High-strength copper-nickel-based resistance alloy foil with adjustable resistance temperature coefficient and preparation method of copper-nickel-based resistance alloy foil

Abstract

The invention discloses a high-strength copper-nickel-based resistance alloy foil with an adjustable resistance temperature coefficient and a preparation method of the copper-nickel-based resistance alloy foil, and belongs to the technical field of resistance alloys. The high-strength copper-nickel-based resistance alloy foil with the adjustable resistance temperature coefficient comprises the following raw material components in percentage by mass: 35.0-47.0% of nickel; 1.0 to 3.0 percent of manganese; 0.2% to 1.2% of iron; 0.3 to 0.8 percent of silicon; 0.1 to 0.4 percent of cobalt; 0.01 to 0.03 percent of chromium; 0.05 to 0.1 percent of rare earth; and the balance of copper and inevitable impurities. According to the high-strength copper-nickel-based resistance alloy foil with the adjustable resistance temperature coefficient and the preparation method of the copper-nickel-based resistance alloy foil, the tensile strength, the resistivity, the resistance temperature coefficient and other comprehensive performance of resistance alloy are improved, and the copper-nickel-based resistance alloy foil with the thickness ranging from 0.0015 mm to 0.01 mm is prepared through plastic processing technology control.

Description

Technical Field

[0001] The present invention belongs to the technical field of resistance alloys, and particularly relates to a copper-nickel-based resistance alloy foil with high strength and adjustable temperature coefficient of resistance and a preparation method thereof. Background Art

[0002] Precision copper-nickel-based resistance alloy foils are basic materials used to manufacture resistance strain gauges, resistance instruments, measuring instruments, and resistance elements of other industrial devices. Due to the development of the modern information industry, traditional resistance copper alloy foils can no longer meet the high-performance requirements of contemporary society for products such as electronic devices and electronic instruments. The development of high-precision and high-reliability copper-nickel-based resistance alloy foils has become increasingly important. In addition, the rapid development of the aerospace, precision instrument, semiconductor, and new energy industries has also posed a great demand for high-performance copper-nickel-based resistance alloy foils. For example: in the battery management system of new energy vehicles, shunt alloy resistors are used. To achieve more accurate measurement of the current flowing through the circuit in the battery management system, the strength, resistivity, temperature coefficient of resistance, etc. of the precision resistance alloy are key parameters. With the development of strategic emerging industries and future industries such as aerospace, new energy, intelligent transportation, electronic information, and equipment manufacturing, as well as the application of foil resistance strain sensors, precision foil resistors, functional sensors, etc. in related fields, it is of great significance to develop precision copper-nickel-based resistance alloy foils with good comprehensive performance, especially foil products with a thickness of 10 microns or less.

[0003] In the prior art, a copper-based resistance alloy and a preparation method thereof provided by a Chinese invention patent with the publication number of CN118308624A, the raw material components by mass percentage include: nickel: 41-43%; manganese: 1-2%; silicon: 0.5-1%; iron: 0-0.8%; cobalt: 0-0.3%; the balance is copper and inevitable impurities. Adding silicon is beneficial to improving the deoxidation property of the constantan alloy and can effectively improve the alloy strength; adding iron helps to improve the high-temperature tolerance of the constantan alloy during processing; adding cobalt can adjust the resistivity while improving the corrosion resistance of the constantan alloy and maintain a suitable resistivity and temperature coefficient of resistance. For resistance strain gauges, precision foil resistors, and functional sensors, etc., maintaining stable resistivity and a smaller temperature coefficient of resistance is the purpose of obtaining better copper-nickel alloy foils, but the resistivity stability and control of the temperature coefficient of resistance are not ideal enough, unable to make the device more precise, the resistance stability at high temperatures is insufficient, and the thermal drift is large when making strain gauges, affecting the use of the device.

[0004] Moreover, the preparation method proposed by this technical solution also has the following problems. There is no clear method for the combination, addition, and control of trace elements. During the smelting process, poor mutual fusibility of trace elements is likely to occur, and partial volatilization of low-melting-point elements causes proportion imbalance, affecting its resistance temperature coefficient. In addition, there are defects in the subsequent preparation method. The plates cut from the alloy ingot lack forging or extrusion forming to enhance the density and strength of the alloy structure. The thickness control of the strip formed in the last hot rolling is missing, which affects the cold rolling forming rate of cold rolling and further affects the resistance temperature coefficient. The temperature during the heat treatment process is too high, which will result in ineffective control of the resistance temperature coefficient, and the tensile strength and tensile deformation limit cannot meet the requirements. The thickness of the cold-rolled alloy thin strip is too thick, reaching 0.5 - 1.0 mm. This is mainly because the cold rolling and heat treatment processes during the process are not reasonably configured, only forming a relatively thick thin strip, with limited application range and poor practicability. Summary of the Invention

[0005] In order to overcome the above-mentioned disadvantages of the prior art, the purpose of the present invention is to provide a copper-nickel-based resistance alloy foil with high strength and adjustable resistance temperature coefficient, which improves the comprehensive properties such as the tensile strength, resistivity, and resistance temperature coefficient of the resistance alloy, and through the control of plastic processing technology, prepares a copper-nickel-based resistance alloy foil with a thickness of 0.0015 - 0.01 mm.

[0006] To achieve the above purpose, the present invention adopts the following technical solutions:

[0007] The present invention discloses a copper-nickel-based resistance alloy foil with high strength and adjustable resistance temperature coefficient. By mass percentage, its raw material components include: nickel: 35.0 - 47.0%; manganese: 1.0 - 3.0%; iron: 0.2 - 1.2%; silicon: 0.3 - 0.8%; cobalt: 0.1 - 0.4%; chromium: 0.01 - 0.03%; rare earth: 0.05 - 0.1%; the balance is copper and unavoidable impurities.

[0008] In one embodiment, the sum of the manganese, iron, and silicon raw materials in the raw material components does not exceed 4.0% of the raw material components of the copper-nickel-based resistance alloy foil with high strength and adjustable resistance temperature coefficient.

[0009] In one embodiment, the structure of the copper-nickel-based resistance alloy foil is uniform, and the copper-nickel-based resistance alloy foil is composed of nano-subgrains with a size less than 100 nm.

[0010] In one embodiment, the tensile strength of the copper-nickel-based resistance alloy foil with high strength and adjustable resistance temperature coefficient reaches above 800 MPa, the tensile deformation limit is 2.5% - 5.5%, the resistivity is 42 - 58 μΩ·cm, and the resistance temperature coefficient is in the range of -120 - 30×10 -6between; the number of annealing times, rolling times, and rolling deformation of the high-strength copper-nickel-based resistance alloy foil with adjustable temperature coefficient of resistance are positively correlated with the temperature coefficient of resistance; the temperature coefficient of resistance of the foil can be adjusted by annealing, and can even be adjusted to ±2.0×10 -6 / °C or less.

[0011] In one embodiment, the thickness of the high-strength copper-nickel-based resistance alloy foil with adjustable temperature coefficient of resistance is 0.0015 - 0.01 mm.

[0012] On the other hand, the present invention also provides a method for preparing a high-strength copper-nickel-based resistance alloy foil with adjustable temperature coefficient of resistance, including the following steps:

[0013] S1: Take various raw materials according to a preset mass percentage, add the raw materials, heat up and keep warm for melting, and obtain a resistance alloy ingot after cooling;

[0014] S2: Remove impurities and oxide layers of the resistance alloy ingot, retain the alloy ingot core of the resistance alloy ingot for cutting, then perform forging or extrusion, and then perform hot rolling to obtain a hot-rolled resistance alloy sheet;

[0015] S3: Remove the scale and oil stain of the hot-rolled resistance alloy sheet and then perform the first annealing to obtain a resistance alloy sheet;

[0016] S4: Cold roll the resistance alloy sheet to obtain a cold-rolled resistance alloy strip;

[0017] S5: Remove the oil from the cold-rolled resistance alloy strip and then perform the second annealing under hydrogen protection to obtain a resistance alloy strip;

[0018] S6: Perform cold rolling deformation on the resistance alloy strip again to obtain a cold-rolled copper-nickel-based resistance alloy thin strip;

[0019] S7: Remove the oil from the cold-rolled copper-nickel-based resistance alloy thin strip and then perform the third annealing under hydrogen protection to obtain an annealed copper-nickel-based resistance alloy thin strip;

[0020] S8: Finish rolling the annealed copper-nickel-based resistance alloy thin strip to obtain a cold-rolled copper-nickel-based resistance alloy foil;

[0021] S9: Finish rolling the cold-rolled copper-nickel-based resistance alloy foil again;

[0022] S10: Perform the fourth annealing on the copper-nickel-based resistance alloy foil obtained after the treatment of S9 under vacuum, hydrogen or inert gas protection to obtain a high-strength copper-nickel-based resistance alloy foil with adjustable temperature coefficient of resistance.

[0023] In one embodiment, the temperature for heating up is 1400 - 1600°C; the temperature for hot rolling is 800 - 1100°C, and the hot rolling deformation is 40 - 60%; the temperature for the first annealing is 650 - 800°C; the cold rolling deformation is 40 - 60%; the temperature for the second annealing is 650 - 800°C; the deformation for the re - cold rolling is 40 - 60%; the temperature for the third annealing is 600 - 800°C; the rolling deformation for finish rolling reaches 80% - 95%; the rolling deformation for the re - finish rolling reaches 90% - 95%; the temperature for the fourth annealing is 300 - 480°C.

[0024] In one embodiment, the thickness of the cold - rolled resistive alloy strip is 0.5 - 1.0 mm; the thickness of the cold - rolled copper - nickel - based resistive alloy thin strip is 0.1 - 0.3 mm; the thickness of the cold - rolled copper - nickel - based resistive alloy foil is 0.005 mm; the thickness of the copper - nickel - based resistive alloy foil is 0.0015 mm - 0.005 mm.

[0025] In one embodiment, the way of adding raw materials is as follows:

[0026] For manganese, iron, and silicon, the mass percentages increase by 1% respectively for the components of manganese: 1.0 - 3.0%, iron: 0.2 - 1.2%, and silicon: 0.3 - 0.8%; for cobalt, chromium, and rare earth, the mass percentages increase by 2% respectively for the components of cobalt: 0.1 - 0.4%, chromium: 0.01 - 0.03%, and rare earth: 0.05 - 0.1%.

[0027] Copper and nickel are added as main raw materials in 3 - 10 times of feeding, and are added in equal portions according to the number of feeding times in sequence; manganese, iron, and silicon are added at half of the number of times of adding main raw materials, with the frequency of adding manganese, iron, and silicon once after adding main raw materials twice, and manganese, iron, and silicon are added in equal portions according to the number of feeding times in sequence; cobalt, chromium, and rare earth are added once concentratedly after adding main raw materials 3 - 5 times, and cobalt, chromium, and rare earth are added in equal portions according to the number of feeding times in sequence.

[0028] In one embodiment, the way of adding raw materials is as follows:

[0029] Manganese, iron, silicon, cobalt, and chromium are added in the form of copper - manganese master alloy, copper - iron master alloy, copper - silicon master alloy, copper - cobalt master alloy, and copper - chromium master alloy;

[0030] The copper - manganese master alloy, copper - iron master alloy, copper - silicon master alloy, copper - cobalt master alloy, copper - chromium master alloy, and nickel are each divided into 2 equal parts;

[0031] Add one equal portion of copper-manganese master alloy, copper-iron master alloy, copper-silicon master alloy, copper-cobalt master alloy, copper-chromium master alloy, and nickel in sequence; then add rare earth; then add the remaining copper-manganese master alloy, copper-iron master alloy, copper-silicon master alloy, copper-cobalt master alloy, copper-chromium master alloy, and nickel in sequence.

[0032] Compared with the prior art, the present invention has the following beneficial effects:

[0033] The present invention provides a copper-nickel-based resistance alloy foil with high strength and adjustable resistance temperature coefficient. By mainly controlling the proportion of manganese, silicon, and iron elements in the copper-nickel alloy, the positive and negative directions and magnitude of the alloy resistance temperature coefficient can be effectively changed. According to the requirements of actual applications, cobalt, chromium, and rare earth trace elements are further added to enhance the tensile strength and tensile deformation limit of the material, meeting the needs of resistance strain gauges, precision foil resistors, and functional sensors, etc., with stable resistivity and smaller resistance temperature coefficient, and matching the linear expansion coefficients of various materials.

[0034] Furthermore, although various alloying elements and rare earth elements are added to the copper-nickel-based resistance alloy foil prepared by the present invention, a single face-centered cubic structure solid solution is still formed. The various alloying elements play the roles of solid solution strengthening and grain refinement, which is beneficial to improving the strength of the alloy. The tensile strength reaches more than 800 MPa, and the tensile deformation reaches 2.5% - 5.5%; combined with appropriate cold working and annealing processes, the structure is effectively refined, the number of defects such as dislocations in the alloy is increased, the uniformity of the structure and the resistivity are improved. The resistivity of the alloy can reach 42 - 58 μΩ·cm, and the resistance temperature coefficient is between -120 and 30×10 -6 / °C. The resistance temperature coefficient of the foil can be adjusted by annealing, and can even be adjusted to within ±2.0×10 -6 / °C. The thickness of the copper-nickel-based resistance alloy foil prepared by the present invention reaches 0.0015 - 0.01 mm, which can meet the performance requirements of resistance instruments, measuring instruments, and other industrial device resistance elements.

[0035] The preparation method of the above-mentioned high-strength copper-nickel-based resistance alloy foil with adjustable temperature coefficient of resistance provided by the present invention in another aspect involves taking materials and melting according to a preset mass percentage, which can ensure the precise proportion of each element and lay a foundation for subsequent performance. Removing impurities and oxide layers from the ingot can improve the purity of the material and make the foil have higher quality and more stable performance. The alternating operations of forging or extrusion, hot rolling, and multiple cold rolling and annealing can effectively break coarse grains, promote grain refinement, and form a uniform and dense nano-subgrain structure, thereby enhancing the strength, hardness, and electrical properties of the material. Through processing technologies in different stages, especially each annealing treatment, the temperature coefficient of resistance of the alloy can be precisely adjusted to meet the requirements for high-precision resistance components in fields such as precision instruments and meters, and electronic information. The entire preparation process involves the synergistic action of multiple processes, strengthening the mechanical properties of the material and ensuring the electrical properties, enabling the foil to adapt to complex and changeable industrial application scenarios and playing a key role in fields such as aerospace and new energy vehicles. The thickness of the prepared foil is 0.0015 - 0.01 mm, which can broaden the application range. Brief Description of the Drawings

[0036] Figure 1 It is the X-ray diffraction pattern of the copper-nickel-based resistance alloy ingot in Example 1 of the present invention;

[0037] Figure 2 It is the grain structure in the copper-nickel-based resistance alloy foil in Example 1 of the present invention;

[0038] Figure 3 It is the subgrain structure in the copper-nickel-based resistance alloy foil in Example 1 of the present invention;

[0039] Figure 4 It is the fine equiaxed grain structure in the copper-nickel-based resistance alloy foil in Example 2 of the present invention;

[0040] Figure 5 It is the subgrain structure in the copper-nickel-based resistance alloy foil in Example 2 of the present invention;

[0041] Figure 6 It is the metallographic structure of the cold-rolled strip of the resistance alloy obtained in Step 4 of Example 3 of the present invention;

[0042] Figure 7 It is the grain structure in the resistance alloy foil obtained in Example 3 of the present invention;

[0043] Figure 8 It is the subgrain structure in the copper-nickel-based resistance alloy foil in Example 3 of the present invention. Detailed Description of the Invention

[0044] To enable those skilled in the art to understand the features and effects of the present invention, the following is a general description and definition of the terms and phrases mentioned in the specification and claims. Unless otherwise specified, all technical and scientific terms used herein shall have the ordinary meanings understood by those skilled in the art for the present invention. In case of conflicts, the definitions in this specification shall prevail.

[0045] The theories or mechanisms described and disclosed herein, whether right or wrong, shall not limit the scope of the present invention in any way, that is, the content of the present invention can be implemented without being limited by any specific theory or mechanism.

[0046] In this article, all features defined in the form of numerical ranges or percentage ranges, such as numerical values, quantities, contents, and concentrations, are only for the sake of brevity and convenience. Accordingly, the description of numerical ranges or percentage ranges should be regarded as having covered and specifically disclosed all possible sub-ranges and individual numerical values within the ranges (including integers and fractions).

[0047] In this article, unless otherwise specified, "comprising", "including", "containing", "having" or similar terms cover the meanings of "consisting of" and "consisting essentially of". For example, "A comprises a" covers the meanings of "A comprises a and others" and "A consists only of a".

[0048] In this article, for the sake of concise description, all possible combinations of all technical features in each embodiment or example are not described. Therefore, as long as there is no contradiction in the combination of these technical features, the technical features in each embodiment or example can be combined arbitrarily, and all possible combinations should be considered as the scope described in this specification.

[0049] On the one hand, the present invention provides a copper-nickel-based resistance alloy foil with high strength and adjustable temperature coefficient of resistance. To meet the requirements of resistance strain gauges, precision foil resistors, and functional sensors, etc., for stable resistivity, smaller temperature coefficient of resistance, and matching the linear expansion coefficients of various materials, mainly by controlling the proportion of manganese, silicon, and iron elements in the copper-nickel alloy, the positive and negative directions and magnitudes of the temperature coefficient of resistance of the alloy can be effectively changed. And according to the actual application requirements, cobalt, chromium, and rare earth trace elements are further added to enhance the tensile strength and tensile deformation limit of the material.

[0050] A copper-nickel-based resistance alloy foil with high strength and adjustable temperature coefficient of resistance, the raw material components of which include, by mass percentage: nickel: 35.0 - 47.0%; manganese: 1.0 - 3.0%; iron: 0.2 - 1.2%; silicon: 0.3 - 0.8%; cobalt: 0.1 - 0.4%; chromium: 0.01 - 0.03%; rare earth: 0.05 - 0.1%; the balance is copper and unavoidable impurities.

[0051] Among them, the combined proportion of manganese, iron, and silicon raw materials needs to be controlled, and the overall combined proportion does not exceed 4.0%. The resistivity of the alloy can be controlled at 42 - 58 μΩ·cm, and the temperature coefficient of resistance can be adjusted and controlled within the range of -120 - 30×10 -6 / ℃; Further adding trace elements of cobalt, chromium, and rare earth can enhance the tensile strength and tensile deformation limit of the material. Especially after adding chromium and rare earth, the tensile deformation of the copper-nickel resistance alloy can reach more than 2.5%.

[0052] The thickness of the copper-nickel-based resistance alloy foil prepared by the present invention reaches 0.0015 - 0.01 mm, mainly composed of nano-sized sub-grains (with a size less than 100 nm), having a uniform structure, with a tensile strength of more than 800 MPa, a tensile deformation limit of 2.5% - 5.5%, a resistivity of 42 - 58 μΩ·cm, and a temperature coefficient of resistance in the range of -120 - 30×10 -6 / ℃. The temperature coefficient of resistance of the alloy foil can be adjusted by annealing and can be adjusted to within ±2.0×10 -6 / ℃.

[0053] On the other hand, the present invention provides a method for preparing a copper-nickel-based resistance alloy foil with high strength and adjustable temperature coefficient of resistance, including: vacuum induction melting, hot rolling, cold rolling, finish rolling, heat treatment, etc., where the rolling deformation amount of the foil finish rolling is controlled at 90% - 95%.

[0054] The present invention also proposes a method for preparing a copper-nickel-based resistance alloy foil with high strength and adjustable temperature coefficient of resistance, including the following steps:

[0055] S1. Add various raw materials into a vacuum induction furnace or a vacuum levitation furnace according to preset mass fractions and in a sequential order, heat up to 1400 - 1600℃, then keep warm for melting, and after cooling, obtain a resistance alloy ingot. To solve the problems such as insufficient uniformity and poor mutual solubility of trace elements that are likely to occur during the melting process, the following two feeding methods can be selected:

[0056] The first feeding method is to feed in 3 - 10 times. Divide the main raw materials of copper and nickel equally according to the number of feeding times. The raw materials of manganese, iron, and silicon that control the temperature coefficient of resistance are controlled according to 50% of the number of times of adding the main raw materials. Basically, add them in the way of adding 1 time for every 2 times of adding the main raw materials. Other trace elements of cobalt, chromium, and rare earth are added according to 1 / 3 - 1 / 5 of the number of times of adding the main raw materials, that is, basically add the main materials 3 - 5 times and add the trace elements 1 time. Considering the partial volatilization of low-melting-point elements and the loss of trace elements, on the one hand, control the feeding order, and on the other hand, increase the mass fraction of manganese, iron, and silicon elements by 1% each, and increase the mass fraction of chromium, cobalt, and rare earth trace elements by 2% each to control the balance.

[0057] The second feeding method is that during the raw material addition process, manganese, iron, silicon, cobalt, and chromium can also be added in the form of copper-manganese master alloy, copper-iron master alloy, copper-silicon master alloy, copper-cobalt master alloy, and copper-chromium master alloy. By precisely controlling the addition ratio of the master alloy and the addition amounts of cobalt, chromium, and rare earth trace elements, the corresponding purpose can also be achieved. The addition method can also refer to the foregoing. Divide the copper-manganese master alloy, copper-iron master alloy, copper-silicon master alloy, copper-cobalt master alloy, copper-chromium master alloy, and nickel into 2 equal parts respectively; sequentially add one equal part of the copper-manganese master alloy, copper-iron master alloy, copper-silicon master alloy, copper-cobalt master alloy, copper-chromium master alloy, and nickel; then add rare earth; then sequentially add the remaining copper-manganese master alloy, copper-iron master alloy, copper-silicon master alloy, copper-cobalt master alloy, copper-chromium master alloy, and nickel. In this way, the initial resistance temperature coefficient, tensile strength, and tensile deformation limit of the resistance alloy can be effectively controlled.

[0058] S2. Remove impurities and oxide layers from the resistance alloy ingot obtained in S1, retain the core of the alloy ingot for cutting to form a plate with a thickness of 3 - 10 mm, and forge or extrude the cut material to make it uniform and strengthened. Remove surface dirt, polish it flat, and then perform hot rolling on it. The hot rolling temperature is 800 - 1100 °C, and the hot rolling deformation amount is 40 - 60%;

[0059] S3. Remove the scale and oil stain from the hot-rolled resistance alloy plate obtained in S2 above, and anneal it at 650 - 800 °C to obtain a resistance alloy plate that can be used for subsequent cold rolling;

[0060] S4. Cold roll the resistance alloy plate obtained in S3, and the cold rolling deformation amount is 40 - 60% to form a 0.5 - 1.0 mm resistance alloy strip;

[0061] S5. After degreasing the cold-rolled resistance alloy strip obtained in S4, anneal it under hydrogen protection, and the annealing temperature is 650 - 800 °C;

[0062] S6. Further cold roll and deform the resistance alloy strip obtained after S5 treatment, and the cold rolling deformation amount is 40 - 60% to obtain the 0.1 - 0.3 mm copper-nickel-based resistance alloy thin strip;

[0063] S7. After degreasing the cold-rolled copper-nickel-based resistance alloy thin strip obtained in S6, anneal it under hydrogen protection, and the annealing temperature is 600 - 800 °C; Preferably, the hydrogen protection annealing temperature in S7 is 690 - 720 °C;

[0064] S8. Further finish-roll the annealed copper-nickel-based resistance alloy thin strip obtained in S7 with a rolling deformation of 80-95% to obtain the 0.005 mm copper-nickel-based resistance alloy foil; preferably, in S8, the copper-nickel-based resistance alloy foil is cold-rolled using a twenty-high rolling mill with a rolling deformation of 90-95% to effectively control the temperature coefficient of resistance and its adjustability.

[0065] S9. Further finish-roll the cold-rolled copper-nickel-based resistance alloy foil obtained in S8 with a rolling deformation reaching 90%-95% to obtain the copper-nickel-based resistance alloy foil with a thickness below 0.005 mm, and the thinnest can reach 0.0015 mm; preferably, when the thickness of the copper-nickel-based resistance alloy foil in S9 is less than 0.005 mm, it is rolled using a thirty-high rolling mill with a rolling deformation of 90-95%.

[0066] S10. Anneal the copper-nickel-based resistance alloy foil obtained after S9 treatment under vacuum or hydrogen or inert gas protection at an annealing temperature of 300-480 °C to change the resistivity, temperature coefficient of resistance, tensile strength, and tensile deformation of the foil to obtain the required copper-nickel-based resistance alloy foil.

[0067] In order to prepare a copper-nickel-based resistance alloy with better performance and meeting actual usage requirements, the present invention provides a novel high-strength copper-nickel-based resistance alloy foil with adjustable temperature coefficient of resistance and its preparation method. With copper and nickel as the main components, adding manganese, iron, silicon elements and other trace elements to adjust its performance, under a series of alloy melting, sheet forming, rolling and heat treatment systems, a novel copper-nickel-based resistance alloy foil is prepared, with the foil thickness reaching 0.0015-0.01 mm, the structure of the resistance alloy is uniform, composed of nano-subgrains, and the subgrain size is less than 100 nm.

[0068] The following further elaborates the present invention in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and not to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of this application.

[0069] The following embodiments use conventional instrument equipment in the art. For the experimental methods without specific conditions indicated in the following embodiments, they are usually carried out under conventional conditions or according to the conditions recommended by the manufacturer. Various raw materials are used in the following embodiments, unless otherwise stated, all using conventional commercially available products with conventional specifications in the art. In the specification of the present invention and the following embodiments, unless otherwise specified, "%" represents weight percentage, "parts" represents weight parts, and the ratio represents weight ratio.

[0070] Example 1

[0071] This embodiment provides a copper-nickel-based resistive alloy foil with high strength and adjustable temperature coefficient of resistance. By mass percentage, its raw material components include: nickel: 42.0%; manganese: 1.5%; iron: 0.6%; silicon: 0.6%; cobalt: 0.3%; chromium: 0.03%; rare earth: 0.1%, and the balance is copper and inevitable impurities.

[0072] This embodiment provides a method for preparing a copper-nickel-based resistive alloy foil with high strength and adjustable temperature coefficient of resistance, including the following steps:

[0073] Step 1: Copper-nickel resistive alloy proportion formula, nickel: 42.0%; manganese: 1.5%; iron: 0.6%; silicon: 0.6%; cobalt: 0.3%; chromium: 0.03%; rare earth: 0.1%, and the balance is copper and inevitable impurities. Among them, manganese, silicon, iron, cobalt, and chromium are added in the form of copper-manganese master alloy, copper-iron master alloy, copper-silicon master alloy, copper-cobalt master alloy, and copper-chromium master alloy. Divide the above various copper master alloys and nickel into 2 equal parts by mass respectively, and add one equal part of them to the vacuum induction furnace or vacuum levitation furnace in the order of the copper master alloys marked above. Then add the rare earth by mass ratio on the added copper master alloys, and finally add the remaining half of the copper master alloys and nickel in sequence. Control the proportion content of manganese, silicon, and iron according to this ratio to solve problems such as alloy melting uniformity and mutual melting of trace elements. The vacuum degree is 2×10 -3 Pa, heat up to 1500 °C, then keep warm and melt, and after cooling, obtain a resistive alloy ingot. As Figure 1 shown, the X-ray diffraction pattern shows that a face-centered copper-nickel solid solution is formed. Since the atomic radius of copper is slightly larger than that of nickel, the lattice constant of the Cu-Ni solid solution becomes smaller; the diffraction peaks of (111), (200), and (220) are stronger, and the constantan alloy foil has a copper-type Gaussian texture, forming a relatively uniform alloy ingot. The resistive alloy ingot is a face-centered cubic structure solid solution.

[0074] Step 2: Remove impurities and oxide layers from the ingot obtained in Step 1 above, retain the alloy ingot core for cutting to form a 10-mm plate, and forge or extrude the cut material to make it uniform and strengthened. Remove surface dirt, polish it flat, and then perform hot rolling on it. The hot rolling temperature is 1080 °C, and the total reduction ratio is 60% to obtain a resistive alloy hot-rolled plate.

[0075] Step 3: Remove the scale and oil from the resistive alloy hot-rolled plate obtained in Step 2 above, and anneal it at 750 °C to obtain a resistive alloy plate that can be used for subsequent cold rolling.

[0076] Step 4: Cold-roll the resistive alloy plate treated in Step 3 above, with a total reduction ratio of 50%, to form a 1.0-mm cold-rolled resistive alloy strip.

[0077] Step 5: Degrease the cold-rolled resistance alloy strip obtained in Step 4, and then anneal it under hydrogen protection at an annealing temperature of 750 °C.

[0078] Step 6: Repeat Step 4 and Step 5 for the annealed resistance alloy strip until the thickness reaches 0.2 mm of the copper-nickel-based resistance alloy thin strip, with a cold rolling deformation of 60%.

[0079] Step 7: Degrease the resistance alloy thin strip obtained in Step 6, and then anneal it under hydrogen protection at an annealing temperature of 710 °C.

[0080] Step 8: Cold roll the annealed resistance alloy thin strip obtained in Step 7 using a twenty-high rolling mill for further finish rolling, with a rolling deformation of 50% and the thickness rolled to 0.1 mm. The temperature coefficient of resistance of the resistance alloy thin strip is -40×10 -6 / °C.

[0081] Step 9: Degrease the cold-rolled resistance alloy thin strip obtained in Step 8, and then anneal it under hydrogen protection at an annealing temperature of 700 °C.

[0082] Step 10: Repeat Step 8 until the thickness reaches 0.005 mm to obtain the copper-nickel-based resistance alloy foil, with a cold rolling deformation of 90%. As Figure 2 shown, through SEM scanning electron microscopy, the grain structure of the copper-nickel alloy foil with a thickness of 0.005 mm in Example 1 can be seen, with obvious elongated fibers, uneven width distribution, and elongated sub-grains inside the fibers, and the width of the sub-grains is about 1.0 μm.

[0083] Step 11: Anneal the resistance alloy foil obtained in Step 10 under vacuum or hydrogen protection at an annealing temperature of 410 °C to obtain the final copper-nickel-based resistance alloy foil.

[0084] As Figure 3 shown, fine sub-grains distributed in the foil can be clearly seen, with slightly weaker distribution uniformity. The size of the sub-grains in the resistance alloy foil is about 80 nm, the tensile strength is 880 MPa, the tensile deformation limit is 3%, the resistivity at room temperature is 50.39 μΩ·cm, and the temperature coefficient of resistance is -5.0×10 -6 / °C.

[0085] Example 2

[0086] This example provides a copper-nickel-based resistance alloy foil with high strength and adjustable temperature coefficient of resistance. By mass percentage, its raw material components include: nickel: 43.0%; manganese: 1.8%; iron: 0.5%; silicon: 1.0%; cobalt: 0.2%; chromium: 0.02%; rare earth: 0.08%, and the balance is copper and unavoidable impurities.

[0087] This embodiment provides a method for preparing a copper-nickel-based resistance alloy foil with high strength and adjustable resistance temperature coefficient, comprising the following steps:

[0088] Step 1: The proportion formula of the copper-nickel resistance alloy is as follows: nickel: 43.0%; manganese: 1.8%; iron: 0.5%; silicon: 1.0%; cobalt: 0.2%; chromium: 0.02%; rare earth: 0.08%, and the balance is copper and inevitable impurities. To solve the problems such as insufficient homogeneity and poor mutual solubility of trace elements easily occurring during the melting process, the raw materials are added in 5 times. The main raw materials of copper and nickel are divided into 5 equal parts, and the raw materials for controlling the resistance temperature coefficient of manganese, iron, and silicon are divided into 3 equal parts. First, they are added in the way of adding the main raw materials once at a time. The other trace elements such as cobalt, chromium, and rare earth are all added at one time after the main raw materials are added in the middle time. Considering the partial volatilization of low-melting-point elements and the loss of trace elements, on the one hand, the feeding order is strictly controlled, and on the other hand, 1% of the respective mass fractions of manganese, iron, and silicon elements and 2% of the respective mass fractions of chromium, cobalt, and rare earth trace elements are increased to control the balance. Various raw materials are added into a vacuum induction furnace according to the preset mass fractions and order. By controlling the proportion content of manganese, silicon, and iron according to this ratio, the resistance temperature coefficient of the alloy material can be effectively changed to a negative direction and be within a reasonable numerical range. Adding the corresponding cobalt, chromium, and rare earth trace elements can enhance the tensile strength and tensile deformation limit of the material. The vacuum degree is 3.4×10 -3 Pa, and it is heated to 1550 °C, then kept warm for melting, and after cooling, a resistance alloy ingot is obtained.

[0089] Step 2: Remove impurities and oxide layers from the ingot obtained in Step 1 above, cut and retain the alloy ingot core to form a 10-mm plate, and forge or extrude the cut material to make it uniform and strengthened. Remove the surface dirt, polish it flat, and then perform hot rolling on it. The hot rolling temperature is 1080 °C, and the total reduction ratio is 60%, obtaining a hot-rolled resistance alloy plate.

[0090] Step 3: Remove the scale and oil from the hot-rolled resistance alloy plate obtained in Step 2 above, and anneal it at 750 °C to obtain a resistance alloy plate that can be used for subsequent cold rolling.

[0091] Step 4: Cold-roll the resistance alloy plate treated in Step 3 above, with a total reduction ratio of 60%, to form a 1.5-mm cold-rolled resistance alloy strip.

[0092] Step 5: After degreasing the cold-rolled resistance alloy strip obtained in Step 4, anneal it under hydrogen protection, and the annealing temperature is 750 °C.

[0093] Step 6: Repeat Step 4 and Step 5 for the annealed resistance alloy strip until the thickness reaches 0.15 mm of the copper-nickel-based resistance alloy thin strip, and the cold rolling deformation amount is 60%.

[0094] Step 7: Degrease the cold-rolled resistive alloy thin strip obtained in Step 6 and then anneal it under hydrogen protection. The annealing temperature is 710 °C.

[0095] Step 8: Cold-roll the annealed resistive alloy thin strip obtained in Step 7 using a twenty-high rolling mill for further finish rolling. The rolling deformation is 35%, and the thickness is rolled to 0.1 mm. The temperature coefficient of resistance of the resistive alloy thin strip is -34×10 -6 / °C.

[0096] Step 9: Degrease the cold-rolled resistive alloy thin strip obtained in Step 8 and then anneal it under hydrogen protection. The annealing temperature is 700 °C.

[0097] Step 10: Repeat Step 8 until the strip thickness reaches 0.005 mm to obtain a resistive alloy foil with a cold rolling deformation of 90%.

[0098] Step 11: Continue to finish roll the resistive alloy foil obtained in Step 10 using a twenty-high rolling mill to obtain a resistive alloy foil with a thickness of 0.003 mm and a cold rolling deformation rate of 95%. As Figure 4 shown, the grain structure of the foil can be seen through SEM scanning electron microscopy, and fine equiaxed grains are evenly distributed.

[0099] Step 12: Anneal the resistive alloy foil obtained in Step 11 under vacuum or hydrogen protection. The annealing temperature is 370 °C to obtain the final copper-nickel-based resistive alloy foil.

[0100] As Figure 5 shown, further magnified, the fine sub-grains distributed in the foil are slightly better in distribution uniformity than that in Example 1, and the sub-grain width is 60 nm.

[0101] The sub-grain size in the resistive alloy foil is about 60 nm, the tensile strength is 890 MPa, the tensile deformation limit is 3.5%, the resistivity at room temperature is 51.04 μΩ·cm, and the temperature coefficient of resistance is -2.1×10 -6 / °C.

[0102] Example 3

[0103] This example provides a copper-nickel-based resistive alloy foil with high strength and adjustable temperature coefficient of resistance. By mass percentage, its raw material components include: nickel: 42.0%; manganese: 2.0%; iron: 0.5%; silicon: 0.8%; cobalt: 0.1%; chromium: 0.03%; rare earth: 0.05%, and the balance is copper and unavoidable impurities.

[0104] This example provides a preparation method for a copper-nickel-based resistive alloy foil with high strength and adjustable temperature coefficient of resistance, including the following steps:

[0105] Step 1: The proportion formula of copper-nickel resistance alloy is as follows: nickel: 42.0%; manganese: 2.0%; iron: 0.5%; silicon: 0.8%; cobalt: 0.1%; chromium: 0.03%; rare earth: 0.05%, and the balance is copper and inevitable impurities. To solve the problems such as insufficient homogeneity and poor mutual solubility of trace elements easily occurring during the smelting process, the materials are added in 5 times. The main raw materials of copper and nickel are divided into 5 equal parts according to the number of adding times, and the raw materials for controlling the resistance temperature coefficient of manganese, iron and silicon are divided into 3 equal parts. First, they are added in the way of adding the main raw materials once at a time. The other trace elements of cobalt, chromium and rare earth are all added at one time after the main raw materials are added in the middle time. Considering the partial volatilization of low-melting-point elements and the loss of trace elements, on the one hand, the feeding order is strictly controlled, and on the other hand, 1% of their respective mass fractions is increased for manganese, iron and silicon elements, and 2% of their respective mass fractions is increased for chromium, cobalt and rare earth trace elements to control the balance. Various raw materials are added into the vacuum induction furnace according to the preset mass fraction and order. By controlling the proportion content of manganese, silicon and iron according to this ratio, the resistance temperature coefficient of the alloy material can be effectively changed to a negative direction and be within a reasonable numerical range. Adding the corresponding cobalt, chromium and rare earth trace elements can enhance the tensile strength and tensile deformation limit of the material. The vacuum degree is 2.5×10 -3 Pa, heated to 1550 °C, then kept warm for smelting, and a resistance alloy ingot is obtained after cooling.

[0106] Step 2: Remove impurities and oxide layers from the ingot obtained in Step 1 above, retain the alloy ingot core for cutting to form a 10-mm plate, and forge or extrude the cut material to make it uniform and strengthened. Remove the surface dirt and polish it flat, and then perform hot rolling on it. The hot rolling temperature is 1100 °C and the total reduction ratio is 60% to obtain a hot-rolled resistance alloy plate.

[0107] Step 3: Remove the scale and oil from the hot-rolled resistance alloy plate obtained in Step 2 above, and anneal it at 710 °C to obtain a resistance alloy plate that can be used for subsequent cold rolling.

[0108] Step 4: Cold-roll the resistance alloy plate treated in Step 3 above, with a total reduction ratio of 60%, to form a 1.0-mm cold-rolled resistance alloy strip. As Figure 6 shown, through observation with a metallographic microscope, obvious rolling plastic processing marks exist on the surface of the cold-rolled strip, which are basically parallelly distributed along the rolling direction and the surface uniformity is good.

[0109] Step 5: Degrease the cold-rolled resistance alloy strip obtained in Step 4 and anneal it under hydrogen protection at an annealing temperature of 710 °C.

[0110] Step 6: Repeat Step 4 and Step 5 for the annealed resistance alloy strip until the thickness reaches 0.2 mm of the copper-nickel-based resistance alloy thin strip, and the cold rolling deformation amount is 50%.

[0111] Step 7: Degrease the cold-rolled resistive alloy thin strip obtained in Step 6, and then anneal it under hydrogen protection at an annealing temperature of 700 °C.

[0112] Step 8: Cold-roll the annealed resistive alloy thin strip obtained in Step 7 using a twenty-high rolling mill for further finish rolling. The rolling deformation is 50%, and the thickness is rolled to 0.1 mm. The temperature coefficient of resistance of the resistive alloy thin strip is -21×10 -6 / °C.

[0113] Step 9: Degrease the cold-rolled resistive alloy thin strip obtained in Step 8, and then anneal it under hydrogen protection at an annealing temperature of 700 °C.

[0114] Step 10: Repeat Step 8 until the strip thickness reaches 0.005 mm to obtain a resistive alloy foil with a cold rolling deformation of 90%.

[0115] Step 11: Continue to finish roll the resistive alloy foil obtained in Step 10 using a thirty-high rolling mill to obtain a resistive alloy foil with a thickness of 0.002 mm and a cold rolling deformation rate of 95%. As Figure 7 shown, through SEM scanning electron microscopy, the grain structure of the foil can be seen, with elongated fibers, uniform width distribution, and fine sub-grains inside the fibers, and the width of the sub-grains is significantly narrowed.

[0116] Step 12: Anneal the resistive alloy foil obtained in Step 11 under vacuum or hydrogen protection at an annealing temperature of 410 °C to obtain the final copper-nickel-based resistive alloy foil. As Figure 8 shown, further magnified, the fine sub-grains distributed in the foil are more uniform compared to those in Example 1 and Example 2, the boundaries of the elongated fibers are not obvious, and the width of the sub-grains is 50 nm.

[0117] The size of the sub-grains in the resistive alloy foil is about 50 nm, the tensile strength is 820 MPa, the tensile deformation limit is 5%, the resistivity at room temperature is 50.08 μΩ·cm, and the temperature coefficient of resistance is 1.6×10 -6 / °C.

[0118] Example 4

[0119] The difference between this example and Example 1 lies in the proportion formula of the copper-nickel resistive alloy: nickel: 35.0%; manganese: 2.5%; iron: 1.2%; silicon: 0.3%; cobalt: 0.4%; chromium: 0.01%; rare earth: 0.05%, and the balance is copper and unavoidable impurities.

[0120] The temperature coefficient of resistance of its 0.1 mm thick resistive alloy thin strip is 30×10 -6 / °C; The tensile strength of the 0.005 mm resistive alloy foil is 825 MPa, the tensile deformation limit is 5.5%, the resistivity at room temperature is 42.04 μΩ·cm, and the temperature coefficient of resistance is 50×10 -6 / °C.

[0121] Example 5

[0122] This example is different from Example 1 in that the proportion formula of the copper-nickel resistive alloy is nickel: 40.0%; manganese: 3.0%; iron: 0.2%; silicon: 0.3%; cobalt: 0.1%; chromium: 0.02%; rare earth: 0.1%, and the balance is copper and unavoidable impurities.

[0123] The temperature coefficient of resistance of its 0.1 mm thick resistive alloy thin strip is -10×10 -6 / °C; The tensile strength of the 0.005 mm resistive alloy foil is 827 MPa, the tensile deformation limit is 2.5%, the resistivity at room temperature is 50.12 μΩ·cm, and the temperature coefficient of resistance is 12×10 -6 / °C.

[0124] Example 6

[0125] This example is different from Example 1 in that the proportion formula of the copper-nickel resistive alloy is nickel: 41.8%; manganese: 1.0%; iron: 0.2%; silicon: 0.3%; cobalt: 0.1%; chromium: 0.01%; rare earth: 0.05%, and the balance is copper and unavoidable impurities.

[0126] The temperature coefficient of resistance of its 0.1 mm thick resistive alloy thin strip is -120×10 -6 / °C; The tensile strength of the 0.005 mm resistive alloy foil is 810 MPa, the tensile deformation limit is 5.5%, the resistivity at room temperature is 50.32 μΩ·cm, and the temperature coefficient of resistance is -89×10 -6 / °C.

[0127] Example 7

[0128] This example is different from Example 2 in that the proportion formula of the copper-nickel resistive alloy is nickel: 47%; manganese: 2.0%; iron: 1.1%; silicon: 0.6%; cobalt: 0.2%; chromium: 0.01%; rare earth: 0.08%, and the balance is copper and unavoidable impurities.

[0129] The temperature coefficient of resistance of its 0.1 mm thick resistive alloy thin strip is -35×10 -6 / °C; The tensile strength of the 0.003 mm resistive alloy foil is 835 MPa, the tensile deformation limit is 2.5%, the resistivity at room temperature is 55.85 μΩ·cm, and the temperature coefficient of resistance is -3.0×10 -6 / °C.

[0130] Example 8

[0131] This example is different from Example 2 in that the proportion formula of the copper-nickel resistance alloy is as follows: nickel: 44%; manganese: 2.1%; iron: 1.2%; silicon: 0.5%; cobalt: 0.3%; chromium: 0.02%; rare earth: 0.1%, and the balance is copper and unavoidable impurities.

[0132] The temperature coefficient of resistance of the 0.1 mm thick resistance alloy thin strip is -25×10 -6 / ℃; the tensile strength of the 0.003 mm thick resistance alloy foil is 830 MPa, the tensile deformation limit is 2.5%, the resistivity at room temperature is 54.98 μΩ·cm, and the temperature coefficient of resistance is -1.5×10 -6 / ℃.

[0133] Example 9

[0134] This example is different from Example 2 in that the proportion formula of the copper-nickel resistance alloy is as follows: nickel: 43%; manganese: 1.3%; iron: 0.5%; silicon: 0.4%; cobalt: 0.3%; chromium: 0.03%; rare earth: 0.07%, and the balance is copper and unavoidable impurities.

[0135] The temperature coefficient of resistance of the 0.1 mm thick resistance alloy thin strip is -55×10 -6 / ℃; the tensile strength of the 0.0025 mm thick resistance alloy foil is 834 MPa, the tensile deformation limit is 2.5%, the resistivity at room temperature is 50.15 μΩ·cm, and the temperature coefficient of resistance is -25×10 -6 / ℃.

[0136] Example 10

[0137] This example is different from Example 3 in that the proportion formula of the copper-nickel resistance alloy is as follows: nickel: 43.5%; manganese: 2.1%; iron: 1.1%; silicon: 0.7%; cobalt: 0.4%; chromium: 0.03%; rare earth: 0.06%, and the balance is copper and unavoidable impurities.

[0138] The temperature coefficient of resistance of the 0.1 mm thick resistance alloy thin strip is -38×10 -6 / ℃; the tensile strength of the 0.002 mm thick resistance alloy foil is 825 MPa, the tensile deformation limit is 4.5%, the resistivity at room temperature is 50.68 μΩ·cm, and the temperature coefficient of resistance is -8×10 -6 / ℃.

[0139] According to different proportioning and process heat treatment combination schemes, the obtained alloy thin strips, as well as the high-strength and low-temperature coefficient of resistance copper-nickel-based resistance alloy foils formed by precision rolling and annealing processes, are specifically shown in Tables 1, 2, 3, and 4.

[0140] The mass percentages of the raw material components of Examples 11 and 12 are as follows. The mass percentages of the raw material components of Examples 13, 14, 17 to 24 are the same as those of Example 1. The mass percentages of the raw material components of Examples 15 and 16 are the same as those of Example 6.

[0141] Table 1 List of mass percentages of raw material components of copper-nickel-based resistance alloys for other examples

[0142] Component Nickel Manganese Silicon Iron Cobalt Chromium Rare earth Copper Example 11 38.0％ 1.0％ 0.2％ 1.2％ 0.1％ 0.01％ 0.05％ Balance Example 12 46.0％ 2.8％ 0.8％ 1.0％ 0.4％ 0.03％ 0.1％ Balance

[0143] The parameters in Steps 1 to 2 of Examples 11, 12, 17 to 24 are the same as those of Example 1. The parameters in Steps 1 to 2 of Examples 13 and 14 are as follows, and the components and other parameters are the same as those of Example 1. The parameters in Steps 1 to 2 of Examples 15 and 16 are as follows, and the components and other parameters are the same as those of Example 6.

[0144] Table 2 List of different melting temperatures and hot rolling parameters in Steps 1 to 2 of other examples

[0145] Parameter Smelting temperature Hot rolling temperature Hot rolling deformation Component and other parameters Example 13 1550℃ 1050℃ 40％ Same as Example 1 Example 14 1600℃ 900℃ 50％ Same as Example 1 Example 15 1400℃ 1100℃ 50％ Same as Example 6 Example 16 1500℃ 800℃ 60％ Same as Example 6

[0146] The parameters in Steps 3 to 8 of Examples 11 to 20 are as follows. The parameters in Steps 3 to 8 of Examples 21 to 24 are the same as those of Example 1.

[0147] Table 3 List of different parameters in Steps 3 to 8 of other examples and properties of 0.1 mm thin strips

[0148]

[0149]

[0150] Table 4 List of different annealing parameters of precision rolled foils and foil properties of other examples

[0151]

[0152]

[0153] The present invention discloses a high-strength copper-nickel-based resistance alloy foil with an adjustable resistance temperature coefficient. The raw material components by mass percentage include: nickel: 35.0 - 47.0%; manganese: 1.0 - 3.0%; iron: 0.2 - 1.2%; silicon: 0.3 - 0.8%; cobalt: 0.1 - 0.4%; chromium: 0.01 - 0.03%; rare earth: 0.05 - 0.1%; the balance is copper and unavoidable impurities. By controlling the proportion of manganese, silicon and iron, the positive and negative directions and magnitudes of the resistance temperature coefficient of the alloy material can be effectively changed. Further adding trace elements of cobalt, chromium and rare earth can enhance the tensile strength and tensile deformation limit of the material. The preparation method includes: vacuum induction melting, hot rolling, cold rolling, finish rolling, heat treatment, etc., wherein the rolling deformation amount is controlled within 50% - 95%. The copper-nickel-based resistance alloy foil prepared by the present invention has a thickness of 0.002 - 0.01 mm, is mainly composed of nano-subgrains (with a size less than 100 nm), has a uniform structure, its tensile strength is above 800 MPa, the tensile deformation limit is 2.5% - 5.5%, the resistivity is 42 - 58 μΩ·cm, and the resistance temperature coefficient is between -120 and 30×10 -6 / °C. By annealing, the resistance temperature coefficient of the foil can be adjusted, and even can be adjusted within ±2.0×10 -6 / °C.

[0154] The above content is only to illustrate the technical idea of the present invention and cannot be used to limit the protection scope of the present invention. Any modification made on the basis of the technical solution according to the technical idea proposed by the present invention falls within the protection scope of the claims of the present invention.

Claims

1. A copper-nickel-based resistive alloy foil with high strength and adjustable temperature coefficient of resistance, characterized in that, By mass percentage, its raw material components include: nickel: 35.0 - 47.0%; manganese: 1.0 - 3.0%; iron: 0.2 - 1.2%; silicon: 0.3 - 0.8%; cobalt: 0.1 - 0.4%; chromium: 0.01 - 0.03%; rare earth: 0.05 - 0.1%; the balance is copper and inevitable impurities.

2. The high-strength copper-nickel-based resistance alloy foil with adjustable temperature coefficient of resistance according to claim 1, characterized in that, The sum of the manganese, iron, and silicon raw materials in the raw material components does not exceed 4.0% of the raw material components of the high-strength copper-nickel-based resistance alloy foil with an adjustable temperature coefficient of resistance.

3. The high-strength copper-nickel-based resistance alloy foil with adjustable temperature coefficient of resistance according to claim 1, characterized in that The high-strength copper-nickel-based resistance alloy foil with an adjustable temperature coefficient of resistance has a uniform structure and is composed of nano-subgrains with a size less than 100 nm.

4. The high-strength copper-nickel-based resistance alloy foil with adjustable temperature coefficient of resistance according to claim 1, wherein The tensile strength of the high-strength copper-nickel-based resistance alloy foil with adjustable temperature coefficient of resistance reaches over 800 MPa, the tensile deformation limit is 2.5% - 5.5%, the resistivity is 42 - 58 μΩ·cm, and the temperature coefficient of resistance is between -120 and 30×10 -6 / ℃.

5. The high-strength copper-nickel-based resistance alloy foil with adjustable temperature coefficient of resistance according to claim 1, characterized in that, The thickness of the high-strength copper-nickel-based resistance alloy foil with an adjustable temperature coefficient of resistance is 0.0015 - 0.01 mm.

6. A method for preparing a high-strength copper-nickel-based resistance alloy foil with an adjustable temperature coefficient of resistance according to any one of claims 1 to 5, characterized in that, It includes the following steps: S1: Take various raw materials according to the preset mass percentage, add the raw materials, heat up and keep warm for melting, and obtain a resistance alloy ingot after cooling. S2: Remove the impurities and oxide layer of the resistance alloy ingot, cut the alloy ingot core of the resistance alloy ingot, then perform forging or extrusion, and then perform hot rolling to obtain a hot-rolled resistance alloy sheet. S3: Remove the scale and oil stain of the hot-rolled resistance alloy sheet and then perform the first annealing to obtain a resistance alloy sheet. S4: Perform cold rolling on the resistance alloy sheet to obtain a cold-rolled resistance alloy strip. S5: Perform degreasing treatment on the cold-rolled resistance alloy strip and then perform the second annealing under hydrogen protection to obtain a resistance alloy strip. S6: Perform cold rolling deformation again on the cold-rolled resistance alloy strip to obtain a cold-rolled copper-nickel-based resistance alloy thin strip. S7: Perform degreasing treatment on the cold-rolled copper-nickel-based resistance alloy thin strip and then perform the third annealing under hydrogen protection to obtain an annealed copper-nickel-based resistance alloy thin strip. S8: Perform precision rolling on the annealed copper-nickel-based resistance alloy thin strip to obtain a cold-rolled copper-nickel-based resistance alloy foil. S9: Perform precision rolling again on the cold-rolled copper-nickel-based resistance alloy foil. S10: Perform the fourth annealing on the copper-nickel-based resistance alloy foil obtained after S9 treatment under vacuum, hydrogen, or inert gas protection to obtain a high-strength copper-nickel-based resistance alloy foil with an adjustable temperature coefficient of resistance.

7. The preparation method of the high-strength and adjustable resistance temperature coefficient copper-nickel-based resistance alloy foil according to claim 6, characterized in that The temperature for heating up is 1400 - 1600 °C; the temperature for hot rolling is 800 - 1100 °C, and the hot rolling deformation is 40 - 60%; the temperature for the first annealing is 650 - 800 °C; the cold rolling deformation is 40 - 60%; the temperature for the second annealing is 650 - 800 °C; the cold rolling deformation again is 40 - 60%; the temperature for the third annealing is 600 - 800 °C; the rolling deformation for precision rolling reaches 80% - 95%; the rolling deformation for precision rolling again reaches 90% - 95%; the temperature for the fourth annealing is 300 - 480 °C.

8. The preparation method of the high-strength and adjustable resistance temperature coefficient copper-nickel-based resistance alloy foil according to claim 6, characterized in that, The thickness of the cold-rolled resistive alloy strip is 0.5 to 1.0 mm; the thickness of the cold-rolled copper-nickel-based resistive alloy thin strip is 0.1 to 0.3 mm; the thickness of the cold-rolled copper-nickel-based resistive alloy foil is 0.005 mm; the thickness of the copper-nickel-based resistive alloy foil is 0.0015 mm to 0.005 mm.

9. The preparation method of the high-strength and adjustable resistance temperature coefficient copper-nickel-based resistance alloy foil according to claim 6, characterized in that, The method of adding raw materials is as follows: For manganese, iron, and silicon, the mass percentages are increased by 1% for each component of 1.0 - 3.0% for manganese, 0.2 - 1.2% for iron, and 0.3 - 0.8% for silicon; for chromium, cobalt, and rare earth, the mass percentages are increased by 2% for each component of 0.1 - 0.4% for cobalt, 0.01 - 0.03% for chromium; 0.05 - 0.1% for rare earth. Copper and nickel are added in 3 to 10 equal portions as the main raw materials, added in sequence according to the equal division of the number of adding times; manganese, iron, and silicon are added at half of the number of times of adding the main raw materials, with a frequency of adding manganese, iron, and silicon once after adding the main raw materials twice, and manganese, iron, and silicon are added in sequence according to the equal division of the number of adding times; cobalt, chromium, and rare earth are added once collectively after adding the main raw materials 3 to 5 times, and cobalt, chromium, and rare earth are added in sequence according to the equal division of the number of adding times.

10. The preparation method of the high-strength and adjustable resistance temperature coefficient copper-nickel-based resistance alloy foil according to claim 6, characterized in that, The method of adding raw materials is as follows: Manganese, iron, silicon, cobalt, and chromium are added in the form of copper-manganese master alloy, copper-iron master alloy, copper-silicon master alloy, copper-cobalt master alloy, and copper-chromium master alloy; The copper-manganese master alloy, copper-iron master alloy, copper-silicon master alloy, copper-cobalt master alloy, copper-chromium master alloy, and nickel are each divided into two equal parts; First, add one equal part of the copper-manganese master alloy, copper-iron master alloy, copper-silicon master alloy, copper-cobalt master alloy, copper-chromium master alloy, and nickel in sequence; then add rare earth; then add the remaining copper-manganese master alloy, copper-iron master alloy, copper-silicon master alloy, copper-cobalt master alloy, copper-chromium master alloy, and nickel in sequence.

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