A copper-based elastic alloy and a method for manufacturing the same

Abstract

The application relates to the metallurgical technical field, and provides a copper-based elastic alloy and a preparation method thereof. The preparation raw material of the copper-based elastic alloy comprises the following components: Zn, 18-25 wt%; Al, 1-5 wt%; Ni, 1-6 wt%; Ce, 0.02-0.12 wt%; and the rest is Cu. The copper-based elastic alloy prepared by Zn, Al, Ni, Cu and Ce realizes the excellent combination of high strength, high elasticity and excellent corrosion resistance.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of metallurgy, and particularly relates to a copper-based elastic alloy and a preparation method thereof. BACKGROUND

[0002] The copper-based elastic alloy refers to an alloy taking copper as a main component and adding specific alloy elements to significantly improve the elasticity and other mechanical properties of the alloy. The alloy usually has a high elastic limit, good fatigue resistance and stable size, and is very valuable in applications requiring high precision and stability.

[0003] Brass is a relatively important alloy in copper alloys. It not only inherits the good electrical conductivity and thermal conductivity of copper metal, but also has good corrosion resistance, excellent mechanical properties and good cold and hot working performance, and belongs to an alloy material that can be widely used in non-ferrous metal application fields. Brass alloy, due to its excellent physical properties and mechanical properties, has become one of the most common alloy materials in the field of non-ferrous metal applications. The characteristics of the alloy adapting to high-speed heavy load and low lubrication working environment make it show obvious advantages in the preparation of high-speed hydraulic rotors, connecting rod bushings, automobile synchronizer ring, bearings and precision parts.

[0004] In the related art, aluminum brass is often used to make condenser pipes as corrosion-resistant parts, but the environment of the condenser pipe is usually harsh. The corrosion resistance in the atmosphere is good, but long-term use in seawater or cooling liquid environment will cause dezincification and corrosion cracking. The oxidation film on the surface of the pipe will be destroyed by various components in the condensed water, such as some acidic, chlorine-containing and ammonia-containing liquids, which will cause 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. The impact resistance of the film is small, and it is easily damaged and cannot protect the material. SUMMARY

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

[0006] To achieve the above application purpose, the technical scheme adopted by the application is as follows:

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

[0008] Zn, 18-25wt%;

[0009] Al, 1-5wt%;

[0010] Ni, 1-6wt%;

[0011] Ce, 0.02-0.12wt%;

[0012] The rest is Cu.

[0013] The copper-based elastic alloy provided in the application can improve the mechanical properties and processing properties of the copper-based elastic alloy by 18-25wt% of Zn combined with Cu to form the basic structure of α and β phases; 1-5wt% of Al can play a solid solution strengthening role, and the high zinc equivalent coefficient of Al can significantly reduce the α phase region and move it to the copper corner, thereby increasing the hardness and strength of the copper-based elastic alloy; meanwhile, 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, Al can combine with oxygen in the corrosion medium preferentially and react to form a dense and hard Al2O3 film to prevent the alloy from being further corroded. 1-6wt% of Ni can be infinitely solid-solved in the Cu matrix to play a solid solution strengthening role, and also refine the grains to increase the strength and hardness of the copper-based elastic alloy, and with the dissolution of Ni atoms, a corbino gas cluster will be formed, and the Ni atoms have a pinning effect on the dislocations with the corbino gas cluster, which hinders the movement of dislocations, thereby strengthening the copper-based elastic alloy. Meanwhile, the AlNi3 and AlNi intermetallic compounds formed by Ni and Al play a precipitation strengthening role, thereby further increasing the resistance to dislocation movement and improving the tensile strength and hardness. The addition of 0.02-0.12wt% of Ce can purify the matrix, refine the grains, remove impurities, and also greatly increase the polarization resistance, reduce the corrosion current, and slow down the corrosion process; and it can also better prevent Zn from diffusing from the surface of the matrix to the medium through the corrosion product, thereby inhibiting dezincification to a certain extent. Therefore, the copper-based elastic alloy prepared by Zn, Al, Ni, Cu and Ce realizes the 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, 19-22wt%;

[0016] Al, 2-4wt%;

[0017] Ni, 1-5wt%;

[0018] Ce, 0.02-0.10wt%;

[0019] The rest is Cu.

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

[0021] The components of the copper-based elastic alloy in any one of the first aspect are provided, and each component is subjected to melting to obtain an alloy ingot;

[0022] The alloy ingot is subjected to annealing and rolling to obtain a copper-based elastic alloy.

[0023] The method for preparing copper-based elastic alloys provided in this application enables uniform mixing of all components after melting, and the annealing and rolling treatment effectively improves the microstructure of the alloy, including refining grains and uniformly distributing second-phase particles. These changes in microstructure directly enhance the mechanical properties of the material, such as strength, elasticity, and corrosion resistance.

[0024] In some embodiments, the process of melting the components to obtain an alloy ingot includes:

[0025] The components are placed in a melting device for melting to obtain an alloy molten liquid;

[0026] The molten alloy is drawn to obtain an alloy ingot.

[0027] In some embodiments, the step of placing the components into a melting device for melting to obtain an alloy melt includes:

[0028] Cu and Ni are placed in a melting device for smelting to obtain a semi-alloy molten liquid;

[0029] Cu-Ce intermediate master alloy, Zn and Al are added to the semi-alloy melt and melted to obtain an alloy melt.

[0030] In some embodiments, the process of melting Cu and Ni in a melting apparatus to obtain a semi-alloy melt includes:

[0031] Place Cu and Ni into a melting apparatus and evacuate to 10 °C. -1 Pa and below;

[0032] Argon gas was introduced to atmospheric pressure, and a vacuum was drawn to 10. -1 Pa and below;

[0033] Argon gas was introduced until the pressure reached 6 × 10⁻⁶. 4 Pa~8×10 4 After Pa, the mixture is heated and melted to obtain a semi-alloy molten liquid; wherein the heating temperature is 1250℃.

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

[0035] Cu-Ce intermediate master alloy, Zn and Al are added to the semi-alloy melt, and after melting, the mixture is kept at a temperature of 5-10 min to obtain the initial alloy melt.

[0036] The initial alloy melt is transferred to a holding device, and is held at a holding temperature of 1050-1100°C to obtain an alloy melt;

[0037] In the process of drawing the alloy melt to obtain the alloy ingot, the drawing speed is 0.20-0.30 m / min, the drawing stop time is 100-300 ms, the reverse push distance is 0.05-0.5 mm, and the drawing frequency is 20-40 Hz.

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

[0039] After the alloy ingot is held in the annealing device, water quenching treatment is performed to obtain a solid solution alloy ingot.

[0040] After the solid solution alloy ingot is held in the annealing device, rolling is performed to obtain an alloy cast.

[0041] The alloy cast is subjected to annealing and cold rolling treatment to obtain a semi-finished copper-based elastic alloy.

[0042] After the semi-finished copper-based elastic alloy is held in the annealing device, pickling is performed to obtain a copper-based elastic alloy.

[0043] In some embodiments, the annealing and rolling treatment of the alloy ingot to obtain the copper-based elastic alloy comprises:

[0044] The alloy ingot is placed in an annealing device at a temperature of 800-950°C, and after being held for 30-90 min, the alloy ingot is water quenched to room temperature to obtain a solid solution alloy ingot.

[0045] In some embodiments, the annealing and rolling treatment of the alloy ingot to obtain the copper-based elastic alloy comprises:

[0046] The solid solution alloy ingot is placed in an annealing device at a temperature of 800-950°C, and after being held for 20-30 min, hot rolling is performed at a temperature of 700-950°C to obtain an alloy cast, wherein the deformation amount of the alloy cast is controlled to be 80%-90%.

[0047] In some embodiments, the annealing and rolling treatment of the alloy ingot to obtain the copper-based elastic alloy comprises:

[0048] The alloy cast is placed in an annealing device at a temperature of 400-500°C and held for 1-2 h, and then the alloy cast is air cooled to room temperature.

[0049] The alloy cast is pickled by 15-25wt% 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 to be 55-65%;

[0050] The first annealed cold-rolled alloy is placed into an annealing device with a temperature of 400-500℃ for 1-2h, and then air-cooled to room temperature;

[0051] The first annealed cold-rolled alloy is pickled by 15-25wt% 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 to be 45-55%;

[0052] The second annealed cold-rolled alloy is placed into an annealing device with a temperature of 400-500℃ for 1-2h, and then air-cooled to room temperature;

[0053] The second annealed cold-rolled alloy is pickled by 15-25wt% 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 to be 75-85%;

[0054] And / or, after the semi-finished copper-based elastic alloy is placed into an annealing device for heat preservation treatment, pickling is performed to obtain a copper-based elastic alloy, which comprises:

[0055] The semi-finished copper-based elastic alloy is placed into an annealing device with a temperature of 300-500℃ for 0.5-8h, and then air-cooled to room temperature;

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

[0057] The above description is only a summary of the technical solutions of the present application. In order to more clearly understand the technical means of the present application, the specific embodiments of the present application can be implemented according to the content of the description, and in order to make the above and other purposes, features and advantages of the present application more obvious and easy to understand, the following specific embodiments of the present application are described. BRIEF DESCRIPTION OF DRAWINGS

[0058] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the following will briefly introduce the drawings needed to be used in the embodiments or prior art description. Obviously, the drawings in the following description are only some embodiments of the present application, and those skilled in the art can obtain other drawings according to these drawings without creating any creative labor.

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

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

[0061] Figure 3 is a schematic flow chart of step S230 of the preparation method of the copper-based elastic alloy provided in an embodiment of the present application. DETAILED DESCRIPTION

[0062] In order to make the technical problems, technical solutions and beneficial effects to be solved in the present application clearer, the present application will be further described in detail in combination 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 the associated objects, which means that there can be three kinds of relationships, for example, A and / or B can mean that A exists alone, A and B exist together, and B exists alone. Wherein A and B can be singular or plural. The character " / " generally represents an "or" relationship between the associated objects before and after it.

[0064] In the present application, "at least one" means one or more, and "multiple" means two or more. "At least one" or similar expressions mean any combination of these items, including any combination of single item or multiple items. For example, "at least one of a, b, or c", or "at least one of a, b, and c", can mean a, b, c, a-b (i.e. a and b), a-c, b-c, or a-b-c, wherein a, b, and c can be single or multiple.

[0065] It should be understood that in various embodiments of the present application, the size of the sequence number of the above-mentioned processes does not mean the order of execution, and part or all of the steps can be executed in parallel or in sequence, and the execution order of the processes should be determined according to its function and inherent logic, and should not constitute any limitation on 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 "a", "said" and "the" 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] The weight of the related components mentioned in the embodiment specification of the present application can not only refer to the specific content of each component, but also represent the proportional relationship between the weights of each component. Therefore, as long as the content of the related components in the embodiment specification of the present application is scaled up or down in proportion, it is within the scope disclosed in the embodiment specification of the present application. Specifically, the mass mentioned in the embodiment specification of the present application can be μg, mg, g, kg, etc. mass units commonly known in the chemical industry.

[0068] The terms "first", "second" are only for descriptive purposes, to distinguish objects such as substances from each other, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of technical features indicated. For example, without departing from the scope 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. Therefore, the features defined with "first", "second" can explicitly or implicitly include one or more of the features.

[0069] Copper-based elastic alloy refers to an alloy with copper as the main component and adding specific alloy elements to significantly improve its elasticity and other mechanical properties. Such alloys usually have a high elastic limit, good fatigue resistance and stable size, making them very valuable in applications requiring high precision and stability.

[0070] Brass is an important alloy among copper alloys. It not only inherits the good electrical conductivity and thermal conductivity of copper metal, but also has good corrosion resistance, excellent mechanical properties, and good cold and hot working performance, etc. It belongs to an alloy material that can be widely used in non-ferrous metal application field. Brass alloy, due to its excellent physical properties and mechanical properties, has become one of the most common alloy materials in the field of non-ferrous metal application. The characteristics of the alloy adapt to high-speed heavy load and low lubrication working environment, making it show obvious advantages in the preparation of high-speed hydraulic rotor, connecting rod bushing, automobile synchronizer ring, bearing and precision parts.

[0071] In related technologies, aluminum brass is often used to make condenser pipes as corrosion-resistant parts, but the environment of the condenser pipe is usually harsh. The corrosion resistance in the atmosphere is good, but long-term use in seawater or cooling liquid environment will cause dezincification and corrosion cracking. The oxidation film on the surface of the pipe will be destroyed by various components in the condensed water, such as some acidic, chlorine-containing and ammonia-containing liquids, which will cause 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 small impact resistance and is easily damaged, which cannot protect the material.

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

[0073] The first aspect of the embodiment of the present application provides a copper-based elastic alloy. The raw material for preparing the copper-based elastic alloy comprises the following components: Zn 18-25wt%; Al 1-5wt%; Ni 1-6wt%; Ce 0.02-0.12wt%; and the rest is Cu.

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

[0075] As can be seen from the above, the copper-based elastic alloy provided by the embodiments of the present application has 18-25wt% of Zn combined with Cu to form the basic structure of α and β phases, which can improve the mechanical properties and processing performance of the copper-based elastic alloy; 1-5wt% of Al can play a solid solution strengthening role, and the high zinc equivalent coefficient of Al can significantly reduce the α phase region and move it to the copper corner, thereby increasing the hardness and strength of the copper-based elastic alloy; meanwhile, 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, Al can combine with oxygen in the corrosion medium preferentially and react to form a dense and hard Al2O3 film, thereby preventing the alloy from being further corroded. 1-6wt% of Ni can be infinitely solid-solved into the Cu matrix to play a solid solution strengthening role, and also refine the grains to increase the strength and hardness of the copper-based elastic alloy, and with the dissolution of Ni atoms, a corbino gas cluster will be formed, and the Ni atoms have a pinning effect on the dislocations with the corbino gas cluster, which hinders the movement of dislocations, thereby strengthening the copper-based elastic alloy. Meanwhile, the AlNi3 and AlNi intermetallic compounds formed by Ni and Al play a precipitation strengthening role, thereby further increasing the resistance to dislocation movement and improving the tensile strength and hardness. The addition of 0.02-0.12wt% of Ce can purify the matrix, refine the grains, degas and remove impurities, and also greatly improve the polarization resistance, reduce the corrosion current, and slow down the corrosion process; Ce can also form a protective layer around the Zn phase to enhance the overall corrosion resistance of the copper-based elastic alloy, especially in a chlorine-containing environment; and in the high-temperature smelting process, Zn is easy to evaporate and lose, and Ce can form stable compounds to reduce the evaporation of Zn, so as to stabilize the proportion of Zn in the final copper-based elastic alloy, that is, to better prevent Zn from diffusing from the surface of the copper matrix to the medium through the corrosion product, and to inhibit the dezincification phenomenon to a certain extent. Therefore, the copper-based elastic alloy prepared by Zn, Al, Ni, Cu and Ce realizes the 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: 19-22wt% of Zn; 2-4wt% of Al; 1-5wt% of Ni; 0.02-0.10wt% of Ce; and the rest is Cu.

[0077] In this way, by using 19-22wt% of Zn; 2-4wt% of Al; 1-5wt% of Ni; 0.02-0.10wt% of Ce; and the rest being Cu, the elastic modulus and strength of the copper-based elastic alloy can be further optimized, the balance between hardness, tensile strength and elongation is achieved, and therefore more excellent mechanical properties can be obtained, and the corrosion resistance of the copper-based elastic alloy can be further improved.

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

[0079] S100, providing 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, annealing and rolling the alloy ingot to obtain the copper-based elastic alloy.

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

[0082] In some embodiments, in step S100, the components are melted to obtain an alloy ingot, including:

[0083] S110, melting the components in a melting device to obtain an alloy melt.

[0084] S120, drawing the alloy melt to obtain an alloy ingot.

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

[0086] In this way, during the melting process, all the components can be fully mixed to form a uniform alloy melt, which is crucial for obtaining consistent material properties; the drawing process can control the formation of the grain structure inside the alloy ingot, effectively improving the quality of the alloy ingot and making it have good mechanical properties and physical properties.

[0087] In some embodiments, in step S110, the components are melted in a melting device to obtain an alloy melt, including:

[0088] S111, melting Cu and Ni in a melting device to obtain a semi-alloy melt.

[0089] S112, adding Cu-Ce intermediate master alloy, Zn, and Al to the semi-alloy melt for melting to obtain an alloy melt.

[0090] It can be understood that the Cu-Ce intermediate master alloy refers to a pre-prepared mixed alloy containing a specific proportion of Cu and Ce. Rare earth elements are easily oxidized, and adding them in a pure state can cause some loss. However, adding them in the form of an intermediate master alloy can reduce such loss.

[0091] In this way, Cu and Ni are first melted. On the one hand, Cu and Ni have similar melting points. On the other hand, Ni can be solid-solved into the Cu matrix to play a solid-solution strengthening role, and also refines the grain to increase the strength and hardness of the alloy. The addition of Ni atoms can form a corbino gas cluster. Ni atoms have a pinning effect on dislocations with a corbino gas cluster, which hinders the movement of dislocations. Early addition helps to form a stable matrix and provides good conditions for the addition of subsequent elements. Then, the Cu-Ce intermediate master alloy, Zn and Al are added to the semi-alloy molten liquid, which can uniformly melt and mix the subsequently added elements, and further enhance the performance of the copper-based elastic alloy.

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

[0093] S1111, Cu and Ni are placed in a melting device, vacuumed to 10 -1 Pa and below.

[0094] S1112, argon is filled to normal pressure, vacuumed to 10 -1 Pa and below.

[0095] S1113, argon is filled to a pressure of 6x10 4 Pa to 8x10 4 Pa, and then heated and smelted to obtain a semi-alloy molten liquid; wherein the heating temperature is 1250°C.

[0096] In this way, the air and other possible gases (such as oxygen, nitrogen, etc.) in the melting device are removed by vacuuming to reduce the possibility of metal oxidation. After filling with inert gas (argon) and vacuuming again, the purity of the environment is further ensured, and a non-oxygen atmosphere is prepared for subsequent operations. Setting a specific range of argon pressure (6x10 4 Pa to 8x10 4 Pa) helps to maintain a stable smelting environment and prevent external air from penetrating. The heating temperature is set to 1250°C, which meets the temperature requirement for complete melting of Cu and Ni, and also does not cause unnecessary element evaporation or material loss due to being too high. Under controlled temperature and atmosphere conditions, Cu and Ni can be fully mixed to form a uniform molten liquid, which is ready for the addition of other components in the next step.

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

[0098] S1121, the Cu-Ce intermediate master alloy, Zn and Al are added into the semi-alloy molten liquid, and after melting, the initial-state alloy molten liquid is obtained after 5-10 min of holding.

[0099] S1122, the initial-state alloy molten liquid is transferred to a holding device, and the alloy molten liquid is obtained after holding at a holding temperature of 1050-1100℃.

[0100] It can be understood that when the Cu-Ce intermediate master alloy, Zn and Al are added into the semi-alloy molten liquid, heating is not required, and the added components can be melted by using the temperature of the semi-alloy molten liquid. The holding device can be a holding furnace, a resistance heating furnace or other holding equipment.

[0101] In this way, since the semi-alloy molten liquid is already in a high-temperature state, the heat thereof can be directly used to melt the added Cu-Ce intermediate master alloy, Zn and Al. This not only simplifies the process flow, but also reduces energy consumption; after the addition of these components, the molten liquid can maintain a certain temperature within 5-10 min, so that all new components are completely dissolved and fully mixed with the semi-alloy molten liquid to form an initial-state alloy molten liquid; after the initial-state alloy molten liquid is transferred to the holding device, holding treatment is performed at 1050-1100℃, which can ensure the fluidity of the molten liquid and also will not be too high to cause unnecessary element evaporation or material loss. Through appropriate holding time and temperature control, all components are uniformly distributed in the molten liquid, reducing inconsistencies and potential defects in the microstructure, and uniform component distribution and stable microstructure help to improve the mechanical properties, elasticity and corrosion resistance of the material.

[0102] In some embodiments, in step S120, 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 is 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. For the same reason, they will not be described here.

[0104] In this way, the pulling speed is 0.20-0.30 m / min, which helps to reduce the thermal stress inside the casting, reduce the generation of cracks and other defects; the pulling stop time is 100-300 ms, which helps to improve the local cooling conditions, promote more uniform temperature distribution, and at the same time can induce more nucleation points, thereby refining the grains and improving the strength and toughness of the material; the reverse pushing stroke is 0.05-0.5 mm, which can further improve the material density; the pulling frequency is 20-40 Hz, which can better adapt to the changes in the flowability and cooling conditions of the molten liquid, so that each pulling can achieve the expected effect. At the same time, through the precise control of the pulling parameters, the quality of the alloy ingot can be improved, and a high-quality alloy ingot with uniform Zn phase distribution can be obtained.

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

[0106] S210, after the alloy ingot is placed in the annealing device for heat preservation, water quenching treatment is performed to obtain a solid solution alloy ingot.

[0107] S220, after the solid solution alloy ingot is placed in the annealing device for heat preservation, rolling is performed to obtain an alloy casting.

[0108] S230, the alloy casting is subjected to annealing and cold rolling treatment to obtain a semi-finished copper-based elastic alloy.

[0109] S240, after the semi-finished copper-based elastic alloy is placed in the annealing device for heat preservation, pickling is performed 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 a process of using pickling solution to remove oxide scale, rust, residues and other impurities on the surface of the metal.

[0111] In this way, after the alloy ingot is placed in the annealing device for heat preservation, water quenching treatment is performed, which can form a fine and uniform grain structure inside the solid solution alloy ingot; after the solid solution alloy ingot is placed in the annealing device for heat preservation, rolling is performed, which can eliminate pores, shrinkage holes, etc. in the solid solution alloy ingot, thereby improving the density of the alloy casting; the alloy casting is subjected to annealing and cold rolling treatment to obtain a semi-finished copper-based elastic alloy, which increases the strength and hardness of the material while maintaining a certain ductility and helping to restore part of the elastic properties; after the semi-finished copper-based elastic alloy is placed in the annealing device for heat preservation, pickling is performed, which stabilizes the microstructure of the material. The treatment at each stage refines and uniformly distributes the grain structure inside the material, thereby improving the quality consistency of the copper-based elastic alloy.

[0112] In some embodiments, after the alloy ingot is placed in the annealing device for heat preservation in step S210, water quenching treatment is performed to obtain a solid solution alloy ingot, including: placing the alloy ingot in the annealing device at a temperature of 800-950°C, heat preservation for 30-90 min, and then water quenching the alloy ingot to room temperature to obtain a solid solution alloy ingot.

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

[0114] In this way, 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 fine and uniform grain size, and also release part of the internal stress generated during casting, reducing the possibility of cracks and other defects; water quenching to room temperature can quickly freeze the microstructure at high temperature, prevent alloy elements from re-precipitating or forming unfavorable phase states, and significantly improve the hardness and strength of the material while maintaining certain ductility.

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

[0116] It can be understood that the deformation amount of the alloy cast is controlled to be 80%-90%, which means that the cross-sectional area of the alloy cast is reduced by a certain percentage after rolling. The deformation amount is controlled to be 80%-90%, for example, it can be 80%, 85%, 90%, etc., but is not limited thereto. The temperature is 800-950°C, the heat preservation time is 20-30 min, and the temperature is 700-950°C, and the same applies here, which will not be repeated here.

[0117] In this way, the solid solution alloy ingot is placed in the annealing device at a temperature of 800-950°C, and heat preservation is performed for 20-30 min, which can soften the material, reduce the hardness, and improve the plasticity, preparing for subsequent hot rolling; hot rolling is performed at a temperature of 700-950°C, and the deformation amount is controlled to be 80%-90%, which can further refine the grain structure, improve the strength and toughness of the material, and at the same time impart the required shape and size to the material, promote dislocation movement and recrystallization, and help 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 cast is subjected to annealing and cold rolling treatment to obtain a semi-finished copper-based elastic alloy, including:

[0119] S231, the alloy cast is placed in an annealing device at a temperature of 400-500℃ for 1-2h, and then the alloy cast is air-cooled to room temperature.

[0120] S232, the alloy cast is pickled with 15-25wt% 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 to be 55-65%.

[0121] S233, the first annealed cold-rolled alloy is placed in an annealing device at a temperature of 400-500℃ for 1-2h, and then the first annealed cold-rolled alloy is air-cooled to room temperature.

[0122] S234, 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 amount of the second annealed cold-rolled alloy is controlled to be 45-55%.

[0123] S235, the second annealed cold-rolled alloy is placed in an annealing device at a temperature of 400-500℃ for 1-2h, and then the second annealed cold-rolled alloy is air-cooled to room temperature.

[0124] S236, 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 amount of the second annealed cold-rolled alloy is controlled to be 75-85%.

[0125] It can be understood that the 15-25wt% dilute phosphoric acid can be 15wt%, 20wt%, 25wt%, etc., but is not limited thereto. The temperature of 400-500℃, the heat preservation for 1-2h, the deformation amount controlled to be 55-65%, the deformation amount controlled to be 45-55%, and the deformation amount controlled to be 75-85% are the same, and will not be repeated here.

[0126] In this way, by multiple cold rolling and deformation amount control, the grain size of the alloy is gradually refined, the overall strength and toughness of the material are improved, the annealing treatment after each cold rolling helps to release internal stress, restore part of the elastic properties, reduce the increase of brittleness caused by cold working hardening, repeated heat treatment and cold working promote dislocation movement and recrystallization, form a favorable microstructure, improve 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 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 high quality and high performance of the final product.

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

[0128] S241, the semi-finished copper-based elastic alloy is placed in an annealing device with a temperature of 300-500℃ for heat preservation for 0.5-8h, and then the semi-finished copper-based elastic alloy is air-cooled to room temperature.

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

[0130] It can be understood that the temperature of 300-500℃, for example, can be 300, 400, 500, etc., but is not limited thereto. The heat preservation time of 0.5-8h and the dilute phosphoric acid of 15-25wt% are the same, and will not be repeated here.

[0131] In this way, the final annealing treatment helps to eliminate any residual internal stress, stabilize the grain structure, and ensure the reliability and consistency of the material in long-term use. By adjusting the annealing temperature and heat preservation 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 copper-based elastic alloy surface smooth and bright, improving the appearance quality and corrosion resistance.

[0132] The following will be described in conjunction with specific embodiments.

[0133] Example 1

[0134] 1) Prepare 22wt% Zn, 4wt% Al, 5wt% Ni, 0.1wt% Ce, and the balance of Cu according to the component allocation ratio. Put the prepared Cu and Ni into a melting crucible, vacuumize to 10 -1 Pa, fill argon to normal pressure, vacuumize again to 10 -1 Pa, and then fill argon to a pressure of 8x10 4 Pa, and then heat melt at a heating temperature of 1250℃ to obtain a semi-alloy molten liquid.

[0135] 2) Then add the prepared Cu-Ce intermediate master alloy, Zn and Al into the semi-alloy molten liquid, melt and heat preserve for 10min to obtain an initial-state alloy molten liquid; transfer the initial-state alloy molten liquid to a heat preservation furnace and heat preserve at a heat preservation temperature of 1100℃ to obtain an alloy molten liquid. Draw the alloy molten liquid, control the drawing speed of the drawing machine to be 0.30m / min, the drawing stop time to be 300ms, the reverse push stroke to be 0.5mm, and the drawing frequency to be 40Hz to obtain an alloy ingot.

[0136] 3) Put the alloy ingot into the annealing furnace at 950℃ for 90min, then water quench the alloy ingot to room temperature, get the solid solution alloy ingot. Put the solid solution alloy ingot into the annealing furnace at 950℃ for 90min, then hot rolling at 950℃, and control the deformation of the alloy ingot to be 90%, get the alloy ingot.

[0137] 4) Put the alloy ingot into the annealing furnace at 500℃ for 2h, then air cool the alloy ingot to room temperature, then acid wash the alloy ingot with 25wt% dilute phosphoric acid, then cold rolling, and control the deformation to be 65%, get the first annealed cold rolled alloy. Put the first annealed cold rolled alloy into the annealing furnace at 500℃ for 2h, then air cool the first annealed cold rolled alloy to room temperature, then acid wash the first annealed cold rolled alloy with 25wt% dilute phosphoric acid, then cold rolling, and control the deformation to be 55%, get the second annealed cold rolled alloy. Then put the second annealed cold rolled alloy into the annealing furnace at 500℃ for 2h, then air cool the second annealed cold rolled alloy to room temperature, acid wash the second annealed cold rolled alloy with 25wt% dilute phosphoric acid, then cold rolling, and control the deformation to be 85%, get the semi-finished copper-based elastic alloy.

[0138] 5) Finally, put the semi-finished copper-based elastic alloy into the annealing furnace at 500℃ for 8h, then air cool the semi-finished copper-based elastic alloy to room temperature, then acid wash the semi-finished copper-based elastic alloy with 25wt% dilute phosphoric acid, to get the copper-based elastic alloy.

[0139] Example 2

[0140] 1) Prepare 20wt% Zn, 3wt% Al, 3wt% Ni, 0.07wt% Ce, and the rest is Cu according to the component allocation ratio. Put the prepared Cu and Ni into the melting crucible, vacuumize to 10 -1 Pa, fill in argon to normal pressure, vacuumize again to 10 -1 Pa, fill in argon to 7×10 4 Pa, then heat melt at a heating temperature of 1250℃, get the semi-alloy molten liquid.

[0141] 2) Then add the prepared Cu-Ce intermediate master alloy, Zn and Al into the semi-alloy molten liquid, melt and keep for 8min, get the initial state alloy molten liquid; transfer the initial state alloy molten liquid to the holding furnace, keep at a holding temperature of 1100℃, get the alloy molten liquid. Pull the alloy molten liquid, control the pulling speed of the pulling machine to be 0.25m / min, the stopping time of the pulling to be 200ms, the reverse pushing stroke to be 0.3mm, and the pulling frequency to be 30Hz, get the alloy ingot.

[0142] 3) Put the alloy ingot into the annealing furnace at 900℃ for 60 min, then water quench the alloy ingot to room temperature to obtain the solid solution alloy ingot. Put the solid solution alloy ingot into the annealing furnace at 900℃ for 60 min, then hot roll at 900℃, and control the deformation of the alloy ingot to be 85% to obtain the alloy ingot.

[0143] 4) First, put the alloy ingot into the annealing furnace at 450℃ for 1.5 h, then air cool the alloy ingot to room temperature, then use 20wt% dilute phosphoric acid to pickle the alloy ingot, then cold roll, and control the deformation to be 60% to obtain the first annealed cold rolled alloy. Then put the first annealed cold rolled alloy into the annealing furnace at 450℃ for 1.5 h, then air cool the first annealed cold rolled alloy to room temperature, then use 20wt% dilute phosphoric acid to pickle the first annealed cold rolled alloy, then cold roll, and control the deformation to be 50% to obtain the second annealed cold rolled alloy. Then put the second annealed cold rolled alloy into the annealing furnace at 450℃ for 1.5 h, then air cool the second annealed cold rolled alloy to room temperature; use 20wt% dilute phosphoric acid to pickle the second annealed cold rolled alloy, then cold roll, and control the deformation to be 80% to obtain the semi-finished copper-based elastic alloy.

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

[0145] Example 3

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

[0147] 2) Then add the prepared Cu-Ce intermediate master alloy, Zn and Al into the semi-alloy molten liquid, melt and keep for 5 min to obtain an initial-state alloy molten liquid; transfer the initial-state alloy molten liquid to a holding furnace, and keep at a holding temperature of 1050℃ to obtain an alloy molten liquid. Draw the alloy molten liquid, control the drawing speed of the drawing machine to be 0.20 m / min, the stopping time of the drawing to be 100 ms, the reverse pushing stroke to be 0.05 mm, and the drawing frequency to be 20 Hz to obtain an alloy ingot.

[0148] 3) Put the alloy ingot into the annealing furnace at 800℃ for 30 min, then water quench the alloy ingot to room temperature to obtain the solid solution alloy ingot. Put the solid solution alloy ingot into the annealing furnace at 800℃ for 30 min, then hot roll at 700℃, and control the deformation of the alloy ingot to be 80% to obtain the alloy ingot.

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

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

[0151] Comparative Example 1

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

[0153] 2) Then add Zn into the Cu molten liquid, melt and keep for 10 min to obtain Cu-Zn alloy molten liquid; transfer the Cu-Zn alloy molten liquid to the holding furnace, and keep at a holding temperature of 1100℃ to obtain 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 the alloy ingot.

[0154] 3) The alloy ingot is placed in an annealing furnace at a temperature of 950°C for 90 min, and then water quenched to room temperature to obtain a solid solution alloy ingot. The solid solution alloy ingot is then placed in an annealing furnace at a temperature of 950°C for 90 min, and then hot rolled at a temperature of 950°C, with the deformation amount of the alloy ingot controlled to be 90% to obtain an alloy cast.

[0155] 4) The alloy cast is first placed in an annealing furnace at a temperature of 500°C for 2 h, and then air cooled to room temperature. The alloy cast is then pickled with 25 wt% dilute phosphoric acid, and then cold rolled with the deformation amount controlled to be 65% to obtain a first annealed and cold rolled alloy. The first annealed and cold rolled alloy is then placed in an annealing furnace at a temperature of 500°C for 2 h, and then air cooled to room temperature. The first annealed and cold rolled alloy is then pickled with 25 wt% dilute phosphoric acid, and then cold rolled with the deformation amount controlled to be 55% to obtain a second annealed and cold rolled alloy. The second annealed and cold rolled alloy is then placed in an annealing furnace at a temperature of 500°C for 2 h, and then air cooled to room temperature. The second annealed and cold rolled alloy is then pickled with 25 wt% dilute phosphoric acid, and then cold rolled with the deformation amount controlled to be 85% to obtain a semi-finished copper-based elastic alloy.

[0156] 5) Finally, the semi-finished copper-based elastic alloy is placed in an annealing furnace at a temperature of 500°C for 8 h, and then air cooled to room temperature. The semi-finished copper-based elastic alloy is then pickled with 25 wt% dilute phosphoric acid to obtain a copper-based elastic alloy.

[0157] Comparative Example 2

[0158] 1) 22 wt% of Zn, 4 wt% of Al, and the balance of Cu are prepared according to the component allocation ratio. The Cu is placed in a melting crucible, vacuumed to 10 -1 Pa, argon is filled to normal pressure, vacuumed again to 10 -1 Pa, and then heated and melted at a heating temperature of 1250°C after argon is filled to a pressure of 6 x 10 4 Pa to obtain a semi-alloy molten liquid.

[0159] 2) The Zn and Al are then added to the semi-alloy molten liquid, melted and held for 5 min to obtain a primary alloy molten liquid. The primary alloy molten liquid is transferred to a holding furnace and held at a holding temperature of 1050°C to obtain an alloy molten liquid. The alloy molten liquid is drawn, with the drawing speed of the drawing machine controlled to be 0.20 m / min, the drawing stop time controlled to be 100 ms, the reverse push stroke controlled to be 0.05 mm, and the drawing frequency controlled to be 20 Hz to obtain an alloy ingot.

[0160] 3) Put the alloy ingot into the annealing furnace at 800℃ for 30 min, then water quench the alloy ingot to room temperature to obtain the solid solution alloy ingot. Put the solid solution alloy ingot into the annealing furnace at 800℃ for 30 min, then hot roll at 800℃, and control the deformation of the alloy ingot to be 80% to obtain the alloy ingot.

[0161] 4) First, put the alloy ingot into the annealing furnace at 400℃ for 1 h, then air cool the alloy ingot to room temperature, then use 15wt% dilute phosphoric acid to pickle the alloy ingot, then cold roll, and control the deformation to be 55% to obtain the first annealed and cold rolled alloy. Then, put the first annealed and cold rolled alloy into the annealing furnace at 400℃ for 1 h, then air cool the first annealed and cold rolled alloy to room temperature, then use 15wt% dilute phosphoric acid to pickle the first annealed and cold rolled alloy, then cold roll, and control the deformation to be 45% to obtain the second annealed and cold rolled alloy. Then, put the second annealed and cold rolled alloy into the annealing furnace at 400℃ for 1 h, then air cool the second annealed and cold rolled alloy to room temperature, then use 15wt% dilute phosphoric acid to pickle the second annealed and cold rolled alloy, then cold roll, and control the deformation to be 75% to obtain the semi-finished copper-based elastic alloy.

[0162] 5) Finally, put the semi-finished copper-based elastic alloy into the annealing furnace at 300℃ for 0.5 h, then air cool the semi-finished copper-based elastic alloy to room temperature, then use 15wt% dilute phosphoric acid to pickle the semi-finished copper-based elastic alloy to obtain the copper-based elastic alloy.

[0163] Comparative Example 3

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

[0165] 2) Then, add Zn and Al into the semi-alloy molten liquid, melt and keep for 8 min to obtain a primary alloy molten liquid; transfer the primary alloy molten liquid to a holding furnace, and keep at a holding temperature of 1100℃ to obtain an alloy molten liquid. Draw the alloy molten liquid, control the drawing speed of the drawing machine to be 0.25 m / min, the drawing stop time to be 200 ms, the reverse push stroke to be 0.3 mm, and the drawing frequency to be 30 Hz to obtain an alloy ingot.

[0166] 3) The alloy ingot is put into an annealing furnace at 900°C for 60 minutes, and then water quenched to room temperature to obtain a solid solution alloy ingot. The solid solution alloy ingot is then put into an annealing furnace at 900°C for 60 minutes, and then hot rolled at 900°C with a deformation of 85% to obtain an alloy cast.

[0167] 4) The alloy cast is first put into an annealing furnace at 450°C for 1.5 hours, and then air cooled to room temperature. The alloy cast is then pickled with 20wt% dilute phosphoric acid, and then cold rolled with a deformation of 60% to obtain a first annealed cold rolled alloy. The first annealed cold rolled alloy is then put into an annealing furnace at 450°C for 1.5 hours, and then air cooled to room temperature. The first annealed cold rolled alloy is then pickled with 20wt% dilute phosphoric acid, and then cold rolled with a deformation of 50% to obtain a second annealed cold rolled alloy. The second annealed cold rolled alloy is then put into an annealing furnace at 450°C for 1.5 hours, and then air cooled to room temperature. The second annealed cold rolled alloy is then pickled with 20wt% dilute phosphoric acid, and then cold rolled with a deformation of 80% to obtain a semi-finished copper-based elastic alloy.

[0168] 5) The semi-finished copper-based elastic alloy is finally put into an annealing furnace at 400°C for 4 hours, and then air cooled to room temperature. The semi-finished copper-based elastic alloy is then pickled with 20wt% dilute phosphoric acid to obtain a copper-based elastic alloy.

[0169] Comparative Example 4

[0170] 1) 22wt% Zn, 4wt% Al, 5wt% Ni, 0.06wt% Ce, and the balance Cu are prepared according to the component allocation ratio. The prepared Cu and Ni are put into a melting crucible, vacuumed to 10 -1 Pa, and then argon is filled to normal pressure. The pressure is vacuumed to 10 -1 Pa again, and then argon is filled to a pressure of 6x104Pa-8x104Pa. The semi-alloy molten liquid is obtained by heating and melting at a heating temperature of 1250°C.

[0171] 2) The Ce, Zn, and Al are then simultaneously added to the semi-alloy molten liquid, and the initial alloy molten liquid is obtained after melting and holding for 10 minutes. The alloy molten liquid is transferred to a holding furnace, and held at a holding temperature of 1100°C to obtain an alloy molten liquid. The alloy ingot is obtained by pulling the alloy molten liquid, controlling the pulling speed of the pulling machine to be 0.30m / min, the stopping time of the pulling to be 300ms, the reverse pushing stroke to be 0.5mm, and the pulling frequency to be 40Hz.

[0172] 3) The alloy ingot is placed in an annealing furnace at a temperature of 950°C for 90 min, and then water quenched to room temperature to obtain a solid solution alloy ingot. The solid solution alloy ingot is then placed in an annealing furnace at a temperature of 950°C for 90 min, and then hot rolled at a temperature of 950°C, with the deformation amount of the alloy ingot controlled at 90% to obtain an alloy cast.

[0173] 4) The alloy cast is first placed in an annealing furnace at a temperature of 500°C for 2 h, and then air cooled to room temperature. The alloy cast is then pickled with 25wt% dilute phosphoric acid, and then cold rolled with the deformation amount controlled at 65% to obtain a first annealed cold rolled alloy. The first annealed cold rolled alloy is then placed in an annealing furnace at a temperature of 500°C for 2 h, and then air cooled to room temperature. The first annealed cold rolled alloy is then pickled with 25wt% dilute phosphoric acid, and then cold rolled with the deformation amount controlled at 55% to obtain a second annealed cold rolled alloy. The second annealed cold rolled alloy is then placed in an annealing furnace at a temperature of 500°C for 2 h, and then air cooled to room temperature. The second annealed cold rolled alloy is then pickled with 25wt% dilute phosphoric acid, and then cold rolled with the deformation amount controlled at 85% to obtain a semi-finished copper-based elastic alloy.

[0174] 5) Finally, the semi-finished copper-based elastic alloy is placed in an annealing furnace at a temperature of 500°C for 8 h, and then air cooled to room temperature. The semi-finished copper-based elastic alloy is then pickled with 25wt% dilute phosphoric acid to obtain a copper-based elastic alloy.

[0175] Comparative Example 5

[0176] 1) 22wt% Zn, 4wt% Al, 5wt% Ni, 0.06wt% Ce and 0.02wt% La are prepared according to the component allocation ratio, with the balance being Cu. The prepared Cu and Ni are placed in a melting crucible, vacuumed to 10 -1 Pa, argon is filled to normal pressure, vacuumed again to 10 -1 Pa, and after argon is filled to a pressure of 6x10 4 Pa, heated melting is carried out at a heating temperature of 1250°C to obtain a semi-alloy molten liquid.

[0177] 2) The prepared Cu-Ce intermediate master alloy, Zn and Al are then added to the semi-alloy molten liquid, melted and held for 5 min to obtain an initial-state alloy molten liquid. The initial-state alloy molten liquid is transferred to a holding furnace and held at a holding temperature of 1050°C to obtain an alloy molten liquid. The alloy molten liquid is drawn, with the drawing speed of the drawing machine controlled at 0.20 m / min, the drawing stop time controlled at 100 ms, the reverse push stroke controlled at 0.05 mm, and the drawing frequency controlled at 20 Hz to obtain an alloy ingot.

[0178] 3) First, the alloy ingot is placed in an annealing furnace at a temperature of 400°C for 1 h, then the alloy ingot is air-cooled to room temperature, then the alloy ingot is pickled with 15wt% dilute phosphoric acid, then cold rolling is performed, and the deformation amount is controlled to be 55%, to obtain a first annealed cold-rolled alloy. Then the first annealed cold-rolled alloy is placed in an annealing furnace at a temperature of 400°C for 1 h, then the first annealed cold-rolled alloy is air-cooled to room temperature, then the first annealed cold-rolled alloy is pickled with 15wt% dilute phosphoric acid, then cold rolling is performed, and the deformation amount is controlled to be 45%, to obtain a second annealed cold-rolled alloy. Then the second annealed cold-rolled alloy is placed in an annealing furnace at a temperature of 400°C for 1 h, then the second annealed cold-rolled alloy is air-cooled to room temperature; the second annealed cold-rolled alloy is pickled with 15wt% dilute phosphoric acid, then cold rolling is performed, and the deformation amount is controlled to be 75%, to obtain a semi-finished copper-based elastic alloy.

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

[0180] Comparative Example 6

[0181] 1) 22wt% of Zn, 4wt% of Al, 5wt% of Ni, 0.06wt% of Ce and 0.02wt% of La are prepared according to the component allocation ratio, and the balance is Cu. The prepared Cu and Ni are placed in a melting crucible, vacuumed to 10 -1 Pa, argon is filled to normal pressure, vacuumed again to 10 -1 Pa, and after argon is filled to a pressure of 7×10 4 Pa, heating melting is performed at a heating temperature of 1250°C, to obtain a semi-alloy molten liquid.

[0182] 2) The prepared Cu-Ce intermediate master alloy, Zn and Al are further added to the semi-alloy molten liquid, and after melting, the initial alloy molten liquid is obtained by maintaining for 8 min; the initial alloy molten liquid is transferred to a holding furnace, and holding is performed at a holding temperature of 1100°C, to obtain an alloy molten liquid. The alloy molten liquid is drawn, the drawing speed of the drawing machine is controlled to be 0.30 m / min, the drawing stop time is 200 ms, the reverse push stroke is 0.3 mm, and the drawing frequency is 30 Hz, to obtain an alloy ingot.

[0183] 3) The alloy ingot is placed in an annealing furnace at a temperature of 900°C for 60 min, and then the alloy ingot is water quenched to room temperature, to obtain a solid solution alloy ingot. Then the solid solution alloy ingot is placed in an annealing furnace at a temperature of 950°C for 60 min, and then hot rolling is performed at a temperature of 800°C, and the deformation amount of the alloy cast is controlled to be 90%, to obtain an alloy cast.

[0184] 4) After the alloy ingot is kept in the annealing furnace at 450°C for 2h, the alloy ingot is air-cooled to room temperature, then the alloy ingot is pickled with 20wt% dilute phosphoric acid, then cold-rolled and the deformation amount is controlled to 94%, to obtain a semi-finished copper-based elastic alloy.

[0185] 5) Finally, the semi-finished copper-based elastic alloy is kept in the annealing furnace at 400°C for 4h, then the semi-finished copper-based elastic alloy is air-cooled to room temperature, then the semi-finished copper-based elastic alloy is pickled with 20wt% dilute phosphoric acid, to obtain a copper-based elastic alloy.

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

[0187] 1. Brinell hardness: HB-3000 type Brinell hardness tester is used.

[0188] 2. Tensile strength: electronic universal testing machine is used for testing.

[0189] 3. Elastic modulus: electronic universal testing machine is used for testing.

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

[0191] 5. Corrosion rate: the sample is immersed in the corrosion solution (3.5% NaCl solution, pH value is 6.5), and the solution is replaced every 7d after standing for 28d. After taking out, the surface corrosion product is removed with 11: HCl solution, and the average corrosion rate is calculated.

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

[0193]

[0194]

[0195] Table 1

[0196] According to the detection data in Table 1, the copper-based elastic alloy prepared by using the preparation raw materials and preparation method of the copper-based elastic alloy has excellent high strength and high corrosion resistance, and can maintain good electrical conductivity and elastic performance.

[0197] The above only describes preferred embodiments of the present application and is not used to limit the present application, and any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.

Claims

1. A copper-based elastic alloy, characterized by, The raw material for preparing the copper-based elastic alloy comprises the following components: Zn, 18-25 wt%; Al, 1-5 wt%; Ni, 1-6 wt%; Ce, 0.02-0.12 wt%; the rest being Cu. The copper-based elastic alloy preparation method comprises the following steps: putting Cu and Ni into a melting device for smelting to obtain a semi-alloy molten liquid; adding Cu-Ce intermediate master alloy, Zn and Al into the semi-alloy molten liquid for smelting to obtain an alloy molten liquid; drawing the alloy molten liquid to obtain an alloy ingot; annealing and rolling the alloy ingot to obtain the copper-based elastic alloy.

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

3. A method of making a copper-based elastic alloy, characterized by, The copper-based elastic alloy preparation method comprises the following steps: providing the components of the copper-based elastic alloy according to any one of claims 1 to 2, putting Cu and Ni into a melting device for smelting to obtain a semi-alloy molten liquid; adding Cu-Ce intermediate master alloy, Zn and Al into the semi-alloy molten liquid for smelting to obtain an alloy molten liquid; drawing the alloy molten liquid to obtain an alloy ingot; annealing and rolling the alloy ingot to obtain the copper-based elastic alloy.

4. The method of producing a copper-based elastic alloy according to claim 3, wherein The step of putting Cu and Ni into a melting device for smelting to obtain a semi-alloy molten liquid comprises the following steps: Cu and Ni were put into the melting device, vacuumed to 10 -1 Pa and below; argon gas was filled to normal pressure, and vacuumed to 10 -1 Pa and below; argon to a pressure of 6 x 10 4 Pa~8 x 10 4 Pa~8 x 10 4 Pa~8 x 10 4 Pa~8 x 10 4 Pa~8 x 10 4 Pa~8 x 10 4 Pa~8 x 10 4 Pa~8 x 10 4 Pa~8 x 5. The method of producing a copper-based elastic alloy according to claim 4, wherein The step of adding Cu-Ce intermediate master alloy, Zn and Al into the semi-alloy molten liquid for smelting to obtain an alloy molten liquid comprises the following steps: adding Cu-Ce intermediate master alloy, Zn and Al into the semi-alloy molten liquid, and after melting, keeping warm for 5-10 min to obtain an initial-state alloy molten liquid; transferring the initial-state alloy molten liquid to a keeping-warm device, keeping warm at a keeping-warm temperature of 1050-1100 ℃ to obtain an alloy molten liquid.

6. The method of producing a copper-based elastic alloy according to claim 3, wherein In the step of drawing the alloy molten liquid 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.

7. The method of making a copper-based elastic alloy of claim 3, wherein, The step of annealing and rolling the alloy ingot to obtain the copper-based elastic alloy comprises the following steps: after keeping warm in an annealing device, performing water quenching treatment on the alloy ingot to obtain a solid-solution alloy ingot; after keeping warm in an annealing device, performing rolling treatment on the solid-solution alloy ingot to obtain an alloy cast; performing annealing and cold rolling treatment on the alloy cast to obtain a semi-finished copper-based elastic alloy; after keeping warm in an annealing device, performing pickling treatment on the semi-finished copper-based elastic alloy to obtain the copper-based elastic alloy.

8. The method of making a copper-based elastic alloy of claim 7, wherein, The step of keeping warm in an annealing device and then performing water quenching treatment on the alloy ingot to obtain a solid-solution alloy ingot comprises the following steps: after keeping warm in an annealing device at a temperature of 800-950 ℃ for 30-90 min, water quenching the alloy ingot to room temperature to obtain a solid-solution alloy ingot.

9. The method of making a copper-based elastic alloy of claim 7, wherein, The step of keeping warm in an annealing device and then performing rolling treatment on the solid-solution alloy ingot to obtain an alloy cast comprises the following steps: Put the solid solution alloy ingot into an annealing device at a temperature of 800-950 DEG C, heat preservation 20-30 min, then hot rolling at a temperature of 700 DEG C-950 DEG C, get alloy cast; wherein the deformation of the alloy cast is controlled at 80%-90%.

10. The method of making a copper-based elastic alloy of claim 7, wherein, The alloy cast is annealed and cold-rolled to obtain a semi-finished copper-based elastic alloy, comprising: Put the alloy cast into an annealing device at a temperature of 400-500 DEG C for 1-2 h, then air cool to room temperature; The alloy cast is pickled with 15-25 wt% dilute phosphoric acid, then cold-rolled to obtain a first annealed and cold-rolled alloy; wherein the deformation of the first annealed and cold-rolled alloy is controlled at 55-65%; Put the first annealed and cold-rolled alloy into an annealing device at a temperature of 400-500 DEG C for 1-2 h, then air cool to room temperature; The first annealed and cold-rolled alloy is pickled with 15-25 wt% dilute phosphoric acid, then cold-rolled to obtain a second annealed and cold-rolled alloy; wherein the deformation of the second annealed and cold-rolled alloy is controlled at 45-55%; Put the second annealed and cold-rolled alloy into an annealing device at a temperature of 400-500 DEG C for 1-2 h, then air cool to room temperature; The second annealed and cold-rolled alloy is pickled with 15-25 wt% dilute phosphoric acid, then cold-rolled to obtain a semi-finished copper-based elastic alloy; wherein the deformation of the second annealed and cold-rolled alloy is controlled at 75-85%.

11. The method of making a copper-based elastic alloy according to claim 7, wherein The semi-finished copper-based elastic alloy is put into an annealing device for heat preservation, then pickled to obtain a copper-based elastic alloy, comprising: Put the semi-finished copper-based elastic alloy into an annealing device at a temperature of 300-500 DEG C for 0.5-8 h, then air cool to room temperature; The semi-finished copper-based elastic alloy is pickled with 15-25 wt% dilute phosphoric acid to obtain a copper-based elastic alloy.

Images