CN111636010A - High-strength high-conductivity copper-iron alloy and preparation method thereof - Google Patents
High-strength high-conductivity copper-iron alloy and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a high-strength high-conductivity copper-iron alloy which is characterized by comprising the following components in percentage by mass: 5.0-15.0 wt% of Fe, 0.0125-0.12 wt% of C, 0.05-0.30 wt% of Mo, 0.01-1.00 wt% of La or/and Ce, and the balance of Cu and inevitable impurities. C, Mo with a specific proportion is added into the copper-iron alloy, the conductivity is not reduced while the matrix strength is improved, the addition of La or/and Ce is beneficial to inhibiting the segregation of iron in the copper-iron alloy, and the performance is more stable.
Description
Technical Field
The invention relates to a copper alloy, in particular to a high-strength high-conductivity copper-iron alloy and a preparation method thereof.
Background
In recent years, with the rapid development of the industries such as aerospace, high-speed rail trains, microelectronics, vacuum electronic devices and the like in China, the demand for high-performance copper and copper alloy materials is more urgent, and particularly, the copper and copper alloy materials are required to have high conductivity and high mechanical properties on many service occasions.
The copper-iron alloy is an alloy material mainly composed of copper element and iron element, and is an immiscible alloy. Because the solubility of the iron element in the copper alloy is very low at room temperature, most of the iron element in the copper-iron alloy exists in the copper alloy independently, the influence of the iron element in the copper-iron alloy on the conductivity of the copper alloy is very small under general conditions; in addition, iron generally has high strength and ferromagnetism, so that a copper-iron alloy material prepared from high iron content and copper tends to have high strength and high conductivity, and even good electromagnetic shielding performance.
At present, the method for preparing the copper-iron alloy at home and abroad mainly comprises the following steps: mechanical alloying method, deformation in-situ composite method, gas atomization method, electromagnetic suspension smelting method, vacuum arc smelting method and the like. For example: the invention patent CN108251684A discloses a high-conductivity high-strength copper-iron alloy and a preparation method thereof, wherein, the content of Fe is 5-25 wt%, the balance is Cu, and alloy powder is prepared by an atomization method; then, sintering the alloy powder to obtain a sintered blank; then, carrying out wire drawing treatment on the sintered blank to obtain a wire material; and finally, carrying out aging treatment on the wire to obtain the copper-iron alloy. The invention patent CN109055801A discloses a preparation method for melting CuFe alloy material by vacuum consumable arc, which comprises the following steps: (1) mixing raw materials: the material comprises the following components in percentage by weight: weighing the required raw materials according to the proportion of Cu 70-30% and Fe 30-70%, and mixing in a mixer for 2-4 h; (2) pressing: loading the mixed powder into a rubber sleeve, performing mechanical vibration for 30-60s, rolling the material for 3-6min, performing reverse heading for 3-5 times, pressing the treated mixed powder by adopting a cold isostatic pressing method, wherein the pressure is 150-300 MPa, and the pressure maintaining time is 3-10 min; (3) and (3) sintering: loading the pressed consumable electrode into a vacuum sintering furnace for sintering, wherein the sintering highest temperature is controlled to be 800-1080 ℃, the heat preservation time is 30-240min, and the vacuum degree is more than 5 pa; (4) smelting: and putting the sintered consumable electrode into a vacuum consumable arc melting furnace for melting, wherein the melting current is 1000-4000A. However, in these copper-iron alloy materials, iron is strengthened by almost pure iron (copper has a very low solid solubility in iron), and the strength of pure iron is limited, so that the strengthening effect of pure iron on copper-iron alloys is also limited.
Therefore, it is necessary to develop a method for improving the strength of the iron phase in the copper-iron alloy without affecting the performance of the copper matrix, so that the copper-iron alloy has high strength and electric conductivity.
Disclosure of Invention
The first technical problem to be solved by the present invention is to provide a high-strength and high-conductivity copper-iron alloy in view of the above-mentioned prior art.
The technical scheme adopted by the invention for solving the first technical problem is as follows: a high-strength high-conductivity copper-iron alloy is characterized by comprising the following components in percentage by mass: 5.0-15.0 wt% of Fe, 0.0125-0.12 wt% of C, 0.05-0.30 wt% of Mo, 0.01-1.00 wt% of La or/and Ce, and the balance of Cu and inevitable impurities.
The C element and the Mo element are added into the copper-iron alloy material according to a specific proportion, the C element and the Mo element are not easy to dissolve in copper and react with a copper matrix, and the C element and the Mo element are almost completely dissolved in molten iron in a molten state. The C element and the Mo element have little influence on the Cu matrix, but have obvious strengthening effect on the Fe phase, thereby obviously improving the mechanical property of the copper-iron alloy while not influencing the conductivity of the copper matrix. The addition of La and/or Ce can refine the Cu matrix and Fe phase in the copper-iron alloy, and contribute to the suppression of component segregation.
Preferably, the copper-iron alloy has a tensile strength of 600 to 900MPa and an electrical conductivity of 50 to 70% IACS.
Preferably, the concentration deviation of the iron content at the head part and the tail part of the copper-iron alloy cast ingot is less than or equal to 10 percent.
The second technical problem to be solved by the present invention is to provide a method for preparing a high-strength high-conductivity copper-iron alloy in view of the above-mentioned current state of the art.
The technical scheme adopted by the invention for solving the second technical problem is as follows: the preparation method of the high-strength high-conductivity copper-iron alloy is characterized by comprising the following process flows of: preparing Fe-C-Mo intermediate alloy → casting copper-iron alloy → extruding → pickling → drawing; the Fe-C-Mo intermediate alloy comprises, by mass, 0.25-0.8 wt% of C, 1.0-2.0 wt% of Mo, and the balance of Fe; taking pure Fe, Fe-C intermediate alloy and Mo-Fe intermediate alloy as raw materials, burdening according to required components, respectively putting the pure Fe, the Fe-C intermediate alloy and the Mo-Fe intermediate alloy into a medium-frequency induction smelting furnace, charging, heating to 1580-1680 ℃, and casting after the raw materials are completely melted to obtain the Fe-C-Mo intermediate alloy.
Preferably, the casting process of the copper-iron alloy comprises the following steps: respectively adding electrolytic Cu, Fe-C-Mo intermediate alloy, Cu-La or/and Cu-Ce intermediate alloy into a smelting furnace, adopting a semi-continuous casting process, adding an electromagnetic stirring and water cooling device into a crystallizer, and casting at 1300-1580 ℃ at a drawing casting speed of 3.0-5.0 m/h; the current of the electromagnetic stirring is 80-120A, and the frequency is 6-10 Hz; the pressure of the cooling water is 0.02-0.06 MPa.
Preferably, the extrusion process of the copper-iron alloy comprises the following steps: the extrusion temperature is 900-960 ℃, the extrusion speed is 0.1-0.15 m/s, the extrusion ratio is 50-80, and water seal extrusion is adopted during extrusion.
Preferably, the pickling process of the copper-iron alloy comprises the following steps: placing the extruded copper-iron alloy into an acid tank → a clean water tank → a high-pressure washing tank → a saponification liquid tank in sequence; wherein, the acid tank is soaked for 80-120 s at the temperature of less than or equal to 34 ℃; soaking in a clean water tank for 30-60 s; the high-pressure flushing tank is used for 30-60s, and the water pressure is 3-8 MPa; soaking the saponification liquid in a tank for 5-20 s at 50-70 ℃.
Preferably, the volume percentage of the pickling solution in the acid tank is as follows: 5.0-15.0% of sulfuric acid, 5.0-10.0% of acetic acid, 10.0-15.0% of hydrogen peroxide, 0.1-2.0% of emulsifier and the balance of water; the pH of the pickling solution is 2.0-3.0.
Preferably, the pH of the saponification liquid in the saponification liquid pool is 7.0-9.0.
Preferably, the drawing process of the copper-iron alloy comprises the following steps: and 5-8 drawing passes, wherein the total deformation is 60-90%.
Compared with the prior art, the invention has the advantages that:
1) the C element and the Mo element are added into the copper-iron alloy material in a specific ratio, the C element and the Mo element are not easy to dissolve in copper and react with a copper matrix, the C element and the Mo element are almost completely dissolved in molten iron, the C element and the Mo element have little influence on the Cu matrix but have obvious strengthening effect on an Fe phase, and the mechanical property of the copper-iron alloy is obviously improved while the conductivity of the copper matrix is not influenced; la or/and Ce elements are added, so that a Cu matrix and an Fe phase in the copper-iron alloy can be refined, the component segregation can be inhibited, and the concentration deviation of iron content at the head and the tail of the ingot is less than or equal to 10%.
2) The copper-iron alloy has high strength and high conductivity, the tensile strength is 600-1000 MPa, the conductivity is 50-80% IACS, and the elongation is 5-12%.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1:
the copper-iron alloy comprises the following components in percentage by mass: 5.0 wt%, C: 0.0125 wt%, Mo: 0.05 wt%, La: 0.01 wt%, and the balance of Cu and unavoidable impurities.
The process flow of the copper-iron alloy is as follows: preparing Fe-C-Mo intermediate alloy → casting copper-iron alloy → extruding → pickling → drawing;
1) preparing Fe-C-Mo alloy: mixing 0.25 wt% of C, 1.0 wt% of Mo and the balance of Fe, and putting pure Fe, Fe-C intermediate alloy and Mo-Fe intermediate alloy which are used as raw materials into a medium-frequency induction smelting furnace for smelting at the casting temperature of 1580 ℃;
2) casting copper-iron alloy: weighing the materials according to the component proportion of the copper-iron alloy material, respectively adding electrolytic Cu, Fe-C-Mo intermediate alloy and Cu-La intermediate alloy into a smelting furnace, wherein the casting temperature is 1300 ℃, the casting speed is 5.0m/h, the electromagnetic stirring current is 80A, the frequency is 6Hz, and the cooling water pressure is 0.02 MPa;
3) extruding: the copper-iron alloy is extruded by a water seal extrusion mode, the extrusion temperature is 900 ℃, the extrusion speed is 0.12m/s, and the extrusion ratio is 80;
4) acid washing: placing the extruded copper-iron alloy into an acid tank → a clean water tank → a high-pressure washing tank → a saponification liquid tank in sequence for acid washing; wherein, the pickling bath is soaked for 80s at 26 ℃, and the pickling solution comprises the following components in percentage by volume: 10% of sulfuric acid, 8% of acetic acid, 10% of hydrogen peroxide, 1.0% of emulsifier and the balance of water, wherein the pH value of the pickling solution is 2.1; soaking in a clean water tank for 30 s; the high-pressure flushing tank is used for 30s, and the water pressure is 5 MPa; soaking in saponification liquid pool for 10s at 50 deg.C and pH of 7.8;
5) drawing: the drawing was carried out for 5 passes, and the total deformation was 80%.
The tensile strength of the copper-iron alloy is 600MPa, the electric conductivity is 70% IACS, the elongation is 10%, and the concentration deviation of iron content at the head and the tail of an ingot is 5%.
Example 2:
the copper-iron alloy comprises the following components in percentage by mass: 6.5 wt%, C: 0.0195 wt%, Mo: 0.08 wt%, Ce: 0.80 wt%, and the balance of Cu and inevitable impurities.
The process flow of the copper-iron alloy is as follows: preparing Fe-C-Mo intermediate alloy → casting copper-iron alloy → extruding → pickling → drawing;
1) preparing Fe-C-Mo alloy: mixing 0.3 wt% of C, 1.2 wt% of Mo and the balance of Fe, and putting pure Fe, Fe-C intermediate alloy and Mo-Fe intermediate alloy as raw materials into a medium-frequency induction smelting furnace for smelting at the smelting and casting temperature of 1680 ℃;
2) casting copper-iron alloy: weighing the materials according to the component proportion of the copper-iron alloy material, respectively adding electrolytic Cu, Fe-C-Mo intermediate alloy and Cu-Ce intermediate alloy into a smelting furnace, wherein the casting temperature is 1390 ℃, the casting speed is 3.5m/h, the electromagnetic stirring current is 100A, the frequency is 8Hz, and the cooling water pressure is 0.04 MPa;
3) extruding: the copper-iron alloy is extruded by a water seal extrusion mode, the extrusion temperature is 920 ℃, the extrusion speed is 0.12m/s, and the extrusion ratio is 60;
4) acid washing: placing the extruded copper-iron alloy into an acid tank → a clean water tank → a high-pressure washing tank → a saponification liquid tank in sequence for acid washing; wherein, the pickling bath is soaked for 120s at the temperature of 34 ℃, and the pickling solution comprises the following components in percentage by volume: 5.0% of sulfuric acid, 5.0% of acetic acid, 15.0% of hydrogen peroxide, 1.2% of emulsifier and the balance of water, wherein the pH value of the pickling solution is 2.1; soaking in a clean water tank for 60 s; the high-pressure flushing tank is used for 60s, and the water pressure is 5 MPa; soaking in saponification liquid pool for 20s at 70 deg.C and pH of 9.0;
5) drawing: the drawing was carried out for 5 passes, and the total deformation was 60%.
The tensile strength of the copper-iron alloy is 630MPa, the electric conductivity is 65% IACS, the elongation is 12%, and the concentration deviation of iron content at the head and the tail of an ingot is 9%.
Example 3:
the copper-iron alloy comprises the following components in percentage by mass: 8.0 wt%, C: 0.04 wt%, Mo: 0.08 wt%, Ce: 0.60 wt%, and the balance of Cu and inevitable impurities.
The process flow of the copper-iron alloy is as follows: preparing Fe-C-Mo intermediate alloy → casting copper-iron alloy → extruding → pickling → drawing;
1) preparing Fe-C-Mo alloy: mixing 0.5 wt% of C, 1.0 wt% of Mo and the balance of Fe, and putting pure Fe, Fe-C intermediate alloy and Mo-Fe intermediate alloy which are used as raw materials into a medium-frequency induction smelting furnace for smelting at the casting temperature of 1580 ℃;
2) casting copper-iron alloy: weighing the materials according to the component proportion of the copper-iron alloy material, respectively adding electrolytic Cu, Fe-C-Mo intermediate alloy and Cu-Ce intermediate alloy into a smelting furnace, wherein the casting temperature is 1300 ℃, the casting speed is 5.0m/h, the electromagnetic stirring current is 100A, the frequency is 8Hz, and the cooling water pressure is 0.04 MPa;
3) extruding: the copper-iron alloy is extruded by a water seal extrusion mode, the extrusion temperature is 920 ℃, the extrusion speed is 0.12m/s, and the extrusion ratio is 50.
4) Acid washing: placing the extruded copper-iron alloy into an acid tank → a clean water tank → a high-pressure washing tank → a saponification liquid tank in sequence for acid washing; wherein, the pickling bath is soaked for 120s at the temperature of 34 ℃, and the pickling solution comprises the following components in percentage by volume: 6.0% of sulfuric acid, 9% of acetic acid, 13% of hydrogen peroxide, 0.5% of emulsifier and the balance of water, wherein the pH value of the pickling solution is 3.0; soaking in a clean water tank for 60 s; the high-pressure flushing tank is used for 60s, and the water pressure is 8 MPa; soaking in saponification liquid pool for 10s at 70 deg.C and pH of 8.0;
5) drawing: the drawing was carried out for 6 passes, and the total deformation was 85%.
The tensile strength of the copper-iron alloy is 660MPa, the conductivity is 61% IACS, and the elongation is 10%.
Example 4:
the copper-iron alloy comprises the following components in percentage by mass: 9.2 wt%, C: 0.028 wt%, Mo: 0.15 wt%, Ce: 0.90 wt%, and the balance of Cu and inevitable impurities.
The process flow of the copper-iron alloy is as follows: preparing Fe-C-Mo intermediate alloy → casting copper-iron alloy → extruding → pickling → drawing;
1) preparing Fe-C-Mo alloy: mixing 0.3 wt% of C, 1.6 wt% of Mo and the balance of Fe, and putting pure Fe, Fe-C intermediate alloy and Mo-Fe intermediate alloy which are used as raw materials into a medium-frequency induction smelting furnace for smelting at the smelting and casting temperature of 1600 ℃;
2) casting copper-iron alloy: weighing the materials according to the component proportion of the copper-iron alloy material, respectively adding electrolytic Cu, Fe-C-Mo intermediate alloy and Cu-Ce intermediate alloy into a smelting furnace, wherein the casting temperature is 1400 ℃, the casting speed is 3.9m/h, the electromagnetic stirring current is 80A, the frequency is 6Hz, and the cooling water pressure is 0.05 MPa;
3) extruding: the copper-iron alloy is extruded by a water seal extrusion mode, the extrusion temperature is 920 ℃, the extrusion speed is 0.12m/s, and the extrusion ratio is 80;
4) acid washing: placing the extruded copper-iron alloy into an acid tank → a clean water tank → a high-pressure washing tank → a saponification liquid tank in sequence for acid washing; wherein, the pickling bath is soaked for 120s at 26 ℃, and the pickling solution comprises the following components in percentage by volume: 7.0% of sulfuric acid, 9% of acetic acid, 11% of hydrogen peroxide, 0.5% of emulsifier and the balance of water, wherein the pH value of the pickling solution is 2.5; soaking in a clean water tank for 60 s; the high-pressure flushing tank is used for 60s, and the water pressure is 8 MPa; soaking in saponification liquid pool for 10s at 70 deg.C and pH of 8.0;
5) drawing: the drawing was carried out for 6 passes, and the total deformation was 80%.
The tensile strength of the copper-iron alloy is 710MPa, the electric conductivity is 60% IACS, the elongation is 8%, and the concentration deviation of iron content at the head and the tail of an ingot is 8%.
Example 5:
the copper-iron alloy comprises the following components in percentage by mass: 10.5 wt%, C: 0.063 wt%, Mo: 0.13 wt%, La: 1.0 wt%, and the balance of Cu and unavoidable impurities.
The process flow of the copper-iron alloy is as follows: preparing Fe-C-Mo intermediate alloy → casting copper-iron alloy → extruding → pickling → drawing;
1) preparing Fe-C-Mo alloy: mixing 0.6 wt% of C, 1.2 wt% of Mo and the balance of Fe, and putting pure Fe, Fe-C intermediate alloy and Mo-Fe intermediate alloy which are used as raw materials into a medium-frequency induction smelting furnace for smelting at a smelting and casting temperature of 1650 ℃;
2) casting copper-iron alloy: weighing the materials according to the component proportion of the copper-iron alloy material, respectively adding electrolytic Cu, Fe-C-Mo intermediate alloy and Cu-La intermediate alloy into a smelting furnace, wherein the casting temperature is 1500 ℃, the casting speed is 3.0m/h, the electromagnetic stirring current is 120A, the frequency is 10Hz, and the cooling water pressure is 0.06 MPa;
3) extruding: the copper-iron alloy is extruded by a water seal extrusion mode, the extrusion temperature is 950 ℃, the extrusion speed is 0.15m/s, and the extrusion ratio is 80;
4) acid washing: placing the extruded copper-iron alloy into an acid tank → a clean water tank → a high-pressure washing tank → a saponification liquid tank in sequence for acid washing; wherein, the pickling bath is soaked for 120s at 26 ℃, and the pickling solution comprises the following components in percentage by volume: 7.5 percent of sulfuric acid, 8.5 percent of acetic acid, 12.5 percent of hydrogen peroxide, 1.25 percent of emulsifier and the balance of water, wherein the pH value of the pickling solution is 2.5; soaking in a clean water tank for 50 s; the high-pressure flushing tank is used for 60s, and the water pressure is 5 MPa; soaking in saponification liquid pool for 10s at 70 deg.C and pH of 8.0;
5) drawing: the drawing was carried out for 5 passes, and the total deformation was 80%.
The tensile strength of the copper-iron alloy is 800MPa, the electric conductivity is 55% IACS, the elongation is 8%, and the concentration deviation of iron content at the head and the tail of an ingot is 9%.
Example 6:
the copper-iron alloy comprises the following components in percentage by mass: 12.0 wt%, C: 0.072 wt%, Mo: 0.14 wt%, Ce: 0.8 wt%, La: 0.05 wt%, and the balance of Cu and inevitable impurities.
The process flow of the copper-iron alloy is as follows: preparing Fe-C-Mo intermediate alloy → casting copper-iron alloy → extruding → pickling → drawing;
1) preparing Fe-C-Mo alloy: mixing 0.6 wt% of C, 1.2 wt% of Mo and the balance of Fe, and putting pure Fe, Fe-C intermediate alloy and Mo-Fe intermediate alloy which are used as raw materials into a medium-frequency induction smelting furnace for smelting at the smelting and casting temperature of 1600 ℃;
2) casting copper-iron alloy: weighing the materials according to the component proportion of the copper-iron alloy material, respectively adding electrolytic Cu, Fe-C-Mo intermediate alloy, Cu-La intermediate alloy and Cu-Ce intermediate alloy into a smelting furnace, wherein the casting temperature is 1520 ℃, the casting speed is 3.0m/h, the electromagnetic stirring current is 120A, the frequency is 10Hz, and the cooling water pressure is 0.06 MPa;
3) extruding: the copper-iron alloy is extruded by a water seal extrusion mode, the extrusion temperature is 950 ℃, the extrusion speed is 0.15m/s, and the extrusion ratio is 60;
4) acid washing: placing the extruded copper-iron alloy into an acid tank → a clean water tank → a high-pressure washing tank → a saponification liquid tank in sequence for acid washing; wherein, the pickling bath is soaked for 80s at 26 ℃, and the pickling solution comprises the following components in percentage by volume: 5.5 percent of sulfuric acid, 6.5 percent of acetic acid, 11 percent of hydrogen peroxide, 0.5 percent of emulsifier and the balance of water, wherein the pH value of the pickling solution is 2.5; soaking in a clean water tank for 60 s; the high-pressure flushing tank is used for 40s, and the water pressure is 8 MPa; soaking in saponification liquid pool for 10s at 70 deg.C and pH of 8.0;
5) drawing: the drawing was carried out for 6 passes, and the total deformation was 80%.
The tensile strength of the copper-iron alloy is 825MPa, the electric conductivity is 55% IACS, the elongation is 6%, and the concentration deviation of iron content at the head and the tail of an ingot is 6%.
Example 7:
the copper-iron alloy comprises the following components in percentage by mass: 13.8 wt%, C: 0.11 wt%, Mo: 0.27 wt%, La: 1.0 wt%, and the balance of Cu and unavoidable impurities.
The process flow of the copper-iron alloy is as follows: preparing Fe-C-Mo intermediate alloy → casting copper-iron alloy → extruding → pickling → drawing;
1) preparing Fe-C-Mo alloy: mixing 0.8 wt% of C, 2.0 wt% of Mo and the balance of Fe, and putting pure Fe, Fe-C intermediate alloy and Mo-Fe intermediate alloy which are used as raw materials into a medium-frequency induction smelting furnace for smelting at a smelting and casting temperature of 1650 ℃;
2) casting copper-iron alloy: weighing the materials according to the component proportion of the copper-iron alloy material, respectively adding electrolytic Cu, Fe-C-Mo intermediate alloy and Cu-La intermediate alloy into a smelting furnace, wherein the casting temperature is 1500 ℃, the casting speed is 5.0m/h, the electromagnetic stirring current is 120A, the frequency is 10Hz, and the cooling water pressure is 0.05 MPa;
3) extruding: the copper-iron alloy is extruded by a water seal extrusion mode, the extrusion temperature is 950 ℃, the extrusion speed is 0.15m/s, and the extrusion ratio is 80;
4) acid washing: placing the extruded copper-iron alloy into an acid tank → a clean water tank → a high-pressure washing tank → a saponification liquid tank in sequence for acid washing; wherein, the pickling solution is soaked in an acid tank for 100s at the temperature of 25 ℃, the volume percentage of the pickling solution is 6.5 percent of sulfuric acid, 9.0 percent of acetic acid, 13 percent of hydrogen peroxide, 0.52 percent of emulsifier and the balance of water, and the pH value of the pickling solution is 2.0; soaking in a clean water tank for 60 s; the high-pressure flushing tank is used for 60s, and the water pressure is 8 MPa; soaking in saponification liquid pool for 10s at 70 deg.C and pH of 8.5;
5) drawing: and 5 times of drawing is carried out, and the total deformation is 90%.
The tensile strength of the copper-iron alloy is 880MPa, the electric conductivity is 50% IACS, the elongation is 6%, and the concentration deviation of iron content at the head and tail of an ingot is 8%.
Example 8:
the copper-iron alloy comprises the following components in percentage by mass: 15.0 wt%, C: 0.12 wt%, Mo: 0.3 wt%, La: 0.8 wt%, and the balance of Cu and inevitable impurities.
The process flow of the copper-iron alloy is as follows: preparing Fe-C-Mo intermediate alloy → casting copper-iron alloy → extruding → pickling → drawing;
1) preparing Fe-C-Mo alloy: mixing 0.8 wt% of C, 2.0 wt% of Mo and the balance of Fe, and putting pure Fe, Fe-C intermediate alloy and Mo-Fe intermediate alloy as raw materials into a medium-frequency induction smelting furnace for smelting at the smelting and casting temperature of 1680 ℃;
2) casting copper-iron alloy: weighing the materials according to the component proportion of the copper-iron alloy material, respectively adding electrolytic Cu, Fe-C-Mo intermediate alloy and Cu-La intermediate alloy into a smelting furnace, wherein the casting temperature is 1580 ℃, the casting speed is 3.0m/h, the electromagnetic stirring current is 120A, the frequency is 10Hz, and the cooling water pressure is 0.06 MPa;
3) extruding: the copper-iron alloy is extruded by a water seal extrusion mode, the extrusion temperature is 960 ℃, the extrusion speed is 0.15m/s, and the extrusion ratio is 60;
4) acid washing: placing the extruded copper-iron alloy into an acid tank → a clean water tank → a high-pressure washing tank → a saponification liquid tank in sequence for acid washing; wherein, the pickling bath is soaked for 120s at 34 ℃, the volume percentage of the pickling solution is 6.5 percent of sulfuric acid, 9.0 percent of acetic acid, 13 percent of hydrogen peroxide, 0.52 percent of emulsifier and the balance of water, and the pH value of the pickling solution is 2.0; soaking in a clean water tank for 60 s; the high-pressure flushing tank is used for 60s, and the water pressure is 5 MPa; soaking in saponification liquid pool for 20s at 70 deg.C and pH of 9.0;
5) drawing: the drawing temperature is room temperature, 8 times of drawing are carried out, and the total deformation is 90%.
The tensile strength of the copper-iron alloy is 900MPa, the electric conductivity is 52% IACS, the elongation is 5%, and the concentration deviation of iron content at the head and the tail of an ingot is 8%.
Comparative example 1:
comparative example 1 the composition of the copper-iron alloy in mass percent is Fe: 5.0 wt%, and the balance of Cu and unavoidable impurities.
Comparative example 1 was prepared in the same manner as in example 1 except that no electromagnetic stirring and water cooling device was applied.
Comparative example 1 the copper-iron alloy had a tensile strength of 400MPa, an electrical conductivity of 75% IACS, an elongation of 10% and a deviation in iron concentration between the head and tail of the ingot of 12%.
Comparative example 2:
comparative example 2 the composition of the copper-iron alloy in mass percent is Fe: 15.0 wt%, the balance being Cu and unavoidable impurities.
Comparative example 2 was prepared in the same manner as in example 1.
Comparative example 1 the copper-iron alloy had a tensile strength of 490MPa, an electrical conductivity of 48% IACS, an elongation of 10% and a deviation in iron concentration between the head and tail of the ingot of 15%.
Claims (10)
1. A high-strength high-conductivity copper-iron alloy is characterized by comprising the following components in percentage by mass: 5.0-15.0 wt% of Fe, 0.0125-0.12 wt% of C, 0.05-0.30 wt% of Mo, 0.01-1.00 wt% of La or/and Ce, and the balance of Cu and inevitable impurities.
2. The high-strength high-conductivity copper-iron alloy according to claim 1, wherein: the copper-iron alloy has the tensile strength of 600-900 MPa, the electric conductivity of 50-70% IACS and the elongation of 5-12%.
3. The high-strength high-conductivity copper-iron alloy according to claim 1, wherein: the concentration deviation of the iron content at the head and the tail of the copper-iron alloy cast ingot is less than or equal to 10 percent.
4. A preparation method of the high-strength high-conductivity copper-iron alloy as claimed in any one of claims 1 to 3, characterized by comprising the following steps: preparing Fe-C-Mo intermediate alloy → casting copper-iron alloy → extruding → pickling → drawing; the Fe-C-Mo intermediate alloy comprises, by mass, 0.25-0.8 wt% of C, 1.0-2.0 wt% of Mo, and the balance of Fe; taking pure Fe, Fe-C intermediate alloy and Mo-Fe intermediate alloy as raw materials, burdening according to required components, respectively putting the pure Fe, the Fe-C intermediate alloy and the Mo-Fe intermediate alloy into a medium-frequency induction smelting furnace, charging, heating to 1580-1680 ℃, and casting after the raw materials are completely melted to obtain the Fe-C-Mo intermediate alloy.
5. The method for preparing the high-strength high-conductivity copper-iron alloy according to claim 4, wherein the method comprises the following steps: the casting process of the copper-iron alloy comprises the following steps: respectively adding electrolytic Cu, Fe-C-Mo intermediate alloy, Cu-La or/and Cu-Ce intermediate alloy into a smelting furnace, adopting a semi-continuous casting process, adding an electromagnetic stirring and water cooling device into a crystallizer, and casting at 1300-1580 ℃ at a drawing casting speed of 3.0-5.0 m/h; the current of the electromagnetic stirring is 80-120A, and the frequency is 6-10 Hz; the pressure of the cooling water is 0.02-0.06 MPa.
6. The method for preparing the high-strength high-conductivity copper-iron alloy according to claim 4, wherein the method comprises the following steps: the extrusion process of the copper-iron alloy comprises the following steps: the extrusion temperature is 900-960 ℃, the extrusion speed is 0.1-0.15 m/s, the extrusion ratio is 50-80, and water seal extrusion is adopted during extrusion.
7. The method for preparing the high-strength high-conductivity copper-iron alloy according to claim 4, wherein the method comprises the following steps: the pickling process of the copper-iron alloy comprises the following steps: placing the extruded copper-iron alloy into an acid tank → a clean water tank → a high-pressure washing tank → a saponification liquid tank in sequence; wherein, the acid tank is soaked for 80-120 s at the temperature of less than or equal to 34 ℃; soaking in a clean water tank for 30-60 s; the high-pressure flushing tank is used for 30-60s, and the water pressure is 3-8 MPa; soaking the saponification liquid in a tank for 5-20 s at 50-70 ℃.
8. The method for preparing the high-strength high-conductivity copper-iron alloy according to claim 7, wherein the method comprises the following steps: the acid washing liquid in the acid bath comprises the following components in percentage by volume: 5.0-15.0% of sulfuric acid, 5.0-10.0% of acetic acid, 10.0-15.0% of hydrogen peroxide, 0.1-2.0% of emulsifier and the balance of water; the pH of the pickling solution is 2.0-3.0.
9. The method for preparing the high-strength high-conductivity copper-iron alloy according to claim 7, wherein the method comprises the following steps: the pH of the saponification liquid in the saponification liquid pool is 7.0-9.0.
10. The method for preparing the high-strength high-conductivity copper-iron alloy according to claim 4, wherein the method comprises the following steps: the drawing process of the copper-iron alloy comprises the following steps: and 5-8 drawing passes, wherein the total deformation is 60-90%.
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