CN114807672B - Cu-Zn-Cr-Zr-Fe-Si alloy and method for producing same - Google Patents

Cu-Zn-Cr-Zr-Fe-Si alloy and method for producing same Download PDF

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CN114807672B
CN114807672B CN202210286129.8A CN202210286129A CN114807672B CN 114807672 B CN114807672 B CN 114807672B CN 202210286129 A CN202210286129 A CN 202210286129A CN 114807672 B CN114807672 B CN 114807672B
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copper
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CN114807672A (en
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姜雁斌
吴子潇
李周
辛钊
秦柳馨
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Central South University
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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
    • C22C9/04—Alloys based on copper with zinc as the next major constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23P—METAL-WORKING NOT OTHERWISE PROVIDED FOR; COMBINED OPERATIONS; UNIVERSAL MACHINE TOOLS
    • B23P15/00—Making specific metal objects by operations not covered by a single other subclass or a group in this subclass
    • 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
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/0081—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for slabs; for billets
    • 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
    • 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
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/10—Alloys based on copper with silicon as the next major constituent
    • 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
    • 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
    • C22F1/02—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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E30/00—Energy generation of nuclear origin
    • Y02E30/30—Nuclear fission reactors

Abstract

The invention relates to a Cu-Zn-Cr-Zr-Fe-Si alloy and a preparation method thereof. The Cu-Zn-Cr-Zr-Fe-Si alloy has the hardness of 180-250 HV, the tensile strength of 600-750 MPa, the yield strength of 550-700 MPa, the elastic modulus of 125-135 MPa, the elongation of 3-10%, the electrical conductivity of 70-85% IACS, the heat-resistant temperature of more than or equal to 580 ℃ and the residual stress of less than or equal to 30MPa, and solves the problems that the strength, the electrical conductivity, the softening resistance and the low residual stress of the traditional Cu-Cr-Zr alloy are difficult to be compatible and matched. The invention also provides a preparation method of the Cu-Zn-Cr-Zr-Fe-Si alloy.

Description

Cu-Zn-Cr-Zr-Fe-Si alloy and method for producing same
Technical Field
The invention belongs to the technical field of alloy preparation, and particularly relates to a Cu-Zn-Cr-Zr-Fe-Si alloy and a preparation method thereof.
Background
The Cu-Cr-Zr alloy has good electrical conductivity, thermal conductivity, wear resistance and moderate strength, and has wide application in modern information industries such as 5G communication, high-end integrated circuits and the like, and high-end manufacturing industries such as rail transit, advanced weapons and the like. In the related art, most Cu-Cr-Zr copper alloys have a tensile strength of 500 to 600MPa and an electrical conductivity of 70 to 85% IACS. With the rapid development of the high and new technology industry, the use requirement on the alloy is higher and higher. Taking an integrated circuit lead frame as an example, as integrated circuits are developed in the direction of extremely large scale, the lead frame is developed in the direction of multi-foot, high density, ultra-thin, miniaturization and the like, copper alloy is required to have high strength and conductivity, high softening temperature resistance, low residual stress, easy welding, good etching performance and the like, and the conventional Cu-Cr-Zr alloy is difficult to meet the requirements for manufacturing the lead frame of the high-end integrated circuit.
CN1254554C discloses a high-strength high-conductivity rare earth copper alloy and a preparation method thereof. The technology adopts the addition of rare earth elements to improve the mechanical property of the alloy, 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 tensile strength of the alloy wire prepared by the technology is 760MPa, the conductivity is 84.7% iacs, and the components consist of: cr 1.5%, zr 0.1%, mg 0.05%, and the balance Cu and unavoidable impurities. The Cr content in the technology is higher and is 1.5-15.0wt%, and because the solid solubility of Cr in the copper matrix is extremely low at room temperature, the maximum solid solubility of Cr in the copper alloy is 0.65% at 1070 ℃, and a large amount of fibrous Cr phase particles formed in the copper matrix strengthen the alloy wire through large deformation drawing processing. However, in the first aspect, for the Cu-Cr-Zr-Mg alloy sheet strip 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, so that the strengthening effect is weak, and the strength of the alloy is low; in the second aspect, the higher Cr content (more than 1 wt%) is easy to form coarse Cr phase particles in the copper matrix, and the difference between the deformation behaviors of the Cr phase and the copper matrix is larger, so that the residual stress in the processed alloy is larger, the difficulty in controlling the band-shaped and size precision of the alloy is large, the phenomenon of uneven micro-area corrosion is serious, and the requirement for manufacturing the lead frame of the integrated circuit cannot be met; in a third aspect, the addition of higher Cr content increases the raw material cost of the alloy. Therefore, there remains a need to develop new alloys with high strength, high electrical conductivity, high softening temperature resistance, low residual stress.
Disclosure of Invention
The present invention aims to solve at least one of the above technical problems in the prior art. Therefore, the invention provides the Cu-Zn-Cr-Zr-Fe-Si alloy, which realizes the comprehensive effects of multiphase collaborative strengthening, strain strengthening, sub-crystal strengthening, solid solution strengthening and the like, and has the characteristics of high strength, high conductivity, high softening temperature resistance, low residual stress and the like.
The invention also provides a method for preparing the Cu-Zn-Cr-Zr-Fe-Si alloy.
The first aspect of the present invention provides a Cu-Zn-Cr-Zr-Fe-Si alloy comprising, in mass percent:
Zn：0.1wt％～1.00wt％，
Cr：0.01wt％～1.00wt％，
Zr：0.10wt％～0.60wt％，
Fe：0.05wt％～1.00wt％，
Si：0.05wt％～1.00wt％，
the balance being copper.
The invention relates to one of the technical schemes of Cu-Zn-Cr-Zr-Fe-Si alloy, which has at least the following beneficial effects:
the Cu-Zn-Cr-Zr-Fe-Si alloy has the hardness of 180-250 HV, the tensile strength of 600-750 MPa, the yield strength of 550-700 MPa, the elastic modulus of 125-135 MPa, the elongation of 3-10%, the electrical conductivity of 70-85% IACS, the heat-resistant temperature of more than or equal to 580 ℃ and the residual stress of less than or equal to 30MPa, and solves the problems that the strength, the electrical conductivity, the softening resistance and the low residual stress of the traditional Cu-Cr-Zr alloy are difficult to be compatible and matched.
The Cu-Zn-Cr-Zr-Fe-Si alloy can meet the requirements of modern information industries such as very large-scale integrated circuits, 5G communication, high-end electronic elements and the like for high-performance alloys in rapid development of rail transit.
According to the Cu-Zn-Cr-Zr-Fe-Si alloy, various strengthening phases are introduced into a copper matrix by adding alloy elements, so that the alloy elements are fully dispersed and separated out by high-hardness and high-heat-resistance nanoscale FeSi and Cr phase particles, interaction between the precipitated phase particles and dislocation is strengthened, comprehensive strengthening effects such as multiphase collaborative dispersion strengthening, strain strengthening, sub-crystal strengthening, solid solution strengthening and the like are realized, and meanwhile, the strength and the conductivity of the copper alloy are improved.
The Cu-Zn-Cr-Zr-Fe-Si alloy of the invention, through reasonably controlling the content and the proportion of Zn and Zr, on one hand, strengthens the copper matrix by utilizing the solid solution effect of Zn element, reduces the residual stress of the alloy and improves the etching performance, and on the other hand, forms Cu with good heat resistance stability in the copper matrix 3 Zr phase, simultaneously plays the role of promoting nano Cr phase particles to disperse and separate out and larger solid solution strengthening by adding Zn, and combines the regulation and control of the preparation process to ensure submicron Cu 3 Zr、Cr 2 The Si phase is intermittently distributed in the grain boundary, so that dislocation and movement of the grain boundary under the high temperature condition can be effectively pinned, and the high temperature softening resistance of the copper alloy is greatly improved on the basis of ensuring the high strength and high conductivity of the copper alloy.
In the Cu-Zn-Cr-Zr-Fe-Si alloy of the present invention:
zn, fe and Si are low in price, and the mechanical properties of the copper alloy can be obviously improved by adding the Zn, fe and Si into the copper alloy and regulating and controlling the processing and heat treatment processes, and meanwhile, the influence on the conductivity is small. The invention utilizes Zn element with larger solid solubility in the copper matrix, has obvious solid solution strengthening effect, can effectively improve the strength of the copper alloy matrix, reduces the strength and hardness between the copper matrix and the precipitated phase, and is beneficial to reducing the residual stress generated in the subsequent processing process of the copper alloy. Meanwhile, the electrode potential of the copper matrix can be regulated and controlled by adding Zn element, which is beneficial to improving the etching performance of the copper alloy.
The invention utilizes the strong binding energy of Fe and Si to form Fe-Si phase with high hardness and high heat resistance. In addition, the Fe-Si phase has stronger precipitation capability than the Fe phase, and promotes the precipitation of Fe atoms in the matrix. Therefore, the addition of base metal Fe element to Si to form hard Fe-Si phase to replace Cr phase can solve the problem of insufficient strength caused by the precipitation strengthening of Cr phase only in the conventional Cu-Cr-Zr alloy, and has great significance in both material cost and use performance improvement.
The precipitated phases formed by Fe element and Si element include FeSi, beta-FeSi 2 、α-FeSi 2 、Fe 2 Si、Fe 5 Si 3 、Fe 11 Si 5 、Fe 3 Si. The FeSi phase has the largest shear modulus and Young's modulus, which indicates that the FeSi phase has the strongest deformation resistance, the largest hardness and the best strengthening effect. Furthermore, the FeSi phase has a smaller poisson's ratio than Fe, which is 0.21 (below 0.25), indicating that the FeSi phase is a hard brittle phase. The higher brittleness makes the FeSi primary phase easier to break during cold working, and the FeSi primary phase is distributed in the matrix in fine dispersed particles during subsequent heat treatment, which is beneficial to improving the dispersion strengthening effect of the alloy. Therefore, the content and the proportion of Fe and Si are very important. The conductivity of the alloy is mainly influenced by the electron scattering effect of solute atoms in the matrix, so that the conductivity of the alloy is obviously improved along with the precipitation of trace elements. In order to synergistically improve the strength and conductivity of the alloy, si and Fe elements dissolved in the matrix must be precipitated as FeSi phases, respectively, as much as possible.
In addition, the key points of the Cu-Zn-Cr-Zr-Fe-Si alloy of the invention also comprise reasonable regulation and control of Zn, cr, zr, fe, si and other element contents and proportions, properly increase the contents of Cr, fe and Si, and pass through target precipitated phases such as Cr and Cr 2 The mass ratio of Si, feSi and the like, the upper limit and the lower limit of the content of each element in the alloy are obtained, and the alloy components are directionally designed by combining Cr-Si and Fe-Si phase diagrams.
If the Zn content is too small, on one hand, the solid solution strengthening effect of the alloy is small, and on the other hand, the effect of controlling the residual stress and etching performance of the alloy is not obvious; if the Zn content is too large, the conductivity of the alloy is significantly reduced. If the Cr content is too small, the number of Cr phases precipitated after aging is small, the precipitation strengthening effect is not obvious, and the strength of the alloy is low; if the Cr content is too much, coarse Cr phase particles are easy to form in the copper matrix, the Cr phase strengthening effect is low, meanwhile, the residual stress in the processed alloy is large due to the large difference of deformation behaviors of the Cr phase and the copper matrix, the difficulty in controlling the band-shaped and size precision of the alloy is large, especially when an etched lead frame is manufactured, the phenomenon of uneven micro-area corrosion is serious, and the requirement of manufacturing the integrated circuit lead frame cannot be met; in addition, the addition of higher Cr content increases the raw material cost of the alloy.
If the Fe content is too small, the quantity of FeSi phases formed in the alloy is small, and the precipitation strengthening effect is not obvious; if the Fe content is too much, on one hand, most Si atoms are consumed to form a coarse brittle FeSi primary phase, so that a casting blank is easy to crack in the subsequent processing process, the yield is low, and on the other hand, the conductivity is reduced due to the excessive Fe.
If the Si content is too small, on the one hand, the Cr and Fe elements are not available as FeSi and Cr 2 Si phase is fully separated out, the strengthening effect is limited, and solute atoms, especially Fe element, remained in the matrix seriously jeopardize the conductivity of the alloy. If the Si content is too large, the second phase is promoted to be precipitated as much as possible, but the excessive Si element remains in the copper matrix, which also results in a decrease in the electrical conductivity of the alloy. Wherein the control of Si content should be based mainly on the sufficient consumption of Fe element.
The Zr element is added to inhibit coarsening of Cr phase and refine matrix grains in aging process. If the Zr content is too small, cr phase is easy to grow and coarsen in the aging process, the precipitation strengthening effect of the Cr phase is reduced, and submicron Cu is formed at the grain boundary 3 Zr is smaller, which is not beneficial to improving the high temperature softening resistance; if Zr content is too much, more coarse Cu is generated in the alloy casting process 3 Zr and Cu 5 Zr phase, reducing strengthening effect. Therefore, the content and the proportion of each element are comprehensively considered to prepare the high-strength high-conductivity Cu-Zn-Cr-Zr-Fe-Si alloy designed by the invention.
According to some embodiments of the present invention, the Cu-Zn-Cr-Zr-Fe-Si alloy comprises the following components in mass percent:
Zn：0.40wt％～1.00wt％，
Cr：0.30wt％～1.00wt％，
Zr：0.15wt％～0.60wt％，
Fe：0.20wt％～1.00wt％，
Si：0.40wt％～1.00wt％，
the balance being copper.
The second aspect of the present invention provides a method for producing the above Cu-Zn-Cr-Zr-Fe-Si alloy, comprising the steps of:
s1: preparing materials according to a proportion, firstly melting copper, then adding zinc and a covering agent, then adding iron, adding silicon after first heat preservation, adding chromium and zirconium after cooling, and carrying out second heat preservation to obtain an ingot;
s2: carrying out homogenizing annealing treatment on the cast ingot obtained in the step S1 in a protective atmosphere;
s3: performing heat processing deformation treatment on the cast ingot processed in the step S2, and then performing quenching treatment to obtain a heat processing blank;
s4: and (3) carrying out solution treatment, cold working treatment and aging treatment on the blank obtained in the step (S3) in a protective atmosphere.
The invention relates to a technical scheme in a method for preparing Cu-Zn-Cr-Zr-Fe-Si alloy, which has at least the following beneficial effects:
the preparation method of the Cu-Zn-Cr-Zr-Fe-Si alloy provided by the invention has the advantages that the hardness of the prepared Cu-Zn-Cr-Zr-Fe-Si alloy is 180-250 HV, the tensile strength is 600-750 MPa, the yield strength is 550-700 MPa, the elastic modulus is 125-135 MPa, the elongation is 3-10%, the conductivity is 70-85% IACS, the heat-resistant temperature is more than or equal to 580 ℃, the residual stress is less than or equal to 30MPa, and the problems that the strength, the conductivity, the softening resistance and the low residual stress of the conventional Cu-Cr-Zr alloy are difficult to be compatible and matched are solved.
According to the method for preparing the Cu-Zn-Cr-Zr-Fe-Si alloy, disclosed by the invention, the existence form and the spatial distribution state of elements such as Zn, cr, zr, fe, si in the alloy are regulated and controlled by designing a combined deformation heat treatment technology of cold working and heat treatment cooperative control, the multi-scale, multi-form and multi-phase cooperative strengthening effect is exerted, the strength and the conductivity can be simultaneously improved, and the excellent comprehensive performance is obtained. Adopts 'large deformation cold working + high temperature short time aging treatment' to crush and refine Cr and FeSi primary phases. Subsequent thermal treatment further refines Cr, feSi, cr 2 Si phase particles and promote the residual Cr, si and Fe atoms to be in a small bean shape and an ellipsoidal shapeThe nanometer level particle forms are nucleated and separated out at the defects of dislocation, sub-crystal, twin crystal, etc. introduced by cold working. However, the precipitation form of solute atoms is very sensitive to factors such as temperature, time and the like, so that the formulation of process parameters plays an important role in the existence form and the spatial distribution state of elements in the alloy.
If the cold working deformation is too small, the nucleation energy storage of Cr phase and FeSi phase can not be provided, the precipitation of other atoms is also influenced, and meanwhile, cu formed in the solidification process of the alloy is not sufficiently crushed 3 Zr、Cr 2 Si primary phase, causing the problems of poor subsequent processing performance and the like; if the cold working deformation is too large, on one hand, the alloy is severely processed and hardened, the defects such as cracks are easy to generate, the yield is reduced, and on the other hand, larger deformation energy storage is formed, the recrystallization of the copper matrix in the subsequent aging process is easy to be induced, and the strength of the alloy is obviously reduced.
If the heat treatment temperature is too low, the diffusion speed of solute atoms is weakened, on one hand, cr phase and FeSi phase cannot be fully dispersed and separated out, the strengthening effect is small, and on the other hand, solute atoms are not diffused and remain in the matrix, so that the scattering of electrons is increased, and the conductivity is not improved. If the heat treatment temperature is too high, cr and FeSi phase particles are easy to grow up, and recrystallization of a copper matrix is easy to be induced, so that the strength of the alloy is obviously reduced; if the aging time is too short, a part of Cr and FeSi phase particles can be precipitated, but most of Cr, si and Fe atoms are not precipitated, and remain in the copper matrix, which also deteriorates the strength and conductivity. If the aging time is too long, various precipitated phase particles grow up and coarsen, and the strengthening effect is poor.
According to the invention, the comprehensive effects among component design and processing-heat treatment systems are comprehensively considered, on one hand, the content and the proportion of elements such as Zn, cr, zr, fe, si are optimized, the solid solution effect of Zn element is utilized to strengthen a copper matrix, the residual stress of the alloy is reduced, the etching performance is improved, fe and Si elements are combined to form a FeSi phase with high hardness and high heat resistance, the defect of the strengthening effect of a single Cr phase is overcome, and the strength and the high-temperature softening resistance of the alloy are improved; on the other hand, elements such as Cr, si, fe and the like are fully separated out and dispersed uniformly in a matrix by regulating and controlling a processing and heat treatment system respectively in nano-scale Cr and FeSi phases, and the pinning dislocation and the grain boundary move to exert the comprehensive effects of multi-scale multi-form multiphase synergistic dispersion strengthening, strain strengthening, sub-crystal strengthening, solid solution strengthening and the like, so that the Cu-Zn-Cr-Zr-Fe-Si alloy is obtained.
According to some embodiments of the invention, in step S1, the temperature of the first incubation is 1300 ℃ to 1500 ℃ for 1min to 3min.
According to some embodiments of the invention, in step S1, the first incubation is performed at a temperature of 1400 ℃ for a period of 2min.
According to some embodiments of the invention, in step S1, after adding silicon, the temperature is reduced to 1250 ℃.
According to some embodiments of the invention, in step S1, the temperature of the second incubation is 1250 ℃ to 1300 ℃ for 2min to 4min.
According to some embodiments of the invention, in step S1, the second incubation time is 3min.
According to some embodiments of the invention, in step S2, the temperature of the homogenizing annealing treatment is 880-980 ℃ for 1-8 hours.
According to some embodiments of the present invention, in step S2, during the homogenizing annealing treatment, charcoal is spread around the melted copper alloy ingot in a protective atmosphere, and the homogenizing annealing treatment is performed.
According to some embodiments of the invention, in step S3, the ingot is milled to the surface without defects prior to the heat treatment.
According to some embodiments of the invention, in step S3, the temperature of the thermal deformation treatment is 880-960 ℃, the time is 0.5-2 h, and the deformation amount is 50-90%.
According to some embodiments of the present invention, in step S3, after the heat processing treatment, a quenching treatment is performed, where the quenching treatment is water quenching, and after quenching, the surface is milled again until the surface of the ingot is free of oxide layer.
According to some embodiments of the invention, in step S4, the temperature of the solution treatment is 880-960 ℃ for 1-8 hours.
According to some embodiments of the invention, in step S4, after the solution treatment, a quenching treatment is performed, wherein the quenching treatment is water quenching, and after the quenching, the surface is milled again until the surface of the ingot is free of oxide layer.
In some embodiments of the invention, in step S4, the deformation amount of the cold working treatment is 50% to 90%.
According to some embodiments of the invention, in step S4, the object shape of the cold working process is a sheet material.
According to some embodiments of the invention, in step S4, after the cold working treatment, aging is performed for 1min to 24h at 400 ℃ to 550 ℃ in a protective atmosphere. And (5) carrying out cold working on the aged sample with the deformation of 40% -90%. The deformation amount for the second or third cold working is determined according to the thickness. In general, if the initial deformation is less than 50%, it is preferable to follow the deformation by 70 to 90%. If the first deformation is larger than 50%, the deformation is performed again by 30% -50%, and finally the final alloy is obtained after aging for 15 min-2 h at 400-500 ℃ according to the same method.
In the present invention, hot working includes hot extrusion, hot rolling and hot forging.
In the present invention, cold working includes drawing, rolling, spinning and swaging.
Drawings
FIG. 1 is a transmission electron microscope test result of the alloy material prepared in example 1.
FIG. 2 is a transmission electron microscope test result of the alloy material prepared in example 2.
Detailed Description
The following are specific embodiments of the present invention, and the technical solutions of the present invention will be further described with reference to the embodiments, but the present invention is not limited to these embodiments.
Example 1
The Cu-Zn-Cr-Zr-Fe-Si alloy specifically prepared in this example comprises the following components:
Zn：0.3wt％，
Cr：0.58wt％，
Zr：0.2wt％，
Fe：0.25wt％，
Si：0.12wt％，
the balance being copper.
The preparation method comprises the following steps:
s1: preparing materials according to a proportion, firstly melting copper, then adding zinc and a covering agent, then adding iron, adding silicon after first heat preservation, adding chromium and zirconium after cooling, and carrying out second heat preservation to obtain an ingot;
s2: carrying out homogenizing annealing treatment on the cast ingot obtained in the step S1 in a protective atmosphere;
s3: performing heat processing deformation treatment on the cast ingot processed in the step S2, and then performing quenching treatment to obtain a heat processing blank;
s4: and (3) carrying out solution treatment, cold working treatment and aging treatment on the blank obtained in the step (S3) in a protective atmosphere.
In step S1:
the temperature of the first heat preservation is 1400 ℃ and the time is 2min.
After the addition of silicon, the temperature was reduced to 1250 ℃.
The temperature of the second heat preservation is 1300 ℃ and the time is 3min.
In step S2:
the temperature of the homogenizing annealing treatment is 960 ℃, and the time is 1-8 hours.
During the homogenizing annealing treatment, the melted copper alloy cast ingot is fully covered with charcoal in a protective atmosphere, and the homogenizing annealing treatment is carried out.
In step S3:
before heat processing, the ingot is milled to the surface without defects.
The temperature of the hot working deformation treatment is 940 ℃, the time is 2h, seven-pass hot rolling is carried out, the deformation of the first pass hot rolling is 25%, the deformation of the second pass to the fifth pass hot rolling is 22%,25%,32%,34%, 24% of the sixth pass and 20% of the seventh pass respectively.
After the heat processing treatment, quenching treatment is carried out in a water quenching mode, and after quenching, milling the surface again until no oxide layer exists on the surface of the cast ingot.
In step S4:
the temperature of the solution treatment is 940 ℃ and the time is 8 hours.
After solution treatment, quenching treatment is carried out in a water quenching mode, and after quenching, milling the surface again until no oxide layer exists on the surface of the cast ingot.
The deformation amount in the cold working treatment was 70%.
After cold working, aging was carried out in a protective atmosphere at 400℃for 150min.
And (3) carrying out cold rolling deformation of 20% for the first time and 40% for the second time on the aged sample to obtain a cold rolled blank. The deformation amount for the second cold working is determined according to the thickness. And (3) carrying out cold rolling on the obtained cold rolled blank with the deformation of 40%, annealing in a 300 ℃ air cushion furnace, and discharging nitrogen for quenching to obtain the copper alloy sheet.
The alloy hardness is 213HV, the tensile strength is 720MPa, the conductivity is 70.2% IACS, and the elongation is 5.5%.
Example 2
The Cu-Zn-Cr-Zr-Fe-Si alloy specifically prepared in this example comprises the following components:
Zn：0.29wt％，
Cr：0.55wt％，
Zr：0.2wt％，
Fe：0.3wt％，
Si：0.6wt％，
the balance being copper.
The preparation method comprises the following steps:
s1: preparing materials according to a proportion, firstly melting copper, then adding zinc and a covering agent, then adding iron, adding silicon after first heat preservation, adding chromium and zirconium after cooling, and carrying out second heat preservation to obtain an ingot;
s2: carrying out homogenizing annealing treatment on the cast ingot obtained in the step S1 in a protective atmosphere;
s3: performing heat processing deformation treatment on the cast ingot processed in the step S2, and then performing quenching treatment to obtain a heat processing blank;
s4: and (3) carrying out solution treatment, cold working treatment and aging treatment on the blank obtained in the step (S3) in a protective atmosphere.
In step S1:
the temperature of the first heat preservation is 1400 ℃ and the time is 2min.
After the addition of silicon, the temperature was reduced to 1250 ℃.
The temperature of the second heat preservation is 1300 ℃ and the time is 3min.
In step S2:
the homogenizing annealing treatment temperature is 960 ℃, and the homogenizing annealing treatment time is 6 hours.
During the homogenizing annealing treatment, the melted copper alloy cast ingot is fully covered with charcoal in a protective atmosphere, and the homogenizing annealing treatment is carried out.
In step S3:
before heat processing, the ingot is milled to the surface without defects.
The temperature of the hot working deformation treatment is 940 ℃, the time is 2h, seven-pass hot rolling is carried out, the deformation of the first pass hot rolling is 25%, the deformation of the second pass to the fifth pass hot rolling is 22%,25%,32%,34%, 24% of the sixth pass and 20% of the seventh pass respectively.
After the heat processing treatment, quenching treatment is carried out in a water quenching mode, and after quenching, milling the surface again until no oxide layer exists on the surface of the cast ingot.
In step S4:
the temperature of the solution treatment is 940 ℃ and the time is 8 hours.
After solution treatment, quenching treatment is carried out in a water quenching mode, and after quenching, milling the surface again until no oxide layer exists on the surface of the cast ingot.
The deformation amount in the cold working treatment was 70%.
After cold working, aging was carried out in a protective atmosphere at 400℃for 150min.
And (3) carrying out cold rolling deformation of 20% for the first time and 40% for the second time on the aged sample to obtain a cold rolled blank. The deformation amount for the second cold working is determined according to the thickness. And (3) carrying out cold rolling on the obtained cold rolled blank with the deformation of 40%, annealing in a 300 ℃ air cushion furnace, and discharging nitrogen for quenching to obtain the copper alloy sheet.
The alloy hardness is 214HV, the tensile strength is 722MPa, the conductivity is 69.2 percent IACS, and the elongation is 5.7 percent
Example 3
The Cu-Zn-Cr-Zr-Fe-Si alloy specifically prepared in this example comprises the following components:
Zn：0.3wt％，
Cr：0.4wt％，
Zr：0.17wt％，
Fe：0.2wt％，
Si：0.4wt％，
the balance being copper.
The preparation method comprises the following steps:
s1: preparing materials according to a proportion, firstly melting copper, then adding zinc and a covering agent, then adding iron, adding silicon after first heat preservation, adding chromium and zirconium after cooling, and carrying out second heat preservation to obtain an ingot;
s2: carrying out homogenizing annealing treatment on the cast ingot obtained in the step S1 in a protective atmosphere;
s3: performing heat processing deformation treatment on the cast ingot processed in the step S2, and then performing quenching treatment to obtain a heat processing blank;
s4: and (3) carrying out solution treatment, cold working treatment and aging treatment on the blank obtained in the step (S3) in a protective atmosphere.
In step S1:
the temperature of the first heat preservation is 1400 ℃ and the time is 2min.
After the addition of silicon, the temperature was reduced to 1250 ℃.
The temperature of the second heat preservation is 1300 ℃ and the time is 3min.
In step S2:
the homogenizing annealing treatment temperature is 960 ℃, and the homogenizing annealing treatment time is 6 hours.
During the homogenizing annealing treatment, the melted copper alloy cast ingot is fully covered with charcoal in a protective atmosphere, and the homogenizing annealing treatment is carried out.
In step S3:
before heat processing, the ingot is milled to the surface without defects.
The temperature of the hot working deformation treatment is 940 ℃, the time is 2h, seven-pass hot rolling is carried out, the deformation of the first pass hot rolling is 25%, the deformation of the second pass to the fifth pass hot rolling is 22%,25%,32%,34%, 24% of the sixth pass and 20% of the seventh pass respectively.
After the heat processing treatment, quenching treatment is carried out in a water quenching mode, and after quenching, milling the surface again until no oxide layer exists on the surface of the cast ingot.
In step S4:
the temperature of the solution treatment is 940 ℃ and the time is 8 hours.
After solution treatment, quenching treatment is carried out in a water quenching mode, and after quenching, milling the surface again until no oxide layer exists on the surface of the cast ingot.
The deformation amount in the cold working treatment was 70%.
After cold working, aging was carried out in a protective atmosphere at 400℃for 150min.
And (3) carrying out cold rolling deformation of 20% for the first time and 40% for the second time on the aged sample to obtain a cold rolled blank. The deformation amount for the second cold working is determined according to the thickness. And (3) carrying out cold rolling on the obtained cold rolled blank with the deformation of 40%, annealing in a 300 ℃ air cushion furnace, and discharging nitrogen for quenching to obtain the copper alloy sheet.
Alloy hardness is 210HV, tensile strength is 715MPa, conductivity is 71.5 percent IACS, and elongation is 6.1 percent
Test example 1
The alloy specimens prepared in examples 1 to 3 were tested for hardness, elongation, tensile strength, yield strength, elastic modulus, elongation, conductivity, heat resistant temperature and residual stress.
Wherein:
the hardness test is based on the standard GB/T7997-2014.
The standards according to which the yield strength, tensile strength, elastic modulus and elongation are tested are GB/T34505-2017.
The conductivity test is based on the standard GB/T32791-2016.
The heat resistance temperature test is based on the standard GB/T33370-2016.
The residual stress test is based on the standard GB/T33163-2016.
The results are shown in Table 1.
The alloy hardness is 213HV, the tensile strength is 720MPa, the conductivity is 70.2% IACS, and the elongation is 5.5%.
The alloy hardness is 214HV, the tensile strength is 722MPa, the conductivity is 69.2 percent IACS, and the elongation is 5.7 percent
Alloy hardness is 210HV, tensile strength is 715MPa, conductivity is 71.5 percent IACS, and elongation is 6.1 percent
Table 1 results of alloy performance tests prepared in examples 1 to 3
Example 1 Example 2 Example 3
hardness/HV 213 214 210
Elongation/% 5.5 5.7 6.1
Tensile strength/MPa 720 722 715
Yield strength/MPa 650 655 648
Modulus of elasticity 125MPa 125MPa 127MPa
conductivity/%IACS 74.2 73.6 70.1
Residual stress/MPa 25MPa 25MPa 24MPa
Test example 2
Microscopic morphologies of the alloy samples prepared in examples 1 to 3 were observed by transmission electron microscopy, and the results are shown in fig. 1 to 2.
As can be seen from fig. 1 to 2, there are a large number of nano-scale precipitated phases in the copper alloy, and a large number of dislocations interact with the precipitated phases, indicating the effect of pinning the dislocations.
The reinforced phase particles pin dislocation movement to form a cellular structure, and the fine crystal reinforcing effect is obvious.
The Cu-Zn-Cr-Zr-Fe-Si alloy has the hardness of 180-250 HV, the tensile strength of 600-750 MPa, the yield strength of 550-700 MPa, the elastic modulus of 125-135 MPa, the elongation of 3-10%, the electrical conductivity of 70-85% IACS and the residual stress of less than or equal to 30MPa, and solves the problems that the strength, the electrical conductivity, the softening resistance and the low residual stress of the conventional Cu-Cr-Zr alloy are difficult to be compatible and matched. The method is not only suitable for preparing the etched lead frame, but also can meet the requirements of modern information industries such as very large scale integrated circuits, 5G communication, high-end electronic elements and the like on high-performance copper alloy.
The present invention has been described in detail with reference to the embodiments, but the present invention is not limited to the embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the spirit of the present invention.

Claims (9)

  1. The Cu-Zn-Cr-Zr-Fe-Si alloy is characterized by comprising the following components in percentage by mass:
    Zn：0.1wt%~1.0wt%，
    Cr：0.30wt%~1.00wt%，
    Zr：0.15wt%~0.60wt%，
    Fe：0.20wt%~1.00wt%，
    Si：0.05wt%~1.00wt%，
    the balance being copper.
  2. 2. A method for producing the Cu-Zn-Cr-Zr-Fe-Si-based alloy as set forth in claim 1, comprising the steps of:
    s1: preparing materials according to a proportion, firstly melting copper, then adding zinc and a covering agent, then adding iron, adding silicon after first heat preservation, adding chromium and zirconium after cooling, and carrying out second heat preservation to obtain an ingot;
    s2: carrying out homogenizing annealing treatment on the cast ingot obtained in the step S1 in a protective atmosphere;
    s3: performing heat processing deformation treatment on the cast ingot processed in the step S2, and then performing quenching treatment to obtain a heat processing blank;
    s4: and (3) carrying out solution treatment, cold working treatment and aging treatment on the blank obtained in the step (S3) in a protective atmosphere.
  3. 3. The method according to claim 2, wherein in step S1, the temperature of the first heat preservation is 1300 ℃ to 1500 ℃ for 1min to 3min.
  4. 4. The method according to claim 2, wherein in step S1, after adding silicon, the temperature is reduced to 1250 ℃.
  5. 5. The method according to claim 2, wherein in step S1, the temperature of the second heat preservation is 1250 ℃ to 1300 ℃ for 2min to 4min.
  6. 6. The method according to claim 2, wherein in step S2, the homogenizing annealing is performed at a temperature of 880 ℃ to 980 ℃ for a time of 1h to 8h.
  7. 7. The method according to claim 2, wherein in the step S3, the temperature of the thermal deformation treatment is 880-960 ℃, the time is 0.5-2 h, and the deformation amount is 50-90%.
  8. 8. The method according to claim 2, wherein in step S4, the solution treatment is performed at a temperature of 880 ℃ to 960 ℃ for a time of 1h to 8h.
  9. 9. The method according to claim 2, wherein in step S4, the deformation amount of the cold working treatment is 50% -90%.
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