Preparation method of high-temperature-resistant manganese-copper alloy material

Abstract

The invention discloses a preparation method of a high-temperature-resistant manganese-copper alloy material, which comprises the following steps: S1, weighing raw materials in proportion, and putting the raw materials into a vacuum arc furnace for smelting; s2, the smelted alloy liquid is subjected to casting or forging forming till the alloy is completely solidified; s3, the cast alloy is sequentially subjected to water quenching and oil quenching to be cooled step by step, and then the alloy is naturally cooled to the room temperature; and S4, the cooled alloy is subjected to aftertreatment, and preparation is completed. Copper serves as an alloy matrix, manganese serves as a secondary main element, and in the smelting process, mixed gas of argon and hydrogen serves as a protective atmosphere, so that oxidation of the alloy is avoided, and the high-temperature stability of the alloy is improved; in the cooling process, through step-by-step cooling (including water quenching, oil quenching and airflow cooling), the oxidation resistance is improved, the service life of the material is prolonged, and the stable working performance for a longer time can be provided in a high-temperature environment.

Description

Technical Field

[0001] The invention relates to the technical field of alloy preparation technology, and in particular to a method for preparing a high-temperature resistant manganese-copper alloy material. Background Art

[0002] With the continuous advancement of industrialization, especially in the fields of aerospace, energy, metallurgy, etc., the demand for high-temperature materials is gradually increasing. Many equipment and parts in high-temperature environments need to have excellent high-temperature resistance, oxidation resistance and mechanical properties. Copper-based alloys are widely used in these fields due to their good conductivity and corrosion resistance.

[0003] However, traditional copper alloys have poor mechanical properties and stability at high temperatures, and their strength loss, poor oxidation resistance, and material fatigue problems at high temperatures limit their application in high-temperature environments.

[0004] At present, the modification of copper alloys mainly focuses on the optimization of alloying elements and the improvement of preparation process. However, if the impurities in the alloy are not strictly controlled, it is easy to cause oxides to form, affecting the oxidation resistance and mechanical properties of the material; the lack of precise temperature control during the cooling process may lead to coarse grains inside the alloy, reducing its high temperature stability; and traditional processing technology is difficult to effectively achieve uniform distribution and grain refinement of high temperature alloys. Therefore, how to optimize the preparation process of alloy materials, improve their high temperature resistance, enable them to work stably for a long time under extreme high temperature conditions, and achieve efficient and low-cost production during the preparation process is an urgent problem to be solved. Summary of the invention

[0005] The purpose of the present invention is to solve the defects in the prior art and to propose a method for preparing a high temperature resistant manganese-copper alloy material.

[0006] In order to achieve the above object, the present invention adopts the following technical solutions: A method for preparing a high temperature resistant manganese-copper alloy material comprises the following steps: Step S1: selecting Cu, Mn, Al, Si, Mo, La and Ti as raw materials, and pre-treating the selected raw materials to ensure that their purity and particle size meet the requirements, weighing the raw materials in proportion, and placing them in a vacuum arc furnace for smelting; Step S2: After melting for 30 minutes, slowly introduce a protective atmosphere until a molten alloy is obtained by melting, and pour the molten alloy into a previously prepared mold for casting or forging until the alloy is completely solidified; Step S3: cooling the cast alloy in steps by water quenching and oil quenching in sequence. After the alloy is cooled to room temperature, the alloy is reheated to 800°C-1000°C, and the steps are repeated to cool to 300-400°C, maintained for more than 3 hours, and then naturally cooled to room temperature. Step S4: performing post-processing on the cooled alloy to complete the preparation.

[0007] Furthermore, the high temperature resistant manganese copper alloy material includes the following percentage component raw materials: Cu: 60%-80%, Mn: 10%-20%, Al: 0.5%-2.0%, Si: 0.5%-2.0%, Mo: 0.5%-2.0%, La: 0.1% to 1 and Ti: 0.1%-0.5%; Furthermore, the high temperature resistant manganese-copper alloy material is specifically composed of the following percentage component raw materials: Cu: 78%, Mn: 16%, Al: 1%, Si: 1.5%, Mo: 1.5%, La: 0.5 and Ti: 1.5%.

[0008] Furthermore, the microstructure of the alloy is a solid solution, wherein each component is uniformly distributed in the alloy matrix.

[0009] Furthermore, in step S1, the melting temperature is set between 1050°C and 1300°C, the pressure in the furnace is controlled between 1-10Pa, and the vacuum melting time does not exceed 2 hours.

[0010] Furthermore, in step S2, the protective atmosphere is a mixture of argon and hydrogen, and the mixing ratio of argon and hydrogen is 1:9. When the protective atmosphere is introduced, the oxygen concentration in the furnace is lower than 1%.

[0011] Furthermore, in step S2, during the smelting process, the oxygen concentration in the furnace is lower than 1%, and argon is introduced as a protective gas. After the argon is introduced, the pressure in the furnace is increased to 0.1~0.2MPa, and the flow rate of the argon is maintained between 5~10L per minute.

[0012] Further, in step S3, during the alloy cooling process, when the temperature is not less than 1000°C, water quenching and high-speed airflow are used for cooling, the water temperature is 10°C-60°C, and the airflow temperature is 50-150°C; At 800-1000℃, replace the water quenching medium with oil quenching medium, and the oil temperature is 50-70℃; At 400°C, cooling is performed by high-speed airflow until reaching room temperature, wherein the cooling rate is controlled at 0.5-2°C / s.

[0013] Furthermore, the water quenching medium is tap water, the oil quenching medium is industrial oil or silicone oil, the cooling rate in the water quenching stage is controlled at 5-50°C / s, and the cooling rate in the oil quenching stage is controlled at 2-10°C / s.

[0014] Compared with the prior art, the present invention has the following beneficial effects: By using copper as the alloy matrix, manganese as the secondary main element, and adding elements such as molybdenum and titanium, the high temperature resistance and oxidation resistance of the alloy are improved; By forming a stable solid solution, the high-temperature strength and oxidation resistance of the alloy are increased. The appropriate addition of elements such as aluminum and silicon also helps to improve the toughness and corrosion resistance of the alloy. The vacuum melting process is used to accurately control the atmosphere and pressure in the furnace, effectively reducing the generation of oxides during the melting process and ensuring the high purity and uniformity of the alloy. During the melting process, a mixed gas of argon and hydrogen is used as a protective atmosphere, and the flow rate of argon and the pressure in the furnace are controlled to ensure a low-oxygen environment, which helps to avoid oxidation of the alloy and improve the high-temperature stability of the alloy. In addition, during the cooling process, step-by-step cooling (including water quenching, oil quenching and air flow cooling) is used to optimize the alloy's microstructure, refine the grains, and enhance the alloy's strength and high temperature resistance. Using corresponding water quenching or oil quenching media at different temperature stages can enhance the alloy's strength, reduce internal stress, and improve the material's toughness, ensuring that it has good mechanical properties and high temperature resistance at high temperatures. The use of a mixed atmosphere of argon and hydrogen can minimize the oxidation of the alloy at high temperatures, improve its antioxidant capacity, extend the material's service life, and provide longer stable working performance in high temperature environments. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] The accompanying drawings are used to provide further understanding of the present invention and constitute a part of the specification. They are used to explain the present invention together with the embodiments of the present invention and do not constitute a limitation of the present invention.

[0016] Figure 1 The present invention is a schematic flow chart of the method for preparing the high temperature resistant manganese-copper alloy material. DETAILED DESCRIPTION

[0017] The technical solutions in the embodiments of the present invention will be described clearly and completely below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments.

[0018] In the description of the present invention, it is necessary to understand that the terms "upper", "lower", "front", "back", "left", "right", "top", "bottom", "inside", "outside", etc., indicating the orientation or position relationship are based on the orientation or position relationship shown in the drawings, and are only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore cannot be understood as a limitation on the present invention.

[0019] High temperature resistant manganese copper alloy material, including the following component raw materials: Cu: 60%-80%, Mn: 10%-20%, Al: 0.5%-2.0%, Si: 0.5%-2.0%, Mo: 0.5%-2.0%, La: 0.1% to 1 and Ti: 0.1%-0.5%.

[0020] In a specific embodiment of the present application, a high temperature resistant manganese copper alloy material is composed of the following component raw materials: Cu: 78%, Mn: 16%, Al: 1%, Si: 1.5%, Mo: 1.5%, La: 0.5 and Ti: 1.5%.

[0021] The microstructure of the alloy is a solid solution, in which each component is uniformly distributed in the alloy matrix.

[0022] In order to better illustrate the technical solution of the present application, the component raw materials in the present application are further described below.

[0023] Cu-78%: Copper is the matrix element of the alloy, providing the basic structure of the alloy. Copper has high thermal conductivity, good electrical conductivity, good corrosion resistance and good machinability. The high content of copper ensures the stability of the alloy in high temperature environment and can improve the toughness and fatigue resistance of the alloy.

[0024] Mn-16%: Manganese is a minor but important alloying element in the alloy. Manganese can effectively form a solid solution in the alloy, refine the grains, enhance the high temperature strength, and improve the oxidation resistance and corrosion resistance of the alloy. Manganese is particularly important for improving the high temperature stability of the alloy, especially in a high temperature oxidation environment, where manganese can react with oxygen to form a stable oxide layer, thereby slowing down the oxidation rate of the alloy matrix.

[0025] Al-1%: The addition of aluminum helps improve the oxidation resistance of the alloy. Aluminum can form a dense aluminum oxide film on the surface of the alloy to protect the alloy from oxidation corrosion. Aluminum can also promote the solid solution strengthening of the alloy and improve the overall strength and hardness of the alloy. Due to its lower density, aluminum can also moderately reduce the overall weight of the alloy.

[0026] Si-1.5%: Silicon plays a major role in strengthening copper alloys. Silicon can improve the strength of the alloy through solid solution strengthening, especially at high temperatures, it can enhance the alloy's thermal stability and high temperature resistance. Silicon can also improve the alloy's oxidation resistance, especially in high temperature environments, silicon can effectively reduce the alloy's oxidation damage.

[0027] Mo-1.5%: Molybdenum is one of the key elements to improve the high temperature performance of copper alloys. Molybdenum can significantly enhance the high temperature strength and creep resistance of the alloy, especially in high temperature environments. The addition of molybdenum helps to improve the corrosion resistance of the alloy, especially in sulfide and chloride environments. Molybdenum can stabilize the lattice structure of the alloy and avoid grain coarsening or crystal structure changes under high temperature conditions.

[0028] La-0.5%: Cerium is a rare earth element with very strong oxidation resistance. Cerium can effectively reduce the oxidation rate of other metals in the alloy and improve the high temperature stability of the alloy. In copper alloys, cerium can form a stable alloy phase with other elements to improve the high temperature resistance of the alloy. At the same time, cerium can also help refine the grains of the alloy and enhance its mechanical properties.

[0029] Ti-1.5%: Titanium plays a major role in copper alloys in refining grains, improving mechanical properties and enhancing oxidation resistance. Titanium can react with other elements in the alloy to form compounds with good stability, thereby reducing grain coarsening and improving the strength and plasticity of the alloy. The addition of titanium can also improve the corrosion resistance and oxidation resistance of the alloy at high temperatures, giving it a longer service life in high temperature environments.

[0030] In this embodiment, the appropriate ratio of manganese, molybdenum, titanium and aluminum improves the high temperature strength, oxidation resistance and corrosion resistance of the alloy, ensuring its working stability at high temperatures. Molybdenum particularly enhances the creep resistance of the alloy at high temperatures, while manganese and aluminum enhance the formation of the alloy's anti-oxidation film.

[0031] The addition of aluminum and cerium greatly improves the oxidation resistance of the alloy, especially at high temperatures. They can promote the formation of a more stable oxide film, reduce the peeling of the surface oxide layer, and extend the service life of the material.

[0032] The addition of titanium and silicon plays an important role in improving the strength of the alloy, especially under high temperature conditions. They can effectively inhibit the coarsening of grains and avoid the degradation of mechanical properties under long-term high temperature environment.

[0033] Manganese, titanium and cerium elements help to refine the alloy's grains, improve the alloy's mechanical properties and processing properties, and avoid excessive growth of the alloy's grains at high temperatures, which would affect its toughness and strength.

[0034] The reasonable ratio of each element helps to maintain the good mechanical properties of the alloy in a high temperature environment, especially the strength, hardness, corrosion resistance and toughness of the alloy are effectively improved.

[0035] According to the embodiment provided by the present invention, a method for preparing a high temperature resistant manganese-copper alloy material is also disclosed.

[0036] Example

[0037] like Figure 1 As shown, a method for preparing a high temperature resistant manganese-copper alloy material comprises the following steps: Step S1: pre-treat the selected raw materials to ensure that their purity and particle size meet the requirements, weigh the raw materials in proportion, and place them in a vacuum arc furnace for smelting; The melting temperature is set between 1050°C and 1300°C, the pressure in the furnace is controlled between 1-10Pa, and the vacuum melting time does not exceed 2 hours.

[0038] Step S2: After melting for 30 minutes, slowly introduce a protective atmosphere until a molten alloy is obtained by melting, and pour the molten alloy into a previously prepared mold for casting or forging until the alloy is completely solidified; Among them: the protective atmosphere is a mixture of argon and hydrogen, the mixing ratio of argon and hydrogen is 1:9, when the protective atmosphere is introduced, the oxygen concentration in the furnace is less than 1%; During the smelting process, the oxygen concentration in the furnace is lower than 1%, and argon is introduced as a protective gas. After the argon is introduced, the pressure in the furnace is increased to 0.1~0.2MPa, and the flow rate of argon is maintained between 5~10L per minute.

[0039] Step S3: cooling the cast alloy in steps by water quenching and oil quenching in sequence. After the alloy is cooled to room temperature, the alloy is reheated to 800°C-1000°C, and the steps are repeated to cool to 300-400°C, maintained for more than 3 hours, and then naturally cooled to room temperature. Wherein: during the alloy cooling process, when the temperature is not less than 1000°C, water quenching and high-speed airflow are used for cooling together, the water temperature is 10°C-60°C, and the airflow temperature is 50-150°C; At 800-1000℃, replace the water quenching medium with oil quenching medium, and the oil temperature is 50-70℃; At 400°C, cooling is performed by high-speed airflow until reaching room temperature, wherein the cooling rate is controlled at 0.5-2°C / s.

[0040] The water quenching medium is tap water, and the oil quenching medium is industrial oil or silicone oil. The cooling rate in the water quenching stage is controlled at 5-50℃ / s, and the cooling rate in the oil quenching stage is controlled between 2-10℃ / s.

[0041] Step S4: performing post-processing on the cooled alloy to complete the preparation.

[0042] In order to better understand the technical solution of the present application, further explanation is given below in conjunction with experiments.

[0043] This solution: The alloy material is prepared by the steps described in the example.

[0044] Comparative Example 1: Copper-nickel alloy, copper (80%), nickel (20%); Comparative Example 2: Copper-aluminum alloy: copper (90%), aluminum (10%).

[0045] High temperature tensile test steps: Sample preparation: Sample A (this scheme): copper (78%), manganese (16%), aluminum (1%), silicon (1.5%), molybdenum (1.5%), titanium (1.5%), La (0.5%); Sample B (Comparative Example 1): copper (80%), nickel (20%); Sample C (Comparative Example 2): copper (90%), aluminum (10%).

[0046] equipment: Use a high temperature tensile testing machine, set the temperature range from room temperature to 1000°C, and heat at a constant temperature; The samples were subjected to tensile tests at 200°C, 400°C, 600°C, 800°C and 1000°C, the tensile curves were recorded, and the yield strength, tensile strength and ductility were measured. The results are shown in Table 1: Table 1

[0047] As can be seen from Table 1, the tensile strength of this scheme is better than that of the comparative alloy materials at high temperatures in all tests. The decrease in tensile strength at high temperatures is small, showing good high-temperature stability. Especially at 1000°C, the tensile strength can still be maintained above 500MPa, which is better than copper-nickel and copper-aluminum alloys.

[0048] High temperature oxidation experimental steps: Sample A, sample B, and sample C were prepared as described above.

[0049] Steps: Use a high temperature furnace to carry out oxidation experiments, subject the sample to oxidation treatment at 1000°C for 100 hours in an oxidation environment of pure oxygen, and measure the thickness and mass loss of the oxide layer; The structure of the oxide layer was analyzed by scanning electron microscope (SEM), and the mass loss was measured by mass measurement method. The specific structure is shown in Table 2: Table 2

[0050] It can be seen from Table 2 that the oxide layer of this scheme is the thinnest and the mass loss is the smallest, indicating that it has excellent anti-oxidation performance at high temperatures.

[0051] High temperature thermal stability test steps: Sample A, sample B, and sample C were prepared as described above.

[0052] Steps: Experiments were conducted using a high temperature furnace, microscope, scanning electron microscope (SEM), and X-ray diffractometer (XRD); The sample was heated to 1000°C and kept at this temperature for 1000 hours. After heating, it was gradually cooled to room temperature and the microstructure of the sample was observed. The microstructure of the samples was analyzed by SEM and XRD to evaluate the grain changes, precipitation phases and other phenomena, as shown in Table 3: Table 3

[0053] It can be seen from Table 3 that after long-term high-temperature exposure, the microstructure of this solution remains stable and the grain size changes slightly, indicating that it has good thermal stability.

[0054] High temperature fatigue test steps: Sample A, sample B, and sample C were prepared as described above.

[0055] Steps: Use a high temperature fatigue testing machine to conduct the experiment; The samples were exposed to high temperatures of 500°C, 700°C and 900°C for fatigue loading. The loading frequency was 1 Hz and the maximum stress amplitude was 50% of the material yield strength. The fatigue life was recorded until the material broke. See Table 4 for details: Table 4

[0056] It can be seen from Table 4 that the fatigue life of this solution is significantly higher than that of the comparative alloy material, especially at high temperatures, the material exhibits stronger fatigue resistance.

[0057] In summary, the preparation process of this scheme has significant advantages under high temperature conditions, especially in terms of mechanical properties, antioxidant properties, thermal stability and fatigue properties at high temperatures. It is suitable for use in equipment and materials that need to work in high temperature environments, and can provide longer service life and stronger high temperature resistance.

[0058] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

Claims

1. A method for preparing a high temperature resistant manganese-copper alloy material, characterized in that: The following steps are involved: Step S1: selecting Cu, Mn, Al, Si, Mo, La and Ti as raw materials, and pre-treating the selected raw materials to ensure that their purity and particle size meet the requirements, weighing the raw materials in proportion, and placing them in a vacuum arc furnace for smelting; Step S2: After melting for 30 minutes, slowly introduce a protective atmosphere until a molten alloy is obtained by melting, and pour the molten alloy into a previously prepared mold for casting or forging until the alloy is completely solidified; Step S3: cooling the cast alloy in steps by water quenching and oil quenching in sequence. After the alloy is cooled to room temperature, the alloy is reheated to 800°C-1000°C, and the steps are repeated to cool to 300-400°C, maintained for more than 3 hours, and then naturally cooled to room temperature. Step S4: performing post-processing on the cooled alloy to complete the preparation; High temperature resistant manganese copper alloy materials include the following percentage components: Cu: 60%-80%, Mn: 10%-20%, Al: 0.5%-2.0%, Si: 0.5%-2.0%, Mo: 0.5%-2.0%, La: 0.1% to 1 and Ti: 0.1%-0.5%.

2. The method for preparing a high temperature resistant manganese-copper alloy material according to claim 1, characterized in that: High temperature resistant manganese copper alloy material is specifically composed of the following percentage components Composition: Cu: 78%, Mn: 16%, Al: 1%, Si: 1.5%, Mo: 1.5%, La: 0.5 and Ti: 1.5%.

3. The method for preparing a high temperature resistant manganese-copper alloy material according to claim 2, characterized in that: The microstructure of the alloy is a solid solution, in which each component is uniformly distributed in the alloy matrix.

4. The method for preparing a high temperature resistant manganese-copper alloy material according to claim 3, characterized in that: In step S1, the melting temperature is set between 1050°C and 1300°C, the pressure in the furnace is controlled between 1-10Pa, and the vacuum melting time does not exceed 2 hours.

5. The method for preparing a high temperature resistant manganese-copper alloy material according to claim 4, characterized in that: In step S2, the protective atmosphere is a mixture of argon and hydrogen, and the mixing ratio of argon and hydrogen is 1:

9. When the protective atmosphere is introduced, the oxygen concentration in the furnace is less than 1%.

6. The method for preparing a high temperature resistant manganese-copper alloy material according to claim 5, characterized in that: In step S2, during the smelting process, the oxygen concentration in the furnace is lower than 1%, and argon is introduced as a protective gas. After the argon is introduced, the pressure in the furnace is increased to 0.1~0.2MPa, and the flow rate of argon is maintained between 5~10L per minute.

7. The method for preparing a high temperature resistant manganese-copper alloy material according to claim 6, characterized in that: In step S3, during the alloy cooling process, when the temperature is not less than 1000°C, water quenching and high-speed airflow are used for cooling, the water temperature is 10°C-60°C, and the airflow temperature is 50-150°C; At 800-1000℃, replace the water quenching medium with oil quenching medium, and the oil temperature is 50-70℃; At 400°C, cooling is performed by high-speed airflow until reaching room temperature, wherein the cooling rate is controlled at 0.5-2°C / s.

8. The method for preparing a high temperature resistant manganese-copper alloy material according to claim 7, characterized in that: The water quenching medium is tap water, and the oil quenching medium is industrial oil or silicone oil. The cooling rate in the water quenching stage is controlled at 5-50℃ / s, and the cooling rate in the oil quenching stage is controlled between 2-10℃ / s.

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