阅读说明：本技术 一种采用真空感应熔炼制备CuMn12Ni合金的方法 (CuMn prepared by vacuum induction melting12Method for Ni alloy ) 是由 刘琦 孙君鹏 刘向东 王群 唐丽尖 田东松 韩依曼 梁建斌 王文斌 于 2020-04-23 设计创作，主要内容包括：本发明公开了一种采用真空感应熔炼制备CuMn<Sub>12</Sub>Ni合金的方法,包括配料：分别称取电解铜板、电解锰片和CuNi<Sub>3</Sub>O中间合金材料；装炉：将配好的合金料装入坩埚内,关闭放气阀；抽真空：开启机械泵,打开低真空挡板阀抽真空,待炉内真空压力р≤0.08MPa时,开启罗茨泵；熔炼：当真空度р≤10Pa时,加热升温,加热功率升至60KW,待坩埚内原料开始熔化,降功率至20KW以下,打开充氩气阀,炉内压力升至约0.08Mpa时,关闭充氩阀,升功率至65KW,精炼2min；浇铸：降功率至40KW±5KW,保持0.2分钟开始浇铸,浇铸时间≦2min；出炉：浇铸完成后,关闭加热,冷却30分钟后出炉；本发明工艺流程设计合理,制备的CuMn<Sub>12</Sub>Ni合金气体含量低、组织均匀、无偏析缺陷,适宜大量推广。(The invention discloses a method for preparing CuMn by adopting vacuum induction melting 12 A method of Ni alloying comprising batching: separately calledTaking an electrolytic copper plate, an electrolytic manganese sheet and CuNi 3 O intermediate alloy material; charging: the prepared alloy material is loaded into a crucible, and a deflation valve is closed; vacuumizing: starting a mechanical pump, opening a low-vacuum baffle valve for vacuumizing, and starting a roots pump when the vacuum pressure in the furnace is less than or equal to 0.08 MPa; smelting: when the vacuum degree P is less than or equal to 10Pa, heating and raising the temperature, raising the heating power to 60KW, opening an argon filling air valve when the raw materials in the crucible begin to melt and the power is reduced to below 20KW, raising the pressure in the furnace to about 0.08Mpa, closing the argon filling valve, raising the power to 65KW, and refining for 2 min; casting: reducing the power to 40KW +/-5 KW, keeping for 0.2 min, and starting casting, wherein the casting time is less than or equal to 2 min; discharging: after the casting is finished, the heating is closed, and the casting is discharged after being cooled for 30 minutes; the process flow of the invention is reasonable in design, and the prepared CuMn 12 The Ni alloy has low gas content, uniform structure and no segregation defect, and is suitable for mass popularization.)

1. CuMn prepared by vacuum induction melting₁₂A method of Ni alloying, comprising the steps of:

1) preparing materials: the raw materials comprise the following elements in percentage by weight: 11-13% of Mn, 1-3% of Ni and the balance of Cu, and weighing the required raw materials in proportion; wherein Cu is added in the form of electrolytic copper plate, Mn is electrolytic manganese sheet, Ni is CuNi₃0 master alloy;

2) charging: loading the prepared alloy material into a crucible, closing a furnace cover of the vacuum smelting furnace, closing an air release valve, and cleaning an observation window;

3) vacuumizing: starting a mechanical pump, opening a low-vacuum baffle valve for vacuumizing, and starting a roots pump when the vacuum pressure in the vacuum smelting furnace reaches a value of less than or equal to 0.08 MPa;

4) smelting: when the vacuum degree P in a vacuum smelting furnace is less than or equal to 10Pa during smelting, heating, raising the temperature, raising the heating power to 20 +/-2 KW, keeping the temperature for 5min, raising the heating power to 30 +/-2 KW, keeping the temperature for 5min, raising the heating power to 40 +/-2 KW, keeping the temperature for 5min, raising the heating power to 50KW, keeping the temperature for 5min, raising the heating power to 60KW, reducing the power to below 20KW when the raw materials in the crucible start to melt, opening an argon filling air valve, slowly filling high-purity argon into the furnace body, closing the argon filling valve when the pressure in the furnace is raised to 0.08MPa, raising the power to 6MPaRefining for 2min at 5 KW; wherein the flow of argon is 0.3m³Min, and the argon filling time is 35-40 s;

5) casting: reducing the heating power of the vacuum melting furnace to 40KW +/-5 KW, keeping the heating power for 0.2 min, and starting casting, wherein the casting speed is firstly slow, then fast, and finally slow, and the whole casting time is less than or equal to 2 min;

6) discharging: and after the casting is finished, stopping heating the vacuum smelting furnace, cooling for 30 minutes, and discharging.

2. The method for preparing CuMn by vacuum induction melting according to claim 1₁₂The method for Ni alloy is characterized in that the specific operation of the step 5) is as follows: firstly, casting 30% of the total amount of alloy solution, and controlling the casting speed to be 3.8-4.8 t/min; then, casting 45% of the total amount of the alloy solution, wherein the casting speed is controlled to be 5.8-6.4 t/min; and finally, casting 25% of the total amount of the alloy solution, wherein the casting speed is controlled to be 2.5-4.1 t/min.

3. The method for preparing CuMn by vacuum induction melting according to claim 1₁₂The method for preparing the Ni alloy is characterized in that after the step 2) is finished, a covering agent is added to the surface of the mixed alloy material, wherein the covering agent is a mixture of cryolite and borax in a weight ratio of 1: 1, and the adding thickness of the covering agent is 0.5-1.2 mm.

4. The method for preparing the CuMn12Ni alloy by vacuum induction melting as claimed in claim 1, wherein the step 1) is completed by using dilute hydrochloric acid to treat the electrolytic copper plate, the electrolytic manganese sheet and the CuNi₃And (3) respectively carrying out acid washing on the 0 intermediate alloy, cleaning for 5-15 min by using ultrasonic cleaning equipment, and then drying for 20-45 min at the temperature of 80-145 ℃.

5. The method for preparing CuMn by vacuum induction melting according to claim 1₁₂The Ni alloy method is characterized in that in the step 2), the crucible is made of a silicon iron material.

6. According to claim 1The CuMn is prepared by adopting vacuum induction melting₁₂The Ni alloy casting method is characterized in that in the step 6), after casting is completed, quenching treatment is carried out on the obtained alloy ingot, and the quenching treatment specifically comprises the following operations: and (3) quenching by using compressed inert gas, setting the quenching temperature to be 80-120 ℃, and the quenching time to be 15-45 min.

7. The method for preparing CuMn by vacuum induction melting according to claim 1₁₂The method for preparing the Ni alloy is characterized in that after the step 6), a metal flaw detector is used for detecting and flaw-detecting the blank.

8. The method for preparing CuMn by vacuum induction melting according to claim 1₁₂The method for preparing the Ni alloy is characterized in that the vacuum smelting furnace in the step 2) comprises a furnace body (1), an induction heating coil (2), a heating crucible (3), a lifting assembly (4) and a translation assembly (5), wherein the upper end of the furnace body (1) is movably provided with a furnace cover (10), the furnace cover (10) is provided with an air inlet pipe (11), the side wall of the furnace body (1) is provided with an observation window (12) and a movable door (13), the movable door (13) is positioned at the lower position of the side wall of the furnace body (1), and the bottom of the furnace body (1) is provided with a base (14); the induction heating coil (2) is fixedly arranged at the upper end inside the furnace body (1), a gap is reserved between the induction heating coil (2) and the furnace body (1), the lifting assembly (4) comprises electromagnetic shielding plates (40), sliding rods (41) and winches (42), the two sliding rods (41) are vertically and fixedly arranged on two sides of the bottom in the furnace body (1) respectively, the electromagnetic shielding plates (40) are connected to the two sliding rods (41) in a sliding mode through sliding sleeves (400), the upper end face of each electromagnetic shielding plate (40) is horizontally provided with a slot (401), each winch (42) is rotatably clamped on the furnace body (1) through a rotating shaft (420), each rotating shaft (420) penetrates through the furnace body (1), and a steel cable (421) is arranged between each rotating shaft (420) and each sliding sleeve (400); the heating crucible (3) is movably arranged on the electromagnetic shielding plate (40) and can ascend to the inner area of the induction heating coil (2) along with the electromagnetic shielding plate (40); translation subassembly (5) include carriage (50) and slide (51), carriage (50) level setting be in on base (14), and with slide (51)The upper end face of the base (14) is located on the same horizontal plane, the sliding seat (51) is arranged on the sliding frame (50) in a sliding mode, the sliding direction of the sliding seat (51) is consistent with the opening direction of the movable door (13), the sliding seat (51) is provided with an inserting rod (52), and the inserting rod (52) can be inserted into the slot (401).

9. The method for preparing CuMn by vacuum induction melting according to claim 1₁₂The method for Ni alloy is characterized in that in the step 2), the crucible is made of silicon material.

Technical Field

The invention relates to the technical field of color metal alloys, in particular to a method for preparing CuMn by vacuum induction melting₁₂A method of Ni alloying.

Background

CuMn₁₂Ni is a resistance material, is a basic material for manufacturing resistance elements in electronic instruments, measuring instruments and other industrial devices, and is widely applied to various fields of motors, instruments, automobiles, aerospace, missile atomic energy and the like. It has very small temperature coefficient of resistance, low electric heating potential to copper, high stability of resistance and high resistivity, is a superior resistance alloy material, and can be made into powder, wire, foil, sheet, strip, rod, tube, etc., and the surface can be coated with various insulating materials. Mainly used forThe method is suitable for manufacturing standard resistors, separators, precision or common resistance elements, precision resistance elements of high-grade measuring voltage, current, bridges, potential difference meters and other instruments and is more suitable for manufacturing resistance elements of standard resistors for reference. The low-temperature-coefficient and low-thermal electromotive force sensor has the characteristics of low temperature coefficient, low thermal electromotive force, good long-term stability, low inductance, high pulse load and the like. CuMn₁₂The Ni alloy material is made into a chip resistor product, and the application range of the chip resistor product is very wide, such as automobile electronics, power electronics, driving technology, power detection, medical technology and the like.

The lap resistance is formed by welding copper and an alloy material by adopting high-energy electron beams, and can be almost punched and bent into any shape, thereby flexibly meeting the requirements of different applications and designs. Due to the excellent performance, the material is widely used in the fields of mobile phones, power grids, new energy automobiles and the like, and has a very wide prospect.

At present, high-end manganese-copper alloys in domestic markets are imported, non-vacuum melting is mostly adopted in domestic production processes, the produced alloy materials are high in impurity content and uneven in component structure, and the resistivity and the resistance temperature coefficient of the produced paster are unqualified.

Disclosure of Invention

Aiming at the technical problems, the invention provides a method for preparing CuMn with low gas content, uniform structure and no segregation by adopting vacuum induction melting₁₂A method of Ni alloying.

The technical scheme of the invention is as follows: CuMn prepared by vacuum induction melting₁₂A method of Ni alloying comprising the steps of:

1) preparing materials: the percentage content of each element in the raw materials is as follows: 11-13% of Mn, 1-3% of Ni and the balance of Cu, and weighing the required raw materials in proportion; wherein Cu is added in the form of electrolytic copper plate, Mn is electrolytic manganese sheet, Ni is CuNi₃0 master alloy;

2) charging: loading the prepared alloy material into a crucible, closing a furnace cover of the vacuum smelting furnace, closing an air release valve, and cleaning an observation window;

3) vacuumizing: starting a mechanical pump, opening a low-vacuum baffle valve for vacuumizing, and starting a roots pump when the vacuum pressure in the vacuum smelting furnace reaches a value of less than or equal to 0.08 MPa;

4) smelting: during smelting, when the pH value of the vacuum degree in a vacuum smelting furnace is less than or equal to 10Pa, heating, raising the temperature, raising the heating power to 20 +/-2 KW, keeping the temperature for 5min, raising the heating power to 30 +/-2 KW, keeping the temperature for 5min, raising the heating power to 40 +/-2 KW, keeping the temperature for 5min, raising the heating power to 60KW, lowering the power to below 20KW when the raw materials in the crucible start to melt, opening an argon filling valve, slowly filling high-purity argon into the furnace body, raising the pressure in the furnace to about 0.08MPa, closing the argon filling valve, raising the power to 65KW, and refining for 2 min; wherein the flow of argon is 0.3m³Min, and the argon filling time is 35-40 s;

5) casting: reducing the power of a vacuum smelting furnace to 40KW +/-5 KW, keeping the time for casting for about 0.2 min, and starting casting, wherein the casting speed is firstly slow, then fast, and finally slow, and the whole casting time is less than or equal to 2 min;

6) discharging: and after the casting is finished, stopping heating the vacuum smelting furnace, cooling for 30 minutes, and discharging.

Further, in step 1), CuNi₃The preparation method of the 0 intermediate alloy comprises the following steps:

proportioning: the percentage content of each element in the raw materials is as follows: weighing 70% of Cu and 30% of Ni according to the proportion; wherein, Cu element is added in the form of an electrolytic copper plate, and Ni element is added in the form of an electrolytic nickel plate;

secondly, charging, namely charging the prepared alloy material into a crucible, closing a furnace cover of the vacuum smelting furnace, closing an air release valve and cleaning an observation window;

vacuumizing, starting a mechanical pump, opening a low-vacuum baffle valve for vacuumizing, and starting a roots pump when the vacuum pressure in the vacuum smelting furnace reaches a value less than or equal to 0.08 MPa;

④ smelting, heating and raising temperature when the vacuum degree in the vacuum smelting furnace is less than or equal to 10Pa, raising the heating power to 20 +/-2 KW, keeping the temperature for 5min, raising the heating power to 30 +/-2 KW, keeping the temperature for 5min, raising the heating power to 40 +/-2 KW, keeping the temperature for 5min, raising the heating power to 50KW, keeping the temperature for 5min, raising the heating power to 65KW, keeping the temperature for 5min, and lowering the temperature when the raw materials in the crucible begin to meltOpening an argon filling gas valve when the power is below 20KW, slowly filling high-purity argon into the furnace body, closing the argon filling valve when the pressure in the furnace is increased to about 0.08Mpa, increasing the power to 60KW, and refining for 3 min; wherein the flow of argon is 0.3m³Min, and the argon filling time is 35-40 s;

fifthly, casting, reducing the power to 40KW +/-5 KW, keeping the casting time for about 0.5 min, and starting casting by using a steel die, wherein the casting time is less than or equal to 2 min;

⑥ discharging, stopping heating the vacuum melting furnace after casting, cooling for 30 minutes, discharging the CuNi prepared by the method₃0 intermediate alloy material, reduced CuMn₁₂The eutectic phase segregation in the Ni alloy ensures that the element properties in the alloy material are uniform.

Further, after the step 1) is finished, dilute hydrochloric acid is used for reacting the electrolytic copper plate, the electrolytic manganese sheet and the CuNi₃0, respectively carrying out acid washing on the intermediate alloys, cleaning for 5-15 min by using ultrasonic cleaning equipment, and then drying for 20-45 min at the temperature of 80-145 ℃; and removing oxides and other impurities on the surface of the raw material by acid washing to improve the quality of the alloy.

Further, in the step 2), the crucible is made of a silicon iron material; the carbon in the carbon-containing crucible is prevented from seriously influencing the smelting of the copper-manganese alloy material.

Further, after the step 2) is finished, adding a covering agent on the surface of the mixed alloy material, wherein the covering agent is a mixture of cryolite and borax in a weight ratio of 1: 1, and the adding thickness of the covering agent is 0.5-1.2 mm; by adding the covering agent formed by mixing cryolite and borax on the surface of the mixed alloy material, the oxidation and volatilization in the alloy smelting process can be effectively reduced, and the alloy loss is reduced.

Further, the specific operation of step 5) is: firstly, casting 30% of the total amount of alloy solution, and controlling the casting speed to be 3.8-4.8 t/min; then, casting 45% of the total amount of the alloy solution, wherein the casting speed is controlled to be 5.8-6.4 t/min; finally, 25% of the total amount of the alloy solution is cast, and the casting speed is controlled to be 2.5-4.1 t/min; different casting speeds are used, so that the alloy cast ingot is solidified layer by layer, the defects of slag inclusion and looseness caused by low temperature of a casting alloy solution are eliminated, and the problem of component segregation caused by long internal solidification time of the cast ingot is eliminated.

Further, in the step 6), after the casting is completed, quenching treatment is performed on the obtained alloy ingot, wherein the quenching treatment specifically comprises the following operations: the method comprises the steps of utilizing compressed inert gas to perform injection quenching, setting the quenching temperature to be 80-120 ℃, and setting the quenching time to be 15-45 min, and performing quenching treatment on an alloy ingot to improve the rigidity of an alloy material and further improve the durability of the alloy.

And further, after the step 6) is finished, the blank is inspected and subjected to flaw detection by using a metal flaw detector, and the blank with unqualified quality is removed by inspecting and performing flaw detection on the blank, so that the quality of a subsequent finished product is ensured, and the using effect is improved.

Further, the vacuum smelting furnace in the step 2) comprises a furnace body, an induction heating coil, a heating crucible, a lifting assembly and a translation assembly, wherein a furnace cover is movably arranged at the upper end of the furnace body, an air inlet pipe is arranged on the furnace cover, an observation window and a movable door are arranged on the side wall of the furnace body, the movable door is positioned at the lower position of the side wall of the furnace body, and a base is arranged at the bottom of the furnace body; the induction heating coil is fixedly arranged at the upper end in the furnace body, a gap is reserved between the induction heating coil and the furnace body, the lifting assembly comprises two electromagnetic shielding plates, two sliding rods and a winch, the two sliding rods are respectively and vertically and fixedly arranged on two sides of the bottom in the furnace body, the electromagnetic shielding plates are slidably connected onto the two sliding rods through sliding sleeves, slots are horizontally formed in the upper end surfaces of the electromagnetic shielding plates, the winch is rotatably clamped on the furnace body through a rotating shaft, the rotating shaft penetrates through the furnace body, a steel cable is arranged between the rotating shaft and the sliding sleeves, and a component for fixing the winch is arranged on the furnace; the heating crucible is movably arranged on the electromagnetic shielding plate and can ascend to the inner area of the induction heating coil along with the electromagnetic shielding plate; the translation assembly comprises a sliding frame and a sliding seat, the sliding frame is horizontally arranged on the base and is positioned on the same horizontal plane with the upper end face of the base, the sliding seat is arranged on the sliding frame in a sliding mode, the sliding direction of the sliding seat is consistent with the opening direction of the movable door, an inserting rod is arranged on the sliding seat and can be inserted into the inserting groove, and the furnace cover, the movable door and the furnace body are in sealing connection; the vacuum smelting furnace can reduce the phenomenon of nonuniform tissue in the cast ingot caused by too fast temperature loss in the casting process of the alloy cast ingot.

Compared with the prior art, the invention has the beneficial effects that: the invention prepares CuNi by adopting a vacuum induction melting method₃0 intermediate alloy, reduces the cost of raw materials and the element burning loss, and the prepared CuMn₁₂The Ni alloy has compact structure, less pores and inclusions, and no defects of macroscopic and microscopic segregation such as Cu and Mn enrichment and the like; the crucible is made of ferrosilicon material, so that the condition that carbon in the carbon-containing crucible seriously affects the smelting of copper-manganese alloy material is avoided; the casting mould is a rigid mould, and can obtain the copper-manganese alloy material with uniform and consistent tissue.

Drawings

FIG. 1 is a process flow diagram of the present invention;

FIG. 2 is a schematic view of an alloy ingot of the present invention;

FIG. 3 is a metallographic mass spectrum of an alloy according to the invention;

FIG. 4 is a schematic view of the structure of the vacuum melting furnace of the present invention;

fig. 5 is a right side view of the vacuum melting furnace of the present invention;

FIG. 6 is a plan view of the vacuum melting furnace of the present invention;

the furnace comprises a furnace body 1, a furnace cover 10, an air inlet pipe 11, an observation window 12, a movable door 13, a base 14, an induction heating coil 2, a heating crucible 3, a lifting assembly 4, an electromagnetic shielding plate 40, a sliding sleeve 400, a slot 401, a sliding rod 41, a winch 42, a rotating shaft 420, a steel cable 421, a translation assembly 5, a sliding frame 50, a sliding seat 51 and an inserted rod 52.

Detailed Description