CN111485132A - Copper alloy strip with excellent comprehensive performance and preparation method thereof - Google Patents
Copper alloy strip with excellent comprehensive performance and preparation method thereof Download PDFInfo
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- CN111485132A CN111485132A CN202010281401.4A CN202010281401A CN111485132A CN 111485132 A CN111485132 A CN 111485132A CN 202010281401 A CN202010281401 A CN 202010281401A CN 111485132 A CN111485132 A CN 111485132A
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C9/00—Alloys based on copper
- C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
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- C22C1/02—Making non-ferrous alloys by melting
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- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
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Abstract
The invention discloses a copper alloy strip with excellent comprehensive performance, which is characterized by comprising the following components in percentage by weight: ni: 2.5 wt% -4.0 wt%, Co: 0.2 wt% to 1.2 wt%, Si: 0.4 wt% -1.4 wt%, Ag: 0.01 wt% -0.2 wt%, and the balance of Cu. The copper alloy strip with excellent comprehensive performance has the yield strength of more than 850MPa, the elastic modulus of more than 120GPa and the electric conductivity of more than 45% IACS, has high yield strength, and simultaneously has good bending performance, and the Badway 90-degree bending R/t is less than or equal to 2.5 without cracking (R is the bending radius, and t is the thickness of the strip), thereby being an ideal material for producing and manufacturing electronic connectors, electronic parts and lead frames.
Description
Technical Field
The invention relates to a copper alloy, in particular to a copper alloy strip with excellent comprehensive properties such as good yield strength, medium conductivity, high elastic modulus and the like, which is mainly applied to the fields of elastic terminals, electronic components, connectors, lead frames, connectors for base stations and servers and the like.
Background
With the rapid development of chip technology, 5G communication, consumer electronics, the Internet of things, industrial robots, artificial intelligence, new energy automobiles, aerospace, high-speed railway traffic and the like, lead frames for chips, communication equipment, high-end manufacturing industry, connectors for consumer electronics, electronic components and the like have higher and higher requirements on the comprehensive performance of copper alloy plates and strips. Electronic products and electronic components are developed towards miniaturization, intellectualization, multifunctionalization and high integration, and the electronic components have higher and higher requirements on heat dissipation while ensuring high-reliability signal transmission, so that the copper alloy strip for preparing the electronic components is required to have high yield strength and large elastic modulus, and the conductivity of the copper alloy strip must be kept at a certain performance level. In order to meet the requirements of miniaturization and high integration of electronic products and electronic components, the yield strength of the copper alloy strip must reach more than 850MPa, the conductivity must reach more than 45% IACS, and the elastic modulus must be more than 120 GPa; in order to be able to be processed by stamping, the copper alloy strip must also have good bending performance, and the Badway 90-degree bend R/t is less than or equal to 2.5 without cracking (R is the bending radius, and t is the thickness of the strip).
The high-performance copper alloys commonly used in consumer electronics, electronic components, electronic connectors, lead frames, etc. are mainly Corson-series copper alloys based on CuNiSi and CuNiCoSi, including C70250, C70350 and their modified products, such as NKC388(C70252), C70350XE/XS, etc.
Known C70250 strip, with a composition of Ni: 2.2-4.2 wt%, Si: 0.25-1.2 wt%, Mg: 0.05 to 0.3 wt%, and the balance being Cu. In all product states, the yield strength and the conductivity of the product cannot meet the performance requirements of more than or equal to 850MPa and more than or equal to 45 percent IACS at the same time. Although the conductivity of the C70250 strip material in a TM03 state can reach above 45% IACS, the yield strength is below 800 MPa; the C70250 alloy strip in other states also has the problem that the yield strength and the electric conductivity cannot simultaneously meet the performance requirements. For the above reasons, the C70250 tape cannot meet the performance requirements of small size, light weight, high integration, intelligence and multi-functionalization of consumer electronics, electronic components, electronic connectors and lead frames.
Another known high-performance copper alloy strip with the American standard number C70350 comprises the following components: 1.0-2.5 wt%, Si: 0.5-1.2 wt%, Co: 1.0-2.0 wt%, Mg: less than or equal to 0.15wt percent, and the balance of Cu. The TM06 strip has an electrical conductivity of 45% IACS, a yield strength ranging from 810MPa to 920MPa, an actual measured value of only 830MPa, and an elastic modulus of 120 GPa. Although the yield strength and the conductivity of the copper alloy strip are improved compared with those of C70250, the actual measured value of the yield strength is only about 830MPa, the yield strength of the copper alloy strip only meets the performance requirements of connectors, connectors and lead frames on the copper alloy strip at the present stage, and the yield strength of the copper alloy strip cannot meet the requirements of the development trend along with the increasing miniaturization of electronic products and electronic components.
Another known copper alloy for electrical connectors and leadframes is the NKC388(C70252) alloy strip, typically consisting of Ni: 3.8 wt%, Si: 0.8 wt%, Mn: 0.13 wt%, Mg: 0.1 wt%, and the balance being Cu. Although the yield strength of the alloy strip can reach above 910MPa, the electrical conductivity of the alloy strip is only 38% IACS, and the NKC388 strip cannot meet the future development requirements of electronic connectors, electronic components and the like due to low electrical conductivity.
Another commonly used material for known connectors and leadframes is a strip of C70350XE/XS alloy having a composition within the composition range of the C70350 alloy. Although the yield strength can reach more than 880MPa, and the yield strength in the C70350 XS state can even reach more than 940MPa, the conductivity of the strip material in the C70350XE state or the C70350 XS state is only 40% IACS, and the requirement of rapidly developed electronic connectors and lead frames on the conductivity of the copper alloy strip material cannot be met.
Obviously, the existing alloy material still can not meet the requirement of rapid development of consumer electronics, electronic components, electronic connectors, connectors and lead frames on high-performance copper alloy materials.
Disclosure of Invention
The invention aims to solve the technical problem of providing a copper alloy strip with excellent comprehensive properties such as high yield strength, high conductivity, high elasticity, excellent bending property and the like and a preparation method thereof aiming at the current state of the prior art.
The technical scheme adopted by the invention for solving the technical problem is as follows: a copper alloy strip with excellent comprehensive performance is characterized in that the copper alloy comprises the following components in percentage by weight: ni: 2.5 wt% -4.0 wt%, Co: 0.2 wt% to 1.2 wt%, Si: 0.4 wt% -1.4 wt%, Ag: 0.01 wt% to 0.2 wt%, and the balance of Cu and unavoidable impurities.
In the invention, Ni, Co and Si are used as main elements, Ni, Co and Si atoms are dissolved into a copper matrix through high-temperature solution treatment, then a supersaturated solid solution is formed through quenching treatment, and Ni is precipitated through aging treatment subsequentlyxSiyAnd CoxSiyThe precipitated phase plays a role in dispersion strengthening, so that the tensile strength, the yield strength and the elastic modulus of the copper alloy strip are improved. And Ni atoms are added to Ni, Co and Si atoms by aging treatmentxSiyAnd CoxSiyThe precipitate phase is separated out from the copper matrix, so that the concentration of solute atoms of Ni, Co and Si in the copper matrix is greatly reduced, the purity of the copper matrix is greatly improved, and the scattering effect of the solute atoms in the copper matrix on electron waves is reduced, so that the electric conductivity of the copper matrix is greatly improved. When the Ni content is less than 2.5 wt%, the Co content is less than 0.2 wt%, and the Si content is less than 0.4 wt% in the present invention, the Ni age-precipitated in the copper alloy strip of the present inventionxSiyAnd CoxSiyThe precipitated phase is less, the dispersion strengthening effect is not obvious, the yield strength of the copper alloy strip is lower than 850MPa, and the elastic modulus is less than 120 GPa. When the Ni content is more than 4.0 wt%, the Co content is more than 1.2 wt% and the Si content is more than 1.4 wt%, too many dispersion strengthening phases are precipitated, and the scattering effect of second phase particles on electron waves is enhanced, so that the electric conductivity of the copper alloy strip is lower than 45% IACS. The components of Ni, Co and Si in the copper alloy strip are as follows: 2.5 wt% -4.0 wt%, Co: 0.2 wt% to 1.2 wt%, Si: 0.4 wt% to 1.4 wt% rangeThe inner is the best. Furthermore, Ni in the copper alloy strip of the inventionxSiyAnd CoxSiyForm cross interval distribution and increase NixSiyPrecipitated phase and CoxSiyThe synergistic strengthening effect of the precipitated phase is beneficial to improving the mechanical property of the copper alloy strip.
In the invention, Ag is a main element, the addition range of the Ag is 0.01-0.2%, in the addition range, the Ag is dissolved in the copper matrix in a replacement solid solution mode, Ag atoms dissolved in the copper matrix play a role in solid solution strengthening, the mechanical property of the copper alloy strip is further improved, and the solid solution of the Ag has small influence on the conductivity of the copper alloy strip because the radius difference between the Ag atoms and the Cu atoms is not large, although the Ag atoms are dissolved in the copper matrix, the Ag atoms and the Cu atoms only have small atomic radius difference, the formed stress field is small, and the scattering effect on electron waves is small, so that the solid solution of the Ag has small influence on the conductivity of the copper alloy strip, and the conductivity of the copper alloy strip can be ensured to be more than 45% IACS. In the copper alloy strip of the present invention, if the content of Ag is less than 0.01%, the solid solution strengthening effect is not significant; if the content of Ag exceeds 0.2%, although the solid solution strengthening effect is more excellent, the electric conductivity of the copper alloy strip of the present invention is less than 45% IACS due to the enhanced scattering effect of Ag atoms, and thus the content of Ag in the copper alloy strip of the present invention is most preferably in the range of 0.01% to 0.2%. Besides the solid solution strengthening effect of Ag, Ag atoms can improve the high-temperature softening resistance and stress relaxation resistance of the copper alloy strip, so that the copper alloy strip can be better applied to the application fields of consumer electronics, electronic components, electronic connectors, lead frames and the like.
Preferably, the texture type and the area ratio of the copper alloy strip are as follows: the area ratio of the cubic texture is 10-30%, the area ratio of the brass texture is 5-20%, the area ratio of the copper texture is 5-20%, the balance is other types of textures, and the area ratio of the textures is the ratio of the area within 15 degrees of deviation angle of each orientation divided by the measured area.
The area ratio of the cubic texture in the strip determines the bending performance of the strip, when the ratio of the cubic texture is higher, the bending performance of the strip is better, and when the ratio of the cubic texture is lower, the bending performance of the strip is poorer; the area occupation ratio of the brass texture and the copper texture in the strip has certain influence on the mechanical property of the strip, when the area occupation ratio of the brass texture and the copper texture is higher, the mechanical property of the strip is relatively higher, and when the area occupation ratio of the brass texture and the copper texture is lower, the mechanical property of the strip is relatively lower. In the processing process, the texture of the alloy can be changed along with the process progress, a copper texture can be formed in the hot rolling processing process, part of the copper texture can be converted into a brass texture in the subsequent rough rolling processing, when high-temperature solution quenching is carried out after the rough rolling processing, the remaining copper texture in the strip can be converted into a cubic texture, then the cubic texture can be converted into the brass texture and the copper texture in the pre-finish rolling processing, the primary aging processing, the finish rolling processing and the secondary aging processing, and the area occupation ratio of the cubic texture, the brass texture and the copper texture of the copper alloy strip can be ensured to meet the range by controlling the whole deformation heat treatment process. When the texture area ratio of the copper alloy strip is within the range, the mechanical property of the copper alloy strip is higher while the good bending property is ensured.
Preferably, the area ratio of the cubic texture to the brass texture to the copper texture of the copper alloy strip satisfies the following conditions: a/(b + c) is more than or equal to 0.3 and less than or equal to 2.0, wherein a is the area proportion of the cubic texture, b is the area proportion of the brass texture, and c is the area proportion of the copper texture.
According to the copper alloy strip, the bending performance of the strip is determined by the content of the cubic texture; the content of brass texture and copper texture has certain influence on the mechanical property of the copper alloy strip. When the area ratio a/(b + c) of the cubic texture, the brass texture and the copper texture is less than 0.3, the bending performance is poor due to the low area ratio of the cubic texture; when the area ratio of the cubic texture, the brass texture, and the copper texture, a/(b + c) > 2, the bending property of the tape is excellent, but the mechanical properties of the tape are deteriorated. The copper alloy strip has good bending performance and high mechanical property only when the area ratio of the cubic texture, the brass texture and the copper texture satisfies that a/(b + c) is more than or equal to 0.3 and less than or equal to 2.0.
Preferably, the copper alloy strip further comprises at least one of the optional elements, the optional elements being present in a total amount of 0.5 wt% or less; optional elements are Mg: 0.001 wt% -0.2 wt%, Ce: 0.001 wt% -0.2 wt%, Cr: 0.001 wt% to 0.1 wt%, Zr: 0.001 wt% -0.1 wt%, Ti: 0.001 wt% -0.1 wt%, Fe: 0.001 wt% -0.2 wt%, Mn: 0.001 wt% -0.2 wt%, Zn: 0.001 wt% -0.2 wt%, Sn: 0.001 wt% -0.2 wt%.
The main function of Mg is to dissolve in copper to strengthen the solution, thus being beneficial to improving the mechanical property of the copper alloy strip. Mg can also improve the high temperature softening resistance and stress relaxation resistance of the copper alloy strip. In addition, Mg is easy to combine with oxygen, plays a role in deoxidation in the smelting process of the copper alloy, ensures that the copper alloy cast ingot does not contain oxides of elements such as Ni, Co, Si, Cr, Zr, Ti, Fe, Mn, Zn, Sn and the like, purifies the melt of the copper alloy, and is beneficial to improving the product quality of the copper alloy strip. When the content of Mg is less than 0.001 wt%, the mechanical property, the high-temperature softening resistance and the stress relaxation resistance cannot be improved, and the effect of full deoxidation cannot be achieved; when the content of Mg is higher than 0.2 wt%, the redundant Mg is dissolved in the copper matrix in a solid solution mode, so that the heat dissipation of electron waves is improved, and the conductivity of the copper alloy strip material is reduced.
In the process of casting the copper alloy, the Ce element can be used as a nucleation center to improve the nucleation rate of the copper alloy strip, thereby playing a role in refining grains. The cast ingot with fine grains provides an initial structure condition for preparing a finished copper alloy strip with fine grains, and is beneficial to improving the strength and the bending performance of the copper alloy strip. In addition, Ce can form Ce with Ni, Mg, etcxNiy、CexCoy、MgxCeyEqual precipitation phase, and dispersion strengthening effect. When the content of Ce is less than 0.001 wt%, the grain-refining effect is not clearIt is clear that an excess of Ce, when it is higher than 0.2 wt%, causes cracking of the strip according to the invention when hot rolled. Therefore, the optimum content range of Ce is 0.001-0.2 wt%.
Cr and Zr can form CrxZryThe precipitated phase plays a role in dispersion strengthening and is beneficial to improving the mechanical property of the copper alloy strip. In the invention, Ti atoms precipitate Cu through solution quenching and subsequent aging treatmentxTiyA precipitated phase with precipitated CrxZry、NixSiy、CoxSiyThe equal precipitation phase plays a role in synergistic dispersion strengthening and is beneficial to further improving the mechanical property of the copper alloy strip. In the present invention, Fe may form Fe with SixSiyThe precipitate phase can reduce the Si dissolved in the copper matrix while forming the precipitate phase to play a role in dispersion strengthening, and is helpful for improving the conductivity of the copper alloy strip. If the content of optional elements Cr, Zr, Ti and Fe in the copper alloy strip is lower than the lower limit, the effect is not obvious; if the upper limit is exceeded, the electrical conductivity of the copper alloy strip of the invention is greatly reduced.
Mn, Zn and Sn in the copper alloy strip mainly play a role in solid solution strengthening, and are beneficial to improving the high-temperature softening resistance and stress relaxation resistance of the copper alloy strip. Mn is also formed from Mn and SixSiyAnd the phase plays a role in dispersion strengthening and improves the mechanical property of the strip. If the content of optional elements Mn, Zn and Sn in the copper alloy strip is lower than the lower limit, the effect is not obvious; if the upper limit is exceeded, the electrical conductivity of the copper alloy strip of the invention is greatly reduced.
Preferably, the copper alloy strip has a yield strength of 850MPa or more, an elastic modulus of 120GPa or more, an electrical conductivity of 45% IACS or more, and a Badway90 DEG bend R/t of 2.5 or less.
The preparation method of the copper alloy strip with excellent comprehensive performance comprises the following preparation processes: batching → smelting → casting → sawing → heating → hot rolling → milling face → rough rolling → solid solution and quenching treatment → medium rolling → first-stage aging → cleaning → pre-finish rolling → second-stage aging → cleaning → finish rolling → stretch bending and straightening; the method is characterized in that the total processing rate of hot rolling is more than 90%, the finishing temperature is controlled to be more than 840 ℃, hot rolling at more than 900 ℃ is the first stage of hot rolling processing, and the rolling rate is 60-90%; the second stage hot rolling processing is carried out between 900 ℃ and the finish rolling temperature of 840 ℃, and the rolling rate is 30-60% of the thickness of the plate blank after the first stage hot rolling processing; the area percentage of the copper texture in the hot rolled strip is more than 40%.
In the invention, the smelting temperature of the copper alloy is 1250-1300 ℃, which ensures that each component element is fully melted to form copper alloy melt with uniform components. The casting temperature of the copper alloy plate blank is within the range of 1200-1250 ℃, and sufficient electromagnetic stirring is carried out in the casting process, so that the crystal grains of the copper alloy melt are uniform and have no obvious columnar crystal when being solidified in the crystallizer, and uniform initial crystal grain structures are provided for forming specific textures and area occupation ratios in the copper alloy strip.
The hot rolling heating temperature of the invention is 1000-1020 ℃, and the heating and heat preservation time is 2-4 h. In the temperature range of 1000-1020 ℃, elements such as Ni, Co, Si, Ag, Mg, Ce, Cr, Zr, Ti, Fe, Mn, Zn, Sn and the like in the copper alloy strip can be dissolved into a copper matrix in a solid solution manner, so that no intermetallic compound exists when the copper alloy strip is subjected to hot rolling and cogging, and uniform deformation and no cracking of a copper alloy cast ingot are ensured when the copper alloy strip is subjected to hot rolling and cogging. When the hot rolling cogging temperature is less than 1000 ℃, the specific hot rolling process according to the present invention cannot be ensured. When the hot rolling temperature is higher than 1020 ℃, overheating or overburning may occur, thereby causing hot rolling cracking. The heating and heat preservation time is 2-4 h, which can ensure that the alloy elements are fully dissolved in the copper matrix and the crystal grains do not grow. The heating and heat preservation time is less than 2h, and partial solute atoms cannot be dissolved into the copper matrix due to insufficient diffusion; the heat preservation time exceeds 4 hours, crystal grains grow up, and the copper alloy plate blank cracks in the hot rolling process.
The copper alloy strip has a total hot rolling reduction of 90% or more, a first stage hot rolling process with a reduction ratio of 60% to 90% is carried out before the temperature is reduced to 900 ℃, the final rolling temperature is maintained at 840 ℃ or more, a second stage hot rolling process is carried out between 900 ℃ and 840 ℃, the rolling reduction is 30% to 60% of the thickness of the plate blank after the first stage hot rolling process, solute atoms are all dissolved in a copper matrix within the range of 1000 ℃ to 1020 ℃, only α phases exist in the copper alloy, and due to the small difference in atomic radius between Ag atoms and Cu atoms, proper distortion energy is formed around Ag atoms due to the hot rolling process, and the proper distortion energy is formed around Ag atoms due to the atomic radius difference between Ag atoms and Cu atoms, and when the copper alloy strip is subjected to the first stage hot rolling process and the hot rolling process of the copper alloy strip, the copper alloy strip with an area of 40% or more is formed in the hot rolling process of the second stage, the copper alloy strip is prepared to have a high specific distortion energy of 40% or more, and the copper alloy is formed in the copper alloy after the hot rolling process, and the copper alloy, the copper alloy strip is prepared to have a high electrical conductivity, and the specific distortion energy of the copper alloy formed in the two stage hot rolling process of the copper alloy, the copper alloy is prepared by the copper alloy, the copper alloy prepared by the copper alloy of.
Preferably, the total reduction ratio of the rough rolling is controlled to 80% or more.
A rough rolling overall reduction of 80% or more may provide sufficient strain energy in the copper alloy strip of the present invention to ensure formation of a cubic texture of 35% or more when subjected to subsequent solution and quenching treatments. If the rough rolling processing rate is lower than 80 percent, the energy storage is insufficient, and enough cubic texture can not be formed during the solid solution and quenching treatment, so that the texture type and the area ratio of the prepared finished strip can not meet the requirements, and the bending performance of the finished strip is poor.
Preferably, the solution quenching temperature is controlled to be 950-1040 ℃, the heat preservation time is 0.1-1 h, the solution heating rate is required to be more than 100 ℃/s, the quenching cooling rate is more than 150 ℃/s, and the area percentage of the cubic texture in the strip after solution treatment is more than 35%.
The solid solution heating temperature of the invention is set to be 950-1040 ℃, firstly, the transformation of the copper texture formed in the hot rolling to the cubic texture is promoted and the formation of more than 35% of the cubic texture is ensured when the strip is subjected to the solid solution treatment, and secondly, solute atoms precipitated in the hot rolling cogging process are ensured to enter the copper matrix again in a solid solution to form a supersaturated solid solution, so that enough precipitation phases are precipitated in the subsequent aging process, and the yield strength of the strip is ensured to reach more than 850 MPa. The heat preservation time is 0.1 h-1 h, so that solute atoms can be fully diffused in the solid solution process to form a supersaturated solid solution. The heat preservation time is less than 0.1h, so that solute atoms are insufficiently dissolved; the holding time of more than 1h can cause excessively coarse grains and influence the bending performance of the finished strip. The solid solution temperature rise speed is ensured to be over 100 ℃/s, and the transformation from the copper texture to the cubic texture is ensured; the quenching cooling speed is required to be more than 150 ℃/s, and solute atoms are not separated out in the quenching process, so that a supersaturated solid solution is formed. Further preferably, the solid solution temperature of the present invention may be set to 980 ℃ to 1040 ℃.
Preferably, the processing rate of the medium rolling is controlled to be 20-65%; the processing rate of the pre-finish rolling after the first-stage aging is controlled to be 10-40%, and the processing rate of the finish rolling after the second-stage aging is controlled to be 5-20%.
If the processing rate of the medium rolling is lower than 20%, enough internal energy cannot be reserved for primary aging, and the primary aging is insufficient, so that the yield strength of the finished copper alloy strip is lower than 850 MPa; if the work rate of the medium rolling is more than 65%, most of the cubic texture formed in the solution quenching treatment is converted into brass texture, so that the bending performance of the finished strip product is poor.
Preferably, the primary aging temperature is 400-500 ℃, and the heat preservation time is 5-8 h; the secondary aging temperature is within the range of 300-400 ℃, and the heat preservation time is 2-5 h.
The copper alloy strip has the primary aging temperature of 400-500 ℃ and the heat preservation time of 5-8 h. The primary aging temperature is set to be 400-500 ℃, the primary aging temperature is used for enabling the supersaturated solid solution to generate solid phase transformation, part of precipitated phase particles are primarily precipitated, a large number of dislocations are formed by taking the primarily precipitated particles as centers in the subsequent pre-finish rolling processing process, solute atom diffusion channels are provided for the secondary aging of the strip, and the full precipitation of solute atoms during the secondary aging is facilitated to form NixSiy、CoxSiy、CrxZryAnd CuxTiyAnd (3) an equal dispersion strengthening phase. When the primary aging temperature is lower than 400 ℃, the diffusion speed of solute atoms is low, and the required number of precipitation phases cannot be separated out from the supersaturated solid solution; when the primary aging temperature is higher than 500 ℃, precipitation phase particles precipitated by the primary aging can grow up, so that the number of the precipitation phase particles is reduced, and the improvement of mechanical properties is not facilitated. The purpose of the holding time of 5 h-8 h is to ensure that solute atoms have enough time to diffuse during first-order aging so as to precipitate a required dispersion strengthening phase from a supersaturated solid solution.
The total processing rate of the pre-finish rolling of the copper alloy strip after the primary aging is 10-40%. If the total processing rate of the pre-finish rolling after the primary aging is lower than 10 percent, enough dislocation can not be formed around the precipitation phase precipitated by the primary aging, so that the precipitation of a secondary aging precipitation phase is influenced, and the yield strength of a strip finished product is less than 850 MPa; if the total processing rate of the pre-finish rolling after the primary aging exceeds 40%, most of the cubic texture in the strip is converted into brass texture, so that the bending performance of the finished strip is poor.
The copper alloy strip is subjected to secondary aging after pre-finish rolling, the secondary aging temperature is within the range of 300-400 ℃, and the heat preservation time is 2-5 h. The pre-finish rolling processing after the primary aging forms a large amount of dislocation around the precipitation phase precipitated by the primary aging, and the secondary aging takes the dislocation around the precipitation phase precipitated by the primary aging as a precipitation channel to form a secondary aging precipitation phase distributed in a star shape around the precipitation phase precipitated by the primary aging. In the secondary aging process, the primary aging precipitation phase particles partially grow up, so that the distribution form of the secondary aging precipitation phase with larger primary aging precipitation phase particles as the center and in planetary distribution at the periphery is formed, the synergistic strengthening effect of the primary aging precipitation phase particles and the secondary aging precipitation phase particles can greatly improve the mechanical property of the copper alloy strip, and the yield strength is ensured to reach above 850 MPa. When the secondary aging temperature is lower than 300 ℃, due to the lower temperature, the diffusion rate of solute atoms is slow during secondary aging, and a precipitation strengthening phase cannot be effectively precipitated; when the secondary aging temperature is higher than 400 ℃, the precipitation phase precipitated by the primary aging and the secondary aging can grow greatly, the synergistic strengthening effect between the primary aging precipitation phase particles and the secondary aging precipitation phase particles can not be fully exerted, and the mechanical property of the strip material can not reach more than 850 MPa. The secondary aging heat preservation time is 2-5 h, if the heat preservation time is less than 2h, enough secondary aging precipitation phase particles cannot be formed, and the mechanical property is not favorable; if the heat preservation time exceeds 5 hours, precipitated phases precipitated by the primary aging and the secondary aging grow excessively, so that the synergistic strengthening effect is poor, and the mechanical property of the strip is reduced.
According to the invention, the copper alloy strip is subjected to finish rolling after secondary aging, and the total processing rate of the finish rolling is 5-20%. If the total processing rate of finish rolling processing is lower than 5%, the mechanical property of the strip cannot be further improved; if the total reduction ratio of the finish rolling is higher than 20%, although the mechanical properties of the strip can be further improved, the bending properties of the strip are drastically reduced because the area ratio of the cubic texture is less than 10% due to the further transformation of the cubic texture in the strip into the brass texture.
The copper alloy strip is subjected to stretch bending and straightening treatment after finish rolling, so that the shape of the strip is improved.
Compared with the prior known technology, the invention has the advantages that:
1. according to the invention, Ni, Co and Si are used as main elements, Ni, Co and Si atoms are dissolved into a copper matrix through high-temperature solution treatment, then a supersaturated solid solution is formed through quenching treatment, NixSiy and CoxSiy precipitate phases are precipitated through aging treatment subsequently, and the precipitated precipitate phases play a role in dispersion strengthening, so that the tensile strength, the yield strength and the elastic modulus of the copper alloy strip are improved. Ag is used as a main additive element, and Ag atoms exist in the copper alloy in a replacement solid solution mode, so that an initial texture basis is provided for forming a specific texture and an area ratio in the copper alloy strip. Besides the solid solution strengthening effect of Ag, Ag atoms can improve the high-temperature softening resistance and the stress relaxation resistance of the copper alloy strip, so that the copper alloy strip has excellent comprehensive performance.
2. The copper alloy strip has the yield strength of more than 850MPa, the elastic modulus of more than 120GPa, the conductivity of more than 45 percent IACS and the Badway 90-degree bending R/t of less than or equal to 2.5, and meets the performance requirements of small size, light weight, high integration, intellectualization and multifunction of consumer electronics, electronic components, electronic connectors and lead frames.
Detailed Description
The present invention will be described in further detail with reference to examples and comparative examples.
30 example alloys and 3 comparative example alloys are selected, and the example alloys are respectively processed into strip finished products with the thickness of 0.2mm by adopting the full-flow preparation method. The full-flow preparation process of the copper alloy strip with excellent comprehensive performance comprises the following steps: batching → smelting → casting → sawing → heating → hot rolling → milling face → rough rolling → solid solution and quenching treatment → medium rolling → first-level aging → cleaning → pre-finish rolling → second-level aging → cleaning → finish rolling → stretch bending and straightening, which comprises the following steps:
1) material preparation and casting: preparing raw materials and proportioning according to the chemical composition of the alloy, smelting by adopting an induction furnace, wherein the adding sequence of the alloy is as follows: firstly adding Cu, adding Ni and Co after melting, adding an intermediate alloy of Ag and CuSi after melting Ni and Co, selectively adding one or more elements of Mg, Ce, Cr, Zr, Ti, Fe, Mn, Zn and Sn, making the components meet the requirements, fully degassing, removing slag and casting, wherein the smelting temperature is 1270 ℃, and the casting temperature is 1220 ℃.
2) Sawing: and sawing the cast ingot to remove the head and the tail of the cast ingot.
3) Hot rolling: heating the cast ingot at 1010 ℃, preserving heat for 3h, and then performing hot rolling cogging, wherein the hot rolling processing is performed in a hot rolling mode with the total processing rate before 900 ℃ of 60-90% and the total processing rate between 900 ℃ and 840 ℃ of 30-60%.
4) Rough rolling: and (3) performing rough rolling processing after milling the surface of the hot rolled strip, wherein the total processing rate of the rough rolling processing is more than 80%.
5) Solid solution and quenching treatment: after rough rolling, the strip is subjected to solution quenching treatment, the solution temperature is 950-1040 ℃, the temperature is kept for 0.5h, and then quenching treatment is carried out. The solid solution heating rate is 120 ℃/s, and the cooling rate is 150 ℃/s.
6) Intermediate rolling: and (3) carrying out medium rolling on the strip subjected to the solution treatment and quenching treatment, wherein the medium rolling rate is 40%.
7) Primary aging: and (3) carrying out primary aging treatment on the strip after the medium rolling, wherein the aging temperature is 400-500 ℃, and the aging time is 6 h.
8) Pre-finish rolling: and (3) performing pre-finish rolling processing on the strip subjected to the primary aging treatment, wherein the processing rate is 30%.
9) Secondary aging: and (3) carrying out secondary aging treatment on the strip subjected to the pre-finish rolling, wherein the aging temperature is within the range of 300-400 ℃, and the aging time is 3 h.
10) Finish rolling: and (3) performing finish rolling processing on the strip subjected to the secondary aging treatment, wherein the processing rate is 5-20%.
11) Stretch bending and straightening: and (4) performing stretch bending and straightening on the strip after finish rolling, improving the shape of the strip, and obtaining a copper alloy strip finished product with excellent comprehensive performance.
Room temperature tensile mechanical property, electric conductivity, texture type and area ratio and Badway 90-degree bending detection are carried out on the finished product of the strip material of the embodiment; and compared to the performance of the comparative example alloy.
Tensile test at room temperature according to GB/T228.1-2010 Metal Material tensile test part 1: room temperature test method was conducted on an electronic universal mechanical property tester, and strip samples having a thickness of 0.2mm were used for the examples and comparative examples, and the stretching speed was 5 mm/min.
The conductivity of the strips of the examples and comparative examples was tested using the GB/T32791-2016 copper and copper alloy conductivity eddy current test method.
The bending properties of the tapes of the examples and comparative examples (evaluated as to whether the bend at Badway90 DEG R/t.ltoreq.2.5 cracks) were tested using JCBA T307-2007 Test method of band formability for sheets and tapes of the coppers and coppers alloys, and the width of the Test tape was 10 mm.
The texture types and area ratios of the tapes of the examples and comparative examples were analyzed by EBSD, and the area ratio of each orientation is the ratio of the area within 15 ° of deviation of each orientation to the measured area.
The compositions, specific thermo-mechanical treatment processes, and the results of the texture and properties measurements for the examples and comparative examples are shown in tables 1, 2, and 3.
TABLE 1 ingredients of examples and comparative examples
TABLE 1
Although the comparative example 1C70250 alloy strip does not crack even at the Badway90 DEG bend R/t ≦ 2.5, the yield strength of the C70250 alloy strip is only 650.2MPa, which is lower than that of the alloy strip according to the invention.
For the comparative example of two C70350 alloy strips, the Badway90 ° bend R/t ≦ 2.5 did not crack when the yield strength was relatively low (832.7MPa), but cracking occurred with the Badway90 ° bend R/t ≦ 2.5 when the yield strength was comparable to that of the strip of the invention (868.2 MPa).
Claims (10)
1. A copper alloy strip with excellent comprehensive performance is characterized in that the copper alloy comprises the following components in percentage by weight: ni: 2.5 wt% -4.0 wt%, Co: 0.2 wt% to 1.2 wt%, Si: 0.4 wt% -1.4 wt%, Ag: 0.01 wt% -0.2 wt%, and the balance of Cu.
2. The copper alloy strip with excellent comprehensive properties as claimed in claim 1, wherein the texture type and the area ratio of the copper alloy strip are as follows: the area ratio of the cubic texture is 10-30%, the area ratio of the brass texture is 5-20%, the area ratio of the copper texture is 5-20%, the balance is other types of textures, and the area ratio of the textures is the ratio of the area within 15 degrees of deviation angle of each orientation divided by the measured area.
3. The copper alloy strip with excellent comprehensive performance as claimed in claim 2, wherein the area ratio of the cubic texture to the brass texture to the copper texture of the copper alloy strip satisfies the following conditions: a/(b + c) is more than or equal to 0.3 and less than or equal to 2.0, wherein a is the area proportion of the cubic texture, b is the area proportion of the brass texture, and c is the area proportion of the copper texture.
4. The copper alloy strip with excellent combination of properties as recited in claim 1 further comprising at least one of the optional elements, wherein the optional elements comprise less than 0.5 wt% in total; optional elements are Mg: 0.001 wt% -0.2 wt%, Ce: 0.001 wt% -0.2 wt%, Cr: 0.001 wt% to 0.1 wt%, Zr: 0.001 wt% -0.1 wt%, Ti: 0.001 wt% -0.1 wt%, Fe: 0.001 wt% -0.2 wt%, Mn: 0.001 wt% -0.2 wt%, Zn: 0.001 wt% -0.2 wt%, Sn: 0.001 wt% -0.2 wt%.
5. The copper alloy strip with excellent comprehensive properties as recited in any one of claims 1 to 4, wherein the copper alloy strip has a yield strength of 850MPa or more, an elastic modulus of 120GPa or more, an electrical conductivity of 45% IACS or more, and a Badway90 ° bend R/t of 2.5 or less.
6. The method for preparing the copper alloy strip with excellent comprehensive performance as claimed in any one of claims 1 to 4, which comprises the following steps: batching → smelting → casting → sawing → heating → hot rolling → milling face → rough rolling → solid solution and quenching treatment → medium rolling → first-stage aging → cleaning → pre-finish rolling → second-stage aging → cleaning → finish rolling → stretch bending and straightening; the method is characterized in that the total processing rate of hot rolling is more than 90%, the finishing temperature is controlled to be more than 840 ℃, hot rolling at more than 900 ℃ is the first stage of hot rolling processing, and the rolling rate is 60-90%; the second stage hot rolling processing is carried out between 900 ℃ and the finish rolling temperature of 840 ℃, and the rolling rate is 30-60% of the thickness of the plate blank after the first stage hot rolling processing; the area percentage of the copper texture in the hot rolled strip is more than 40%.
7. The method for preparing the copper alloy strip with excellent comprehensive performance as claimed in claim 6, wherein the total processing rate of the rough rolling is controlled to be more than 80%.
8. The method for preparing a copper alloy strip with excellent comprehensive performance according to claim 6, wherein the solution quenching temperature is controlled to be 950-1040 ℃, the holding time is 0.1-1 h, the solution heating rate is required to be more than 100 ℃/s, the quenching cooling rate is more than 150 ℃/s, and the area percentage of the cubic texture in the strip after solution treatment is more than 35%.
9. The method for preparing the copper alloy strip with excellent comprehensive performance as claimed in claim 6, wherein the processing rate of the medium rolling is controlled to be 20-65%; the processing rate of the pre-finish rolling after the first-stage aging is controlled to be 10-40%, and the processing rate of the finish rolling after the second-stage aging is controlled to be 5-20%.
10. The method for preparing the copper alloy strip with excellent comprehensive performance according to claim 6, wherein the primary aging temperature is 400-500 ℃, and the heat preservation time is 5-8 h; the secondary aging temperature is within the range of 300-400 ℃, and the heat preservation time is 2-5 h.
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