CN111996411B - High-strength high-conductivity copper alloy material and preparation method and application thereof - Google Patents

High-strength high-conductivity copper alloy material and preparation method and application thereof Download PDF

Info

Publication number
CN111996411B
CN111996411B CN202010678959.6A CN202010678959A CN111996411B CN 111996411 B CN111996411 B CN 111996411B CN 202010678959 A CN202010678959 A CN 202010678959A CN 111996411 B CN111996411 B CN 111996411B
Authority
CN
China
Prior art keywords
copper alloy
alloy material
conductivity
strength
alloy
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202010678959.6A
Other languages
Chinese (zh)
Other versions
CN111996411A (en
Inventor
李吉宝
孟祥鹏
裴勇军
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ningbo Powerway Alloy Plate & Strip Co ltd
Ningbo Powerway Alloy Material Co Ltd
Original Assignee
Ningbo Powerway Alloy Plate & Strip Co ltd
Ningbo Powerway Alloy Material Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ningbo Powerway Alloy Plate & Strip Co ltd, Ningbo Powerway Alloy Material Co Ltd filed Critical Ningbo Powerway Alloy Plate & Strip Co ltd
Priority to CN202010678959.6A priority Critical patent/CN111996411B/en
Publication of CN111996411A publication Critical patent/CN111996411A/en
Application granted granted Critical
Publication of CN111996411B publication Critical patent/CN111996411B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • C22C9/06—Alloys based on copper with nickel or cobalt 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
    • C22F1/08—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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
    • H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
    • H01L23/495—Lead-frames or other flat leads

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Conductive Materials (AREA)

Abstract

The invention discloses a high-strength high-conductivity copper alloy material which comprises the following components in percentage by weight: 0.3 to 0.8wt% of Cr, 0.05 to 0.5wt% of Fe, 0.05 to 0.3wt% of Ti, 0.01 to 0.1wt% of Si, and the balance of Cu and unavoidable impurities. The high-strength and high-conductivity copper alloy is prepared by alloying design of elements such as Cr, Fe, Ti, Si and the like and by a thermomechanical treatment process mainly based on two-stage aging. The invention controls CrFe phase, (Cr, Fe) in alloy microstructure2Ti and Cr3The size and density of the Si composite precipitated phase and the Cr elementary phase realize the functions of strengthening the alloy and improving the conductivity of the alloy. The copper alloy material can be applied to products such as large-scale integrated circuit lead frames, folding screens and the like, the yield strength of the manufactured strip is more than 650MPa, the electric conductivity is more than 65% IACS, and the copper alloy material has better high-temperature softening resistance.

Description

High-strength high-conductivity copper alloy material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of copper alloy, and particularly relates to a high-strength high-conductivity copper alloy material, and a preparation method and application thereof.
Background
With the rapid development of the technical fields of consumer electronics, communication base stations and the like in modern industrial systems, the miniaturization, light weight and rapid charging requirements of equipment have become research hotspots in various fields. With the continuous improvement of the requirements on the performance of the terminal product, the requirements on the material per se are also improved. For example, the rapidly developed large-scale integrated circuit lead frame requires that the yield strength of the material is more than 600MPa, and the conductivity reaches more than 60% IACS, so that the stable operation of the large-scale integrated circuit can be supported. Therefore, high-strength and high-conductivity environmentally-friendly copper alloy materials are receiving much attention. However, for copper alloy, the strength and the conductivity are two mutually restricted performances, namely, as the strength of the alloy is improved, the conductivity is correspondingly reduced; with increasing conductivity, the strength decreases accordingly. For example, the C70250 alloy has yield strength of more than 700MPa, but the conductivity of the alloy is only about 40% IACS, so that the alloy is relatively suitable for working conditions with higher requirements on strength; the C18080 alloy has high electrical conductivity of 79% IACS, but the yield strength is only about 550MPa, so the C18080 alloy is more suitable for working conditions with high requirements on electrical conductivity.
In addition, in the process of processing copper alloy, processes such as welding and packaging are required, so that the copper alloy is required to have good strength and conductivity and good high-temperature softening resistance. In a conventional semiconductor package or electronic component, the requirement for the high temperature softening temperature of the material is generally 380 ℃, but with the complication of the shape of the element, higher requirements are put on the welding or wire bonding process of the copper alloy material of the semiconductor package, electronic component, etc., and therefore, the high temperature softening temperature of the material needs to be increased to a higher level to meet the requirement of the development of modern materials.
In order to meet the higher requirements of various high and new technology industries which are rapidly developed on high-strength and high-conductivity copper alloy materials, fill the blank in the field of copper alloy research and the market, and develop a copper alloy material with high strength and high conductivity to meet the current urgent need, the invention provides a high-strength and high-conductivity copper alloy material and a preparation method and application thereof.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: aiming at the defects of the prior art, a high-strength high-conductivity copper alloy material, a preparation method and application thereof are provided. The copper alloy material can be applied to products such as large-scale integrated circuit lead frames, folding screens and the like, the yield strength of the manufactured strip is more than 650MPa, the electric conductivity is more than 65% IACS, and the copper alloy material has better high-temperature softening resistance.
The technical scheme adopted by the invention for solving the technical problems is as follows: a high-strength high-conductivity copper alloy material comprises the following components in percentage by weight: 0.3 to 0.8wt% of Cr, 0.05 to 0.5wt% of Fe, 0.05 to 0.3wt% of Ti, 0.01 to 0.1wt% of Si, and the balance of Cu and unavoidable impurities.
The Cr element added into the high-strength and high-conductivity copper alloy material has the solid solubility of only 0.7 percent in Cu at 1076 ℃, and the solid solubility is rapidly reduced along with the reduction of the temperature, so the Cr element can be used as a precipitation strengthening type alloying element to be added into the copper alloy. The strengthening of the Cu-Cr binary alloy mainly depends on a Cr-rich phase which is dispersed and distributed, and the size of the Cr-rich phase is generally between 5 and 10 nm. During the precipitation from the Cu matrix, the G.P zones are formed first, followed by the formation of face-centered cubic Cr-rich phases in coherent relation with the matrix, and as the aging time increases, body-centered cubic Cr-rich phases in non-coherent relation with the matrix are formed. The Cr-rich phase precipitates to improve the electrical conductivity of the alloy, so that the Cr element has a remarkable strengthening effect on the copper alloy and meets the requirement on the electrical conductivity of the copper alloy, and is used as a main alloying element in the invention. In the present invention, the content of Cr is set to 0.3 to 0.8wt%, since the strength of the copper alloy concerned is too low due to insufficient precipitated phase content, and the conductivity of the alloy is too low due to excessive solid solution of Cr in the matrix when the content of Cr is higher than 0.8 wt%.
Both Fe and Ti elements may be present in the copper alloy in the form of binary alloys. Fe element can be precipitated as a strengthening phase in the form of Fe simple substance, and can also form Fe with P element2And (4) precipitating a P phase. And Ti element is Cu3Ti and Cu4The Ti is formed in the copper alloy in an AM decomposition mode, and the Cu-Ti binary alloy has very high strength but low conductivity as a substitute product of the Cu-Be alloy; fe and Ti elements capable of forming Fe2Ti phase, which simultaneously improves the tensile mechanical property and the conductivity of the alloy, so that Fe and Ti elements are used as the secondary alloying elements in the invention. In the invention, the content of Fe element is controlled between 0.05 wt% and 0.5 wt%. When the content of the Fe element is lower than 0.05 wt%, the Cr elemental strengthening phase is reduced, and the strength of the alloy is further reduced; when the content of Fe element is higher than 0.5wt%This may lead to a decrease in the conductivity of the alloy. In the invention, the content of Ti element is controlled between 0.05 wt% and 0.3 wt%. When the content of the Ti element is higher than 0.3wt%, excessive Ti element is caused to be dissolved in the matrix in a solid way, and the conductivity of the alloy is reduced; when the content of Ti element is less than 0.05 wt%, the strengthening effect on the alloy is not significant. Further, when Fe and Ti elements satisfy the above control range, Fe and Ti elements can also be combined with Cr element to form (Cr, Fe)2The Ti phase not only can improve the strength of the alloy, but also can greatly improve the conductivity and the high-temperature softening resistance of the alloy.
The Si element can form a compound with elements such as Ni, Co, and Cr in the copper alloy and precipitate as a strengthening phase. In the design of the invention, Cr element is precipitated as a main strengthening phase, and excessive Cr element can form Cr with Si element3Si phase is precipitated from the matrix, further improving the strength and conductivity of the alloy of the invention. In the invention, the content of Si element is controlled between 0.01-0.1 wt%. When the Si element content is less than 0.01 wt%, it is not bonded with an excessive amount of Cr element to precipitate from the matrix, thereby lowering the Cr content3The Si phase content can reduce the conductivity and the alloy strength; when the content of the Si element is more than 0.1wt%, the Si element is excessively increased, thereby lowering the conductivity of the alloy.
Preferably, in the composition of the copper alloy material of the invention by weight percentage, the content of Ti, Cr, Fe and Si by weight percentage satisfies: ti<0.44(Cr + Fe) -5.55Si + 0.1. In (Cr, Fe)2In the Ti phase, the ratio of the Ti content to the sum of the Cr and Fe contents is about 0.44; in Cr3In the Si phase, the ratio of the Cr content to the Si content is about 5.5. Therefore, in an ideal situation, all of the Ti element and the Si element form intermetallic compounds to be precipitated from the matrix, and to achieve the effect, the weight percentage contents of Ti, Cr, Fe and Si need to satisfy: ti<0.44(Cr + Fe) -5.55Si +0.1, and in the range, Ti element can be greatly precipitated, so that the conductivity and the yield strength of the alloy are ensured. Cr element participates in CrFe phase, (Cr, Fe)2Ti phase and Cr phase3Besides Si phase precipitation, the Si phase can also be precipitated in the form of a simple substance, and the strength of the alloy is further improved. When the contents of the added Ti, Cr, Fe and Si elements are notWhen the requirements are met, ideal strength and conductivity cannot be obtained, and the bending performance of the alloy is adversely affected, so that the weight percentage content of Ti, Cr, Fe and Si is controlled to meet the following requirements: ti<0.44(Cr + Fe) -5.55Si +0.1 to ensure the balance of alloy strength, conductivity and bending property.
Microscopic observation and analysis of the cross section of the strip of the copper alloy material by an electron microscope revealed that a CrFe phase of 1 to 10 μm and (Cr, Fe) of 100 to 500nm in size were present in the microstructure2Ti and Cr3Si composite precipitated phase and a large amount of spherical Cr elementary substance of 1-10 nm. Wherein the CrFe phase has a density of 3.0 × 105Per mm2Hereinafter, (Cr, Fe)2Ti and Cr3The density of Si composite precipitate phase was 1.0X 106～5.0×106Per mm2The density of the elementary Cr is 3.75 multiplied by 108Per mm2The above.
The size and number of the precipitated phase particles reflect the effectiveness of the aging treatment. The Cr elementary substance precipitated phase particles with the diameter of less than 10nm are the most main strengthening phases of the alloy, and the density of the Cr elementary substance precipitated phase particles is 3.75 multiplied by 108Per mm2In the above case, the strength of the alloy can be remarkably improved, and the improvement of the conductivity, bending workability and high-temperature softening resistance of the alloy is facilitated. (Cr, Fe) having a size of 100 to 500nm2Ti and Cr3Although Si composite precipitated phase particles can also improve the strength and high-temperature softening resistance of the alloy, when the particle size of the precipitated phase is increased, the bending effect of the alloy is not remarkably improved, and the density should be controlled to 1.0X 106～5.0×106Per mm2. The CrFe phase precipitated phase particles of 1 μm or more are residual precipitated phases in the cast original structure, and their excessive size is disadvantageous for improving the alloy strength, and causes deterioration in bending workability and high-temperature softening resistance of the alloy, and the positions of the precipitated phases are likely to be the origin of crack generation, so that the CrFe phase density should be controlled to 3.0X 105Per mm2The following.
In the invention, the final state of the product is an aging state, a large amount of dislocation generated by cold deformation is in a state with lower energy,meanwhile, the dislocation is tangled, and a large amount of precipitated fine Cr elementary phase and (Cr, Fe)2Ti and Cr3The Si compound precipitation has stronger pinning effect relative to dislocation, so that the dislocation is not easy to slide or climb at high temperature, and in addition, the precipitation strengthening alloy has lower residual stress and is not easy to generate softening defect after secondary aging. Therefore, the alloy of the invention has higher high-temperature softening resistance, and does not cause hardness reduction and product defects in the processing of materials and the packaging process of semiconductors.
Preferably, the hardness value of the strip made of the copper alloy material is kept at 650 ℃ for 10min, and the reduction rate of the hardness value after the temperature is kept is less than 20% compared with the initial hardness value before the temperature is kept.
Preferably, the copper alloy material of the invention also comprises Sn with the content of 0.05-0.15 wt% in percentage by weight. Sn element is often used as an alloying element in copper alloys together with Ni element to form Ni — Sn compounds. In the present invention, the Sn element is an optional element and functions to refine the Cr-rich phase, prevent coarsening of the strengthening phase, and prevent the Cr phase which is in a coherent relationship with the matrix from being transformed into a noncoherent relationship. In the invention, the content of Sn element is controlled to be 0.05-0.15 wt%. When the content of Sn element is less than 0.05 wt%, the refining effect on the Cr-rich phase is limited, and the strength of the alloy cannot be improved; when the content of the Sn element is more than 0.15 wt%, the conductivity of the alloy is lowered by an excessive amount of the Sn element dissolved in the matrix.
Preferably, the copper alloy material of the invention also comprises 0.05 to 0.3wt% of Ag. The Ag element mainly improves the strength of the copper alloy by a solid solution strengthening mechanism, and the addition of a small amount of the Ag element has very small influence on the conductivity of the alloy. Different from alloying elements in other copper alloys, the excessive addition of Ag causes strong lattice distortion in the copper alloy, thereby enhancing the scattering effect of electrons and reducing the conductivity of the alloy. When a small amount of Ag element is added, the alloy can play a role in solid solution strengthening, has small influence on the conductivity of the alloy, and can improve the high-temperature softening resistance of the alloy. Ag is used as an optional additive element, and the content of the Ag is controlled to be 0.05-0.3 wt%. When the content is less than 0.05 wt%, the improvement of the alloy strength and the improvement of the high-temperature softening resistance of the alloy are extremely limited; when the content is more than 0.3wt%, the lattice distortion of the alloy due to the Ag element may cause a decrease in the conductivity of the alloy.
Preferably, the strip made of the copper alloy material has a yield strength of 650MPa or more and an electrical conductivity of more than 65% IACS.
Preferably, the copper alloy material of the invention further comprises 0.01-0.5 wt% of X element in percentage by weight, wherein the X element is selected from any one or more of Mg, P, Co, Ni and Zr. The addition of one or more elements selected from Mg, P, Co, Ni and Zr contributes to the refinement of crystal grains, and the density of precipitated phase particles can be controlled even by performing solution treatment at a high temperature. In addition, any one or more of Mg, P, Co, Ni, and Zr can promote the aging strengthening effect, so that the copper alloy has good strength, electrical conductivity, and bending workability. The above-mentioned effects are exhibited when the content of any one or more of Mg, P, Co, Ni and Zr is 0.01% or more, but if the content exceeds 0.5wt%, the solubility limit of Ti, Cr, Fe and Si is lowered, coarse precipitated phase particles tend to precipitate, and the strength is improved, but the bending workability is lowered. Therefore, the content of any one or more of Mg, P, Co, Ni and Zr is controlled to be 0.01 to 0.5 wt%.
The preparation method of the high-strength high-conductivity copper alloy material is characterized in that the preparation process of the strip of the copper alloy material comprises the following steps: vacuum casting → primary surface milling → hot rolling → secondary surface milling → primary cold rolling → solution treatment → secondary cold rolling → primary aging treatment → cold finish rolling → secondary aging treatment, wherein the heat preservation temperature of the primary aging treatment is 400-550 ℃, the heat preservation time is 6-10 h, the heat preservation temperature of the secondary aging treatment is 200-450 ℃, and the heat preservation time is 6-10 h. The preparation process comprises the following steps:
1) preparing materials: taking the raw materials according to the mixture ratio.
2) Vacuum casting: vacuum casting is carried out at 1200-1300 ℃, the vacuum degree is less than or equal to 10Pa, argon is introduced for protection after the raw materials are completely melted, so as to protect Ti element from oxygen in the casting processEnsuring the content of Ti element to ensure that (Cr, Fe) can be separated out in the subsequent thermomechanical treatment process2A Ti phase.
3) Primary face milling: used for removing oxide skin on the surface of the alloy after fusion casting.
4) Hot rolling: in order to ensure that coarse second phases separated out in the casting and cooling process are re-dissolved and weld casting defects in cast ingots, the hot rolling temperature of the alloy is controlled to be 850-900 ℃, the heat preservation time is 2-4 hours, the alloy can achieve the purpose of homogenization under the process, the final rolling temperature of the alloy is controlled to be above 650 ℃, and the rolling rate is controlled to be above 85% in order to reduce the separation of phase particles after hot rolling as much as possible.
5) Secondary face milling: the surface oxide skin is thicker after hot rolling, and the upper and lower milling surfaces of the hot rolled plate are 0.5-1.0 mm in order to ensure the surface quality of the later-stage strip.
6) Primary cold rolling: the total rolling rate is controlled to be more than 80 percent, thereby not only obtaining a deformed structure, but also being beneficial to the later solid solution process.
7) Solution treatment: in order to realize sufficient re-dissolution of phase particles and improve the supersaturation degree of a matrix, the solid solution temperature is controlled to be 950-1050 ℃, the temperature is kept for 30-200 s, and water cooling is carried out.
In the solid solution process, coarse precipitated phases in the original cast structure and precipitated phases in the hot rolling cooling process fully dissolve the matrix, and the matrix is rapidly cooled to room temperature under the condition that the cooling rate is more than 800 ℃/s, so that a supersaturated solid solution is ensured.
8) Secondary cold rolling: the secondary cold rolling aims to provide more energy and channels for precipitation of precipitated phases, and the rolling rate is 20-60%.
9) Primary aging treatment: the first-stage aging treatment enables the alloy to reach an overaged state, fully precipitates strengthening phases and simultaneously fully improves the conductivity of the alloy.
The primary aging treatment is a key process for realizing primary aging precipitation strengthening, the high temperature is favorable for complete recrystallization of tissues and precipitation of a second phase, and the low-temperature aging is not favorable for recrystallization of strips and precipitation of the second phase, so that the primary aging temperature is controlled to be 400-550 ℃, the temperature rise rate is more than 250 ℃/s, and the heat preservation is 6-10 hoursAnd air cooling after the time is over. In the first-stage aging process, the elementary substances Cr, CrFe, (Cr, Fe) are subjected to higher temperature2Ti and Cr3The Si phase is fully precipitated, and the effect of overaging is achieved.
10) Cold finish rolling: the alloy after the primary aging treatment has already reached the overaging state, obtains higher conductivity, and precipitation power and passageway have been consumed up this moment, if carry out the processing of secondary aging immediately this moment, the strengthening phase can't be separated out from the base member, and the strengthening phase that separates out in the primary aging process will continue growing up, causes the reduction of alloy performance. Therefore, after the primary aging treatment, the cold finish rolling treatment is carried out on the alloy, so that the redistribution of precipitated phases is facilitated, more precipitated channels are provided for the secondary aging treatment, and the strength of the strip is further improved. When the rolling reduction is less than 40 percent and the rolling pass is less than 5 passes, the work hardening effect and the redistribution effect of precipitated phases under the action of shear stress are poor, and meanwhile, too little energy and precipitation channels are provided for secondary aging, so that the strength and the electric conductivity of the alloy are reduced. When the rolling rate is more than 80%, the excessive cold deformation causes the defects of cracks and the like at the hard precipitated phase position of the alloy in the deformation process, the alloy structure is cut, and the strength of the alloy is reduced. Therefore, the rolling rate of the cold finish rolling treatment is controlled to be 40-80%, and the rolling pass is more than 5.
11) Secondary aging treatment: the secondary aging treatment has the effect of stress relief annealing on one hand and can further precipitate a strengthening phase, although the alloy reaches an overaged state in the primary aging treatment stage, an additional precipitation channel and power are provided for the aging treatment after cold working deformation, a small amount of elements which are dissolved in a matrix can be further precipitated, the conductivity of the alloy is mainly improved, and the strength of the alloy is improved. When the temperature of the secondary aging treatment is lower than 200 ℃, the excessively low temperature only enables the alloy to release internal stress and cannot enable the alloy to be continuously precipitated, and meanwhile, the strength and the conductivity of the alloy are reduced; when the temperature of the secondary aging treatment is higher than 450 ℃, the existing precipitation strengthening phase can grow up rapidly at an excessively high temperature, and the strength of the alloy can be greatly reduced. Therefore, the temperature of the secondary aging treatment is not too high, and the air cooling is carried out after the heat preservation is carried out for 6 to 10 hours at the temperature of between 200 and 450 ℃.
Compared with the prior art, the invention has the advantages that:
(1) the high-strength and high-conductivity copper alloy is prepared by alloying design of elements such as Cr, Fe, Ti, Si and the like and by a thermomechanical treatment process mainly based on two-stage aging.
(2) According to the invention, through carrying out cold finish rolling treatment for multiple times between two aging treatment processes, the precipitated phases are favorably and fully precipitated and uniformly distributed, and the improvement of the alloy strength, the conductivity and the bending performance is further favorably realized.
(3) The size of CrFe phase precipitated in the copper alloy material is 1-10 mu m, and the density is 3.0 multiplied by 105Per mm2Hereinafter, (Cr, Fe)2Ti and Cr3The size of the Si composite precipitated phase is 100-500 nm, and the density is 1.0 x 106～5.0×106Per mm2The elementary Cr substance has a size of 1-10 nm and a density of 3.75 × 108Per mm2In this way, the effects of strengthening the alloy and improving the conductivity of the alloy are achieved under these conditions.
(4) The strip made of the copper alloy material has the yield strength of more than 650MPa, the conductivity of more than 65% IACS, and better high-temperature softening resistance.
(5) The copper alloy material can be applied to products such as large-scale integrated circuit lead frames, folding screens and the like.
Drawings
FIG. 1 shows the SEM test results for the copper alloy material of example 4, in which the particles are (Cr, Fe)2Ti and Cr3Si composite precipitated phase;
FIG. 2 is a TEM test result of the Cu alloy material of example 4;
FIG. 3 shows the TEM test result of the precipitated phase of Cr in the Cu alloy material of example 4.
Detailed Description
The invention is described in further detail below with reference to the accompanying examples.
According to the copper alloy ingredients shown in the components of the examples and comparative examples in the tables 1 and 2, vacuum casting is carried out at 1200-1300 ℃, and cast ingots are formed and subjected to primary surface milling treatment; keeping the temperature of the cast ingot at 850-900 ℃ for 2-4 h, and then carrying out hot rolling at a rolling rate of not less than 85%; secondly, milling the surfaces of the hot rolled plate for 0.5-1.0 mm; then, carrying out primary cold rolling at a rolling rate of not less than 80%; then, carrying out solution treatment on the plate subjected to the primary cold rolling at 950-1050 ℃ for 30-200 seconds; secondly, carrying out secondary cold rolling on the plate subjected to the solution treatment at a rolling rate of 20-60%, then carrying out primary aging treatment at 400-550 ℃, and then carrying out cold finish rolling at a processing rate of 40-80%; and finally, carrying out secondary aging treatment at the temperature of 200-450 ℃ to obtain a strip sample.
The characteristics of each of the obtained tape samples were evaluated under the following conditions.
Tensile test at room temperature according to GB/T228.1-2010 Metal Material tensile test part 1: room temperature test method was performed on an electronic universal mechanical property tester using a tape head specimen having a width of 12.5mm and a drawing speed of 5 mm/min.
Conductivity testing according to GB/T3048.2-2007 test method for electric properties of wires and cables part 2: resistivity test of metal material, the tester is ZFD microcomputer bridge DC resistance tester, sample width is 20mm, length is 500 mm.
High temperature softening resistance test: and (3) keeping the temperature of each strip sample at 650 ℃ for 10min, quickly taking out, and quenching and cooling in water at room temperature. Then, the microhardness (HV) of each strip sample and the hardness value HV after annealing were measured1To the initial hardness value HV0In contrast, the reduction rate of 20% or less is considered to be excellent in high-temperature softening resistance.
The bending properties of the tapes of the examples and comparative examples (evaluated as whether the Goodway 90R/T2.5 bend cracks) were tested using JCBA T307-2007 Test method of band formability for sheets and strips of tapes of the examples and comparative examples, and the width of the Test tapes was 10 mm.
And observing the structure of the sample under a scanning electron microscope and a transmission electron microscope when the size of the precipitate is tested, calculating the average grain diameter of intermetallic compounds precipitated from the alloy according to the observation result, and respectively calculating the number density of the intermetallic compounds. Fig. 1 is a scanning electron microscope test result of the copper alloy material of example 4, fig. 2 is a transmission electron microscope test result of the copper alloy material of example 4, and fig. 3 is a transmission electron microscope test result of the Cr simple substance precipitation phase in the copper alloy material of example 4.
According to the embodiment, the copper alloy in the embodiment of the invention realizes the performances of yield strength of 650MPa or more and electric conductivity of 65% IACS or more. The copper alloy of the invention can meet the following high temperature softening resistance: after the alloy is subjected to heat preservation for 10 minutes at 650 ℃, the alloy is quenched at room temperature, and compared with the initial hardness value, the hardness value after annealing is reduced within 20 percent, so that the alloy has good high-temperature softening resistance. Meanwhile, the comparative examples 1 to 5 show that the content of alloying elements has different influences on the strength, the conductivity and the bending property of the alloy if the content of the alloying elements exceeds the design range of the invention.
Figure BDA0002585172640000091
Figure BDA0002585172640000101

Claims (10)

1. The high-strength high-conductivity copper alloy material is characterized by comprising the following components in percentage by weight: 0.3 to 0.8wt% of Cr, 0.05 to 0.5wt% of Fe, 0.05 to 0.3wt% of Ti, 0.01 to 0.1wt% of Si, and the balance of Cu and unavoidable impurities; in the microstructure of the cross section of the strip of the copper alloy material under an electron microscope, the size of a CrFe phase is 1-10 mu m, and the density is 3.0 multiplied by 105Per mm2The following; (Cr, Fe)2Ti and Cr3The size of Si composite precipitated phase is 100-500 nm, and the density is 1.0 x 106～5.0×106Per mm2(ii) a The size of the Cr simple substance is 1-10 nm, and the density is 3.75 multiplied by 108Per mm2The above.
2. The copper alloy material with high strength and high conductivity as claimed in claim 1, wherein the weight percentage of Ti, Cr, Fe, Si in the composition of the copper alloy material satisfies the following requirements: ti <0.44(Cr + Fe) -5.55Si + 0.1.
3. A high-strength high-conductivity copper alloy material according to claim 1, wherein the hardness value of the strip made of the copper alloy material after being kept at 650 ℃ for 10min is reduced by less than 20% compared with the initial hardness value before being kept.
4. A high-strength high-conductivity copper alloy material according to claim 1, wherein the composition of the copper alloy material further comprises 0.05-0.15 wt% of Sn.
5. A high-strength high-conductivity copper alloy material according to claim 1, wherein the composition of the copper alloy material further comprises 0.05-0.3 wt% of Ag.
6. A high strength and high conductivity copper alloy material according to claim 1, wherein the yield strength of the strip made of the copper alloy material is 650MPa or more, and the electrical conductivity is more than 65% IACS.
7. The copper alloy material as claimed in claim 1, wherein the composition of the copper alloy material further comprises 0.01-0.5 wt% of X element, wherein the X element is selected from one or more of Mg, P, Co, Ni and Zr.
8. The method for preparing the high-strength high-conductivity copper alloy material according to any one of claims 1 to 7, wherein the strip of the copper alloy material is prepared by the following steps: vacuum casting → primary surface milling → hot rolling → secondary surface milling → primary cold rolling → solution treatment → secondary cold rolling → primary aging treatment → cold finish rolling → secondary aging treatment, wherein the heat preservation temperature of the primary aging treatment is 400-550 ℃, the heat preservation time is 6-10 h, the heat preservation temperature of the secondary aging treatment is 200-450 ℃, and the heat preservation time is 6-10 h.
9. The method for preparing a high-strength high-conductivity copper alloy material according to claim 8, wherein the cold finish rolling has a rolling rate of 40 to 80% and a rolling pass of 5 or more.
10. Use of the high-strength high-conductivity copper alloy material according to any one of claims 1 to 7 in large-scale integrated circuit lead frames and folding screens.
CN202010678959.6A 2020-07-15 2020-07-15 High-strength high-conductivity copper alloy material and preparation method and application thereof Active CN111996411B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010678959.6A CN111996411B (en) 2020-07-15 2020-07-15 High-strength high-conductivity copper alloy material and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010678959.6A CN111996411B (en) 2020-07-15 2020-07-15 High-strength high-conductivity copper alloy material and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN111996411A CN111996411A (en) 2020-11-27
CN111996411B true CN111996411B (en) 2021-11-30

Family

ID=73466914

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010678959.6A Active CN111996411B (en) 2020-07-15 2020-07-15 High-strength high-conductivity copper alloy material and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN111996411B (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115233031B (en) * 2021-09-07 2022-12-30 大连理工大学 High-performance copper alloy and preparation method thereof
CN113913642B (en) * 2021-09-26 2022-07-05 宁波博威合金板带有限公司 Copper alloy strip and preparation method thereof
CN114807672B (en) * 2022-03-23 2023-09-08 中南大学 Cu-Zn-Cr-Zr-Fe-Si alloy and method for producing same
CN115198133B (en) * 2022-06-07 2023-02-24 太原理工大学 High-strength heat-resistant conductive copper alloy pipe and preparation method thereof
CN116065053B (en) * 2023-04-03 2023-07-11 凯美龙精密铜板带（河南）有限公司 Copper alloy and preparation method thereof
CN116970839B (en) * 2023-09-19 2023-12-19 宁波兴业盛泰集团有限公司 Copper-chromium alloy material and preparation method thereof

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6749699B2 (en) * 2000-08-09 2004-06-15 Olin Corporation Silver containing copper alloy
JP4563495B1 (en) * 2009-04-27 2010-10-13 Ｄｏｗａメタルテック株式会社 Copper alloy sheet and manufacturing method thereof
JP6611222B2 (en) * 2015-02-24 2019-11-27 株式会社神戸製鋼所 Copper alloy plate for electric and electronic parts having high strength, high conductivity and excellent stress relaxation characteristics, and method for producing the same
CN105568039B (en) * 2015-12-22 2017-09-05 宁波博威合金板带有限公司 The preparation method of high-intensity high-conductivity copper Cr-Zr alloy and its strip
CN106350698B (en) * 2016-09-09 2018-03-27 宁波博威合金板带有限公司 Anti-softening copper alloy, preparation method and applications

Also Published As

Publication number Publication date
CN111996411A (en) 2020-11-27

Similar Documents

Publication Publication Date Title
CN111996411B (en) High-strength high-conductivity copper alloy material and preparation method and application thereof
KR100929276B1 (en) Copper alloy
KR100360131B1 (en) Method for improving the bendability of copper alloy and copper alloy manufactured therefrom
KR101576715B1 (en) Copper alloy and method for producing copper alloy
JP4677505B1 (en) Cu-Ni-Si-Co-based copper alloy for electronic materials and method for producing the same
JP4303313B2 (en) Cu-Ni-Si-Co-based copper alloy for electronic materials and method for producing the same
KR101570556B1 (en) Method for Producing Copper Alloy Material for Electrical/Electronic Component
JP3699701B2 (en) Easy-to-process high-strength, high-conductivity copper alloy
WO2006019035A1 (en) Copper alloy plate for electric and electronic parts having bending workability
EP2728025A2 (en) Cu-Ni-Co-Si based copper alloy sheet material and method for producing the same
JP5451674B2 (en) Cu-Si-Co based copper alloy for electronic materials and method for producing the same
CN109338151B (en) Copper alloy for electronic and electrical equipment and application
CN111020280B (en) Cu-Al-Hf-Ti-Zr copper alloy material and preparation method thereof
CN110863120B (en) Copper alloy for lead frame and preparation method thereof
US20110005644A1 (en) Copper alloy material for electric/electronic parts
EP2270242A1 (en) Copper alloy material for electric and electronic apparatuses, and electric and electronic components
WO2019213789A1 (en) Copper alloy material and use thereof
JP3511648B2 (en) Method for producing high-strength Cu alloy sheet strip
US11913102B2 (en) Titanium-copper alloy strip containing Nb and Al and method for producing same
CA1119920A (en) Copper based spinodal alloys
JP4646192B2 (en) Copper alloy material for electrical and electronic equipment and method for producing the same
CN112281023B (en) Copper alloy material with excellent bending property and preparation method and application thereof
JP4664584B2 (en) High strength copper alloy plate and method for producing high strength copper alloy plate
JP2012229467A (en) Cu-Ni-Si BASED COPPER ALLOY FOR ELECTRONIC MATERIAL
JP5524901B2 (en) Cu-Ni-Si-Co based copper alloy for electronic materials

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant