A precision manganese-copper resistance alloy material and a preparation method thereof

Abstract

The application discloses a kind of precision manganese-copper resistance alloy materials and preparation method thereof, belong to the preparation and processing technical field of high-precision resistance material, the material includes following mass percentage raw materials: Mn11.7wt%, Ni 2.5wt%, Sn 0.27-0.3wt%, Fe 0.2-0.5wt%, Ge 0.6-1.0wt%, La 0.3-0.5wt%, Nd 0.2-0.6wt%, Y 0.4-0.7wt%, the balance is Cu;The process for preparing precision manganese-copper resistance wire material using the material is in turn batching, preheating, rotary forging, shot blasting treatment, primary annealing, wire drawing treatment, secondary gradient annealing.The alloy resistance prepared using the method disclosed in the application is not prone to deformation during use, can be used stably, and effectively ensures the service life of the resistance.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of preparation and processing of high-precision resistance materials, and particularly relates to a precision manganese-copper resistance alloy material and a preparation method thereof. BACKGROUND

[0002] With the precision of electronic devices, low resistance change rate and high-precision resistance elements are paid more and more attention, and precision resistance alloys have become indispensable key materials in electronic components. These precision resistance alloys generally have the characteristics of high resistivity, low resistance temperature coefficient, stable resistance value and uniform alloy composition. Precision resistance alloys have wide application prospects and are related to the development of cutting-edge science and technology such as electronic computers, missiles, atomic energy and space navigation. Due to the rapid development of these cutting-edge science and technology, higher requirements are put forward for the precision of electronic instruments and meters, and precision resistance alloys are key materials in these instruments and meters. Therefore, it is necessary to use precision resistance materials with a wide temperature range, a small resistance temperature coefficient and a small annual change rate of resistance value.

[0003] Compared with other precision resistance alloys, the manganese-copper resistance alloy has a parabolic resistance temperature curve in the use temperature range, and the relative change value of resistance is smaller and more stable in the use temperature range compared with the linear resistance temperature curve of general precision resistance materials. However, due to less research on manganese-copper precision resistance alloys in recent years, the preparation process and heat treatment process of manganese-copper blanks are not very clear. In the long-term use process, due to the non-uniform organization of the resistance material, local heating is caused, which seriously affects the service life of the manganese-copper resistance. In the sample preparation process, due to the influence of forging process, the heat treatment process is not uniform, stress exists in the material, and the resistance material deforms in the use process, causing unstable resistance. SUMMARY

[0004] The purpose of the present application is to overcome the shortcomings of the prior art and provide a precision manganese-copper resistance alloy material and a preparation method thereof, so as to solve the problem that the internal stress of the alloy material is caused due to non-uniform heating of the alloy material in the preparation and heat treatment process of the precision manganese-copper resistance, causing unstable resistance.

[0005] The purpose of the present application can be achieved by the following technical solutions:

[0006] A precision manganese-copper resistance alloy material comprises the following mass percentage raw materials: Mn 11.7wt%, Ni 2.5wt%, Sn 0.27-0.3wt%, Fe 0.2-0.5wt%, Ge 0.636-0.88wt%, La 0.3-0.5wt%, Nd 0.1-0.6wt%, Y 0.4-0.7wt%, and the balance is Cu.

[0007] The mass percentage of Ni, Fe, Nd, Y components satisfies the relationship: Ni (wt%) = 1 x Fe (wt%) + 2 x Nd (wt%) + 3 x Y (wt%);

[0008] The mass percentage of Ge, Sn, La components satisfies the relationship: Ge (wt%) = 1.2 x Sn (wt%) + 1.04 x La (wt%).

[0009] The preparation method of the precise manganese-copper resistance alloy material comprises the following steps:

[0010] S1. The surfaces of Cu, Mn, Ni, Sn, Fe, Ge, La, Nd, Y components are cleaned, and the components are proportioned according to the above mass percentage, vacuum melting is performed, and the blank is cast;

[0011] S2. The blank is preheated;

[0012] S3. The preheated blank is subjected to rotary forging to obtain a forged piece;

[0013] S4. The forged piece is subjected to shot blasting treatment;

[0014] S5. S3 and S4 are repeated until the processing is completed to obtain the treated workpiece, and the workpiece is segmented into a rod with a length of not more than 1000 mm and a diameter of 20-30 mm.

[0015] S6. The rod is subjected to primary annealing treatment to remove stress;

[0016] S7. The sample obtained in S6 is subjected to wire drawing treatment to obtain a wire with a diameter of 0.8-1.5 mm;

[0017] S8. The wire is subjected to secondary annealing treatment, and the secondary annealing treatment comprises a gradient heating process and a gradient cooling process.

[0018] Further, in S2, the surface of the blank is treated, 3-4 mm thick alloy material is cut off from the surface of the blank, and then preheating treatment is performed, and the preheating temperature is 900-950 DEG C.

[0019] Further, the rotary forging processing pressure is 90-110 MPa, and the loading frequency is 500-600 times / min.

[0020] Further, the primary annealing treatment in S6 specifically comprises the following steps: the rod is first polished to remove surface impurities, then the rod is heated to 10 e- 2 Pa vacuum state, heated to 850 DEG C within 30 min, and then naturally cooled to room temperature (25-30 DEG C).

[0021] Further, the S7 is specifically to remove the surface impurities of the sample obtained in S6, and then the sample is placed in a wire drawing machine, and the sample is gradually reduced in cross-sectional area by pulling outward through a pulling force to form a linear or elongated shape, and the whole wire drawing process is immersed in a wire drawing liquid.

[0022] Further, the vacuum degree of the secondary annealing treatment in S8 is 10 e-2 Pa.

[0023] Further, the gradient temperature rising process in S8 is specifically to raise the temperature from 0 DEG C to 200 DEG C at a speed of 100 DEG C / h, and keep the temperature for 2h; then raise the temperature from 200 DEG C to 300 DEG C at a speed of 50 DEG C / h, and keep the temperature for 2h; then raise the temperature from 300 DEG C to 400 DEG C at a speed of 50 DEG C / h, and keep the temperature for 2h; and the gradient temperature falling process is specifically to lower the temperature from 400 DEG C to 300 DEG C at a speed of 25 DEG C / h, and keep the temperature for 2h, and then lower the temperature from 300 DEG C to 0 DEG C at a speed of 150 DEG C / h.

[0024] The present application has the following beneficial effects:

[0025] 1. The present application provides a kind of precision manganese copper resistance alloy material and preparation method thereof, wherein the component elements of alloy material include Cu, Mn, Ni, Sn, Fe, Ge, La, Nd, Y, by proportioning each component content, the conductivity of alloy material is significantly improved;The manganese copper alloy resistance prepared by using the alloy material described in the present application can effectively eliminate internal stress due to uniform heating of alloy material during heat treatment, and the resistance prepared is not prone to deformation during use, and the service life of the resistance is effectively guaranteed.

[0026] 2. The present application provides a kind of precision manganese copper resistance alloy material, wherein based on manganese copper precision resistance alloy, La, Nd and Y are added, by the three kinds of rare earth elements, dissolved in the metal, since the affinity of rare earth elements and oxygen elements is relatively strong, the free oxygen elements in the alloy will be greatly reduced, the electron movement is promoted, and the resistance temperature coefficient of the alloy is reduced. The content of the three alloy elements is adjusted, so that the alloy has good physical properties and electrical properties, and meets the production and application requirements.

[0027] 3.The application is in the preparation of precision manganese copper resistance process, on the one hand, the good billet after smelting using the processing method of rotary forging, can further improve the uniformity and plasticity of alloy material. The improvement of the uniformity of the organization is conducive to preventing the heat accumulation of the resistance in the use process, reducing the service life of the resistance, preventing the possible resistance fuse, and causing the problem of safety accident. The improvement of plasticity makes the alloy material become more simple in the processing process, and the requirement of equipment is reduced, which is conducive to the simplification of the preparation process. On the other hand, the annealing treatment of the wire material with step temperature rise is not only can make the alloy heat uniformly, refine the grain, reduce the stress caused by uneven heating, reduce the possibility of deformation of the resistance in the use process, but also can avoid the too large resistance value difference caused by the difference of the organization caused by uneven temperature. BRIEF DESCRIPTION OF DRAWINGS

[0028] The application will be further described below in combination with the drawings.

[0029] Figure 1 is a preparation flow chart of a precision manganese copper resistance alloy material of the application;

[0030] Figure 2 is a schematic diagram of the rotary forging process in embodiment 1 of the application;

[0031] Figure 3 is a temperature and time relationship diagram of the gradient temperature rise and holding of the secondary annealing treatment in embodiment 1 of the application;

[0032] Figure 4 is a metallographic structure diagram of the finished wire material prepared in embodiment 1 of the application;

[0033] Figure 5 is a resistance temperature curve diagram of the finished wire material prepared in embodiment 1 of the application. DETAILED DESCRIPTION

[0034] The technical solutions in the embodiments of the application will be described below in combination with the embodiments of the application, obviously, the described embodiments are only a part of the embodiments of the application, not all the embodiments. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the application.

[0035] Embodiment 1

[0036] A preparation method of a precision manganese copper resistance alloy material, the preparation flow chart is as shown in Figure 1 , including the following steps:

[0037] S1. The components are proportioned by mass percentage of Mn 11.7wt%, Ni 2.5wt%, Sn 0.28wt%, Fe 0.4%, Ge 0.752%, La 0.4%, Nd 0.3%, Y 0.5wt%, and the balance is Cu, and the surface of each component is cleaned, and then vacuum melting is performed, and the blank is cast;

[0038] S2. The blank is surface treated, and the surface of the blank is cut off by 3.5mm thick alloy material and then preheated, and the preheating temperature is 900℃;

[0039] S3. The preheated blank is subjected to rotary forging, and the rotary forging processing pressure is 100MPa, and the loading frequency is 550 times / min, and the forged piece is obtained;

[0040] The schematic diagram of the rotary forging processing process is shown in Figure 2 The rotary forging treatment is that the blank is placed in the die of the rotary forging press, and the two hammer dies rotate at high speed around the longitudinal axis while making periodic reciprocating motion in the sliding slot, and the blank is forged at high speed and high frequency, and the blank is uniformly stressed by continuous rotary forging to obtain the forged piece;

[0041] S4. The forged piece is subjected to shot blasting treatment;

[0042] S5. Repeat S3 and S4 until the processed workpiece is completely obtained, and the workpiece is cut into a rod with a length of 850mm and a diameter of 30mm.

[0043] S6. After the rod is polished to remove surface impurities, it is placed in a vacuum heat treatment furnace with a vacuum degree of 10 e-20 Pa for primary annealing treatment, which is heated to 850℃ within 30min and naturally cooled to room temperature;

[0044] S7. The rod after primary annealing treatment is polished to remove surface impurities, and is placed in a wire drawing machine, and is gradually reduced in cross-sectional area by pulling outward by traction force, to form a linear or elongated shape, and the entire wire drawing process ensures that it is immersed in the drawing liquid, to obtain a wire with a diameter of 1mm;

[0045] S8. The wire is subjected to secondary annealing treatment, which adopts gradient heating and gradient cooling, and the relationship diagram of the gradient heating and cooling and the temperature and time of the holding stage is as shown in Figure 3As shown in the figure, the gradient temperature rising stage of the secondary annealing treatment is specifically to raise the temperature from 0℃ to 200℃ at a speed of 100℃ / h, and keep the temperature for 2h; then raise the temperature from 200℃ to 300℃ at a speed of 50℃ / h, and keep the temperature for 2h; then raise the temperature from 300℃ to 400℃ at a speed of 50℃ / h, and keep the temperature for 2h; the gradient temperature falling stage is specifically to lower the temperature from 400℃ to 300℃ at a speed of 25℃ / h, and keep the temperature for 2h, and then lower the temperature from 300℃ to 0℃ at a speed of 150℃ / h. The finished wire material prepared has a precision manganese-copper resistance alloy material.

[0046] The metallographic structure diagram of the finished wire material prepared in Example 1 is as shown in Figure 4 Figure 4 A and B in the figure are the metallographic structure diagrams of the non-passing parts of the finished wire material, and it can be seen from the figure that the grain sizes of different parts are uniform, and the structures are also relatively uniform.

[0047] The resistance of the finished wire material prepared in Example 1 is tested at different temperatures, and the test results are shown in Figure 5 As shown in the figure, the resistance changes little with temperature in the use temperature range of 20-110℃, and the maximum resistance is within the use temperature range, meeting the use requirements.

[0048] Example 2

[0049] A preparation method of a precision manganese-copper resistance alloy material, and the preparation flow chart is as shown in Figure 1 , comprising the following steps:

[0050] S1. The mass percentages of Mn 11.7wt%, Ni 2.5wt%, Sn 0.352wt%, Fe 0.2%, Ge 0.65%, La 0.25%, Nd 0.55%, Y 0.4wt%, and the balance of Cu are matched, and the surfaces of each component are cleaned, and then vacuum melting is performed to melt and cast into a blank;

[0051] S2. The surface of the blank is treated, and the alloy material with a thickness of 4mm on the surface of the blank is cut off and then preheated, and the preheating temperature is 920℃;

[0052] S3. The preheated blank is subjected to rotary forging, the rotary forging processing pressure is 90MPa, and the loading frequency is 520 times / min, to obtain a forged piece;

[0053] S4. The forged piece is subjected to shot blasting treatment;

[0054] S5. Repeat S3 and S4 until the processing of the treated workpiece is completed, and then the workpiece is segmented into a rod with a length of 850mm and a diameter of 25mm.

[0055] ​S6. After the bar is polished to remove surface impurities, it is placed in a vacuum heat treatment furnace with a vacuum degree of 10 e-20 Pa for one annealing treatment, specifically heated to 850℃ within 30min and naturally cooled to room temperature;

[0056] S7. The bar after one annealing treatment is polished to remove surface impurities and placed in a wire drawing machine. By pulling outward with traction, its cross-sectional area is gradually reduced to form a linear or elongated shape. The entire wire drawing process ensures that it is immersed in the drawing liquid to obtain a wire with a diameter of 1mm;

[0057] S8. The wire is subjected to secondary annealing treatment using gradient heating and gradient cooling. Specifically, the temperature is raised from 0℃ to 200℃ at a rate of 100℃ / h, and held for 2h. Then the temperature is raised from 200℃ to 300℃ at a rate of 50℃ / h, and held for 2h. Then the temperature is raised from 300℃ to 400℃ at a rate of 50℃ / h, and held for 2h. In the gradient cooling stage, the temperature is lowered from 400℃ to 300℃ at a rate of 25℃ / h, and held for 2h. Then the temperature is lowered from 300℃ to 0℃ at a rate of 150℃ / h. The finished wire material prepared is a precision manganese-copper resistance alloy material.

[0058] The finished wire material prepared in Example 2 has uniform grain size and uniform structure. The resistance changes little with temperature in the use temperature range of 20-110℃, and the maximum resistance is within the use temperature range, meeting the use requirements.

[0059] Example 3

[0060] A preparation method of a precision manganese-copper resistance alloy material, with a preparation flowchart same as Figure 1 , comprising the following steps:

[0061] S1. The mass percentages of Mn 11.7wt%, Ni 2.5wt%, Sn 0.3wt%, Fe 0.5%, Ge 0.88%, La 0.5%, Nd 0.1%, Y 0.6wt%, and the balance Cu are proportioned, and the surfaces of the components are cleaned. Then vacuum melting is performed, and the billet is cast;

[0062] S2. The billet is subjected to surface treatment, and the alloy material 3mm thick on the surface of the billet is cut off and then subjected to preheating treatment at a preheating temperature of 950℃;

[0063] S3. The billet after preheating is subjected to rotary forging at a rotary forging processing pressure of 110MPa and a loading frequency of 600times / min to obtain a forged piece;

[0064] S4. The forged piece is subjected to shot blasting treatment;

[0065] S5. Repeat S3 and S4 until the processing is completed to obtain the processed workpiece, and the processed workpiece is cut into a rod with a length of 900 mm and a diameter of 20 mm.

[0066] S6. After the rod is polished to remove surface impurities, it is placed in a vacuum heat treatment furnace with a vacuum degree of 10 e-20 Pa for primary annealing treatment, specifically, heated to 850 DEG C within 30 min and naturally cooled to room temperature;

[0067] S7. The rod after primary annealing treatment is polished to remove surface impurities, placed in a wire drawing machine, and gradually reduced in cross-sectional area by pulling outward to form a linear or elongated shape. The entire wire drawing process ensures that the rod is immersed in the drawing liquid, and a wire with a diameter of 1 mm is obtained.

[0068] S8. The wire is subjected to secondary annealing treatment, using gradient heating and gradient cooling, specifically, the temperature is increased from 0 DEG C to 200 DEG C at a rate of 100 DEG C / h, and held for 2 h; then the temperature is increased from 200 DEG C to 300 DEG C at a rate of 50 DEG C / h, and held for 2 h; then the temperature is increased from 300 DEG C to 400 DEG C at a rate of 50 DEG C / h, and held for 2 h; the gradient cooling stage specifically includes: the temperature is decreased from 400 DEG C to 300 DEG C at a rate of 25 DEG C / h, and held for 2 h; then the temperature is decreased from 300 DEG C to 0 DEG C at a rate of 150 DEG C / h, and the finished wire prepared is a precision manganese-copper resistance alloy material.

[0069] The finished wire prepared in Example 3 has uniform grain size and uniform structure, and the resistance changes little with temperature in the use temperature range of 20-110 DEG C, and the maximum resistance is within the use temperature range, meeting the use requirements.

[0070] It should be noted that, in this text, relational terms such as first and second are used only to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between the entities or operations. Moreover, the terms "include", "contain" or any other variant thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements not only includes those elements, but also includes other elements not explicitly listed or inherent to such process, method, article or device.

[0071] Although embodiments of the present application have been shown and described, it will be understood by those of ordinary skill in the art that various changes, modifications, substitutions and alterations can be made thereto without departing from the principles and spirit of the present application, and the scope of the present application is defined by the appended claims and their equivalents.

Claims

1. A method for producing a precision manganese-copper resistance alloy material, characterized by comprising: The precision manganese-copper resistance alloy material comprises the following raw materials in mass percentage: Mn 11.7wt%, Ni 2.5wt%, Sn 0.27-0.3wt%, Fe 0.2-0.5wt%, Ge 0.636-0.88wt%, La 0.3-0.5wt%, Nd 0.1-0.6wt%, Y 0.4-0.7wt%, and the balance being Cu; the mass percentages of Ni, Fe, Nd and Y in the raw materials satisfy the relationship: Ni=1×Fe+2×Nd+3×Y; and the mass percentages of Ge, Sn and La satisfy the relationship: Ge=1.2×Sn+1.04×La. ​ The method comprises the following steps: S1. cleaning the surfaces of the component raw materials, and proportioning according to the mass percentages, and casting into a blank; S2. preheating the blank; S3. performing rotary forging on the preheated blank to obtain a forged piece; S4. performing shot blasting treatment on the forged piece; S5. repeating S3 and S4 until the processing is completed to obtain a treated workpiece, and the workpiece is segmented into a rod; S6. performing primary annealing treatment on the rod to remove stress; S7. performing wire drawing treatment on the sample obtained in S6 to obtain a wire; S8. performing secondary annealing treatment on the wire, and the secondary annealing treatment comprises a gradient heating process and a gradient cooling process; In the gradient heating process in S8, the temperature is increased from 0℃ to 200℃ at a speed of 100℃ / h, and then the temperature is kept for 2h; then the temperature is increased from 200℃ to 300℃ at a speed of 50℃ / h, and then the temperature is kept for 2h; then the temperature is increased from 300℃ to 400℃ at a speed of 50℃ / h, and then the temperature is kept for 2h; in the gradient cooling process, the temperature is decreased from 400℃ to 300℃ at a speed of 25℃ / h, and then the temperature is kept for 2h; then the temperature is decreased from 300℃ to 0℃ at a speed of 150℃ / h.

2. The method of claim 1, wherein the method is characterized by: In S2, the blank is surface treated, and 3-4mm thick alloy material on the surface of the blank is cut off and then preheated, and the preheating temperature is 900-950℃.

3. The method of claim 1, wherein the method further comprises the step of: In S3, the rotary forging processing pressure is 90-110MPa, and the loading frequency is 500-600 times / min. ​

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