CN113564408B - High-strength high-conductivity rare earth copper alloy Cu-Cr-Zr-Y and preparation method thereof - Google Patents

High-strength high-conductivity rare earth copper alloy Cu-Cr-Zr-Y and preparation method thereof Download PDF

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CN113564408B
CN113564408B CN202110862597.0A CN202110862597A CN113564408B CN 113564408 B CN113564408 B CN 113564408B CN 202110862597 A CN202110862597 A CN 202110862597A CN 113564408 B CN113564408 B CN 113564408B
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zirconium
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刘慧敏
乔振兴
峰山
新巴雅尔
王俊
史志铭
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Inner Mongolia University of Technology
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Abstract

The invention discloses a high-strength high-conductivity rare earth copper alloy Cu-Cr-Zr-Y and a preparation method thereof, wherein the preparation method comprises the following steps: step (1): placing pure copper, a chromium raw material, a zirconium raw material and an yttrium raw material in a medium-frequency induction smelting furnace, smelting in an atmospheric environment, and obtaining a rare earth copper chromium zirconium alloy ingot after smelting; step (2): carrying out solid solution treatment on the rare earth copper chromium zirconium alloy ingot to obtain a rare earth copper chromium zirconium alloy blank; and (3) performing rolling and aging alternate treatment on the rare earth copper chromium zirconium alloy blank to obtain the high-strength high-conductivity rare earth copper alloy Cu-Cr-Zr-Y. The high-strength high-conductivity rare earth copper alloy Cu-Cr-Zr-Y is prepared by the method. The rare earth copper alloy prepared by the invention has excellent performance, the tensile strength exceeds 700MPa, the relative conductivity is higher than 80% IACS, the requirements of the industry on the performance of the high-strength high-conductivity copper alloy can be met, and the advanced technical requirements of high performance can be met; meanwhile, the preparation and processing process flow is also beneficial to the industrial large-scale production of the high-strength high-conductivity copper-chromium-zirconium alloy.

Description

High-strength high-conductivity rare earth copper alloy Cu-Cr-Zr-Y and preparation method thereof
Technical Field
The invention relates to the technical field of rare earth copper alloy. In particular to a high-strength high-conductivity rare earth copper alloy Cu-Cr-Zr-Y and a preparation method thereof.
Background
Copper and copper alloys are widely used in large scale integrated circuit lead frames and high speed track contact wires due to their good electrical and thermal conductivity, high strength and good plasticity. With the rapid development of the electronic industry and the high-speed railway in China, higher requirements are put forward on the use performance of the copper alloy, and the copper alloy which is isotropic, has tensile strength of over 600MPa and relative conductivity of more than 80 percent ICSA and can meet the large-scale production is expected to be obtained in engineering. In Japan, a method for producing the copper-chromium-zirconium alloy by adopting a non-vacuum production technology has been developed, several high-strength and high-conductivity copper-chromium-zirconium series lead frame materials have been successfully developed, and the industrialization scale is formed. Currently, representative copper-chromium-zirconium alloys produced by adopting a non-vacuum production technology in Japan are OMCL-1 and NK120, wherein the tensile strength and the electric conductivity of the OMCL-1 alloy are 592MPa and 82.7 percent IACS respectively; the tensile strength and the electric conductivity of the NK120 alloy are 580MPa and 80% IACS respectively. The production application and actual service performance of domestic copper-chromium-zirconium alloy still have a large gap with international high-strength high-conductivity copper-chromium-zirconium copper alloy.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to provide a high-strength high-conductivity rare earth copper alloy Cu-Cr-Zr-Y and a preparation method thereof, so as to solve the problem that the high strength and the high conductivity of the common copper-chromium-zirconium alloy are difficult to coexist, provide a high-strength high-conductivity copper alloy which can meet the advanced technical requirements of high performance, and provide a method which is beneficial to the industrial large-scale production of the high-strength high-conductivity copper-chromium-zirconium alloy.
In order to solve the technical problems, the invention provides the following technical scheme:
a preparation method of a high-strength high-conductivity rare earth copper alloy Cu-Cr-Zr-Y comprises the following steps:
step (1): placing pure copper, a chromium raw material, a zirconium raw material and an yttrium raw material in a medium-frequency induction smelting furnace, smelting in an atmospheric environment, and obtaining a rare earth copper chromium zirconium alloy ingot after smelting;
step (2): carrying out solid solution treatment on the rare earth copper chromium zirconium alloy ingot to obtain a rare earth copper chromium zirconium alloy blank;
and (3) performing rolling and aging alternate treatment on the rare earth copper chromium zirconium alloy blank to obtain the high-strength high-conductivity rare earth copper alloy Cu-Cr-Zr-Y.
In the preparation method of the high-strength high-conductivity rare earth copper alloy Cu-Cr-Zr-Y, the mass percentages of chromium and zirconium are respectively 0.55wt% and 0.18wt%, and the mass percentage of yttrium is 0.15 wt%. Multiple tests show that the mechanical property of the alloy is obviously improved along with the increase of the mass percent of the chromium and zirconium elements, but solute atoms (chromium atoms and zirconium atoms) have certain damage to the electrical property of the alloy, while the mass percent of the chromium and zirconium elements in the rare earth copper alloy is respectively controlled to be 0.55wt% and 0.18wt%, so that the prepared high-strength and high-conductivity rare earth copper alloy Cu-Cr-Zr-Y has better electrical property on the premise of better mechanical property. Through a plurality of tests, when the mass fraction of the rare earth Y in the rare earth copper alloy Cu-Cr-Zr-Y is 0.15wt%, the grain structure of the alloy consists of fine and uniform equiaxial grains, and the alloy has good mechanical properties at the moment.
In the step (1), the purity of pure copper is greater than or equal to 99.95wt%, the chromium raw material is a copper-chromium intermediate alloy, the zirconium raw material is a copper-zirconium intermediate alloy, and the yttrium raw material is a copper-yttrium intermediate alloy. The reason why the master alloy is selected as the chromium raw material, the zirconium raw material, and the yttrium raw material without using the metal simple substance in the present invention is that: the metal simple substance has high cost and large burning loss rate, the cost of the intermediate alloy is lower, and the impurity content of the three intermediate alloys can be ignored; in addition, the addition of the intermediate alloy can make the elements in the alloy more easily and uniformly dispersed in the melt.
According to the preparation method of the high-strength high-conductivity rare earth copper alloy Cu-Cr-Zr-Y, the mass fraction of chromium in the copper-chromium intermediate alloy is 10 wt%; in the copper-zirconium intermediate alloy, the mass fraction of zirconium is 40 wt%; in the copper-yttrium master alloy, the mass fraction of yttrium is 20 wt%.
In the step (1), the smelting method comprises the following steps:
step (1-1): adding pure copper into a graphite crucible, and heating along with the furnace to melt the pure copper to obtain a copper melt;
step (1-2): continuously heating the copper melt, then sequentially adding the copper-chromium intermediate alloy, the copper-zirconium intermediate alloy and the copper-yttrium intermediate alloy into the copper melt to melt the copper-chromium intermediate alloy, the copper-zirconium intermediate alloy and the copper-yttrium intermediate alloy, and continuously heating and preserving heat to obtain a mixed melt;
step (1-3): and casting the mixed melt into a preheated graphite mold by adopting a near liquidus casting method to obtain the rare earth copper-chromium-zirconium alloy cast ingot.
In the step (1), the smelting method comprises the following steps:
step (1-1): adding pure copper into a graphite crucible, and heating along with the furnace to melt the pure copper to obtain a copper melt; the graphite crucible has better heat resistance, and compared with other crucibles, the graphite crucible has lower cost and does not have the possibility of reaction of C element and other alloy elements in the temperature range of the smelting process.
Step (1-2): continuing to heat the copper melt to 1240-1260 ℃, then sequentially adding the copper-chromium intermediate alloy, the copper-zirconium intermediate alloy and the copper-yttrium intermediate alloy into the copper melt to melt the copper-chromium intermediate alloy, the copper-zirconium intermediate alloy and the copper-yttrium intermediate alloy, continuing to heat to 1300-1400 ℃, and finding that alloy elements can be fully diffused in the temperature range without serious burning loss through research, and preserving heat for 15min in the temperature range to obtain a mixed melt; when 3 kinds of intermediate alloys are added into the copper melt, the copper-chromium intermediate alloy with the smaller burning loss rate is added firstly, then the copper-zirconium intermediate alloy with the higher burning loss rate is added, and finally the copper-yttrium intermediate alloy with the most serious burning loss rate is added; the three alloys are added in sequence from small to large according to the burning loss rate, so that the burning loss rate of alloy elements can be effectively reduced, the quality of the obtained alloy product is ensured, and the production cost is effectively controlled.
Step (1-3): and casting the mixed melt into a preheated graphite mold at 1100-1150 ℃ by adopting a near liquidus casting method, wherein the preheating temperature of the mold is 300 ℃, and thus obtaining the rare earth copper chromium zirconium alloy cast ingot. Because the liquidus temperature of the copper-chromium-zirconium alloy can change along with the content change of each element in the alloy, in the high-strength high-conductivity rare earth copper alloy to be prepared by the invention, when the casting temperature range is 1100-1150 ℃, the supercooling degree of the rare earth copper-chromium-zirconium alloy is larger, the crystalline structure is finer, and particularly when the casting temperature is 1120 ℃, the fineness of the crystalline structure of the alloy is better. In addition, the preheating temperature of the die is not too high during casting, and when the preheating temperature of the die is 300 ℃, the internal and external crystal structures of the rare earth copper chromium zirconium alloy prepared by casting are relatively uniform.
In the step (2), the method for solution treatment comprises the following steps: and (3) placing the rare earth copper chromium zirconium alloy ingot in a heat treatment furnace, preserving the heat for 30-180min at the temperature of 980 ℃ of 900-. Test research proves that the solid solution treatment is carried out at the temperature of 900-. When the solid solution treatment condition of the rare earth copper alloy is 920 ℃ multiplied by 1h, the solid solution effect is optimal; if the temperature is too high, the mechanical property of the alloy is obviously reduced, and a good solid solution strengthening effect cannot be generated. Quenching the alloy subjected to solution treatment in cold water, wherein the temperature of the cold water is room temperature; the quenching process is to ensure that the alloy elements are not precipitated by natural aging after the solution treatment, so the quenching process is carried out by selecting water at room temperature.
In the step (3), the alternative treatment of rolling and aging comprises the following steps:
step (3-1): rolling the rare earth copper chromium zirconium alloy blank at room temperature for the first time at the room temperature, wherein the deformation is 60%; carrying out primary aging treatment on the rare earth copper chromium zirconium alloy blank rolled for the first time at 360 ℃ for 30 min;
step (3-2): carrying out secondary room temperature rolling on the rare earth copper chromium zirconium alloy blank subjected to the primary aging treatment at room temperature, wherein the deformation amount is 50%; carrying out secondary aging treatment on the rare earth copper chromium zirconium alloy blank rolled for the second time at 340 ℃ for 30 min;
step (3-3): carrying out third room temperature rolling on the rare earth copper chromium zirconium alloy blank subjected to the secondary aging treatment at room temperature, wherein the deformation amount is 40%; and carrying out three-stage aging treatment on the rare earth copper chromium zirconium alloy blank rolled for the third time at 320 ℃ for 30 min.
In the preparation method of the high-strength high-conductivity rare earth copper alloy Cu-Cr-Zr-Y, in the step (1), the purity of pure copper is more than or equal to 99.95wt%, the chromium raw material is a copper-chromium intermediate alloy, the zirconium raw material is a copper-zirconium intermediate alloy, and the yttrium raw material is a copper-yttrium intermediate alloy; in the copper-chromium intermediate alloy, the mass fraction of chromium is 10 wt%; in the copper-zirconium intermediate alloy, the mass fraction of zirconium is 40 wt%; in the copper-yttrium master alloy, the mass fraction of yttrium is 20 wt%;
in step (1), the smelting process comprises the steps of:
step (1-1): adding pure copper into a graphite crucible, and heating along with the furnace to melt the pure copper to obtain a copper melt;
step (1-2): continuously heating the copper melt to 1250 ℃, then sequentially adding the copper-chromium intermediate alloy, the copper-zirconium intermediate alloy and the copper-yttrium intermediate alloy into the copper melt to melt the copper-chromium intermediate alloy, the copper-zirconium intermediate alloy and the copper-yttrium intermediate alloy, continuously heating to 1350 ℃, and keeping the temperature within the temperature range for 15min to obtain a mixed melt;
step (1-3): casting the mixed melt into a preheated graphite mold at 1120 ℃ by adopting a near liquidus casting method, wherein the preheating temperature of the mold is 300 ℃, and thus obtaining the rare earth copper chromium zirconium alloy cast ingot;
in the step (2), the solution treatment method comprises the following steps: placing the rare earth copper chromium zirconium alloy cast ingot in a heat treatment furnace, preserving heat for 60min at 920 ℃, and then performing water quenching, wherein the temperature during water quenching is room temperature;
in the high-strength high-conductivity rare earth copper alloy Cu-Cr-Zr-Y, the mass percent of chromium element and zirconium element is 0.55wt% and 0.18wt% respectively, and the mass percent of yttrium is 0.15 wt%.
A high-strength high-conductivity rare earth copper alloy Cu-Cr-Zr-Y is prepared by the preparation method of the high-strength high-conductivity rare earth copper alloy Cu-Cr-Zr-Y.
The technical scheme of the invention achieves the following beneficial technical effects:
(1) the rare earth copper alloy prepared by the method has excellent performance, the tensile strength is over 700MPa, the relative conductivity is higher than 80% IACS, the requirements of the industry on the performance of the high-strength high-conductivity copper alloy can be met, and the advanced technical requirements on high performance can be met. The copper chromium zirconium alloy prepared by the traditional method can not meet the requirements of the current industrial production, and the preparation and processing process flow of the invention is beneficial to the industrial large-scale production of the high-strength high-conductivity copper chromium zirconium alloy.
(2) The method of the invention is a novel rare earth copper alloy, which ensures the high conductivity of the material and simultaneously keeps the strength at a higher level, which benefits from the effects of precipitated phases with different sizes. The contradiction that the common copper-chromium-zirconium alloy is difficult to coexist in high strength and high conductivity is broken through, and the real high strength and high conductivity are realized.
(3) According to the invention, the rare earth element Y is added into the copper-chromium-zirconium alloy, so that crystal grains can be effectively refined, meanwhile, the rare earth element can react with impurities to purify a matrix, and the Y element can promote the precipitation of a Cr phase in the aging process and inhibit the growth of the Cr phase.
(4) At room temperature, the solubility of chromium and zirconium in copper chromium zirconium alloys is low. Excess chromium and zirconium atoms in the alloy will precipitate out of a supersaturated solid solution to strengthen the matrix and improve electrical conductivity. Meanwhile, when the alloy is rolled, the second phase precipitated by aging generates dislocation pinning effect on the alloy, so that the tensile strength of the alloy can be greatly increased, and the conductivity of the alloy can be reduced. The method adopts the method of rolling the rare earth copper chromium zirconium alloy blank for multiple times and alternately treating the rare earth copper chromium zirconium alloy blank by multiple aging, and the rolling process is introduced before the aging, so that the obtained rare earth copper alloy Cu-Cr-Zr-Y has better mechanical property. Since a large amount of distortion energy is generated during rolling, the distortion energy promotes the precipitation of second phase atoms. Meanwhile, point defects such as vacancies and linear defects such as dislocations and the like can be generated in the rolling process with larger deformation, and the defects can provide nucleation positions for the precipitation of solute atoms in the aging process of the alloy, so that the defects introduced in the rolling process provide conditions for the precipitation of the solute atoms, are beneficial to the generation of precipitated phases with different sizes in the alternating process of the alloy, and reduce the influence of a second phase precipitated by aging treatment on the electrical conductivity while obtaining high strength, thereby ensuring that the prepared copper-chromium-zirconium alloy can realize the effective combination of the high strength (more than or equal to 700MPa) and the high electrical conductivity (more than or equal to 80 percent IACS).
Drawings
FIG. 1 is a view of a Cu-Cr-Zr microstructure of a non-vacuum-smelted near-liquidus cast Cu-Cr-Zr alloy according to a comparative example of the present invention;
FIG. 2 is a Cu-Cr-Zr-Y microstructure diagram of a non-vacuum melting near liquidus casting rare earth-Cu-Cr-Zr alloy according to an embodiment of the present invention;
FIG. 3 is a microstructure diagram of a rare earth-Cu-Cr-Zr-Y alloy after the first rolling (room temperature, deformation 60%) in an embodiment of the present invention;
FIG. 4 is a microstructure diagram of a rare earth-Cu-Cr-Zr-Y alloy after primary aging (360 ℃ C. times.30 min) treatment according to an embodiment of the present invention;
FIG. 5 is a microstructure diagram of a rare earth-Cu-Cr-Zr-Y alloy after a second rolling (room temperature, 50% deformation) according to an embodiment of the present invention;
FIG. 6 is a microstructure diagram of a rare earth-Cu-Cr-Zr-Y alloy after secondary aging (340 ℃ C. times.30 min) treatment according to an embodiment of the present invention;
FIG. 7 is a microstructure diagram of a rare earth-Cu-Cr-Zr-Y alloy after a third rolling (room temperature, deformation 40%) in an embodiment of the present invention;
FIG. 8 is a microstructure diagram of a rare earth-Cu-Cr-Zr-Y alloy after three-stage aging (320 ℃ C. x 30min) treatment according to an embodiment of the present invention;
FIG. 9 is a graph showing tensile strength at room temperature in different states of alloy materials prepared in examples of the present invention and comparative examples;
FIG. 10 is a graph showing relative electric conductivity in different states of alloy materials prepared in examples of the present invention and comparative examples.
Detailed Description
Examples
A preparation method of a high-strength high-conductivity rare earth copper alloy Cu-Cr-Zr-Y comprises the following steps:
step (1): preparing pure copper, a chromium raw material, a zirconium raw material and an yttrium raw material in proportion, putting the mixture into a medium-frequency induction smelting furnace, smelting in an atmospheric environment, and smelting to obtain a rare earth copper chromium zirconium alloy ingot;
step (2): carrying out solid solution treatment on the rare earth copper chromium zirconium alloy ingot to obtain a rare earth copper chromium zirconium alloy blank;
and (3) performing rolling and aging alternate treatment on the rare earth copper chromium zirconium alloy blank to obtain the high-strength high-conductivity rare earth copper alloy Cu-Cr-Zr-Y.
The microstructure of the high-strength and high-conductivity rare earth copper alloy Cu-Cr-Zr-Y prepared by the embodiment is shown in figure 2. As can be seen from FIG. 2, the grain structure of the alloy consists of uniform and fine equiaxed crystals, the average grain size is about 11 μm, and the alloy has the characteristic of a rapid solidification structure, and compared with the alloy without rare earth addition shown in FIG. 1, the alloy grains are obviously refined, and the defects are reduced.
In the step (1), the purity of pure copper is more than 99.95wt%, the chromium raw material is a copper-chromium intermediate alloy, the zirconium raw material is a copper-zirconium intermediate alloy, and the yttrium raw material is a copper-yttrium intermediate alloy; in the copper-chromium intermediate alloy, the mass fraction of chromium is 10 wt%; in the copper-zirconium intermediate alloy, the mass fraction of zirconium is 40 wt%; in the copper-yttrium master alloy, the mass fraction of yttrium is 20 wt%. In this example, 3 kinds of master alloys were purchased from Zhongnuo New materials Co., Ltd.
In step (1), the smelting process comprises the steps of:
step (1-1): adding pure copper into a graphite crucible, and heating along with the furnace to melt the pure copper to obtain a copper melt;
step (1-2): continuously heating the copper melt to 1250 ℃, then sequentially adding the copper-chromium intermediate alloy, the copper-zirconium intermediate alloy and the copper-yttrium intermediate alloy into the copper melt to melt the copper-chromium intermediate alloy, the copper-zirconium intermediate alloy and the copper-yttrium intermediate alloy, continuously heating to 1350 ℃, and preserving heat for 15min to obtain a mixed melt;
step (1-3): and casting the mixed melt into a preheated graphite mold at 1120 ℃ by adopting a near liquidus casting method, wherein the preheating temperature of the mold is 300 ℃, and thus obtaining the rare earth copper chromium zirconium alloy cast ingot.
In the step (2), the solution treatment method comprises the following steps: and (3) placing the rare earth copper chromium zirconium alloy ingot in a heat treatment furnace, preserving heat for 1h at 920 ℃, and then performing water quenching, wherein the temperature of water during water quenching is room temperature.
In step (3), the alternating process of rolling and aging comprises the following steps:
step (3-1): rolling the rare earth copper chromium zirconium alloy blank at room temperature for the first time at the room temperature, wherein the deformation is 60%; carrying out primary aging treatment on the rare earth copper chromium zirconium alloy blank rolled for the first time at 360 ℃ for 30 min; the microstructure of the rolled blank is shown in figure 3, and as can be seen from figure 3, the alloy is obviously deformed after being rolled, and the alloy crystal grains are oriented due to large deformation; the microstructure of the treated blank is shown in FIG. 4, and it can be seen from FIG. 4 that the deformed crystal grains of the alloy are partially recovered after aging treatment, and recrystallization occurs;
step (3-2): carrying out secondary room temperature rolling on the rare earth copper chromium zirconium alloy blank subjected to the primary aging treatment at room temperature, wherein the deformation amount is 50%; carrying out secondary aging treatment on the rare earth copper chromium zirconium alloy blank rolled for the second time at 340 ℃ for 30 min; the microstructure of the rolled blank is shown in figure 5, and after the rolling amount is reduced, the deformation degree of alloy crystal grains is weaker than that of the alloy crystal grains rolled at room temperature for the first time; the microstructure of the processed blank is shown in figure 6, compared with the primary aging, partial twin crystals are generated in the alloy, and the size of recrystallized grains is smaller due to temperature;
step (3-3): carrying out third room temperature rolling on the rare earth copper chromium zirconium alloy blank subjected to the secondary aging treatment at room temperature, wherein the deformation amount is 40%; carrying out three-stage aging treatment on the rare earth copper chromium zirconium alloy blank rolled for the third time at 320 ℃ for 30 min; the microstructure of the rolled blank is shown in figure 7, the rolling amount is further reduced, and the shape change of the microstructure of the alloy is not obvious; the microstructure of the processed blank is shown in figure 8, twin crystals are increased after three-stage aging, and solute atoms in the rare earth copper alloy are completely separated out.
A high-strength high-conductivity rare earth copper alloy Cu-Cr-Zr-Y is prepared by the preparation method; in the prepared high-strength high-conductivity rare earth copper alloy Cu-Cr-Zr-Y, the mass percentages of chromium element and zirconium element are respectively 0.55wt% and 0.18wt%, the mass percentage of yttrium element is 0.15wt%, and the mass percentage of copper element is 99.12 wt%.
The high-strength high-conductivity rare earth copper alloy Cu-Cr-Zr-Y material prepared by the embodiment has good comprehensive performance, the room-temperature tensile strength is 730.96MPa, the room-temperature elongation is 7.1%, and the room-temperature conductivity is 82.10% IACS. The rare earth copper alloy prepared by the preparation method of the embodiment solves the contradiction between high conductivity and high strength of the alloy, and the mechanical property and the electrical property of the alloy are better matched.
In the alloy ingot cast by the non-vacuum melting near liquidus casting method in this example, the mass percentages of the elements Cr and Zr are 0.55% and 0.18%, respectively, and the mass percentage of the element Y is 0.15%. The smelting condition is atmospheric environment, the smelting temperature is controlled at 1350 ℃, and the casting temperature is 1120 ℃. The solution treatment is carried out on the as-cast Cu-Cr-Zr-Y alloy for 1h at 920 ℃. The multiple rolling and multistage aging alternate process is that room temperature rolling and low temperature aging are alternately carried out: the deformation is 60 percent (first room temperature rolling), the aging treatment temperature/time is 360 ℃/30min, the deformation is 50 percent (second room temperature rolling), the aging treatment temperature/time is 340 ℃/30min, the deformation is 40 percent (third room temperature rolling), and the aging treatment temperature/time is 320 ℃/30 min; the deformation of rolling is reduced in sequence, the temperature of aging treatment is reduced in sequence, the aging time of each stage is unchanged, and the temperature is kept at 30 min. The novel rare earth copper alloy with integrated structure and function, which has tensile strength of over 700MPa and relative conductivity of more than 80 percent ICSA, is obtained by orderly combining solid solution, rolling and aging by adopting the rare earth copper alloy cast by a non-vacuum melting near liquidus casting method.
Comparative example
The comparative example differs from the examples in that the copper chromium zirconium alloy was prepared without the rare earth yttrium element. The preparation method comprises the following steps:
step (1): placing pure copper, chromium raw materials and zirconium raw materials in a medium-frequency induction smelting furnace, smelting in an atmospheric environment, and obtaining a copper-chromium-zirconium alloy ingot after smelting;
step (2): carrying out solution treatment on the copper-chromium-zirconium alloy cast ingot to obtain a copper-chromium-zirconium alloy blank;
and (3) rolling and aging treatment alternate processing are carried out on the copper chromium zirconium alloy blank, and the copper chromium zirconium alloy Cu-Cr-Zr (the microstructure figure of the copper chromium zirconium alloy is shown in figure 1) is obtained.
In the step (1), the purity of pure copper is more than 99.95wt%, the chromium raw material is copper-chromium intermediate alloy, and the zirconium raw material is copper-zirconium intermediate alloy; in the copper-chromium intermediate alloy, the mass fraction of chromium is 10 wt%; in the copper-zirconium intermediate alloy, the mass fraction of zirconium is 40 wt%. The 2 master alloys in this comparative example were purchased by Zhongnuo New materials Co Ltd.
In step (1), the smelting process comprises the steps of:
step (1-1): adding pure copper into a graphite crucible, and heating along with the furnace to melt the pure copper to obtain a copper melt;
step (1-2): continuously heating the copper melt to 1250 ℃, then sequentially adding the copper-chromium intermediate alloy and the copper-zirconium intermediate alloy into the copper melt to melt the copper-chromium intermediate alloy and the copper-zirconium intermediate alloy, continuously heating to 1350 ℃, and preserving heat for 15min to obtain a mixed melt;
step (1-3): and casting the mixed melt into a preheated graphite mold at 1120 ℃ by adopting a near liquidus casting method, wherein the preheating temperature of the mold is 300 ℃, and thus obtaining the copper-chromium-zirconium alloy cast ingot.
In the step (2), the solution treatment method comprises the following steps: and (3) placing the copper-chromium-zirconium alloy cast ingot in a heat treatment furnace, preserving heat for 1h at 920 ℃, and then performing water quenching, wherein the temperature of water during water quenching is room temperature.
In step (3), the alternating process of rolling and aging comprises the following steps:
step (3-1): carrying out primary room temperature rolling on the copper-chromium-zirconium alloy blank at room temperature, wherein the deformation is 60%; carrying out primary aging treatment on the copper-chromium-zirconium alloy blank subjected to primary rolling at 360 ℃ for 30 min;
step (3-2): carrying out secondary room temperature rolling on the copper-chromium-zirconium alloy blank subjected to the primary aging treatment at room temperature, wherein the deformation amount is 50%; carrying out secondary aging treatment on the copper chromium zirconium alloy blank rolled for the second time at 340 ℃ for 30 min;
step (3-3): carrying out third room temperature rolling on the copper-chromium-zirconium alloy blank subjected to the secondary aging treatment at room temperature, wherein the deformation amount is 40%; and carrying out three-stage aging treatment on the copper-chromium-zirconium alloy blank rolled for the third time at 320 ℃ for 30 min.
In the copper-chromium-zirconium alloy prepared by the method, the mass percentages of chromium and zirconium are 0.55wt% and 0.18wt%, respectively, and the balance is copper.
The tensile strength at room temperature of the copper-chromium-zirconium alloy material prepared by the comparative example is 405.91MPa, the elongation at room temperature is 26%, and the relative conductivity at room temperature is 88.21% IACS.
Compared with the examples, the tensile strength at room temperature of the copper-chromium-zirconium alloy material prepared by the comparative example is far lower than that of the high-strength high-conductivity rare earth copper alloy Cu-Cr-Zr-Y prepared by the examples, but the relative conductivity at room temperature of the copper-chromium-zirconium alloy material and the high-strength high-conductivity rare earth copper alloy Cu-Cr-Zr-Y is not greatly different, and the elongation at room temperature of the high-strength high-conductivity rare earth copper alloy Cu-Cr-Zr-Y is obviously lower than that of the copper-chromium-zirconium alloy material prepared by the comparative example. This shows that the addition of rare earth element yttrium to the copper chromium zirconium alloy can significantly improve the tensile strength of the alloy material at room temperature, but also significantly reduce the elongation at room temperature of the copper chromium zirconium alloy, and at the same time, affect the room temperature conductivity of the material to a certain extent. Therefore, the strength of the copper chromium zirconium alloy material is improved by adding the rare earth element yttrium into the copper chromium zirconium alloy, and the addition amount of the yttrium element needs to be controlled. It can be seen from fig. 9 and 10 that the tensile strength and the relative conductivity of the high-strength and high-conductivity rare earth copper alloy Cu-Cr-Zr-Y and copper-chromium-zirconium alloy material can be significantly improved by the alternating treatment of room temperature rolling and aging, which illustrates that the adverse effects of the elements of chromium, zirconium and yttrium on the tensile strength and conductivity can be reduced, and particularly the adverse effects on the conductivity of the alloy can be reduced by the preparation process of the alternating treatment of rolling and aging, which may be because the generation of precipitated phases with different sizes can be promoted under the conditions of the alternating treatment of room temperature rolling and aging in this embodiment, the mechanical properties of the alloy can be significantly improved by the phases with multiple size grades and the precipitated twin crystals, but because the precipitated phases are smaller in size and the twin crystals have no strong electron scattering effect, the influence of the second phase precipitated by aging on the conductivity can be reduced, so that the alloy can simultaneously maintain the high strength and the high conductivity after the alternating process of room temperature rolling and aging.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications are possible which remain within the scope of the appended claims.

Claims (5)

1. A preparation method of a high-strength high-conductivity rare earth copper alloy Cu-Cr-Zr-Y is characterized by comprising the following steps:
step (1): placing pure copper, a chromium raw material, a zirconium raw material and an yttrium raw material in a medium-frequency induction smelting furnace, smelting in an atmospheric environment, and obtaining a rare earth copper chromium zirconium alloy ingot after smelting;
step (2): carrying out solid solution treatment on the rare earth copper chromium zirconium alloy ingot to obtain a rare earth copper chromium zirconium alloy blank;
step (3) rolling and aging the rare earth copper chromium zirconium alloy blank alternately to obtain high-strength high-conductivity rare earth copper alloy Cu-Cr-Zr-Y;
in the high-strength high-conductivity rare earth copper alloy Cu-Cr-Zr-Y, the mass percentages of chromium element and zirconium element are respectively 0.55wt% and 0.18wt%, and the mass percentage of yttrium is 0.15 wt%;
in the step (1), the purity of pure copper is more than or equal to 99.95wt%, the chromium raw material is a copper-chromium intermediate alloy, the zirconium raw material is a copper-zirconium intermediate alloy, and the yttrium raw material is a copper-yttrium intermediate alloy;
in step (1), the smelting process comprises the steps of:
step (1-1): adding pure copper into a graphite crucible, and heating along with the furnace to melt the pure copper to obtain a copper melt;
step (1-2): continuously heating the copper melt, then sequentially adding the copper-chromium intermediate alloy, the copper-zirconium intermediate alloy and the copper-yttrium intermediate alloy into the copper melt to melt the copper-chromium intermediate alloy, the copper-zirconium intermediate alloy and the copper-yttrium intermediate alloy, and continuously heating and preserving heat to obtain a mixed melt;
step (1-3): casting the mixed melt into a preheated graphite mold by adopting a near liquidus casting method to obtain the rare earth copper chromium zirconium alloy cast ingot;
in step (3), the alternating process of rolling and aging comprises the following steps:
step (3-1): rolling the rare earth copper chromium zirconium alloy blank at room temperature for the first time at the room temperature, wherein the deformation is 60%; carrying out primary aging treatment on the rare earth copper chromium zirconium alloy blank rolled for the first time at 360 ℃ for 30 min;
step (3-2): carrying out secondary room temperature rolling on the rare earth copper chromium zirconium alloy blank subjected to the primary aging treatment at room temperature, wherein the deformation amount is 50%; carrying out secondary aging treatment on the rare earth copper chromium zirconium alloy blank rolled for the second time at 340 ℃ for 30 min;
step (3-3): carrying out third room temperature rolling on the rare earth copper chromium zirconium alloy blank subjected to the secondary aging treatment at room temperature, wherein the deformation amount is 40%; and carrying out three-stage aging treatment on the rare earth copper chromium zirconium alloy blank rolled for the third time at 320 ℃ for 30 min.
2. The method for preparing the high-strength high-conductivity rare earth copper alloy Cu-Cr-Zr-Y according to claim 1, wherein the mass fraction of chromium in the copper-chromium intermediate alloy is 10 wt%; in the copper-zirconium intermediate alloy, the mass fraction of zirconium is 40 wt%; in the copper-yttrium master alloy, the mass fraction of yttrium is 20 wt%.
3. The method for preparing the high-strength high-conductivity rare earth copper alloy Cu-Cr-Zr-Y according to claim 1, wherein in the step (1), the smelting method comprises the following steps:
step (1-1): adding pure copper into a graphite crucible, and heating along with the furnace to melt the pure copper to obtain a copper melt;
step (1-2): continuously heating the copper melt to 1240-1260 ℃, then sequentially adding the copper-chromium intermediate alloy, the copper-zirconium intermediate alloy and the copper-yttrium intermediate alloy into the copper melt to melt the copper-chromium intermediate alloy, the copper-zirconium intermediate alloy and the copper-yttrium intermediate alloy, continuously heating to 1300-1400 ℃, and preserving heat for 15min within the temperature range to obtain a mixed melt;
step (1-3): and casting the mixed melt into a preheated graphite mold at 1100-1150 ℃ by adopting a near liquidus casting method, wherein the preheating temperature of the mold is 300 ℃, and thus obtaining the rare earth copper-chromium-zirconium alloy ingot.
4. The method for preparing the high-strength high-conductivity rare earth copper alloy Cu-Cr-Zr-Y according to claim 1, wherein in the step (2), the solution treatment method comprises: and (3) placing the rare earth copper chromium zirconium alloy ingot in a heat treatment furnace, preserving the heat for 30-180min at the temperature of 980 ℃ of 900-.
5. A high-strength high-conductivity rare earth copper alloy Cu-Cr-Zr-Y, which is prepared by the method of any one of claims 1 to 4.
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