 °C, and control the deformation amount of the alloy ingot to 85% to obtain the alloy ingot.

[0167] 4) First, put the alloy ingot into an annealing furnace at a temperature of 450 °C and hold it for 1.5 h. Then, air-cool the alloy ingot to room temperature. Next, pickle the alloy ingot with 20 wt% dilute phosphoric acid, followed by cold rolling, and control the deformation amount to 60% to obtain the first annealed cold-rolled alloy. Then, put the first annealed cold-rolled alloy into an annealing furnace at a temperature of 450 °C and hold it for 1.5 h. After that, air-cool the first annealed cold-rolled alloy to room temperature. Then, pickle the first annealed cold-rolled alloy with 20 wt% dilute phosphoric acid, followed by cold rolling, and control the deformation amount to 50% to obtain the second annealed cold-rolled alloy. Then, put the second annealed cold-rolled alloy into an annealing furnace at a temperature of 450 °C and hold it for 1.5 h. Then, air-cool the second annealed cold-rolled alloy to room temperature; pickle the second annealed cold-rolled alloy with 20 wt% dilute phosphoric acid, followed by cold rolling, and control the deformation amount to 80% to obtain the semi-finished copper-based elastic alloy.

[0168] 5) Finally, put the semi-finished copper-based elastic alloy into an annealing furnace at a temperature of 400 °C and hold it for 4 h. Then, air-cool the semi-finished copper-based elastic alloy to room temperature; then pickle the semi-finished copper-based elastic alloy with 20 wt% dilute phosphoric acid to obtain the copper-based elastic alloy.

[0169] Comparative Example 4

[0170] 1) Prepare 22 wt% Zn, 4 wt% Al, 5 wt% Ni, 0.06 wt% Ce according to the component ratio, and the balance is Cu. Put the prepared Cu and Ni into a melting crucible, evacuate to 10 -1 Pa, fill with argon to normal pressure, then evacuate to 10 -1 Pa, fill with argon to a pressure of 6×10⁴ Pa - 8×10⁴ Pa, and then heat and melt at a heating temperature of 1250 °C to obtain a semi-alloy molten liquid.

[0171] 2) Then, add Ce, Zn, and Al to the semi-alloy molten liquid simultaneously. After melting, hold for 10 min to obtain the initial alloy molten liquid; transfer the initial alloy molten liquid to a holding furnace and hold it at a holding temperature of 1100 °C to obtain the alloy molten liquid. Pull the alloy molten liquid, control the pulling speed of the pulling machine to 0.30 m / min, the pulling stop time to 300 ms, the reverse push stroke to 0.5 mm, and the pulling frequency to 40 Hz to obtain the alloy ingot.

[0172] 3) Put the alloy ingot into an annealing furnace at a temperature of 950 °C and hold it for 90 min. Then, water-quench the alloy ingot to room temperature to obtain a solution-treated alloy ingot. Then, put the solution-treated alloy ingot into an annealing furnace at a temperature of 950 °C and hold it for 90 min. Then, perform hot rolling at a temperature of 950 °C and control the deformation amount of the alloy ingot to 90% to obtain the alloy ingot.

[0173] 4) First, put the alloy ingot into an annealing furnace at a temperature of 500 °C and hold for 2 h, then air-cool the alloy ingot to room temperature. Then, pickle the alloy ingot with 25 wt% dilute phosphoric acid, followed by cold rolling, and control the deformation amount to 65% to obtain the first annealed and cold-rolled alloy. Next, put the first annealed and cold-rolled alloy into an annealing furnace at a temperature of 500 °C and hold for 2 h, then air-cool the first annealed and cold-rolled alloy to room temperature. Then, pickle the first annealed and cold-rolled alloy with 25 wt% dilute phosphoric acid, followed by cold rolling, and control the deformation amount to 55% to obtain the second annealed and cold-rolled alloy. Then, put the second annealed and cold-rolled alloy into an annealing furnace at a temperature of 500 °C and hold for 2 h, then air-cool the second annealed and cold-rolled alloy to room temperature; pickle the second annealed and cold-rolled alloy with 25 wt% dilute phosphoric acid, followed by cold rolling, and control the deformation amount to 85% to obtain the semi-finished copper-based elastic alloy.

[0174] 5) Finally, put the semi-finished copper-based elastic alloy into an annealing furnace at a temperature of 500 °C and hold for 8 h, then air-cool the semi-finished copper-based elastic alloy to room temperature; then pickle the semi-finished copper-based elastic alloy with 25 wt% dilute phosphoric acid to obtain the copper-based elastic alloy.

[0175] Comparative Example 5

[0176] 1) Prepare 22 wt% Zn, 4 wt% Al, 5 wt% Ni, 0.06 wt% Ce, and 0.02 wt% La according to the component ratio, with the balance being Cu. Put the prepared Cu and Ni into a melting crucible, evacuate to 10 -1 Pa, fill with argon to atmospheric pressure, then evacuate to 10 -1 Pa, and fill with argon until the pressure is 6×10 4 Pa, and then heat and melt at a heating temperature of 1250 °C to obtain a semi-alloy molten liquid.

[0177] 2) Then, add the prepared Cu-Ce master alloy, Zn, and Al to the semi-alloy molten liquid, dissolve and hold for 5 min to obtain the initial alloy molten liquid; transfer the initial alloy molten liquid to a holding furnace and hold at a holding temperature of 1050 °C to obtain the alloy molten liquid. Pull the alloy molten liquid, control the pulling speed of the pulling machine to 0.20 m / min, the pulling stop time to 100 ms, the reverse push stroke to 0.05 mm, and the pulling frequency to 20 Hz to obtain the alloy ingot.

[0178] 3) First, place the alloy ingot in an annealing furnace at a temperature of 400 °C and hold for 1 h, then air-cool the alloy ingot to room temperature. Then, pickle the alloy ingot with 15 wt% dilute phosphoric acid, followed by cold rolling, and control the deformation amount to 55% to obtain the first annealed cold-rolled alloy. Next, place the first annealed cold-rolled alloy in an annealing furnace at a temperature of 400 °C and hold for 1 h, then air-cool the first annealed cold-rolled alloy to room temperature. Then, pickle the first annealed cold-rolled alloy with 15 wt% dilute phosphoric acid, followed by cold rolling, and control the deformation amount to 45% to obtain the second annealed cold-rolled alloy. Then, place the second annealed cold-rolled alloy in an annealing furnace at a temperature of 400 °C and hold for 1 h, then air-cool the second annealed cold-rolled alloy to room temperature; pickle the second annealed cold-rolled alloy with 15 wt% dilute phosphoric acid, followed by cold rolling, and control the deformation amount to 75% to obtain the semi-finished copper-based elastic alloy.

[0179] 5) Finally, place the semi-finished copper-based elastic alloy in an annealing furnace at a temperature of 300 °C and hold for 0.5 h, then air-cool the semi-finished copper-based elastic alloy to room temperature; then pickle the semi-finished copper-based elastic alloy with 15 wt% dilute phosphoric acid to obtain the copper-based elastic alloy.

[0180] Comparative Example 6

[0181] 1) Prepare 22 wt% Zn, 4 wt% Al, 5 wt% Ni, 0.06 wt% Ce, and 0.02 wt% La according to the component ratio, with the balance being Cu. Put the prepared Cu and Ni into a melting crucible, evacuate to 10 -1 Pa, fill with argon to normal pressure, then evacuate to 10 -1 Pa, fill with argon to a pressure of 7×10 4 Pa, and then heat and melt at a heating temperature of 1250 °C to obtain a semi-alloy molten liquid.

[0182] 2) Then, add the prepared Cu-Ce intermediate master alloy, Zn, and Al to the semi-alloy molten liquid, hold for 8 min after melting to obtain the initial alloy molten liquid; transfer the initial alloy molten liquid to a holding furnace and hold at a holding temperature of 1100 °C to obtain the alloy molten liquid. Pull the alloy molten liquid, control the pulling speed of the pulling machine to 0.30 m / min, the pulling stop time to 200 ms, the reverse push stroke to 0.3 mm, and the pulling frequency to 30 Hz to obtain the alloy ingot.

[0183] 3) Place the alloy ingot in an annealing furnace at a temperature of 900 °C and hold for 60 min, then water-quench the alloy ingot to room temperature to obtain a solution-treated alloy ingot. Then, place the solution-treated alloy ingot in an annealing furnace at a temperature of 950 °C and hold for 60 min, and then perform hot rolling at a temperature of 800 °C, and control the deformation amount of the alloy casting to 90% to obtain the alloy casting.

[0184] 4) Put the alloy ingot into an annealing furnace at a temperature of 450 °C and hold for 2 h, then air-cool the alloy ingot to room temperature. Then pickle the alloy ingot with 20 wt% dilute phosphoric acid, and then perform cold rolling, and control the deformation amount to 94% to obtain a semi-finished copper-based elastic alloy.

[0185] 5) Finally, put the semi-finished copper-based elastic alloy into an annealing furnace at a temperature of 400 °C and hold for 4 h, then air-cool the semi-finished copper-based elastic alloy to room temperature; then pickle the semi-finished copper-based elastic alloy with 20 wt% dilute phosphoric acid to obtain a copper-based elastic alloy.

[0186] Detect the Brinell hardness, tensile strength, electrical conductivity, elastic modulus and corrosion rate of the copper-based elastic alloys prepared in all the above examples and comparative examples. The detection methods are as follows:

[0187] 1. Brinell hardness: Use an HB-3000 type Brinell hardness tester.

[0188] 2. Tensile strength: Test with an electronic universal testing machine.

[0189] 3. Elastic modulus: Test with an electronic universal testing machine.

[0190] 4. Electrical conductivity: Use a DQ-1 type bridge-type resistance tester to test the resistance of the sample, and calculate through the formula σ = 0.017241 / (ρkS / L)×100% (σ is the electrical conductivity, ρ is the resistance, k is the temperature coefficient, S is the cross-sectional area, L is the sample length).

[0191] 5. Corrosion rate: Immerse the sample in the corrosion solution (3.5% NaCl solution, pH value of 6.5), stand still for corrosion for 28 d, and replace the solution every 7 d. After taking out, use 11:HCl solution to remove the surface corrosion products and calculate the average corrosion rate.

[0192] The detection results are shown in Table 1 below.

[0193]

[0194]

[0195] Table 1

[0196] According to the detection data in Table 1, it can be seen that the copper-based elastic alloy prepared by using the preparation raw materials and preparation method of the copper-based elastic alloy of the present application has excellent high-strength and high-corrosion-resistant characteristics, and can maintain good electrical conductivity and elastic properties.

[0197] The above are only the preferred embodiments of the present application and are not intended to limit the present application. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present application shall be included within the protection scope of the present application.

Claims

1. A copper-based elastic alloy, characterized in that: The raw materials for preparing the copper-based elastic alloy include the following components: Zn, 18-25wt%; Al, 1-5wt%; Ni, 1-6 wt%; Ce, 0.02-0.12wt%; The rest is Cu.

2. The copper-based elastic alloy according to claim 1, characterized in that: The raw materials for preparing the copper-based elastic alloy include the following components: Zn, 19-22 wt%; Al, 2-4 wt%; Ni, 1-5wt%; Ce, 0.04-0.10wt%; The rest is Cu.

3. A method for preparing a copper-based elastic alloy, characterized in that: The copper-based elastic alloy preparation method comprises: Providing the components of the copper-based elastic alloy according to any one of claims 1 to 3, and smelting the components to obtain an alloy ingot; The alloy ingot is subjected to annealing and rolling treatment to obtain a copper-based elastic alloy.

4. The method for preparing a copper-based elastic alloy according to claim 3, characterized in that: The process of smelting the components to obtain an alloy ingot comprises: Putting each component into a melting device for smelting to obtain alloy melt; The alloy melt is pulled to obtain an alloy ingot.

5. The method for preparing a copper-based elastic alloy according to claim 4, characterized in that: The process of placing each component into a melting device for smelting to obtain a molten alloy comprises: Putting Cu and Ni into a melting device for smelting to obtain a semi-alloy molten liquid; Cu-Ce intermediate master alloy, Zn and Al are added into the semi-alloy molten liquid for melting to obtain alloy molten liquid.

6. The method for preparing a copper-based elastic alloy according to claim 5, characterized in that: The step of placing Cu and Ni into a melting device for smelting to obtain a semi-alloy melt comprises: Put Cu and Ni into the melting device and evacuate to 10 -1 Pa and below; Fill with argon to normal pressure and evacuate to 10 -1 Pa and below; Fill with argon to a pressure of 6×10 4 Pa~8×10 4 Pa is then heated and smelted to obtain a semi-alloy melt; wherein the heating temperature is 1250°C.

7. The method for preparing a copper-based elastic alloy according to claim 6, characterized in that: The step of adding Cu-Ce intermediate master alloy, Zn and Al into the semi-alloy molten liquid for melting to obtain the alloy molten liquid comprises: Adding Cu-Ce intermediate master alloy, Zn and Al into the semi-alloy molten liquid, and keeping the temperature for 5 to 10 minutes after melting to obtain an initial alloy molten liquid; The initial alloy melt is transferred to a heat preservation device and kept warm at a temperature of 1050 to 1100° C. to obtain an alloy melt; And / or, when pulling the alloy melt to obtain the alloy ingot, the pulling speed is 0.20-0.30 m / min, the pulling stop time is 100-300 ms, the reverse pushing distance is 0.05-0.5 mm, and the pulling frequency is 20-40 Hz.

8. The method for preparing a copper-based elastic alloy according to claim 4, characterized in that: The alloy ingot is subjected to annealing and rolling treatment to obtain a copper-based elastic alloy, comprising: The alloy ingot is placed in an annealing device for heat preservation, and then subjected to water quenching treatment to obtain a solid solution alloy ingot; The solid solution alloy ingot is placed in an annealing device for heat preservation, and then rolled to obtain an alloy casting; The alloy is cast and annealed and cold-rolled to obtain a semi-finished copper-based elastic alloy; The semi-finished copper-based elastic alloy is placed in an annealing device for heat preservation treatment, and then pickled to obtain the copper-based elastic alloy.

9. The method for preparing a copper-based elastic alloy according to claim 8, characterized in that: The step of placing the alloy ingot in an annealing device for heat preservation and then performing water quenching to obtain a solid solution alloy ingot comprises: The alloy ingot is placed in an annealing device at a temperature of 800 to 950° C., and after keeping the temperature for 30 to 90 minutes, the alloy ingot is water quenched to room temperature to obtain a solid solution alloy ingot; And / or, the solid solution alloy ingot is placed in an annealing device for heat preservation, and then rolled to obtain an alloy casting, comprising: The solid solution alloy ingot is placed in an annealing device at a temperature of 800-950°C, kept warm for 20-30 minutes, and then hot rolled at a temperature of 700-950°C to obtain an alloy casting; wherein the deformation amount of the alloy casting is controlled at 80%-90%.

10. The method for preparing a copper-based elastic alloy according to claim 8, characterized in that: The alloy casting is subjected to annealing and cold rolling treatment to obtain a semi-finished copper-based elastic alloy, comprising: The alloy casting is placed in an annealing device at a temperature of 400 to 500° C. and kept warm for 1 to 2 hours, and then the alloy casting is air-cooled to room temperature; The alloy casting is pickled with 15-25wt% dilute phosphoric acid, and then cold-rolled to obtain a first annealed cold-rolled alloy; wherein the deformation of the first annealed cold-rolled alloy is controlled to be 55-65%; The first annealed cold-rolled alloy is placed in an annealing device at a temperature of 400 to 500° C. and kept warm for 1 to 2 hours, and then the first annealed cold-rolled alloy is air-cooled to room temperature; The first annealed cold-rolled alloy is pickled with 15-25wt% dilute phosphoric acid, and then cold-rolled to obtain a second annealed cold-rolled alloy; wherein the deformation of the second annealed cold-rolled alloy is controlled to be 45-55%; The second annealed cold-rolled alloy is placed in an annealing device at a temperature of 400 to 500° C. and kept warm for 1 to 2 hours, and then the second annealed cold-rolled alloy is air-cooled to room temperature; The second annealed cold-rolled alloy is pickled with 15-25wt% dilute phosphoric acid, and then cold-rolled to obtain a semi-finished copper-based elastic alloy; wherein the deformation of the second annealed cold-rolled alloy is controlled at 75-85%; And / or, the semi-finished copper-based elastic alloy is placed in an annealing device for heat preservation treatment, and then pickled to obtain the copper-based elastic alloy, comprising: The semi-finished copper-based elastic alloy is placed in an annealing device at a temperature of 300 to 500° C. for 0.5 to 8 hours, and then the semi-finished copper-based elastic alloy is air-cooled to room temperature; The semi-finished copper-based elastic alloy is pickled with 15-25wt% of dilute phosphoric acid to obtain the copper-based elastic alloy.

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