CN115896534A - Chromium-containing copper alloy strip and preparation method and application thereof - Google Patents
Chromium-containing copper alloy strip and preparation method and application thereof Download PDFInfo
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- CN115896534A CN115896534A CN202211505786.3A CN202211505786A CN115896534A CN 115896534 A CN115896534 A CN 115896534A CN 202211505786 A CN202211505786 A CN 202211505786A CN 115896534 A CN115896534 A CN 115896534A
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- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 73
- 239000011651 chromium Substances 0.000 title claims abstract description 32
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000005096 rolling process Methods 0.000 claims abstract description 42
- 230000032683 aging Effects 0.000 claims abstract description 39
- 238000005452 bending Methods 0.000 claims abstract description 30
- 238000005098 hot rolling Methods 0.000 claims abstract description 30
- 239000010949 copper Substances 0.000 claims abstract description 26
- 238000004321 preservation Methods 0.000 claims abstract description 25
- 230000035882 stress Effects 0.000 claims abstract description 25
- 239000006104 solid solution Substances 0.000 claims abstract description 17
- 238000004806 packaging method and process Methods 0.000 claims abstract description 16
- 238000010791 quenching Methods 0.000 claims abstract description 13
- 230000000171 quenching effect Effects 0.000 claims abstract description 13
- 238000004140 cleaning Methods 0.000 claims abstract description 10
- 238000005266 casting Methods 0.000 claims abstract description 7
- 230000004927 fusion Effects 0.000 claims abstract description 5
- 238000003801 milling Methods 0.000 claims abstract description 5
- 239000012535 impurity Substances 0.000 claims abstract description 3
- 239000002245 particle Substances 0.000 claims description 44
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 22
- 229910052802 copper Inorganic materials 0.000 claims description 22
- 238000012545 processing Methods 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- HZEWFHLRYVTOIW-UHFFFAOYSA-N [Ti].[Ni] Chemical compound [Ti].[Ni] HZEWFHLRYVTOIW-UHFFFAOYSA-N 0.000 claims description 10
- UMUXBDSQTCDPJZ-UHFFFAOYSA-N chromium titanium Chemical compound [Ti].[Cr] UMUXBDSQTCDPJZ-UHFFFAOYSA-N 0.000 claims description 10
- CLDVQCMGOSGNIW-UHFFFAOYSA-N nickel tin Chemical compound [Ni].[Sn] CLDVQCMGOSGNIW-UHFFFAOYSA-N 0.000 claims description 10
- 229910001000 nickel titanium Inorganic materials 0.000 claims description 8
- 229910001369 Brass Inorganic materials 0.000 claims description 5
- 239000010951 brass Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000011534 incubation Methods 0.000 claims 1
- 238000003754 machining Methods 0.000 claims 1
- 229910045601 alloy Inorganic materials 0.000 description 20
- 239000000956 alloy Substances 0.000 description 20
- 239000000463 material Substances 0.000 description 13
- 239000011159 matrix material Substances 0.000 description 12
- 238000001556 precipitation Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 238000005728 strengthening Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 238000005336 cracking Methods 0.000 description 2
- 238000006880 cross-coupling reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910019580 Cr Zr Inorganic materials 0.000 description 1
- 229910019817 Cr—Zr Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- IUYOGGFTLHZHEG-UHFFFAOYSA-N copper titanium Chemical compound [Ti].[Cu] IUYOGGFTLHZHEG-UHFFFAOYSA-N 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005111 flow chemistry technique Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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Abstract
The invention discloses a chromium-containing copper alloy strip which comprises the following components in percentage by mass: 0.2wt% to 1.3wt%, sn:0.3wt% -1.3 wt%, cr:0.1wt% -1.2 wt%, ti:0.1wt% -1.0 wt%, the balance of Cu and inevitable impurities, and the preparation process flow comprises the following steps: batching → fusion casting → hot rolling → face milling → rough rolling → solid solution and quenching → medium rolling → primary aging treatment → cleaning → pre-finish rolling → secondary aging treatment → cleaning → finish rolling → stretch bending and straightening. The copper alloy strip has the tensile strength of more than 550MPa, the electric conductivity of more than 50 percent IACS, the badway 90-degree bending R/t of less than or equal to 1.0 and the stress relaxation rate of less than or equal to 15 percent after the heat preservation at 150 ℃ for 1000 hours, has excellent bending performance and stress relaxation resistance while keeping high tensile strength and good electric conductivity, and can meet the performance requirements of the copper alloy strip for the new generation of stamping type packaging.
Description
Technical Field
The invention belongs to the technical field of copper alloy, and particularly relates to a chromium-containing copper alloy strip and a preparation method and application thereof.
Background
The lead frame plays three main roles in chip packaging: (1) providing mechanical support for the chip; (2) providing electrical connections to communicate the chip with external circuitry; and (3) providing a chip heat dissipation path. With the rapid development of semiconductor technology, chips are developed towards miniaturization, multifunctionalization and ultra-large scale integration, and increasingly stringent requirements are provided for the strength, the electric conductivity, the stamping performance, the stress relaxation resistance and the like of lead frame copper alloy strips for chip packaging. The miniaturization of chip packaging leads to the smaller and smaller pin size, thereby putting higher and higher requirements on the strength of the copper alloy strip for packaging; the super-large scale integration of the chip leads the heat productivity of the chip to be larger and larger, thereby putting higher and higher requirements on the electric conductivity of the copper alloy strip for packaging; the complexity of a chip packaging structure puts higher and higher requirements on the stamping performance of a copper alloy strip for packaging, and the copper alloy strip is required to have excellent bending performance; the use condition of the chip is more and more severe, and the stress relaxation resistance of the copper alloy strip for packaging is required to be better and better. The above conditions require that the tensile strength of the copper alloy strip for chip packaging is 550MPa or more, the electric conductivity is 50% IACS or more, the badway90 DEG bending R/t is less than or equal to 1.0, and the stress relaxation rate after the heat preservation at 150 ℃ for 1000 hours is less than or equal to 15%.
Although the electric conductivity of the copper alloy strip for the CuFe2P lead frame which is widely used at present can reach more than 60% IACS, the tensile strength is only about 550MPa at most, the requirement of the mechanical property of the medium-scale integrated circuit chip package with larger pin size can only be met, and the requirement of the mechanical property required by smaller and smaller pin size of the lead frame can not be met.
Aiming at the future development requirements of the stamped lead frame for chip packaging, the invention provides a high-performance chromium-containing copper alloy strip with high strength, high conductivity, excellent bending performance and excellent stress relaxation resistance, and a preparation method and application thereof, so as to meet the performance requirements of a new generation of copper alloy strip for stamped packaging.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a chromium-containing copper alloy strip with high strength, high conductivity, excellent bending performance and excellent stress relaxation resistance, and a preparation method and application thereof aiming at the defects of the prior art.
The technical scheme adopted by the invention for solving the technical problems is as follows: a chromium-containing copper alloy strip comprises the following components in percentage by mass: 0.2wt% -1.3 wt%, sn:0.3wt% -1.3 wt%, cr:0.1wt% -1.2 wt%, ti:0.1wt% to 1.0wt%, and the balance of Cu and unavoidable impurities.
In the invention, ni, sn, cr and Ti can form and precipitate precipitated phases such as a nickel-tin compound, a chromium-titanium compound, a nickel-titanium compound, a chromium simple substance and the like, and the precipitated phases play a role in dispersion strengthening on one hand and form cross-coupling distribution on the other hand, so that the synergistic strengthening effect of the precipitated phases such as the nickel-tin compound, the chromium-titanium compound, the nickel-titanium compound, the chromium simple substance and the like is improved, and the tensile strength of the copper alloy strip is improved. And the purity of the copper matrix is greatly improved due to the precipitation of the precipitate phase, so that the conductivity of the copper matrix is greatly improved. When the Ni content is less than 0.2wt%, the Sn content is less than 0.3wt%, the Cr content is less than 0.1wt%, and the Ti content is less than 0.1wt%, the precipitated phase in the strip is less, the dispersion strengthening effect is not obvious, the tensile strength of the strip is obviously reduced, and the mechanical property does not meet the requirement. When the Ni content is more than 1.3wt%, the Sn content is more than 1.3wt%, the Cr content is more than 1.2wt%, and the Ti content is more than 1.0wt%, too many dispersion-strengthened phases are precipitated, and the scattering effect of second phase particles on electron waves is enhanced, so that the conductivity of the strip material is sharply reduced. Therefore, the Ni content of the copper alloy strip is controlled within the range of 0.2wt% -1.3 wt%, the Sn content is controlled within the range of 0.3wt% -1.3 wt%, the Cr content is controlled within the range of 0.1wt% -1.2 wt%, and the Ti content is preferably controlled within the range of 0.1wt% -1.0 wt%.
Preferably, the precipitated phase of the copper alloy strip comprises a nickel-tin compound, a chromium-titanium compound, a nickel-titanium compound and a chromium simple substance which are granular and have the maximum length of 0.01-1 mu m, and the maximum length is respectively expressed by D 1 、D 2 、D 3 Represents the maximum length of the particles which are different in the range of 0.01 to 1 mu m, wherein the maximum length of the particles satisfies the condition that D is more than or equal to 0.5 mu m 1 The ratio of the number of the particles with the diameter less than or equal to 1 mu m is 10 to 20 percent, and the maximum length of the particles satisfies that D is less than or equal to 0.1 mu m 2 The percentage of the number of the particles less than 0.5 mu m is 30 to 60 percent, and the maximum length of the rest particles satisfies that D is more than or equal to 0.01 mu m 3 Less than 0.1 μm. When the maximum length of the precipitated phase particles is less than 0.01 mu m, although the number of the precipitated phase particles is more, the tensile strength and the stress relaxation resistance of the strip material are favorably improved, the scattering effect of a plurality of precipitated phase particles below 0.01 mu m on the electron wave is very strong, and the electric conductivity of the strip material is greatly reduced; when the maximum length of the precipitated phase particles is greater than 1 μm, the total amount of the precipitated phase particles is reduced, which is not favorable for improving the tensile strength and the stress relaxation resistance of the strip. According to the invention, by controlling the sizes of precipitated phase particles such as nickel-tin compounds, chromium-titanium compounds, nickel-titanium compounds, chromium simple substances and the like and the proportion of the number of the particles, the synergistic coupling strengthening effect of the precipitated phase particles can be exerted, and the tensile strength and the stress relaxation resistance of the copper alloy strip can be further improved.
The bending performance of the copper alloy strip is determined by the texture type and the ratio. Among all texture types of the copper alloy strip, the anisotropy of the cubic texture is the lowest, and the area ratio of the cubic texture in the strip has the greatest influence on the bending performance of the strip. When the cubic texture is high in percentage, the strip cannot crack during stamping and bending, so that the quality of the stamped lead frame is ensured; when the cubic texture accounts for a relatively low ratio, the strip material can crack during stamping and bending, and the quality of the stamping type lead frame cannot be ensured. The area occupation ratio of the copper texture and the brass texture in the strip material has certain influence on the mechanical property of the strip material, and when the area occupation ratio of the brass texture and the copper texture is higher, the tensile strength of the strip material is favorably improved. The inventor finds that the main texture types of the copper alloy strip material are a cubic texture, a copper texture and a brass texture, and the proportion of the area of the cubic texture in the measured area is controlled to be 10-40%, so that the tensile strength of the copper alloy strip material can be ensured to reach a higher level, and the strip material can be endowed with good bending performance.
Preferably, the copper alloy strip further comprises one or more elements selected from the group consisting of Mg, zr, ag, zn, fe, mn in a total amount of 0.2wt% in the composition in mass percent. The main function of the elements is to dissolve in copper to achieve the solid solution strengthening effect, so that the mechanical property and the stress relaxation resistance of the copper alloy strip are improved. In addition, a certain amount of Zr can also form a Cr-Zr precipitation phase with Cr to play a role in dispersion strengthening, so that the tensile strength and the stress relaxation resistance of the copper alloy strip are improved, and simultaneously, the purity of a copper matrix can be further improved due to precipitation of the precipitation phase, so that the conductivity of the alloy is improved. When the content of the above optional element is more than 0.2wt%, an excessive amount of the above element is caused to be dissolved in the copper matrix, resulting in a significant decrease in the electrical conductivity of the alloy.
Preferably, the copper alloy strip has a tensile strength of 550MPa or more, an electric conductivity of 50% IACS or more, a badway90 DEG bend R/t of 1.0 or less, and a stress relaxation rate after 1000 hours of heat preservation at 150 ℃ of 15 or less.
The preparation method of the chromium-containing copper alloy strip comprises the following preparation process flows: batching → fusion casting → hot rolling → face milling → rough rolling → solid solution and quenching → medium rolling → primary aging treatment → cleaning → pre-finish rolling → secondary aging treatment → cleaning → finish rolling → stretch bending and straightening.
The copper alloy is smelted at 1250-1300 ℃, semi-continuous casting is carried out at 1200-1250 ℃ to prepare a plate blank, and the plate blank is subjected to heat preservation at 940-980 ℃ for 3-5 h and then hot rolling cogging is carried out. In the heat preservation process before hot rolling cogging, elements such as Ni, sn, cr, ti, mg, zr and the like in the copper alloy can be dissolved in a copper matrix to form a supersaturated solid solution, so that no precipitate exists during the hot rolling cogging of the copper alloy, and the uniform deformation and no cracking of the copper alloy ingot during the hot rolling cogging are ensured. When the hot rolling cogging temperature is lower than 940 ℃, part of elements cannot be dissolved into the copper matrix, and the alloy is cracked in the hot rolling process; when the hot rolling cogging temperature is higher than 980 ℃, the alloy can be overheated or overburnt, and hot rolling cracking is also caused. The heat preservation time of 940-980 ℃ is 3-5 h, which can ensure that elements such as Ni, sn, cr, ti, mg, zr and the like are fully dissolved into the copper matrix and the crystal grains do not grow. If the heat preservation time is less than 3h, part of solute atoms cannot be dissolved into the copper matrix due to insufficient diffusion; if the heat preservation time exceeds 5 hours, crystal grains grow up, and the plate blank cracks in the hot rolling process.
The invention controls the total processing rate of hot rolling to be more than 90%, and controls the finishing temperature to be more than 800 ℃, so as to ensure that copper type textures with the area percentage of more than 60% are formed in the alloy after hot rolling processing, and prepare for forming specific textures and area percentages in subsequent finished strips. In the hot rolling cogging process of the copper alloy plate blank, when hot rolling processing is carried out in the range of more than 800 ℃, part of solute atoms of Ni, sn, cr and Ti are separated out and dynamically recrystallized in the hot rolling process by precipitation phases of a nickel-tin compound, a chromium-titanium compound, a nickel-titanium compound, a chromium simple substance and the like, and due to the hot rolling processing, proper distortion energy can be formed around the separated nano-scale precipitation phase, and the distortion energy and the dynamic recrystallization structure are deformation energy storage and microstructure guarantee for the hot rolling processing carried out in the temperature range of more than 800 ℃ at the final rolling temperature, so that a copper type texture with the area accounting for more than 60% is formed after the hot rolling of the alloy plate blank, and an initial texture basis is provided for forming a specific texture and an area accounting ratio in the copper alloy strip.
After the copper alloy plate blank is subjected to hot rolling and cogging, surface milling treatment is carried out to remove oxide skin on the surface of the alloy, and then rough rolling processing with the processing rate of more than 80% is carried out. The rough rolling with a work rate of more than 80 percent can further store energy in the copper alloy, and make energy reserve for recrystallization in the subsequent solution treatment process. The temperature of the solution treatment is 960-1000 ℃, the heat preservation time is 0.1-0.5 h, and the quenching cooling speed after the solution treatment is more than 120 ℃/s. The solid solution treatment process of the invention can ensure that the precipitated phase precipitated in the hot rolling cogging process enters the copper matrix again to form a supersaturated solid solution, simultaneously ensure that the copper texture formed in the hot rolling process of the alloy is promoted to be converted to the cubic texture in the solid solution treatment process and ensure that the cubic texture with the area percentage of more than 50 percent is formed, thereby forming the texture type and the area percentage of the texture type defined by the invention in the finished strip product, and further ensuring that the stamping bending performance of the strip reaches the use requirement while ensuring that the tensile strength of the strip is higher. The heat preservation time of the solution treatment is 0.1 h-0.5 h, so that solute atoms can be fully diffused in the solution process to form a supersaturated solid solution. The heat preservation time of the solution treatment is less than 0.1h, which can cause insufficient solute atom solution; the holding time of the solution treatment exceeds 0.5h, which can cause excessively coarse grains and influence the bending property of the finished strip. The quenching cooling speed after the solution treatment is controlled to be more than 120 ℃/s so as to ensure that no solute atoms are precipitated in the quenching process, thereby forming a supersaturated solid solution.
The copper alloy strip is subjected to medium rolling after solid solution and quenching treatment, and then is subjected to primary aging treatment. The temperature of the primary aging treatment is 400-460 ℃, and the heat preservation time is 5-8 h. The temperature of the first-stage aging treatment is set to be 400-460 ℃, solute atoms can be separated out from the supersaturated solid solution, dispersion strengthening phase particles such as nickel-tin compounds, chromium-titanium compounds, nickel-titanium compounds, chromium simple substances and the like with the maximum length range of 0.01-0.5 mu m are formed, and the size and the quantity of the separated phase particles are prepared for the subsequent pre-finish rolling and second-stage aging treatment while the first-stage precipitation strengthening effect is achieved. If the temperature of the primary aging treatment is higher than 460 ℃ and the heat preservation time exceeds 8 hours, the size of precipitated phase particles precipitated by the primary aging treatment is larger and cannot be controlled within the range of 0.01-0.5 mu m; if the temperature of the primary aging treatment is lower than 400 ℃ and the heat preservation time is lower than 5h, the primary aging precipitation is insufficient, and the number of precipitated phase particles cannot be ensured.
Hair brushAnd after finishing the primary aging treatment and cleaning, carrying out pre-finish rolling processing and secondary aging treatment on the bright copper alloy strip. The pre-finish rolling processing can form dislocation loops around the primary aging precipitated phase particles in the copper alloy strip, and provides a precipitation channel for secondary aging treatment. The temperature of the secondary aging treatment is 350-400 ℃, the heat preservation time is 3-5 h, solute atoms in the copper alloy strip material are ensured to be separated out along dislocation loops around the precipitated phase particles separated out by the primary aging treatment, and the particles separated out by the primary aging treatment grow up, so that the maximum length of the precipitated phase particles in the copper alloy strip material is 0.01-1 mu m, wherein the maximum length of the particles satisfies that D is more than or equal to 0.5 mu m and less than or equal to D 1 The ratio of the number of the particles with the diameter less than or equal to 1 mu m is 10 to 20 percent, and the maximum length of the particles satisfies that D is less than or equal to 0.1 mu m 2 The percentage of the number of the particles less than 0.5 mu m is 30 to 60 percent, and the maximum length of the rest particles satisfies that D is more than or equal to 0.01 mu m 3 Is less than 0.1 mu m. The precipitation and the proportion of the precipitated phase are controlled, so that on one hand, a copper matrix can be purified, and the tensile strength and the electric conductivity of the copper alloy strip can meet the requirements at the same time; on the other hand, the stress relaxation resistance of the copper alloy strip can be improved, and the effect that the stress relaxation rate is less than or equal to 15 percent after the temperature is kept at 150 ℃ for 1000 hours is achieved. When the temperature of the secondary aging treatment is lower than 350 ℃ and the heat preservation time is lower than 3h, the diffusion speed of solute atoms is low, and the required number of precipitated phases cannot be separated out from the supersaturated solid solution; when the temperature of the secondary aging treatment is higher than 400 ℃ and the heat preservation time is longer than 5 hours, precipitated phase particles precipitated by aging grow up, so that the number of the precipitated phase particles is reduced, and the effects of the size and the specific proportion of the precipitated phase particles cannot be achieved.
After the secondary aging treatment and cleaning are completed, the copper alloy strip is subjected to finish rolling processing and stretch bending straightening, so that the shape of the copper alloy strip meets the requirements of the copper alloy strip for stamping type packaging. In addition, after the copper alloy strip is subjected to medium rolling, primary aging treatment, pre-finish rolling and secondary aging treatment, part of the cubic texture in more than 50% of the cubic texture formed in the solution treatment process is converted into a copper texture, a brass texture and other textures, and after the strip is subjected to finish rolling processing and stretch bending straightening, the area ratio of the cubic texture remained in a finished strip product is 10-40%, so that the excellent bending performance of the copper alloy strip is ensured.
The chromium-containing copper alloy strip is applied to the preparation of a stamping type lead frame for chip packaging.
Compared with the prior art, the invention has the beneficial effects that:
1) According to the invention, ni, sn, cr and Ti are added, and at least one of Mg, zr, ag, zn, fe and Mn is selectively added, so that precipitation phases such as a nickel-tin compound, a chromium-titanium compound, a nickel-titanium compound and a chromium simple substance which are granular and have the maximum length of 0.01-1 mu m are formed in the copper alloy strip, wherein the maximum length of the granules satisfies that D is more than or equal to 0.5 mu m and less than or equal to D 1 The ratio of the number of the particles with the diameter less than or equal to 1 mu m is 10 to 20 percent, and the maximum length of the particles satisfies that D is less than or equal to 0.1 mu m 2 The percentage of the number of the particles less than 0.5 mu m is 30 to 60 percent, and the maximum length of the rest particles satisfies that D is more than or equal to 0.01 mu m 3 Less than 0.1 μm. The precipitated phases of the nickel-tin compound, the chromium-titanium compound, the nickel-titanium compound, the chromium elementary substance and the like form cross-coupling distribution, so that the synergistic strengthening effect of the precipitated phases of the nickel-tin compound, the chromium-titanium compound, the nickel-titanium compound, the chromium elementary substance and the like is improved, and the tensile strength and the stress relaxation resistance of the copper alloy strip are improved; and the purity of the copper matrix is greatly improved due to the precipitation of the precipitate phase, so that the conductivity of the copper matrix is greatly improved. The full-flow processing technology developed by the invention enables the area ratio of the cubic texture in the finished product of the copper alloy strip to be 10-40%, so that the copper alloy strip has excellent bending performance and meets the bending requirement of punch forming.
2) The copper alloy strip has the tensile strength of more than 550MPa, the electric conductivity of more than 50 percent IACS, the badway 90-degree bending R/t of less than or equal to 1.0 and the stress relaxation rate of less than or equal to 15 percent after the temperature is kept for 1000 hours at 150 ℃, has excellent bending performance and stress relaxation resistance while keeping high tensile strength and good electric conductivity, and can meet the performance requirements of the copper alloy strip for the next generation of stamping type packaging.
Detailed Description
The present invention is described in further detail below with reference to examples.
15 example alloys and 2 comparative example alloys are selected and respectively processed into strip finished products with the thickness of 0.2mm by adopting the preparation method, and the preparation process flow is as follows: batching → fusion casting → hot rolling → face milling → rough rolling → solid solution and quenching → medium rolling → primary aging treatment → washing → pre-finish rolling → secondary aging treatment → washing → finish rolling → stretch bending straightening, which comprises the following steps:
1) Material preparation and fusion casting: preparing raw materials and proportioning according to chemical components of the alloy, and smelting by using an induction furnace, wherein the adding sequence of the alloy is as follows: firstly adding Cu, adding Ni, sn and Cr after melting, adding a copper-titanium intermediate alloy after the alloy elements are melted, selectively adding one or more elements of Mg, zr, ag, zn, fe and Mn, fully degassing and deslagging the components according with requirements, and then casting at the melting temperature of 1280 ℃ and the casting temperature of 1230 ℃.
2) Sawing: and sawing the cast ingot to remove the head and the tail of the cast ingot.
3) Hot rolling: and (3) carrying out hot rolling cogging after heat preservation for 3-5 h at 940-980 ℃, wherein the total processing rate of hot rolling is 90%, and the final rolling temperature is above 800 ℃.
4) Rough rolling: and (3) carrying out rough rolling processing after the surface of the hot rolled strip is milled, wherein the total processing rate of the rough rolling processing is 85%.
5) Solid solution and quenching treatment: the temperature of the solution treatment is 960-1000 ℃, the heat preservation time is 0.1-0.5 h, and the quenching cooling speed after the solution treatment is more than 120 ℃/s.
6) Intermediate rolling: and (3) carrying out medium rolling on the strip subjected to the solid solution and quenching treatment, wherein the medium rolling rate is 50%.
7) Primary aging treatment: and performing primary aging treatment on the strip after the medium rolling, wherein the aging temperature is 400-460 ℃, and the heat preservation time is 5-8 h.
8) Pre-finish rolling: and cleaning the strip subjected to the primary aging treatment, and then performing pre-finish rolling processing, wherein the processing rate is 20%.
9) Secondary aging treatment: and (3) carrying out secondary aging treatment on the strip subjected to the pre-finish rolling, wherein the aging temperature is 350-400 ℃, and the heat preservation time is 3-5 h.
10 Fine rolling and stretch bending straightening: and cleaning the strip after the secondary aging treatment, then performing finish rolling and stretch bending straightening to prepare a finished strip product.
The finished alloy strip products of the examples and the comparative examples are respectively tested for tensile mechanical property at room temperature, conductivity, texture type and area ratio, bending property, stress relaxation resistance and the like.
Tensile test at room temperature according to part 1 of the GB/T228.1-2010 tensile test for metallic materials: room temperature test method is carried out on an electronic universal mechanical property tester, and the stretching speed is 5mm/min. The conductivity of the strip is tested by a GB/T32791-2016 copper and copper alloy conductivity eddy current test method.
And analyzing the texture type and the cubic texture area ratio of the strip by adopting EBSD (Electron Back scattering), wherein the texture area ratio refers to the ratio of the area within 15 degrees of deviation angle of each orientation to the measured area.
And analyzing precipitated phase particles with different sizes and the number ratio of the precipitated phase particles by adopting a transmission electron microscope.
The bending properties of the strip were tested using JCBA T307-2007 Test method of band formability and strips of cooper and cooper alloys.
The stress relaxation resistance of the tape was tested using JCBA T309-2004 Standard method for stress relaxation test by bonding for thin sheets and strips.
The compositions of the examples and comparative examples are shown in Table 1, and the results of the measurements of the structure and properties are shown in Table 2.
As can be seen from tables 1 and 2, the yield strength of the copper alloy strip of the present invention can be up to 550MPa or more, the conductivity can be up to 50% IACS or more, the badway90 DEG bend R/t is less than or equal to 1.0, and the stress relaxation rate after the heat preservation at 150 ℃ for 1000 hours is less than or equal to 15%.
It can be seen from comparative examples 1 and 2 that when the composition of the alloy does not satisfy the control range, the precipitated phase size fraction, the cubic texture, etc. of the alloy are not within the target range, and the conductivity of the alloy in comparative example 1 can meet the target requirements, but the strength, the stress relaxation resistance, and the bending resistance are poor; the alloy of comparative example 2 is excellent in strength and stress relaxation resistance, but poor in conductivity and bending property.
TABLE 1 ingredients of examples and comparative examples
Claims (9)
1. The chromium-containing copper alloy strip is characterized by comprising the following components in percentage by mass: 0.2wt% -1.3 wt%, sn:0.3wt% -1.3 wt%, cr:0.1wt% to 1.2wt%, ti:0.1wt% to 1.0wt%, and the balance of Cu and unavoidable impurities.
2. The chromium-containing copper alloy strip according to claim 1, wherein the precipitated phases of the copper alloy strip comprise a nickel-tin compound, a chromium-titanium compound, a nickel-titanium compound and a chromium element in the form of particles with a maximum length of 0.01-1 μm, respectively denoted by D 1 、D 2 、D 3 Represents the maximum length of the particles which are different in the range of 0.01 to 1 mu m, wherein the maximum length of the particles satisfies the condition that D is more than or equal to 0.5 mu m 1 The ratio of the number of the particles with the diameter less than or equal to 1 mu m is 10 to 20 percent, and the maximum length of the particles satisfies that D is less than or equal to 0.1 mu m 2 The percentage of the number of the particles less than 0.5 mu m is 30 to 60 percent, and the maximum length of the rest particles satisfies that D is more than or equal to 0.01 mu m 3 ＜0.1μm。
3. The chromium-containing copper alloy strip according to claim 1, wherein the copper alloy strip comprises the main texture types of cubic texture, copper texture and brass texture, and the area ratio of the cubic texture in the measured area is 10-40%.
4. The chromium-containing copper alloy strip according to claim 1, further comprising a total of 0.2wt% of one or more elements selected from the group consisting of Mg, zr, ag, zn, fe, mn.
5. The chromium-containing copper alloy strip according to claim 1, wherein the copper alloy strip has a tensile strength of 550MPa or greater, an electrical conductivity of 50% IACS or greater, a badway90 ° bend R/t of 1.0 or less, and a stress relaxation rate of 15% or less after 1000 hours of incubation at 150 ℃.
6. The method for preparing the chromium-containing copper alloy strip according to any one of claims 1 to 5, wherein the preparation process comprises the following steps: batching → fusion casting → hot rolling → face milling → rough rolling → solid solution and quenching → medium rolling → primary aging treatment → cleaning → pre-finish rolling → secondary aging treatment → cleaning → finish rolling → stretch bending and straightening.
7. The method for preparing chromium-containing copper alloy strip according to claim 6, wherein the hot rolling process parameters are as follows: after preserving heat at 940-980 ℃ for 3-5 h, performing hot rolling and cogging, wherein the total processing rate of hot rolling is more than 90%, and the final rolling temperature is controlled to be more than 800 ℃; the machining rate of the rough rolling is more than 80%; the technological parameters of the solid solution and quenching treatment are as follows: the temperature of the solution treatment is 960-1000 ℃, the heat preservation time is 0.1-0.5 h, and the quenching cooling speed after the solution treatment is more than 120 ℃/s.
8. The method for preparing the chromium-containing copper alloy strip according to claim 6, wherein the temperature of the primary aging treatment is 400-460 ℃, and the heat preservation time is 5-8 h; the temperature of the secondary aging treatment is 350-400 ℃, and the heat preservation time is 3-5 h.
9. Use of the chromium-containing copper alloy strip according to any one of claims 1 to 5 for preparing a stamped lead frame for chip packaging.
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