CN116179887A - Cu-Cr-Zr alloy for high-current electric connector and preparation method thereof - Google Patents
Cu-Cr-Zr alloy for high-current electric connector and preparation method thereof Download PDFInfo
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 239
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910017526 Cu-Cr-Zr Inorganic materials 0.000 title claims abstract description 13
- 229910017810 Cu—Cr—Zr Inorganic materials 0.000 title claims abstract description 13
- 230000032683 aging Effects 0.000 claims abstract description 86
- 238000005096 rolling process Methods 0.000 claims abstract description 35
- 239000010949 copper Substances 0.000 claims abstract description 30
- 238000005098 hot rolling Methods 0.000 claims abstract description 23
- 238000000265 homogenisation Methods 0.000 claims abstract description 21
- 238000005266 casting Methods 0.000 claims abstract description 20
- 238000000748 compression moulding Methods 0.000 claims abstract description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 108
- 238000010438 heat treatment Methods 0.000 claims description 95
- 238000001816 cooling Methods 0.000 claims description 79
- 229910052786 argon Inorganic materials 0.000 claims description 54
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
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- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
- C21D8/0226—Hot rolling
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
- C21D8/0236—Cold rolling
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
- C21D8/0242—Flattening; Dressing; Flexing
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- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/002—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working by rapid cooling or quenching; cooling agents used therefor
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- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
- H01B1/026—Alloys based on copper
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/0016—Apparatus or processes specially adapted for manufacturing conductors or cables for heat treatment
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
- H01R13/00—Details of coupling devices of the kinds covered by groups H01R12/70 or H01R24/00 - H01R33/00
- H01R13/02—Contact members
- H01R13/03—Contact members characterised by the material, e.g. plating, or coating materials
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Abstract
The invention discloses a Cu-Cr-Zr alloy for a high-current electric connector and a preparation method thereof. The copper alloy material consists of the following components: 0.80-1.20wt% of Cr, 0.10-0.30wt% of Zr, 0.10-0.30wt% of Ge, 0.01-0.06wt% of Nb and the balance of Cu. The preparation method comprises the following steps: alloy casting, homogenization treatment, hot rolling, solution treatment, compression molding deformation, stage aging treatment, room temperature rolling, variable temperature aging treatment and the like. The copper alloy material prepared by the invention has fine crystal grains and forms fine and dispersed precipitated phase particles, thereby having good comprehensive properties of hardness, strength, high-temperature softening resistance, conductivity and the like, and being widely applied to the related fields of electronic power and the like, in particular to an electric connector which needs to work in a high-current environment.
Description
Technical Field
The invention belongs to the technical field of copper alloy materials, and particularly relates to a method for preparing copper alloy by combining die pressing deformation, cold rolling and combined heat treatment.
Background
Copper and copper alloy are widely applied to a plurality of fields of electronic power, rail transit, national defense and military industry and the like due to good electrical conductivity, thermal conductivity and mechanical properties, and the application is not only closely related to our daily life, but also is the basis of the healthy development of national economy. Pure copper has excellent electrical conductivity and thermal conductivity, but the lower strength of pure copper (the tensile strength of industrial pure copper is only about 230 MPa) greatly limits the application range of pure copper. For copper alloy, high strength and high conductivity are a pair of contradictory properties, and how to effectively improve the strength of copper alloy material and maintain the high conductivity of copper alloy material at the same time has become a research hot spot of high-strength high-conductivity copper alloy. At present, the strength of the copper alloy is generally improved by alloying, changing the processing technology and other methods, and meanwhile, the higher conductivity of the copper alloy is ensured.
The current strengthening methods of copper alloys include solid solution strengthening, precipitation strengthening, and the like. For solid solution strengthening copper alloys, the alloying elements are solid-dissolved in the copper matrix, resulting in lattice distortion of the copper matrix, which increases the probability of electrons being scattered while increasing the alloy strength to a limited extent, thereby reducing the conductivity thereof. For example, the Cu-Sn-Ti-P-Zn-Mg alloy prepared in China patent (issued to publication number: CN 109266877B) has a hardness of 225HV, a tensile strength of 720MPa, but a conductivity of only 12.6% IACS. For precipitation strengthening copper alloy, the copper alloy in a supersaturated solid solution state is subjected to cold deformation processing, the density of microscopic defects such as dislocation and vacancy is improved, and then, by combining an aging heat treatment process, solute atoms dissolved in a copper matrix are nucleated and separated out from the microscopic defects in the heat treatment process to form fine dispersed precipitated phase particles, so that the precipitation strengthening effect is achieved, the lattice distortion of the copper matrix can be reduced due to the precipitation of the solute atoms, the probability of scattering electrons is reduced, and the conductivity of the alloy is improved. For example, liu Hai et al, "influence of Rolling and aging treatment on the structure and performance of Cu-Cr-Zr alloy", chinese nonferrous metals journal, 2020, 30 (9): 9, prepared Cu-Cr-Zr alloy has a strength of 411.7MPa and a conductivity of 63.7% IACS, and the strength and conductivity of the alloy do not fully satisfy the performance requirements of high-current electrical connectors.
With the advent of the 5G era, various electrical connectors such as new energy automobile connectors, space connectors and new generation intelligent terminal high-speed transmission standardized ports are being developed toward miniaturization, thinning, high density, long service life and the like, and this puts higher demands on various electrical connectors (particularly, high-current power connectors), such as: greater operating current density, better high temperature resistance, higher reliability, good plug resistance, etc. On the one hand, the materials used have to have higher strength and hardness in order to ensure the reliability of connection and to prevent plastic deformation during the plugging process, due to the miniaturization, which results in the thinner materials. On the other hand, in order to adapt to a high-current working scene and prevent the failure of the electric connector caused by the excessive heating value in the current transmission process, the materials used need higher conductivity and higher softening resistance. The invention carries out component improvement and process innovation on the basis of the Cu-Cr-Zr ternary alloy, and the copper alloy has higher hardness, higher strength, good high-temperature softening resistance, higher conductivity and other comprehensive properties by combining the mode of compression molding deformation, cold rolling and combined heat treatment so as to meet the performance requirements of a high-current electric connector.
Disclosure of Invention
The invention aims to provide a Cu-Cr-Zr alloy for a high-current electric connector and a preparation method thereof, wherein the Cu-Cr-Zr alloy has high hardness, high strength, good high-temperature softening resistance, high conductivity and other good comprehensive properties, and can be widely applied to the related fields of electronic power and the like, in particular to an electric connector which needs to work in a high-current environment.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the Cu-Cr-Zr alloy for the high-current electric connector comprises the following components in percentage by mass as 100 percent: 0.80-1.20wt% of Cr, 0.10-0.30wt% of Zr, 0.10-0.30wt% of Ge, 0.01-0.06wt% of Nb and the balance of Cu.
Further, the sum of the mass percentages of Cr and Zr is 0.90 to 1.50wt%, and the sum of the mass percentages of Ge and Nb is 0.11 to 0.36wt%.
The invention discloses a preparation method of Cu-Cr-Zr alloy for a high-current electric connector, which comprises the following steps:
(1) Alloy casting: under the protection of pure argon (the volume fraction of Ar is more than or equal to 99.99%), the raw materials are put into an induction furnace for smelting, then the obtained alloy melt is heated to more than 1200 ℃, kept stand for 10 minutes, then cast into a die and cooled to room temperature, and an alloy cast ingot is obtained. The raw materials are pure copper blocks with the purity of more than or equal to 99.9wt%, and contain 5-10 wt% of Cu-Cr intermediate alloy, 40-60 wt% of Cu-Zr intermediate alloy, 10-20 wt% of Cu-Ge intermediate alloy and 0.5-1.0 wt% of Cu-Nb intermediate alloy;
(2) Homogenizing: under the protection of pure argon, placing the obtained cast ingot into a heat treatment furnace for homogenization treatment, wherein the homogenization treatment temperature is 900-980 ℃, the heat preservation time is 5-8 hours, and then cooling to room temperature along with the furnace;
(3) And (3) hot rolling: heating the homogenized alloy material to 700-850 ℃, preserving heat for 5-10 minutes, taking out and rapidly hot-rolling the alloy material into a strip, wherein the total deformation of hot rolling is 60-85%, immediately performing water quenching treatment on the hot-rolled alloy strip, and rapidly cooling the hot-rolled alloy strip to room temperature;
(4) Solution treatment: under the protection of pure argon, placing the hot rolled alloy strip into a heat treatment furnace for solution treatment, wherein the solution temperature is 900-1050 ℃, the heat preservation time is 30-60 minutes, then immediately performing water quenching treatment on the alloy strip, and rapidly cooling to room temperature;
(5) Compression set: and removing surface oxide skin of the alloy strip subjected to solution treatment, and then performing die pressing deformation for 8-20 times at room temperature. The die pressing deformation die comprises a groove die (tooth die) and a flattening die, wherein the upper die of the groove die (tooth die) is provided with a groove, the lower die is provided with convex teeth, the convex teeth and the groove can be mutually meshed, the groove height and the groove width of the groove of the upper die are equal to the tooth height and the tooth width of the convex teeth of the lower die, and the groove height and the tooth width are 3-10 mm and are distributed at equal intervals. The compression molding deformation step comprises the following steps: (1) placing the alloy strip with the surface oxide skin removed in the middle of a groove die, and performing die pressing deformation on the involution Jin Daicai through mutual engagement of an upper die groove and a lower die convex tooth; (2) and then flattening the deformed alloy strip by flattening die pressing: (3) placing the alloy strip in the middle of a groove die, moving the placing position by an odd number of tooth width distances along the transverse direction of the convex teeth relative to the last placing position, and then performing die pressing deformation on the alloy strip Jin Daicai to deform the part of the alloy strip which is not deformed; (4) then flattening the deformed alloy strip by flattening die; (5) the alloy strip was rotated 90 ° horizontally (clockwise or counterclockwise) and steps (1) (2) (3) (4) were repeated. Wherein, one-time mould pressing deformation consists of the steps of (1) (2) (3) (4) which are completely implemented;
(6) Stage aging treatment: putting the alloy strip subjected to die pressing deformation into a heat treatment furnace, and carrying out stage aging under the protection of pure argon, wherein the aging process is as follows: firstly, heating the temperature to 200-250 ℃ from room temperature at a speed of 5-15 ℃/min, and preserving heat for 30-60 min; then, heating to 400-460 ℃ at a speed of 5-15 ℃/min, and preserving heat for 90-120 min; then, cooling to 150-250 ℃ at a speed of 5-15 ℃/min, and preserving heat for 30-60 min; finally, cooling to room temperature in an air cooling mode;
(7) And (3) rolling at room temperature: rolling the alloy strip subjected to the stage aging treatment at room temperature, wherein the total rolling deformation is 50% -90%;
(8) And (3) variable temperature aging treatment: placing the alloy strip rolled at room temperature into a heat treatment furnace, and carrying out variable-temperature ageing treatment under the protection of pure argon, wherein the ageing process is as follows: firstly, heating the temperature from room temperature to 300-350 ℃ at a speed of 5-15 ℃/min, and preserving heat for 1-2 min; then, heating to 400-500 ℃ at a speed of 5-15 ℃/min, and preserving heat for 15-30 min; finally, cooling to room temperature in an air cooling mode to obtain a final sample.
The invention has the advantages that
(1) The invention takes Cu, cr, zr, ge, nb as main element in alloy composition. Cr, zr, ge and Nb elements are added in the alloy component in a compounding way, so that the stacking fault energy in a copper matrix can be effectively reduced, the cross sliding and climbing of dislocation are restrained, more microscopic defects such as twin crystals and stacking faults are formed in the compression molding deformation and cold deformation process, a cold deformation structure is thinned, more precipitated phase nucleation sites are provided, and the hardness, the strength and the high-temperature softening resistance of the alloy are improved. Furthermore, according to the Miedema mixing enthalpy theory, the mixing enthalpy between Ge-Nb and Ge-Zr is greater than that of Cu-Zr, cu-Ge and Cu-Nb. Therefore, the copper alloy material can form a plurality of precipitation phases such as fine and dispersed Ge-Nb phase, ge-Zr phase, cu-Zr phase, cr-enriched phase and the like in the matrix through a proper preparation process. The cooperation of various precipitated phases, pinning dislocation and blocking dislocation movement, thereby improving the hardness, strength and high-temperature softening resistance of the material; meanwhile, the precipitation of the precipitated phase particles can reduce lattice distortion of the copper matrix, reduce the probability of scattering electrons and improve the conductivity of the copper matrix.
(2) Compared with cold rolling, the method provided by the invention has the advantages that the die pressing deformation technology is adopted for the alloy, the die pressing deformation can apply larger effective strain to the alloy material than the cold rolling, the original size of the material is not changed basically, the microstructure of the alloy is refined after the die pressing deformation, and the density of microscopic defects such as dislocation, vacancy and the like is obviously increased, so that more precipitated phase nucleation sites are provided, more fine and dispersed precipitated phases can be obtained in the subsequent aging heat treatment process, and the comprehensive performance of the alloy is improved.
(3) The method adopts the stage aging treatment on the alloy after the die pressing, because a large amount of effective strain is accumulated in the alloy in the die pressing process, the internal stress is larger, the stage aging treatment can effectively reduce the internal stress of the alloy under the condition of keeping the alloy in a work hardening state and avoid the buckling deformation of the alloy strip, and on the other hand, a large amount of tiny and dispersed precipitation phases are more fully precipitated, thereby playing the role of precipitation strengthening, and further improving the strength, the hardness and the electric conductivity of the alloy.
(4) According to the invention, the alloy after the stage aging is subjected to room temperature rolling and variable temperature aging, and the alloy sample is subjected to room temperature rolling, so that the thickness required by a finished product strip can be obtained on one hand, and the downstream industrial requirement is met; on the other hand, the strain can be introduced again to improve the density of microscopic defects such as dislocation, vacancy and the like, and more new precipitated phase nucleation sites are formed, so that solute atoms which are not precipitated in the stage aging process can be sufficiently precipitated in the temperature-changing aging process. In the temperature-changing aging process, precipitated phase particles cannot grow up excessively to cause the reduction of dislocation pinning effect, so that a final sample with good comprehensive performance can be obtained by combining room-temperature rolling with the temperature-changing aging process.
(5) The copper alloy material has excellent comprehensive mechanical properties and conductivity, the hardness is 200-250 HV, the yield strength is 600-695 MPa, the tensile strength is 625-720 MPa, the elongation after breaking is 6-13%, the softening temperature is 650-730 ℃, and the conductivity is 80-90% IACS.
Drawings
FIG. 1 is a schematic view of a molding deformation mold, namely a slot die (tooth mold), of the present invention;
FIG. 2 is a schematic view of a press-forming deformation mold-flattening mold structure of the present invention;
FIG. 3 is a schematic illustration of an example one-shot compression set of the present invention;
FIG. 4 is a schematic illustration of two press-molding deformations of an example of the present invention;
FIG. 5 is a metallographic structure diagram of the copper alloy material obtained in example 1;
FIG. 6 is a transmission electron microscope image of the copper alloy material prepared in example 1;
FIG. 7 is a metallographic structure diagram of the copper alloy material obtained in comparative example 1;
FIG. 8 is a transmission electron microscopic image of the copper alloy material prepared in comparative example 1.
Detailed Description
The invention is further illustrated, but is not limited, by the following examples. The main testing method and standard related to the invention are as follows: according to GB/T4340.1-2009 Vickers hardness test of Metal materials section 1: testing method to determine the hardness of copper alloy material; GB/T34505-2017 "copper and copper alloy Material room temperature tensile experiment method" is used for measuring the yield strength, tensile strength and elongation after breaking of a copper alloy material; the softening temperature of the copper alloy material is measured according to GB/T33370-2016 method for measuring softening temperature of copper and copper alloy; the conductivity of the copper alloy material was measured according to GB/T351-2019 method for measuring resistivity of metallic materials and the values were compared with the International annealed copper Standard (International Annealed Copper Standard,100% IACS).
Example 1
The alloy comprises the following components in percentage by mass: 0.80wt% Cr, 0.10wt% Zr, 0.15wt% Ge, 0.01wt% Nb, and the balance Cu.
The preparation method comprises the following steps:
(1) Alloy casting: placing the raw materials into crucible of induction furnace, and vacuumizing to 3.0X10 -3 Pa, then 1.1X10 g of 5 Smelting pure argon (the volume fraction of Ar is more than or equal to 99.99%) of Pa under the protection of pure argon, heating the alloy melt to 1250 ℃ after the solid is completely melted to form alloy melt, standing for 10 minutes, casting into a graphite mold, cooling, and opening the mold to take out an alloy cast ingot;
(2) Homogenizing: under the protection of pure argon, placing the obtained cast ingot into a heat treatment furnace for homogenization treatment, wherein the homogenization treatment temperature is 900 ℃, the heat preservation time is 6 hours, and then cooling to room temperature along with the furnace;
(3) And (3) hot rolling: heating the homogenized alloy material to 750 ℃ and preserving heat for 5 minutes, then taking out and rapidly hot-rolling the alloy material into a strip, wherein the total deformation of the hot-rolled alloy strip is 80%, immediately performing water quenching treatment on the hot-rolled alloy strip, and rapidly cooling the hot-rolled alloy strip to room temperature;
(4) Solution treatment: under the protection of pure argon, placing the hot rolled alloy strip into a heat treatment furnace for solution treatment, wherein the solution temperature is 950 ℃, the heat preservation time is 30 minutes, then immediately performing water quenching treatment on the alloy strip, and rapidly cooling to room temperature;
(5) Compression set: the alloy strip after the solution treatment was subjected to surface scale removal and then to press-molding deformation at room temperature for 20 times. Wherein, the groove height and the groove width of an upper die groove of a groove pressing die (tooth die) are 7mm, and the tooth height and the tooth width of a lower die convex tooth are all 7mm; the compression molding deformation step comprises the following steps: (1) placing the alloy strip with the surface oxide skin removed in the middle of a groove die, and performing die pressing deformation on the involution Jin Daicai through mutual engagement of an upper die groove and a lower die convex tooth; (2) and then flattening the deformed alloy strip by flattening die pressing: (3) placing the alloy strip in the middle of a groove die, moving the placement position by 1 tooth width distance along the transverse direction of the convex teeth relative to the last placement position, and then performing die pressing deformation on the alloy strip Jin Daicai to deform the part of the alloy strip which is not deformed; (4) then flattening the deformed alloy strip by flattening die; (5) rotating the alloy strip horizontally (clockwise or anticlockwise) by 90 degrees, and repeating the steps (1) (2) (3) (4);
(6) Stage aging treatment: putting the alloy strip subjected to die pressing deformation into a heat treatment furnace, and carrying out stage aging under the protection of pure argon, wherein the aging process is as follows: firstly, heating to 200 ℃ from room temperature at a speed of 10 ℃/min, and preserving heat for 60 minutes; then, heating to 430 ℃ at a speed of 10 ℃/min, and preserving heat for 120 min; then, the temperature is reduced to 150 ℃ at the speed of 10 ℃/min, and the temperature is kept for 60 minutes; finally, cooling to room temperature in an air cooling mode;
(7) And (3) rolling at room temperature: rolling the alloy strip subjected to the stage aging treatment at room temperature, wherein the total rolling deformation is 85%;
(8) And (3) variable temperature aging treatment: placing the alloy strip rolled at room temperature into a heat treatment furnace, and carrying out variable-temperature ageing treatment under the protection of pure argon, wherein the ageing process is as follows: firstly, heating to 300 ℃ from room temperature at a speed of 10 ℃/min, and preserving heat for 1 min; then, the temperature is increased to 430 ℃ at the speed of 10 ℃/min, and the temperature is kept for 30 min; finally, cooling to room temperature in an air cooling mode to obtain a final sample;
the hardness of the obtained copper alloy material is 242HV, the yield strength is 685MPa, the tensile strength is 707MPa, the elongation after breaking is about 13%, the softening temperature is 708 ℃, and the conductivity is 88% IACS.
Fig. 5 is a metallographic structure diagram of the copper alloy material obtained in this example. As can be seen from the figure, the crystal grains are fine and uniform, the grain size is about 5-10 mu m, and coarse grains are fewer.
Fig. 6 is a transmission electron microscope image of the copper alloy material prepared in this example. From the figure, we can see the precipitated phases with different shapes and different sizes, and the precipitated phases have larger quantity and smaller size, and are dispersed in the copper alloy matrix.
Example 2
The alloy comprises the following components in percentage by mass: 1.20wt% Cr, 0.15wt% Zr, 0.20wt% Ge, 0.01wt% Nb, the remainder being Cu.
The preparation method comprises the following steps:
(1) Alloy casting: placing the raw materials into crucible of induction furnace, and vacuumizing to 3.0X10 -3 Pa, then 1.1X10 g of 5 Smelting under the protection of pure argon (the volume fraction of Ar is more than or equal to 99.99%) of Pa, heating the alloy melt to 1340 ℃ after the solid is completely melted to form alloy melt, standing for 10 minutes, casting into a graphite mold, cooling, and opening the mold to take out alloy cast ingots;
(2) Homogenizing: under the protection of pure argon, placing the obtained cast ingot into a heat treatment furnace for homogenization treatment, wherein the homogenization treatment temperature is 980 ℃, the heat preservation time is 7 hours, and then cooling to room temperature along with the furnace;
(3) And (3) hot rolling: heating the homogenized alloy material to 850 ℃ and preserving heat for 5 minutes, then taking out and rapidly hot-rolling the alloy material into a strip, wherein the total deformation of the hot-rolled alloy strip is 80%, immediately performing water quenching treatment on the hot-rolled alloy strip, and rapidly cooling the hot-rolled alloy strip to room temperature;
(4) Solution treatment: under the protection of pure argon, placing the hot rolled alloy strip into a heat treatment furnace for solution treatment, wherein the solution temperature is 1050 ℃, the heat preservation time is 45 minutes, then immediately performing water quenching treatment on the alloy strip, and rapidly cooling to room temperature;
(5) Compression set: the alloy strip after the solution treatment was subjected to surface scale removal and then to 12 press-molding deformations at room temperature. Wherein, the groove height and the groove width of an upper die groove of a groove pressing die (tooth die) are 5mm, and the tooth height and the tooth width of a lower die convex tooth are all 5mm; the compression molding deformation step comprises the following steps: (1) placing the alloy strip with the surface oxide skin removed in the middle of a groove die, and performing die pressing deformation on the involution Jin Daicai through mutual engagement of an upper die groove and a lower die convex tooth; (2) and then flattening the deformed alloy strip by flattening die pressing: (3) placing the alloy strip in the middle of a groove die, moving the placement position by 1 tooth width distance along the transverse direction of the convex teeth relative to the last placement position, and then performing die pressing deformation on the alloy strip Jin Daicai to deform the part of the alloy strip which is not deformed; (4) then flattening the deformed alloy strip by flattening die; (5) rotating the alloy strip horizontally (clockwise or anticlockwise) by 90 degrees, and repeating the steps (1) (2) (3) (4);
(6) Stage aging treatment: putting the alloy strip subjected to die pressing deformation into a heat treatment furnace, and carrying out stage aging under the protection of pure argon, wherein the aging process is as follows: firstly, heating to 250 ℃ from room temperature at a speed of 5 ℃/min, and preserving heat for 60 minutes; then, heating to 450 ℃ at a speed of 5 ℃/min, and preserving heat for 100 min; then, the temperature is reduced to 230 ℃ at a speed of 5 ℃/min, and the temperature is kept for 45 minutes; finally, cooling to room temperature in an air cooling mode;
(7) And (3) rolling at room temperature: rolling the alloy strip subjected to the stage aging treatment at room temperature, wherein the total rolling deformation is 80%;
(8) And (3) variable temperature aging treatment: placing the alloy strip rolled at room temperature into a heat treatment furnace, and carrying out variable-temperature ageing treatment under the protection of pure argon, wherein the ageing process is as follows: firstly, heating to 340 ℃ from room temperature at a speed of 5 ℃/min, and preserving heat for 2 min; then, the temperature is increased to 480 ℃ at a speed of 5 ℃ per minute, and the temperature is kept for 30 minutes; finally, cooling to room temperature in an air cooling mode to obtain a final sample;
the hardness of the obtained copper alloy material is 206HV, the yield strength is 615MPa, the tensile strength is 634MPa, the elongation after breaking is about 10%, the softening temperature is 694 ℃, and the conductivity is 86% IACS.
Example 3
The alloy comprises the following components in percentage by mass: 1.00wt% Cr, 0.10wt% Zr, 0.10wt% Ge, 0.04wt% Nb, and the balance Cu.
The preparation method comprises the following steps:
(1) Alloy casting: placing the raw materials into crucible of induction furnace, and vacuumizing to 3.0X10 -3 Pa, then 1.1X10 g of 5 Smelting under the protection of pure argon (the volume fraction of Ar is more than or equal to 99.99%) of Pa, heating the alloy melt to 1220 ℃ after the solid is completely melted to form alloy melt, standing for 10 minutes, casting into a graphite mold, cooling, and opening the mold to take out alloy cast ingots;
(2) Homogenizing: under the protection of pure argon, placing the obtained cast ingot into a heat treatment furnace for homogenization treatment, wherein the homogenization treatment temperature is 930 ℃, the heat preservation time is 5 hours, and then cooling to room temperature along with the furnace;
(3) And (3) hot rolling: heating the homogenized alloy material to 720 ℃ and preserving heat for 8 minutes, then taking out and rapidly hot-rolling the alloy material into a strip, wherein the total deformation of the hot-rolled alloy strip is 75%, immediately performing water quenching treatment on the hot-rolled alloy strip, and rapidly cooling the hot-rolled alloy strip to room temperature;
(4) Solution treatment: under the protection of pure argon, placing the hot rolled alloy strip into a heat treatment furnace for solution treatment at 900 ℃ for 30 minutes, immediately performing water quenching treatment on the alloy strip, and rapidly cooling to room temperature;
(5) Compression set: the alloy strip after the solution treatment was subjected to surface scale removal and then to press-molding deformation at room temperature 16 times. Wherein, the groove height and the groove width of an upper die groove of a used groove pressing die (tooth die) are 4mm, and the tooth height and the tooth width of a lower die convex tooth are all 4mm; the compression molding deformation step comprises the following steps: (1) placing the alloy strip with the surface oxide skin removed in the middle of a groove die, and performing die pressing deformation on the involution Jin Daicai through mutual engagement of an upper die groove and a lower die convex tooth; (2) and then flattening the deformed alloy strip by flattening die pressing: (3) placing the alloy strip in the middle of a groove die, moving the placement position by 1 tooth width distance along the transverse direction of the convex teeth relative to the last placement position, and then performing die pressing deformation on the alloy strip Jin Daicai to deform the part of the alloy strip which is not deformed; (4) then flattening the deformed alloy strip by flattening die; (5) rotating the alloy strip horizontally (clockwise or anticlockwise) by 90 degrees, and repeating the steps (1) (2) (3) (4);
(6) Stage aging treatment: putting the alloy strip subjected to die pressing deformation into a heat treatment furnace, and carrying out stage aging under the protection of pure argon, wherein the aging process is as follows: firstly, heating to 200 ℃ from room temperature at a speed of 10 ℃/min, and preserving heat for 60 minutes; then, heating to 420 ℃ at a speed of 10 ℃/min, and preserving heat for 120 min; then, the temperature is reduced to 180 ℃ at the speed of 10 ℃/min, and the temperature is kept for 30 min; finally, cooling to room temperature in an air cooling mode;
(7) And (3) rolling at room temperature: rolling the alloy strip subjected to the stage aging treatment at room temperature, wherein the total rolling deformation is 75%;
(8) And (3) variable temperature aging treatment: placing the alloy strip rolled at room temperature into a heat treatment furnace, and carrying out variable-temperature ageing treatment under the protection of pure argon, wherein the ageing process is as follows: firstly, heating to 330 ℃ from room temperature at a speed of 12 ℃/min, and preserving heat for 1.5 min; then, the temperature is increased to 420 ℃ at a speed of 12 ℃/min, and the temperature is kept for 30 min; finally, cooling to room temperature in an air cooling mode to obtain a final sample.
The hardness of the obtained copper alloy material is 223HV, the yield strength is 643MPa, the tensile strength is 675MPa, the elongation after break is about 9%, the softening temperature is 687 ℃, and the conductivity is 84% IACS.
Example 4
The alloy comprises the following components in percentage by mass: 0.90wt% Cr, 0.20wt% Zr, 0.25wt% Ge, 0.03wt% Nb, and the balance Cu.
The preparation method comprises the following steps:
(1) Alloy casting: placing the raw materials into crucible of induction furnace, and vacuumizing to 3.0X10 -3 Pa, then 1.1X10 g of 5 Smelting under the protection of pure argon (the volume fraction of Ar is more than or equal to 99.99%) of Pa, heating the alloy melt to 1280 ℃ after the solid is completely melted to form alloy melt, standing for 10 minutes, casting into a graphite mold, cooling, and opening the mold to take out alloy cast ingots;
(2) Homogenizing: under the protection of pure argon, placing the obtained cast ingot into a heat treatment furnace for homogenization treatment, wherein the homogenization treatment temperature is 950 ℃, the heat preservation time is 6 hours, and then cooling to room temperature along with the furnace;
(3) And (3) hot rolling: heating the homogenized alloy material to 820 ℃ and preserving heat for 5 minutes, then taking out and rapidly hot-rolling the alloy material into a strip, wherein the total deformation of the hot-rolled alloy strip is 85%, immediately performing water quenching treatment on the hot-rolled alloy strip, and rapidly cooling the hot-rolled alloy strip to room temperature;
(4) Solution treatment: under the protection of pure argon, placing the hot rolled alloy strip into a heat treatment furnace for solution treatment at 900 ℃ for 60 minutes, immediately performing water quenching treatment on the alloy strip, and rapidly cooling to room temperature;
(5) Compression set: the alloy strip after the solution treatment was subjected to surface scale removal and then to press-molding deformation at room temperature for 20 times. Wherein, the groove height and the groove width of an upper die groove of a used groove pressing die (tooth die) are 8mm, and the tooth height and the tooth width of a lower die convex tooth are all 8mm; the compression molding deformation step comprises the following steps: (1) placing the alloy strip with the surface oxide skin removed in the middle of a groove die, and performing die pressing deformation on the involution Jin Daicai through mutual engagement of an upper die groove and a lower die convex tooth; (2) and then flattening the deformed alloy strip by flattening die pressing: (3) placing the alloy strip in the middle of a groove die, moving the placement position by 1 tooth width distance along the transverse direction of the convex teeth relative to the last placement position, and then performing die pressing deformation on the alloy strip Jin Daicai to deform the part of the alloy strip which is not deformed; (4) then flattening the deformed alloy strip by flattening die; (5) rotating the alloy strip horizontally (clockwise or anticlockwise) by 90 degrees, and repeating the steps (1) (2) (3) (4);
(6) Stage aging treatment: putting the alloy strip subjected to die pressing deformation into a heat treatment furnace, and carrying out stage aging under the protection of pure argon, wherein the aging process is as follows: firstly, heating the mixture from room temperature to 230 ℃ at a speed of 12 ℃/min, and preserving the heat for 30 min; then, heating to 430 ℃ at a speed of 12 ℃/min, and preserving heat for 90 min; then, the temperature is reduced to 150 ℃ at the speed of 12 ℃/min, and the temperature is kept for 45 min; finally, cooling to room temperature in an air cooling mode;
(7) And (3) rolling at room temperature: rolling the alloy strip subjected to the stage aging treatment at room temperature, wherein the total rolling deformation is 80%;
(8) And (3) variable temperature aging treatment: placing the alloy strip rolled at room temperature into a heat treatment furnace, and carrying out variable-temperature ageing treatment under the protection of pure argon, wherein the ageing process is as follows: firstly, heating to 320 ℃ from room temperature at a speed of 15 ℃/min, and preserving heat for 1 min; then, the temperature is increased to 450 ℃ at a speed of 15 ℃/min, and the temperature is kept for 20 min; finally, cooling to room temperature in an air cooling mode to obtain a final sample.
The hardness of the obtained copper alloy material is 238HV, the yield strength is 678MPa, the tensile strength is 696MPa, the elongation after breaking is about 12%, the softening temperature is 706 ℃, and the conductivity is 87% IACS.
Comparative example 1
The alloy comprises the following components in percentage by mass: 0.80wt% Cr, 0.10wt% Zr, 0.15wt% Ge, 0.01wt% Nb, and the balance Cu.
The preparation method comprises the following steps:
(1) Alloy casting: placing the raw materials into crucible of induction furnace, and vacuumizing to 3.0X10 -3 Pa, then 1.1X10 g of 5 Smelting pure argon (the volume fraction of Ar is more than or equal to 99.99%) of Pa under the protection of pure argon, heating the alloy melt to 1250 ℃ after the solid is completely melted to form alloy melt, standing for 10 minutes, casting into a graphite mold, cooling, and opening the mold to take out an alloy cast ingot;
(2) Homogenizing: under the protection of pure argon, placing the obtained cast ingot into a heat treatment furnace for homogenization treatment, wherein the homogenization treatment temperature is 900 ℃, the heat preservation time is 6 hours, and then cooling to room temperature along with the furnace;
(3) And (3) hot rolling: heating the homogenized alloy material to 750 ℃ and preserving heat for 5 minutes, then taking out and rapidly hot-rolling the alloy material into a strip, wherein the total deformation of the hot-rolled alloy strip is 80%, immediately performing water quenching treatment on the hot-rolled alloy strip, and rapidly cooling the hot-rolled alloy strip to room temperature;
(4) Solution treatment: under the protection of pure argon, placing the hot rolled alloy strip into a heat treatment furnace for solution treatment, wherein the solution temperature is 950 ℃, the heat preservation time is 30 minutes, then immediately performing water quenching treatment on the alloy strip, and rapidly cooling to room temperature;
(5) Stage aging treatment: putting the alloy strip subjected to die pressing deformation into a heat treatment furnace, and carrying out stage aging under the protection of pure argon, wherein the aging process is as follows: firstly, heating to 200 ℃ from room temperature at a speed of 10 ℃/min, and preserving heat for 60 minutes; then, heating to 430 ℃ at a speed of 10 ℃/min, and preserving heat for 120 min; then, the temperature is reduced to 150 ℃ at the speed of 10 ℃/min, and the temperature is kept for 60 minutes; finally, cooling to room temperature in an air cooling mode;
(6) And (3) rolling at room temperature: rolling the alloy strip subjected to the stage aging treatment at room temperature, wherein the total rolling deformation is 85%;
(7) And (3) variable temperature aging treatment: placing the alloy strip rolled at room temperature into a heat treatment furnace, and carrying out variable-temperature ageing treatment under the protection of pure argon, wherein the ageing process is as follows: firstly, heating to 300 ℃ from room temperature at a speed of 10 ℃/min, and preserving heat for 1 min; then, the temperature is increased to 430 ℃ at the speed of 10 ℃/min, and the temperature is kept for 30 min; finally, cooling to room temperature in an air cooling mode to obtain a final sample.
The hardness of the obtained copper alloy material is 165HV, the yield strength is 497MPa, the tensile strength is 519MPa, the elongation after breaking is about 6%, the softening temperature is 535 ℃, and the conductivity is 69% IACS.
That is, it is proved that the molding deformation has an obvious effect on the comprehensive performance of the alloy, the mechanical property and the high-temperature softening resistance of the copper alloy material prepared without the molding deformation treatment are obviously deteriorated, and meanwhile, the conductivity is also obviously reduced.
Fig. 7 is a metallographic structure diagram of the copper alloy material obtained in this comparative example. As can be seen from the figure, the crystal grains are coarse and uneven in size, and the grain size is about 8-40 mu m.
Fig. 8 is a transmission electron microscope image of the copper alloy material produced in this comparative example. From the figure, we can see that the number of precipitated phases is smaller and the size is larger.
Comparative example 2
The alloy comprises the following components in percentage by mass: 1.30wt% Cr, 0.40wt% Zr, 0.50wt% Ge, 0.10wt% Nb, and the balance Cu.
The preparation method comprises the following steps:
(1) Alloy casting: placing raw materials into a crucible of an induction furnace, vacuumizing to 3.0X10-3 Pa, then introducing pure argon (the volume fraction of Ar is more than or equal to 99.99%) of 1.1X105 Pa, smelting under the protection of the pure argon (the volume fraction of Ar is more than or equal to 99.99%), forming an alloy melt after the solid is completely melted, then heating the alloy melt to 1340 ℃, standing for 10 minutes, casting into a graphite mold, cooling, and opening the mold to take out an alloy cast ingot;
(2) Homogenizing: under the protection of pure argon, placing the obtained cast ingot into a heat treatment furnace for homogenization treatment, wherein the homogenization treatment temperature is 980 ℃, the heat preservation time is 7 hours, and then cooling to room temperature along with the furnace;
(3) And (3) hot rolling: heating the homogenized alloy material to 850 ℃ and preserving heat for 5 minutes, then taking out and rapidly hot-rolling the alloy material into a strip, wherein the total deformation of the hot-rolled alloy strip is 80%, immediately performing water quenching treatment on the hot-rolled alloy strip, and rapidly cooling the hot-rolled alloy strip to room temperature;
(4) Solution treatment: under the protection of pure argon, placing the hot rolled alloy strip into a heat treatment furnace for solution treatment, wherein the solution temperature is 1050 ℃, the heat preservation time is 45 minutes, then immediately performing water quenching treatment on the alloy strip, and rapidly cooling to room temperature;
(5) Compression set: the alloy strip after the solution treatment was subjected to surface scale removal and then to 12 press-molding deformations at room temperature. Wherein, the groove height and the groove width of an upper die groove of a groove pressing die (tooth die) are 5mm, and the tooth height and the tooth width of a lower die convex tooth are all 5mm; the compression molding deformation step comprises the following steps: (1) placing the alloy strip with the surface oxide skin removed in the middle of a groove die, and performing die pressing deformation on the involution Jin Daicai through mutual engagement of an upper die groove and a lower die convex tooth; (2) and then flattening the deformed alloy strip by flattening die pressing: (3) placing the alloy strip in the middle of a groove die, moving the placement position by 1 tooth width distance along the transverse direction of the convex teeth relative to the last placement position, and then performing die pressing deformation on the alloy strip Jin Daicai to deform the part of the alloy strip which is not deformed; (4) then flattening the deformed alloy strip by flattening die; (5) rotating the alloy strip horizontally (clockwise or anticlockwise) by 90 degrees, and repeating the steps (1) (2) (3) (4);
(6) Stage aging treatment: putting the alloy strip subjected to die pressing deformation into a heat treatment furnace, and carrying out stage aging under the protection of pure argon, wherein the aging process is as follows: firstly, heating to 250 ℃ from room temperature at a speed of 5 ℃/min, and preserving heat for 60 minutes; then, heating to 450 ℃ at a speed of 5 ℃/min, and preserving heat for 100 min; then, the temperature is reduced to 230 ℃ at a speed of 5 ℃/min, and the temperature is kept for 45 minutes; finally, cooling to room temperature in an air cooling mode;
(7) And (3) rolling at room temperature: rolling the alloy strip subjected to the stage aging treatment at room temperature, wherein the total rolling deformation is 80%;
(8) And (3) variable temperature aging treatment: placing the alloy strip rolled at room temperature into a heat treatment furnace, and carrying out variable-temperature ageing treatment under the protection of pure argon, wherein the ageing process is as follows: firstly, heating to 340 ℃ from room temperature at a speed of 5 ℃/min, and preserving heat for 2 min; then, the temperature is increased to 480 ℃ at a speed of 5 ℃ per minute, and the temperature is kept for 30 minutes; finally, cooling to room temperature in an air cooling mode to obtain a final sample;
the hardness of the obtained copper alloy material is 192HV, the yield strength is 571MPa, the tensile strength is 590MPa, the elongation after breaking is about 3%, the softening temperature is 600 ℃, and the conductivity is 71% IACS.
That is, it has been demonstrated that when the content of Cr, zr, ge, nb element in the alloy component is higher than the defined range, the mechanical properties and high-temperature softening resistance of the copper alloy material obtained therefrom are remarkably deteriorated, and at the same time, the electrical conductivity is remarkably lowered.
Comparative example 3
The alloy comprises the following components in percentage by mass: 0.70wt% Cr, 0.05wt% Zr, 0.05wt% Ge, 0.005wt% Nb, and the balance Cu.
The preparation method comprises the following steps:
(1) Alloy casting: placing the raw materials into crucible of induction furnace, and vacuumizing to 3.0X10 -3 Pa, then 1.1X10 g of 5 Smelting under the protection of pure argon (the volume fraction of Ar is more than or equal to 99.99%) of Pa, heating the alloy melt to 1220 ℃ after the solid is completely melted to form alloy melt, standing for 10 minutes, casting into a graphite mold, cooling, and opening the mold to take out alloy cast ingots;
(2) Homogenizing: under the protection of pure argon, placing the obtained cast ingot into a heat treatment furnace for homogenization treatment, wherein the homogenization treatment temperature is 930 ℃, the heat preservation time is 5 hours, and then cooling to room temperature along with the furnace;
(3) And (3) hot rolling: heating the homogenized alloy material to 720 ℃ and preserving heat for 8 minutes, then taking out and rapidly hot-rolling the alloy material into a strip, wherein the total deformation of the hot-rolled alloy strip is 75%, immediately performing water quenching treatment on the hot-rolled alloy strip, and rapidly cooling the hot-rolled alloy strip to room temperature;
(4) Solution treatment: under the protection of pure argon, placing the hot rolled alloy strip into a heat treatment furnace for solution treatment at 900 ℃ for 30 minutes, immediately performing water quenching treatment on the alloy strip, and rapidly cooling to room temperature;
(5) Compression set: the alloy strip after the solution treatment was subjected to surface scale removal and then to press-molding deformation at room temperature 16 times. Wherein, the groove height and the groove width of an upper die groove of a used groove pressing die (tooth die) are 4mm, and the tooth height and the tooth width of a lower die convex tooth are all 4mm; the compression molding deformation step comprises the following steps: (1) placing the alloy strip with the surface oxide skin removed in the middle of a groove die, and performing die pressing deformation on the involution Jin Daicai through mutual engagement of an upper die groove and a lower die convex tooth; (2) and then flattening the deformed alloy strip by flattening die pressing: (3) placing the alloy strip in the middle of a groove die, moving the placement position by 1 tooth width distance along the transverse direction of the convex teeth relative to the last placement position, and then performing die pressing deformation on the alloy strip Jin Daicai to deform the part of the alloy strip which is not deformed; (4) then flattening the deformed alloy strip by flattening die; (5) rotating the alloy strip horizontally (clockwise or anticlockwise) by 90 degrees, and repeating the steps (1) (2) (3) (4);
(6) Stage aging treatment: putting the alloy strip subjected to die pressing deformation into a heat treatment furnace, and carrying out stage aging under the protection of pure argon, wherein the aging process is as follows: firstly, heating to 200 ℃ from room temperature at a speed of 10 ℃/min, and preserving heat for 60 minutes; then, heating to 420 ℃ at a speed of 10 ℃/min, and preserving heat for 120 min; then, the temperature is reduced to 180 ℃ at the speed of 10 ℃/min, and the temperature is kept for 30 min; finally, cooling to room temperature in an air cooling mode;
(7) And (3) rolling at room temperature: rolling the alloy strip subjected to the stage aging treatment at room temperature, wherein the total rolling deformation is 75%;
(8) And (3) variable temperature aging treatment: placing the alloy strip rolled at room temperature into a heat treatment furnace, and carrying out variable-temperature ageing treatment under the protection of pure argon, wherein the ageing process is as follows: firstly, heating to 330 ℃ from room temperature at a speed of 12 ℃/min, and preserving heat for 1.5 min; then, the temperature is increased to 420 ℃ at a speed of 12 ℃/min, and the temperature is kept for 30 min; finally, cooling to room temperature in an air cooling mode to obtain a final sample.
The hardness of the obtained copper alloy material is 155HV, the yield strength is 466MPa, the tensile strength is 487MPa, the elongation after breaking is about 4%, the softening temperature is 554 ℃, and the conductivity is 75% IACS.
That is, it has been demonstrated that when the content of Cr, zr, ge, nb element in the alloy composition is below the defined range, the mechanical properties and high-temperature softening resistance of the copper alloy material obtained therefrom are significantly deteriorated, and at the same time, the electrical conductivity is significantly reduced.
Comparative example 4
The alloy comprises the following components in percentage by mass: 0.90wt% Cr, 0.20wt% Zr, 0.25wt% Ge, 0.03wt% Nb, and the balance Cu.
The preparation method comprises the following steps:
(1) Alloy casting: placing the raw materials into crucible of induction furnace, and vacuumizing to 3.0X10 -3 Pa, then 1.1X10 g of 5 Smelting under the protection of pure argon (the volume fraction of Ar is more than or equal to 99.99%) of Pa, heating the alloy melt to 1280 ℃ after the solid is completely melted to form alloy melt, standing for 10 minutes, casting into a graphite mold, cooling, and opening the mold to take out alloy cast ingots;
(2) Homogenizing: under the protection of pure argon, placing the obtained cast ingot into a heat treatment furnace for homogenization treatment, wherein the homogenization treatment temperature is 950 ℃, the heat preservation time is 6 hours, and then cooling to room temperature along with the furnace;
(3) And (3) hot rolling: heating the homogenized alloy material to 820 ℃ and preserving heat for 5 minutes, then taking out and rapidly hot-rolling the alloy material into a strip, wherein the total deformation of the hot-rolled alloy strip is 85%, immediately performing water quenching treatment on the hot-rolled alloy strip, and rapidly cooling the hot-rolled alloy strip to room temperature;
(4) Solution treatment: under the protection of pure argon, placing the hot rolled alloy strip into a heat treatment furnace for solution treatment at 900 ℃ for 60 minutes, immediately performing water quenching treatment on the alloy strip, and rapidly cooling to room temperature;
(5) Compression set: the alloy strip after the solution treatment was subjected to surface scale removal and then to press-molding deformation at room temperature for 20 times. Wherein, the groove height and the groove width of an upper die groove of a used groove pressing die (tooth die) are 8mm, and the tooth height and the tooth width of a lower die convex tooth are all 8mm; the compression molding deformation step comprises the following steps: (1) placing the alloy strip with the surface oxide skin removed in the middle of a groove die, and performing die pressing deformation on the involution Jin Daicai through mutual engagement of an upper die groove and a lower die convex tooth; (2) and then flattening the deformed alloy strip by flattening die pressing: (3) placing the alloy strip in the middle of a groove die, moving the placement position by 1 tooth width distance along the transverse direction of the convex teeth relative to the last placement position, and then performing die pressing deformation on the alloy strip Jin Daicai to deform the part of the alloy strip which is not deformed; (4) then flattening the deformed alloy strip by flattening die; (5) rotating the alloy strip horizontally (clockwise or anticlockwise) by 90 degrees, and repeating the steps (1) (2) (3) (4);
(6) And (3) constant-temperature aging treatment: placing the alloy strip subjected to die pressing deformation into a heat treatment furnace, carrying out constant-temperature aging under the protection of pure argon, wherein the aging temperature is 460 ℃, the heat preservation time is 2 hours, then immediately carrying out water quenching treatment on the alloy strip, and rapidly cooling to room temperature;
(7) And (3) rolling at room temperature: rolling the alloy strip subjected to the stage aging treatment at room temperature, wherein the total rolling deformation is 80%;
(8) And (3) constant-temperature aging treatment: and (3) placing the alloy strip rolled at room temperature into a heat treatment furnace, performing constant-temperature aging treatment under the protection of pure argon, wherein the aging temperature is 450 ℃, the heat preservation time is 2 hours, then immediately performing water quenching treatment on the alloy strip, and rapidly cooling to room temperature.
The hardness of the obtained copper alloy material is 179HV, the yield strength is 540MPa, the tensile strength is 559MPa, the elongation after breaking is about 6%, the softening temperature is 582 ℃, and the conductivity is 77% IACS.
That is, when the stage aging and the variable temperature aging are changed into constant temperature aging, the mechanical property and the high temperature softening resistance of the prepared copper alloy material are obviously deteriorated, and meanwhile, the conductivity is obviously reduced.
The above examples and comparative examples are only preferred examples of the present invention, and it should not be construed that the present invention is limited thereto, and all equivalent changes and modifications made according to the claims of the present invention shall fall within the scope of the present invention.
Claims (5)
1. A Cu-Cr-Zr alloy for a high-current electric connector is characterized in that the Cu-Cr-Zr alloy comprises the following components in percentage by mass as 100 percent: 0.80-1.20wt% of Cr, 0.10-0.30wt% of Zr, 0.10-0.30wt% of Ge, 0.01-0.06wt% of Nb and the balance of Cu; further, the sum of the mass percentages of Cr and Zr is 0.90 to 1.50wt%, and the sum of the mass percentages of Ge and Nb is 0.11 to 0.36wt%.
2. The method for preparing a Cu-Cr-Zr alloy for use in high current electrical connectors according to claim 1, comprising the steps of:
(1) Alloy casting: under the protection of pure argon, smelting raw materials in an induction furnace, heating the obtained alloy melt to above 1200 ℃, standing for 10 minutes, casting into a die, and cooling to room temperature to obtain an alloy cast ingot;
(2) Homogenizing: under the protection of pure argon, placing the obtained cast ingot into a heat treatment furnace for homogenization treatment, wherein the homogenization treatment temperature is 900-980 ℃, the heat preservation time is 5-8 hours, and then cooling to room temperature along with the furnace;
(3) And (3) hot rolling: placing the homogenized alloy material into a heat treatment furnace, heating to 700-850 ℃, preserving heat for 5-10 minutes, taking out and rapidly hot-rolling the alloy material into a strip, wherein the total deformation of hot rolling is 60-85%, immediately performing water quenching treatment on the hot-rolled alloy strip, and rapidly cooling to room temperature;
(4) Solution treatment: under the protection of pure argon, placing the hot rolled alloy strip into a heat treatment furnace for solution treatment, wherein the solution temperature is 900-1050 ℃, the heat preservation time is 30-60 minutes, then immediately performing water quenching treatment on the alloy strip, and rapidly cooling to room temperature;
(5) Compression set: removing surface oxide skin of the alloy strip subjected to solution treatment, and then performing die pressing deformation for 8-20 times at room temperature; the die pressing deformation die comprises a groove die and a flattening die, wherein the upper die of the groove die is provided with a groove, the lower die is provided with convex teeth, the convex teeth and the groove can be mutually meshed, the groove height and the groove width of the groove of the upper die are equal to the tooth height and the tooth width of the convex teeth of the lower die and are 3-10 mm, and the groove height and the tooth width of the convex teeth of the upper die are distributed at equal intervals;
(6) Stage aging treatment: putting the alloy strip subjected to die pressing deformation into a heat treatment furnace, and carrying out stage aging under the protection of pure argon, wherein the aging process is as follows: firstly, heating the temperature to 200-250 ℃ from room temperature at a speed of 5-15 ℃/min, and preserving heat for 30-60 min; then, heating to 400-460 ℃ at a speed of 5-15 ℃/min, and preserving heat for 90-120 min; then, cooling to 150-250 ℃ at a speed of 5-15 ℃/min, and preserving heat for 30-60 min; finally, cooling to room temperature in an air cooling mode;
(7) And (3) rolling at room temperature: rolling the alloy strip subjected to the stage aging treatment at room temperature, wherein the total rolling deformation is 50% -90%;
(8) And (3) variable temperature aging treatment: placing the alloy strip rolled at room temperature into a heat treatment furnace, and carrying out variable-temperature ageing treatment under the protection of pure argon, wherein the ageing process is as follows: firstly, heating the temperature from room temperature to 300-350 ℃ at a speed of 5-15 ℃/min, and preserving heat for 1-2 min; then, heating to 400-500 ℃ at a speed of 5-15 ℃/min, and preserving heat for 15-30 min; finally, cooling to room temperature in an air cooling mode to obtain a final sample.
3. The preparation method according to claim 2, wherein the raw materials are pure copper blocks with a purity of not less than 99.9wt%, a Cu-Cr intermediate alloy with a purity of 5-10 wt%, a Cu-Zr intermediate alloy with a purity of 40-60 wt%, a Cu-Ge intermediate alloy with a purity of 10-20 wt% and a Cu-Nb intermediate alloy with a purity of 0.5-1.0 wt%.
4. The method according to claim 2, wherein the volume fraction of Ar in the pure argon is 99.99% or more.
5. The method according to claim 2, wherein the specific operation steps of the compression molding comprises: (1) placing the alloy strip with the surface oxide skin removed in the middle of a groove die, and performing die pressing deformation on the involution Jin Daicai through mutual engagement of an upper die groove and a lower die convex tooth; (2) and then flattening the deformed alloy strip by flattening die pressing: (3) placing the alloy strip in the middle of a groove die, moving the placing position by an odd number of tooth width distances along the transverse direction of the convex teeth relative to the last placing position, and then performing die pressing deformation on the alloy strip Jin Daicai to deform the part of the alloy strip which is not deformed; (4) then flattening the deformed alloy strip by flattening die; (5) the alloy strip is rotated horizontally by 90 degrees, and the steps (1) (2) (3) (4) are repeated.
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