CN114507793A - High-strength high-conductivity Cu-Zn-Cr-Zr copper alloy, and preparation method and application thereof - Google Patents
High-strength high-conductivity Cu-Zn-Cr-Zr copper alloy, and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a high-strength high-conductivity Cu-Zn-Cr-Zr copper alloy, a preparation method and application thereof. The high-strength high-conductivity Cu-Zn-Cr-Zr copper alloy has the characteristics of high strength, high conductivity, easy soldering and easy etching processing through specific component and proportioning design, and can be widely applied to large-scale integrated circuit lead frames. The invention also provides a preparation method and application of the copper alloy.
Description
Technical Field
The invention belongs to the technical field of copper alloys, and particularly relates to a high-strength high-conductivity Cu-Zn-Cr-Zr copper alloy, and a preparation method and application thereof.
Background
The Cu-Cr-Zr copper alloy has good electrical conductivity, thermal conductivity, wear resistance and moderate strength, and can be widely applied to modern information industries such as 5G communication, high-end integrated circuits and the like and high-end manufacturing industries such as rail transit and the like. At present, most of Cu-Cr-Zr series copper alloys in the market have the tensile strength of 500-600 MPa and the electric conductivity of 70-80% IACS. With the rapid development of the high and new technology industry, the use requirement of the copper alloy is higher and higher. Taking an integrated circuit lead frame as an example, with the development of an integrated circuit towards a very large scale, the lead frame is developed towards multi-pin, high-density, ultra-thin, micro and the like, and besides the requirement that the copper alloy has higher strength and conductivity, the lead frame also has the requirements of high softening temperature resistance, low residual stress, easy welding, good etching performance and the like so as to meet the ultra-fine processing requirement of the high-end integrated circuit pin.
In the related technology, CN1254554C discloses a high-strength high-conductivity rare earth copper alloy and a preparation method thereof, the mechanical property of the copper alloy is improved by adding rare earth elements, the tensile strength of the prepared alloy is only 500-600 MPa, and the conductivity is 70-80% IACS. CN108060323B discloses a high-strength high-conductivity Cu-Cr-Zr-Mg alloy wire and a preparation method thereof, the prepared alloy wire has the tensile strength of 760MPa, the conductivity of 84.7 percent IACS and the components and the compositions are as follows: 1.5 percent of Cr1, 0.1 percent of Zr0, 0.05 percent of Mg0, and the balance of Cu and inevitable impurities. The Cr content in the alloy is higher and is 1.5-15.0 wt%, the solid solubility of Cr in a copper matrix at room temperature is extremely low, the maximum solid solubility of Cr in the copper alloy is 0.65% at 1076 ℃, and a large amount of fibrous Cr phase particles formed in the copper matrix strengthen the alloy wire through large deformation drawing processing. However, not only the raw material cost of the alloy is increased by adding higher Cr content, but on the one hand, for Cu-Cr-Zr-Mg alloy plate strips with large industrial application amount, Cr phases in a copper matrix exist in a lamellar form through large-deformation hot rolling and cold rolling processing, the strengthening effect is weaker, and the strength of the alloy is lower; on the other hand, addition of a high Cr content (> 1 wt%) tends to form coarse primary Cu in the copper matrix during solidification during smeltingxThe Cr precipitate particles increase the brittleness of the material, and cause cracking easily during cold rolling. Coarse CuxCr precipitate particles cause sharp reduction of bending property of the strip, strength reduction, elongation reduction, difficulty in controlling strip shape and dimension precision of the alloy, particularly when manufacturing an etched lead frame,the phenomenon of uneven corrosion of the micro-area is serious, and the requirement of manufacturing an integrated circuit lead frame cannot be met.
Disclosure of Invention
The present invention is directed to solving at least one of the above problems in the prior art. Therefore, the invention provides a high-strength high-conductivity Cu-Zn-Cr-Zr copper alloy, and a preparation method and application thereof.
The invention also provides a preparation method of the high-strength high-conductivity Cu-Zn-Cr-Zr copper alloy.
The invention also provides application of the high-strength and high-conductivity Cu-Zn-Cr-Zr copper alloy.
The invention provides a high-strength high-conductivity Cu-Zn-Cr-Zr copper alloy, which comprises the following components in percentage by mass:
Zn：0.1wt％～1.0wt％，
Cr：0.01wt％～0.8wt％，
Zr：0.1wt％～0.5wt％，
Mg：0.05wt％～1.0wt％，
Ca：0.05wt％～1.0wt％，
V：0.05wt％～0.2wt％，
the balance being copper.
The invention relates to a technical scheme of a high-strength high-conductivity Cu-Zn-Cr-Zr series copper alloy, which at least has the following beneficial effects:
the high-strength high-conductivity Cu-Zn-Cr-Zr copper alloy has the characteristics of high strength, high conductivity and easy soldering processing through specific component and proportion design, and can be widely applied to large-scale integrated circuit lead frames.
In the high-strength high-conductivity Cu-Zn-Cr-Zr copper alloy, the accurate addition of Zr element in the non-vacuum melting process becomes a common problem in the industry because the chemical property of Zr is very active. According to the invention, by adding the Zn element into the alloy, oxygen in the copper melt can be effectively removed in the smelting process, and the phenomenon that inclusions formed by the reaction of Zr and oxygen are removed by slagging is avoided, so that the accurate addition of the Zr element is realized. The addition of a small amount of Zn element can be solid-dissolved in the copper matrix, and the effect of solid-solution strengthening can be achieved on the basis of not obviously reducing the conductivity. Zn element is dissolved in the copper matrix in a solid solution mode, the electrode potential of the copper matrix is regulated and controlled, and etching processing of the ultra-large scale integrated circuit can be achieved. Zn can play the role of self-fluxing agent and ensure the smooth operation in the brazing process. In addition, the surface of the lead frame strip needs to be plated with Zn, and the old material can be directly used as a raw material without being recycled after the surface plating Zn layer is removed, so that the energy consumption is reduced, and the pollution caused by removing the plating Zn layer is avoided.
In the high-strength high-conductivity Cu-Zn-Cr-Zr copper alloy, 0.8 wt% of chromium element is dissolved in the matrix at high temperature, but the solid solubility at room temperature is only 0.03%, so that a large amount of nano-scale bean-shaped particles can be separated out from the matrix by Cr under a certain aging process, the degree of electron scattering is reduced by separating out the particles from the matrix, the precipitation strengthening effect is achieved, and the strength and the electric conductivity of the material are greatly improved.
In the high-strength high-conductivity Cu-Zn-Cr-Zr copper alloy, the Mg element can be added into the copper matrix in a solid solution manner, so that the effects of solid solution and remarkable work hardening can be achieved on the premise of not remarkably reducing the conductivity of the alloy, and the alloy is strengthened. Meanwhile, Mg element is added into the copper alloy, so that grains can be refined, and the bending property and the stress relaxation resistance of the alloy are improved.
The Ca element can effectively form high-melting-point intermetallic compounds with trace elements such as S, O, Bi, Pb and the like in the copper melt, slag formation and removal are realized, the copper melt is obviously purified, and the conductivity of the finally prepared alloy is obviously improved. Ca contributes to sufficient removal of oxygen, and can further ensure accurate addition of Zr element.
In the high-strength high-conductivity Cu-Zn-Cr-Zr copper alloy, the added V can be segregated in the grain boundary, so that the grain structure is refined, and the effects of improving the heat resistance of the alloy and strengthening fine grains are achieved.
The high-strength high-conductivity Cu-Zn-Cr-Zr copper alloy disclosed by the invention does not contain toxic and harmful elements and precious elements in the component ratio, and the alloy components are rich in yield elements. Meanwhile, the old alloy material containing the zinc coating can be directly recycled, and the environmental protection and energy saving significance is great.
The high-strength high-conductivity Cu-Zn-Cr-Zr copper alloy disclosed by the invention is reasonable in components, low in raw material price, simple in production process, low in production cost, good in processability, large in environmental protection and energy saving significance, and suitable for industrial production.
According to some embodiments of the present invention, the high-strength high-conductivity Cu-Zn-Cr-Zr-based copper alloy includes the following components in percentage by mass:
Zn：0.4wt％～1.0wt％，
Cr：0.3wt％～0.8wt％，
Zr：0.2wt％～0.5wt％，
Mg：0.1wt％～1.0wt％，
Ca：0.05wt％～1.0wt％，
V：0.05wt％～0.2wt％，
the balance being copper.
The second aspect of the present invention provides a method for producing the above-mentioned high-strength and high-conductivity Cu-Zn-Cr-Zr-based copper alloy, comprising the steps of:
s1: weighing a copper-chromium intermediate alloy, a copper-zirconium intermediate alloy, zinc, a copper-magnesium intermediate alloy, a copper-calcium intermediate alloy, a copper-vanadium intermediate alloy and electrolytic copper according to a ratio, heating and melting the electrolytic copper, and adding the copper-chromium intermediate alloy to obtain a first alloy melt;
s2: adding a copper-magnesium intermediate alloy, a copper-calcium intermediate alloy and a copper-vanadium intermediate alloy into the first alloy melt to obtain a second alloy melt;
s3: after the zinc is added into the second alloy melt, adding the copper-zirconium intermediate alloy, and carrying out semi-continuous casting to obtain a copper alloy ingot;
s4: carrying out hot rolling on the copper alloy cast ingot and then carrying out primary quenching to obtain a hot rolling blank;
s5: sequentially carrying out primary cold rolling, primary aging, secondary cold rolling and secondary aging treatment on the hot rolled blank to obtain a cold rolled blank;
s6: and after the cold rolled blank is subjected to finish rolling, annealing and secondary quenching treatment are carried out.
The invention relates to a technical scheme for preparing high-strength high-conductivity Cu-Zn-Cr-Zr series copper alloy, which at least has the following beneficial effects:
according to the preparation method of the high-strength and high-conductivity Cu-Zn-Cr-Zr copper alloy, the combined heat treatment mode formed from the step S1 to the step S6 can ensure that alloy elements can be fully precipitated from a copper matrix to form the reinforced alloy, and meanwhile, the electrical conductivity is obviously improved due to the purification of the matrix.
The preparation method of the high-strength high-conductivity Cu-Zn-Cr-Zr copper alloy has the advantages of simple production process and low production cost.
According to some embodiments of the invention, the temperature of the heat melting is 1250 ℃ to 1290 ℃ in step S1.
In the process of heating and melting, cryolite, calcium fluoride, zirconium carbonate and calcium carbonate are used as covering agents, and the volume percentage is 1: 1: 1: 1: 1, covering the calcined charcoal on the upper surface. The melt is covered by acetylene fire in the process of transferring from the smelting furnace to the holding furnace through the flow channel.
In step S1, after the electrolytic copper is heated and melted, the copper-chromium intermediate alloy is added to obtain a first alloy melt, and the furnace temperature is controlled at 1250-1280 ℃.
In step S3, before the semi-continuous casting, the converter performs the semi-continuous casting.
According to some embodiments of the invention, the temperature of the semi-continuous casting is 1270 ℃ to 1320 ℃ in step S3.
According to some embodiments of the invention, the average casting speed of the semi-continuous casting is 4.5m/h to 6.5m/h in step S3.
In step S4, before hot rolling, the copper alloy cast ingot is kept at 920-950 ℃ for 6-10 h.
According to some embodiments of the invention, in step S4, the hot rolling passes are 7 to 9.
The hot rolling passes are 7 to 9, wherein the deformation of the first pass is 25 to 27 percent, the deformation of the second pass to the fifth pass can be increased, and the processing of the later passes is gradually reduced. The large deformation of the first few passes can improve the production efficiency in actual production, and meanwhile, the large deformation can crush coarse grains, reduce or eliminate casting defects and improve the subsequent processing performance of the alloy. And then, the material size is accurately controlled through small-pass deformation, so that conditions are provided for the continuity and automation of the subsequent process.
According to some embodiments of the invention, in step S5, the first cold rolling pass is two.
Before the first cold rolling, the hot rolled blank is milled, and the milling thickness of the two surfaces is 0.3 mm-0.6 mm respectively.
The first cold rolling pass is twice, wherein the deformation of the first cold rolling pass is 20-26%, and the deformation of the second cold rolling pass is 30-40%.
According to some embodiments of the invention, the temperature of the first aging treatment in step S5 is 450 to 480 ℃.
According to some embodiments of the invention, in step S5, the time of the first aging treatment is 120min to 180 min.
And obtaining the strip after the first aging treatment.
The strip is cold rolled a second time. In the second cold rolling, the deformation of the first cold rolling is 20-22%, and the deformation of the second cold rolling is 30-35%.
The second time aging is performed for 120min to 180min at the temperature of 450 ℃ to 480 ℃.
In step S6, the cold rolled blank is finish rolled, and then annealed and subjected to secondary quenching. Wherein the deformation amount of finish rolling is 35-55%. The annealing temperature is 300-350 ℃, and the annealing is carried out in an air cushion furnace. After annealing, discharging and quenching by nitrogen.
The third aspect of the invention provides the application of the high-strength and high-conductivity Cu-Zn-Cr-Zr series copper alloy in the preparation of lead frames.
For the lead frame, the lead frame not only needs to meet the requirements of high strength and high heat conductivity, but also needs to have good brazing performance, processing performance, etching performance and other performances.
The invention mainly adds Zn, Cr, Zr, Mg, Ca, V and the like into the copper alloy, utilizes the aging precipitation strengthening of Cr, and Zr inhibits the growth of precipitated phases and the growth of crystal grains, thereby improving the strength of the alloy. Zn element is used for regulating and controlling the electrode potential of a copper matrix, the etching performance of the alloy is improved, the brazing performance of the alloy is improved under the action of a self-brazing agent, and the strength of the alloy is improved through solid solution strengthening. V refines the grain structure of the alloy, makes the grain boundary eccentric, hinders the movement of the grain boundary and improves the heat resistance. The copper alloy has the advantages of easily obtained selected alloy elements, low price, low production cost and low production cost by adopting a semi-continuous casting process, and is an important material for a lead frame of a very large-scale integrated circuit.
Drawings
FIG. 1 is a transmission electron microscope test chart of a high-strength and high-conductivity Cu-Zn-Cr-Zr alloy prepared in example 1.
FIG. 2 is a transmission electron microscope test chart of the high-strength and high-conductivity Cu-Zn-Cr-Zr-based copper alloy prepared in example 2.
FIG. 3 is a transmission electron microscope test chart of the high-strength and high-conductivity Cu-Zn-Cr-Zr alloy prepared in example 3.
Detailed Description
The following are specific examples of the present invention, and the technical solutions of the present invention will be further described with reference to the examples, but the present invention is not limited to the examples.
The invention provides a high-strength high-conductivity Cu-Zn-Cr-Zr copper alloy, which comprises the following components in percentage by mass:
Zn：0.1wt％～1.0wt％，
Cr：0.01wt％～0.8wt％，
Zr：0.1wt％～0.5wt％，
Mg：0.05wt％～1.0wt％，
Ca：0.05wt％～1.0wt％，
V：0.05wt％～0.2wt％，
the balance being copper.
It can be understood that the accurate addition of Zr element in the non-vacuum melting process becomes a common problem in the industry due to the very active chemical property of Zr. According to the invention, by adding the Zn element into the alloy, oxygen in the copper melt can be effectively removed in the smelting process, and the phenomenon that inclusions formed by the reaction of Zr and oxygen are removed by slagging is avoided, so that the accurate addition of the Zr element is realized. The addition of a small amount of Zn element can be solid-dissolved in the copper matrix, and the effect of solid-solution strengthening can be achieved on the basis of not obviously reducing the conductivity. Zn element is dissolved in the copper matrix in a solid solution mode, the electrode potential of the copper matrix is regulated and controlled, and etching processing of the ultra-large scale integrated circuit can be achieved. Zn can play the role of self-fluxing agent and ensure the smooth operation in the brazing process. In addition, the surface of the lead frame strip needs to be plated with Zn, and the old material can be directly used as a raw material without being recycled after the surface plating Zn layer is removed, so that the energy consumption is reduced, and the pollution caused by removing the plating Zn layer is avoided.
Furthermore, the high-strength high-conductivity Cu-Zn-Cr-Zr copper alloy has the characteristics of high strength, high conductivity and easy soldering processing through specific component and proportioning design, and can be widely applied to large-scale integrated circuit lead frames. In addition, 0.8 wt% of chromium element is dissolved in the matrix at high temperature, but the solid solubility is only 0.03% at room temperature, so that under a certain aging process, a large amount of nano-scale bean-shaped particles are precipitated from the matrix by Cr, the precipitation of the particles from the matrix reduces the degree of electron scattering, plays a role in precipitation strengthening, and greatly improves the strength and the electric conductivity of the material.
Specifically, in the high-strength high-conductivity Cu-Zn-Cr-Zr copper alloy, the Mg element can be added into the copper matrix in a solid solution mode, so that the effects of solid solution and remarkable work hardening can be achieved on the premise of not remarkably reducing the conductivity of the alloy, and the alloy is reinforced. Meanwhile, Mg element is added into the copper alloy, so that grains can be refined, and the bending property and the stress relaxation resistance of the alloy are improved. The Ca element can effectively form high-melting-point intermetallic compounds with trace elements such as S, O, Bi, Pb and the like in the copper melt, slag formation and removal are realized, the copper melt is obviously purified, and the conductivity of the finally prepared alloy is obviously improved. Ca contributes to sufficient removal of oxygen, and can further ensure accurate addition of Zr element. The added V can be segregated at the grain boundary, so that the grain structure is refined, the heat resistance of the alloy is improved, and the effect of fine grain strengthening is achieved.
It can be understood that the high-strength and high-conductivity Cu-Zn-Cr-Zr copper alloy does not contain toxic and harmful elements and precious elements in the component ratio, and the alloy components are rich in yield elements. Meanwhile, the old alloy material containing the zinc coating can be directly recycled, and the environmental protection and energy saving significance is great.
Furthermore, the high-strength high-conductivity Cu-Zn-Cr-Zr copper alloy disclosed by the invention is reasonable in components, low in raw material price, simple in production process, low in production cost, good in processability, great in environmental protection and energy saving significance and suitable for industrial production.
The second aspect of the present invention provides a method for producing the above-mentioned high-strength and high-conductivity Cu-Zn-Cr-Zr-based copper alloy, comprising the steps of:
s1: weighing a copper-chromium intermediate alloy, a copper-zirconium intermediate alloy, zinc, a copper-magnesium intermediate alloy, a copper-calcium intermediate alloy, a copper-vanadium intermediate alloy and electrolytic copper according to a ratio, heating and melting the electrolytic copper, and adding the copper-chromium intermediate alloy to obtain a first alloy melt;
s2: adding a copper-magnesium intermediate alloy, a copper-calcium intermediate alloy and a copper-vanadium intermediate alloy into the first alloy melt to obtain a second alloy melt;
s3: after the zinc is added into the second alloy melt, adding the copper-zirconium intermediate alloy, and carrying out semi-continuous casting to obtain a copper alloy ingot;
s4: carrying out hot rolling on the copper alloy cast ingot and then carrying out primary quenching to obtain a hot rolling blank;
s5: sequentially carrying out primary cold rolling, primary aging, secondary cold rolling and secondary aging treatment on the hot rolled blank to obtain a cold rolled blank;
s6: and after the cold rolled blank is subjected to finish rolling, annealing and secondary quenching treatment are carried out.
The combined heat treatment mode formed from the step S1 to the step S6 can ensure that alloy elements are fully precipitated and strengthened alloy from the copper matrix, and the electrical conductivity is obviously improved due to the purification of the matrix. In addition, the preparation method of the high-strength and high-conductivity Cu-Zn-Cr-Zr copper alloy has the advantages of simple production process and low production cost.
In some embodiments of the present invention, in step S1, the temperature of the heating and melting is 1250 ℃ to 1290 ℃.
In the process of heating and melting, cryolite, calcium fluoride, zirconium carbonate and calcium carbonate are used as covering agents, and the volume percentage is 1: 1: 1: 1: 1, covering the calcined charcoal on the upper surface. The melt is covered by acetylene fire in the process of transferring from the smelting furnace to the holding furnace through the flow channel.
In step S1, after the electrolytic copper is heated and melted, the copper-chromium intermediate alloy is added to obtain a first alloy melt, and the furnace temperature is controlled at 1250-1280 ℃.
In step S3, before the semi-continuous casting, the converter performs the semi-continuous casting.
In other embodiments of the present invention, the temperature of the semi-continuous casting is 1270 ℃ to 1320 ℃ in step S3.
In other embodiments of the present invention, in step S3, the average casting speed for the semi-continuous casting is 4.5m/h to 6.5 m/h.
In step S4, before hot rolling, the copper alloy cast ingot is kept at 920-950 ℃ for 6-10 h.
In other embodiments of the present invention, in step S4, the hot rolling passes are 7 to 9.
The hot rolling passes are 7 to 9, wherein the deformation of the first hot rolling pass is 25 to 27 percent, the deformation of the second to fifth hot rolling passes can be increased, and the processing of the subsequent hot rolling passes is gradually reduced. The large deformation of the first few passes can improve the production efficiency in actual production, and meanwhile, the large deformation can crush coarse grains, reduce or eliminate casting defects and improve the subsequent processing performance of the alloy. And then, the material size is accurately controlled through small pass deformation, so that conditions are provided for the continuity and automation of the subsequent process.
In some embodiments of the present invention, in step S5, the first cold rolling pass is two.
Before the first cold rolling, the hot rolled blank is milled, and the milling thickness of the two surfaces is 0.3 mm-0.6 mm respectively.
The first cold rolling pass is twice, wherein the deformation of the first cold rolling pass is 20-26%, and the deformation of the second cold rolling pass is 30-40%.
In other embodiments of the present invention, in step S5, the temperature of the first aging treatment is 450 to 480 ℃.
In other embodiments of the present invention, in step S5, the time of the first aging treatment is 120min to 180 min.
And obtaining the strip after the first aging treatment.
The strip is cold rolled a second time. In the second cold rolling, the deformation of the first cold rolling is 20-22%, and the deformation of the second cold rolling is 30-35%.
The second time aging is performed for 120min to 180min at the temperature of 450 ℃ to 480 ℃.
In step S6, the cold rolled blank is finish rolled, and then annealed and subjected to secondary quenching. Wherein the deformation amount of finish rolling is 35-55%. The annealing temperature is 300-350 ℃, and the annealing is carried out in an air cushion furnace. After annealing, discharging and quenching by nitrogen.
The third aspect of the invention also provides application of the high-strength and high-conductivity Cu-Zn-Cr-Zr copper alloy in preparing a lead frame.
Specifically, the lead frame is required to have not only high strength and high thermal conductivity but also good brazing properties, processing properties, etching properties, and the like. The invention mainly adds Zn, Cr, Zr, Mg, Ca, V and the like into the copper alloy, utilizes the aging precipitation strengthening of Cr, and Zr inhibits the growth of precipitated phases and the growth of crystal grains, thereby improving the strength of the alloy. Zn element is used for regulating and controlling the electrode potential of a copper matrix, the etching performance of the alloy is improved, the brazing performance of the alloy is improved under the action of a self-brazing agent, and the strength of the alloy is improved through solid solution strengthening. V refines the grain structure of the alloy, makes the grain boundary eccentric, hinders the movement of the grain boundary and improves the heat resistance. The copper alloy has the advantages of easily obtained selected alloy elements, low price, low production cost and low production cost by adopting a semi-continuous casting process, and is an important material for a lead frame of a very large-scale integrated circuit.
The technical solution of the present invention can be better understood by referring to the specific examples below.
Example 1
The embodiment prepares the high-strength high-conductivity Cu-Zn-Cr-Zr copper alloy, and concretely adopts the following raw materials for smelting:
electrolytic copper, copper-20% Cr intermediate alloy, copper-25% Ca intermediate alloy, copper-13% zirconium alloy, copper-20% vanadium intermediate alloy, pure zinc and pure magnesium.
The alloy comprises the following components:
Zn：0.4wt％，
Cr：0.38wt％，
Zr：0.2wt％，
Mg：0.10wt％，
Ca：0.05wt％，
V：0.08wt％，
the balance being Cu.
The preparation method comprises the following steps:
smelting:
firstly, drying, heating and melting electrolytic copper, then adding copper-chromium intermediate alloy into electrolytic copper melt to obtain alloy melt, controlling the furnace temperature at 1250-1280 ℃, and adopting cryolite, calcium fluoride, sodium carbonate and pyroborax as covering agents in the melting process, wherein the volume percentage is 1: 1: 1: 1: 1, covering the calcined charcoal on the upper surface. Adding copper-magnesium and copper-calcium intermediate alloys to obtain a melt, adding a zinc ingot to obtain a melt, adding a copper-zirconium intermediate alloy to the melt, and performing semi-continuous casting in a converter at the temperature of 1290-;
hot rolling:
heating and preserving the obtained copper alloy ingot at 940 ℃ for 8 hours, carrying out seven-pass hot rolling, wherein the deformation of the first-pass hot rolling is 25%, the deformation of the second-pass to the fifth-pass are 29%, 30%, 34%, 32%, 24% of the sixth-pass and 20% of the seventh-pass respectively, and quenching to obtain a hot rolling blank; quenching to obtain a hot rolled blank;
first cold rolling and aging:
milling the hot rolled blank, wherein the milled thickness of two surfaces is 0.6mm, the cold rolling deformation of the first pass is 20%, and the cold rolling deformation of the second pass is 40%, so as to obtain a cold rolled blank; aging the obtained cold rolled blank at 450 ℃ for 120 min;
secondary cold rolling and ageing
Cold rolling the obtained aged strip, wherein the deformation of the first cold rolling is 20%, and the deformation of the second cold rolling is 35%, so as to obtain a cold rolling blank; aging the obtained cold rolled blank at 450 ℃ for 150 min;
finish rolling and finished product annealing:
and (3) carrying out cold rolling on the obtained cold rolled blank with 40% of deformation, annealing in a 300 ℃ air cushion furnace, and discharging and quenching in nitrogen to obtain the copper alloy plate.
The actual measurement components of the copper alloy plate are as follows: 0.38 wt% of Zn, 0.35 wt% of Cr, 0.18 wt% of Zr, 0.08 wt% of Mg, 0.08 wt% of Ca, 0.05 wt% of V and the balance of copper.
Example 2
The embodiment prepares the high-strength high-conductivity Cu-Zn-Cr-Zr copper alloy, and concretely adopts the following raw materials for smelting:
electrolytic copper, copper-20% Cr intermediate alloy, copper-25% Ca intermediate alloy, copper-20% vanadium intermediate alloy, copper-13% zirconium alloy, pure zinc and pure magnesium.
The alloy comprises the following components:
Zn：0.4wt％，
Cr：0.38wt％，
Zr：0.2wt％，
Mg：0.10wt％，
Ca：0.05wt％，
V：0.08wt％，
the balance being Cu.
The preparation method comprises the following steps:
smelting:
firstly, drying electrolytic copper, heating and melting, then adding copper-chromium intermediate alloy into electrolytic copper melt to obtain alloy melt, controlling the furnace temperature at 1250-: 1: 1: 1: 1, covering the calcined charcoal on the upper surface. Adding copper-magnesium and copper-calcium intermediate alloys to obtain a melt, adding a zinc ingot to obtain a melt, adding a copper-zirconium intermediate alloy to obtain a melt, and performing semi-continuous casting in a converter at 1280-1300 ℃ with the average casting speed of 5.2 m/h;
hot rolling:
heating and preserving the obtained copper alloy ingot at 940 ℃ for 8 hours, carrying out seven-pass hot rolling, wherein the deformation of the first-pass hot rolling is 25%, the deformation of the second-pass to the fifth-pass are respectively 29%, 30%, 36%, 30%, 22% and 20% of the deformation of the seventh-pass, and quenching to obtain a hot rolling blank; quenching to obtain a hot rolled blank;
first cold rolling and aging:
milling the obtained hot rolled blank to obtain a cold rolled blank, wherein the milled thickness of two surfaces is 0.5mm, the cold rolling deformation of the first pass is 20%, and the cold rolling deformation of the second pass is 45%; aging the obtained cold rolled blank at 450 ℃ for 120 min;
second cold rolling and aging:
cold rolling the obtained aged strip, wherein the deformation of the first cold rolling is 20%, and the deformation of the second cold rolling is 40%, so as to obtain a cold rolling blank; aging the obtained cold rolled blank at 450 ℃ for 90 min;
finish rolling and finished product annealing
And (3) carrying out cold rolling on the obtained cold rolled blank with 50% of deformation, annealing in a 320 ℃ air cushion furnace, discharging and quenching in nitrogen to obtain the copper alloy plate.
The actual measurement of the copper alloy sheet material is as follows: 0.37 wt% of Zn, 0.36 wt% of Cr, 0.19 wt% of Zr, 0.07 wt% of Mg, 0.08wt% of Ca0.06 wt% of V and the balance of copper.
Example 3
The embodiment prepares the high-strength high-conductivity Cu-Zn-Cr-Zr copper alloy, and concretely adopts the following raw materials for smelting:
electrolytic copper, copper-20% Cr intermediate alloy, copper-25% Ca intermediate alloy, copper-20% vanadium intermediate alloy, copper-13% zirconium alloy, pure zinc and pure magnesium.
The alloy comprises the following components:
Zn：0.4wt％，
Cr：0.35wt％，
Zr：0.35wt％，
Mg：0.15wt％，
Ca：0.05wt％，
V：0.08wt％，
the balance being Cu.
The preparation method comprises the following steps:
smelting:
firstly, drying, heating and melting electrolytic copper, then adding a copper-chromium intermediate alloy into electrolytic copper melt to obtain an alloy melt, controlling the furnace temperature at 1270-: 1: 1: 1: 1, covering the calcined charcoal on the upper surface. Adding copper-magnesium and copper-calcium intermediate alloys to obtain a melt, adding a zinc ingot to obtain a melt, adding a copper-zirconium intermediate alloy to obtain a melt, and performing semi-continuous casting in a converter at 1280-1300 ℃ with the average casting speed of 4.7 m/h;
hot rolling:
heating and preserving the obtained copper alloy ingot at 970 ℃ for 8 hours, carrying out seven-pass hot rolling, wherein the deformation of the first-pass hot rolling is 19%, the deformation of the second-pass to the fifth-pass hot rolling is 22%, 27%, 35%, 30%, 20% of the sixth-pass and 19% of the seventh-pass hot rolling, and quenching to obtain a hot rolling blank; quenching to obtain a hot rolled blank;
first cold rolling and aging:
milling the obtained hot rolled blank to obtain a cold rolled blank, wherein the milled thickness of two surfaces is 0.8mm, the cold rolling deformation of the first pass is 20%, and the cold rolling deformation of the second pass is 45%; aging the obtained cold rolled blank at 450 ℃ for 120 min;
second cold rolling and aging:
cold rolling the obtained aged strip, wherein the deformation of the first cold rolling is 20%, and the deformation of the second cold rolling is 40%, so as to obtain a cold rolling blank; aging the obtained cold rolled blank at 450 ℃ for 90 min;
finish rolling and finished product annealing:
and (3) carrying out cold rolling on the obtained cold rolled blank with 50% of deformation, annealing in a 320 ℃ air cushion furnace, discharging and quenching in nitrogen to obtain the copper alloy plate.
The actual measurement of the copper alloy sheet material is as follows: 0.37 wt% of Zn, 0.33 wt% of Cr, 0.31 wt% of Zr, 0.05 wt% of Ca, 0.12wt% of Mg0.05, 0.05 wt% of V, and the balance of copper
Example 4
The embodiment prepares the high-strength high-conductivity Cu-Zn-Cr-Zr copper alloy, and concretely adopts the following raw materials for smelting:
electrolytic copper, copper-20% Cr intermediate alloy, copper-25% Ca intermediate alloy, copper-20% vanadium intermediate alloy, copper-13% zirconium alloy, pure zinc and pure magnesium.
The alloy comprises the following components:
Zn：0.3wt％，
Cr：0.35wt％，
Zr：0.15wt％，
Mg：0.1wt％，
Ca：0.1wt％，
V：0.05wt％，
the balance being Cu.
The preparation method comprises the following steps:
smelting:
firstly, drying, heating and melting electrolytic copper, then adding a copper-chromium intermediate alloy into an electrolytic copper melt to obtain an alloy melt, controlling the furnace temperature at 1260-: 1: 1: 1: 1, covering the calcined charcoal on the upper surface. Adding copper-magnesium and copper-calcium intermediate alloys to obtain a melt, adding a zinc ingot to obtain a melt, adding a copper-zirconium intermediate alloy to the melt, and performing semi-continuous casting at 1270-;
hot rolling:
heating and preserving heat of the copper alloy cast ingot at 970 ℃ for 8 hours, carrying out seven-pass hot rolling, wherein the deformation of the first-pass hot rolling is 19%, the deformation of the second-pass to the fifth-pass are 22%, 29%, 35%, 30%, 20% of the sixth-pass and 19% of the seventh-pass hot rolling, and quenching to obtain a hot rolling blank; quenching to obtain a hot rolled blank;
first cold rolling and aging:
milling the obtained hot rolled blank to obtain a cold rolled blank, wherein the milled thickness of two surfaces is 0.8mm, the cold rolling deformation of the first pass is 20%, and the cold rolling deformation of the second pass is 45%; aging the obtained cold rolled blank at 450 ℃ for 120 min;
second cold rolling and aging:
cold rolling the obtained aged strip, wherein the deformation of the first cold rolling is 20%, and the deformation of the second cold rolling is 40%, so as to obtain a cold rolling blank; aging the obtained cold rolled blank at 450 ℃ for 90 min;
finish rolling and finished product annealing:
and (3) carrying out cold rolling on the obtained cold rolled blank with 50% of deformation, annealing in a 330 ℃ air cushion furnace, discharging and quenching in nitrogen to obtain the copper alloy plate.
The actual measurement of the copper alloy sheet material is as follows: 0.29 wt% of Zn, 0.32 wt% of Cr, 0.12 wt% of Zr, 0.07 wt% of Mg, 0.06 wt% of Ca, 0.08 wt% of V and the balance of copper.
Comparative example 1
The comparative example prepares a copper alloy, and the actual measurement components are as follows: 0.4 wt% of Cr, 0.19 wt% of Zr, 0.08 wt% of Mg, 0.05 wt% of Ca, 0.08 wt% of V and the balance of copper.
The preparation method is the same as in example 4.
Comparative example 2
The comparative example prepares a copper alloy, and the actual measurement components are as follows: 0.4 wt% of Cr, 0.19 wt% of Zr, 0.08 wt% of Mg, 0.05 wt% of Ca, 0.08 wt% of V and the balance of copper.
The preparation method is the same as in example 4.
Test example 1
The copper alloys prepared in examples 1 to 4 were tested for tensile strength, electrical conductivity and elongation.
Wherein, the standard of the test basis of the tensile strength and the elongation is GB/T34505-2017.
The conductivity test is based on the standard GB/T32791-2016.
The results are shown in Table 1.
TABLE 1
| Tensile strength/MPa | Conductivity/% IACS | Elongation/% of | |
| Example 1 | 712 | 70.2 | 5.8 |
| Example 2 | 718 | 73.3 | 5.6 |
| Example 3 | 734 | 71.3 | 4.3 |
| Example 4 | 687 | 76.8 | 6.4 |
| Comparative example 1 | 553 | 82.5 | 6.5 |
| Comparative example 2 | 530 | 83.0 | 6.7 |
Test example 2
The microscopic morphologies of the copper alloys prepared in examples 1 to 3 were observed by transmission electron microscopy, as shown in fig. 1 to 3, respectively.
As can be seen from fig. 1 to 3, the copper alloys prepared in examples 1 to 3 have a large amount of dislocation pinning (black lines in fig. 1 to 3), indicating that there is a pinning dislocation effect.
As can be seen from fig. 1 to 3, the copper alloys prepared in examples 1 to 3 precipitate a large amount of nano strengthening phases (indicated by white dashed boxes in fig. 1 to 3), and form a cellular structure by the movement of pinning dislocations of strengthening phase particles, so that the fine-grain strengthening effect is remarkable.
The present invention has been described in detail with reference to the embodiments, but the present invention is not limited to the embodiments described above, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention.
Claims (10)
1. A high-strength high-conductivity Cu-Zn-Cr-Zr copper alloy is characterized by comprising the following components in percentage by mass:
Zn：0.1wt％～1.0wt％，
Cr：0.01wt％～0.8wt％，
Zr：0.1wt％～0.5wt％，
Mg：0.05wt％～1.0wt％，
Ca：0.05wt％～1.0wt％，
V：0.05wt％～0.2wt％，
the balance being copper.
2. The high-strength high-conductivity Cu-Zn-Cr-Zr alloy according to claim 1, wherein said high-strength high-conductivity Cu-Zn-Cr-Zr alloy comprises the following components in mass percent:
Zn：0.4wt％～1.0wt％，
Cr：0.3wt％～0.8wt％，
Zr：0.2wt％～0.5wt％，
Mg：0.1wt％～1.0wt％，
Ca：0.05wt％～1.0wt％，
V：0.05wt％～0.2wt％，
the balance being copper.
3. A method for producing the high-strength high-conductivity Cu-Zn-Cr-Zr-based copper alloy according to claim 1 or 2, characterized by comprising the steps of:
s1: weighing a copper-chromium intermediate alloy, a copper-zirconium intermediate alloy, zinc, a copper-magnesium intermediate alloy, a copper-calcium intermediate alloy, a copper-vanadium intermediate alloy and electrolytic copper according to a ratio, heating and melting the electrolytic copper, and adding the copper-chromium intermediate alloy to obtain a first alloy melt;
s2: adding the copper-magnesium intermediate alloy, the copper-calcium intermediate alloy and the copper-vanadium intermediate alloy into the first alloy melt to obtain a second alloy melt;
s3: after the zinc is added into the second alloy melt, adding the copper-zirconium intermediate alloy, and carrying out semi-continuous casting to obtain a copper alloy ingot;
s4: carrying out hot rolling on the copper alloy cast ingot and then carrying out primary quenching to obtain a hot rolling blank;
s5: sequentially carrying out primary cold rolling, primary aging, secondary cold rolling and secondary aging treatment on the hot rolled blank to obtain a cold rolled blank;
s6: and after the cold rolled blank is subjected to finish rolling, annealing and secondary quenching treatment are carried out.
4. The method as claimed in claim 3, wherein the temperature of the heating and melting in step S1 is 1250 ℃ to 1290 ℃.
5. The method according to claim 3, wherein in step S3, the temperature of the semi-continuous casting is 1270 ℃ to 1320 ℃.
6. The method according to claim 3, wherein in step S3, the average casting speed of the semi-continuous casting is 4.5m/h to 6.5 m/h.
7. The method according to claim 3, wherein in step S4, the hot rolling passes are 7 to 9.
8. The method of claim 3, wherein in step S5, the first cold rolling pass is performed in two passes.
9. The method according to claim 3, wherein the temperature of the first aging in step S5 is 450-480 ℃.
10. Use of the high-strength high-conductivity Cu-Zn-Cr-Zr-based copper alloy according to claim 1 or 2 for the preparation of lead frames.
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| CN115896512A (en) * | 2022-12-25 | 2023-04-04 | 中国兵器科学研究院宁波分院 | Preparation method of copper alloy material for high-precision etched lead frame |
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