CN112281023B - Copper alloy material with excellent bending property and preparation method and application thereof - Google Patents
Copper alloy material with excellent bending property and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a copper alloy material with excellent bending property, which comprises the following components in percentage by weight: 0.05 to 0.25wt% of Ni, 0.3 to 0.8wt% of Cr, 0.05 to 0.5wt% of Fe, 0.05 to 0.3wt% of Ti, 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, Ni and the like and a thermomechanical treatment process combining two-stage aging and recrystallization annealing. The invention controls Cr single and Ni in alloy microstructure3Ti phase and (Cr, Fe)2The size and the density of the Ti phase realize the effects of strengthening the alloy and improving the bending property and the electric conductivity of the alloy, the yield strength of the strip made of the copper alloy material is more than 700MPa, the electric conductivity is more than 55 percent IACS, and the Goodway90 DEG bending R1No cracking at/t =0, bend R at Badway90 °2The material does not crack when the/t is less than or equal to 1, has excellent bending property, and can be applied to products such as large-scale integrated circuit lead frames and folding screens.
Description
Technical Field
The invention belongs to the technical field of copper alloy, and particularly relates to a copper alloy material with excellent bending property, a preparation method and application thereof.
Background
With the progress of the times, new technologies such as a 5G communication technology, a chip technology, a communication base station, artificial intelligence, consumer electronics and the like are rapidly developed, electronic and electrical equipment is continuously developed towards miniaturization, high load and high reliability, and electronic and electrical equipment systems are increasingly complicated and highly integrated, so that the service environment of the copper alloy material is more severe, the performance of the copper alloy material is subject to higher requirements, the copper alloy material is required to have higher strength and conductivity, and the copper alloy material is required to have better bending property to cope with the complex shape processing of elements, so that the balanced high-strength high-conductivity copper alloy material is more and more focused on various parties.
However, for copper alloys, strength and electrical conductivity are two properties that are mutually hampered: along with the improvement of the strength of the alloy, the conductivity is bound to be correspondingly reduced; while the conductivity is improved, the strength of the material is correspondingly reduced. On the other hand, strength and bending workability (i.e., bendability) are also restricted: generally, a high-strength material is inferior in bending workability, and a material excellent in bending workability is not high in strength. For example, the yield strength of the Cu-Ni-Mg-Si alloy strip can reach more than 700MPa, but the electric conductivity of the Cu-Ni-Mg-Si alloy strip is only about 40% IACS, so that the Cu-Ni-Mg-Si alloy strip is only suitable for electronic components with higher requirements on strength and cannot meet the performance requirements of the fields of consumer electronics, electronic connectors, large-scale integrated circuit lead frames and the like on the copper alloy; although the Cu-Cr-Zr alloy has the conductivity of more than 80 percent IACS, the yield strength is only about 550MPa, so the Cu-Cr-Zr alloy is more suitable for the working condition environment with more strict conductivity requirements; the Cu-Ti alloy has higher strength and good bending processability, but has lower conductivity, so the Cu-Ti alloy is suitable for environments with higher requirements on strength.
In order to develop a copper alloy material with excellent bending property, high yield strength and high conductivity to meet the requirements of various rapidly-developed high and new technology industries and fill the blank in the research field and the market of copper alloys, the invention provides a copper alloy material with excellent bending property and a preparation method thereof.
Disclosure of Invention
The inventionThe technical problem to be solved is that: aiming at the application in the fields of large-scale integrated circuit lead frames, folding screens and the like, the product has the yield strength of more than 700MPa, the electric conductivity of more than 55 percent IACS and the Goodway 90-degree bending R10/t does not crack, and is bent at Badway90 DEG R2No cracking (R) when t is less than or equal to 11、R2A bending radius, t is a strip thickness) and a method for preparing the same.
The technical scheme adopted by the invention for solving the technical problems is as follows: a copper alloy material with excellent bending property comprises the following components in percentage by weight: 0.05 to 0.25wt% of Ni, 0.3 to 0.8wt% of Cr, 0.05 to 0.5wt% of Fe, 0.05 to 0.3wt% of Ti, and the balance of Cu and unavoidable impurities.
The Ni element added into the copper alloy material has high solid solubility in Cu, can form a continuous solid solution with the Cu, has a wider single-phase region, can greatly improve the mechanical property of the copper alloy, and can reduce the conductivity of the copper alloy. Ni element is often combined with Si or Al element in copper alloy as common alloying to improve the strength of the alloy, and the formed Ni2Si or Ni5Si3And Ni3Al phase is precipitated in the aging process, plays the roles of pinning dislocation and inhibiting grain growth, and further improves the strength and the conductivity of the alloy. Meanwhile, Ni element may form Ni with Ti element3Ti phase, Ni3In addition to higher hardness, stable chemical composition and crystal structure, Ti phase also has higher yield strength and abnormal yield effect, i.e. the yield strength increases with the increase of temperature and with Ni3And the precipitation of Ti phase, Ni and Ti elements which have great influence on the conductivity in the alloy are also precipitated in a large amount, so that the conductivity of the alloy is obviously improved while the strength is improved. In the invention, the Ni is formed in advance in the alloy processing process through the accurate control of the temperature3Ti phase, reduction of Fe2The number of Ti phase particles further improves the strength and the bending property of the alloy. In view of the adverse effect of Ni element on the conductivity of copper alloy, the content of Ni element is controlled to 0.05-0.25 wt% of the total amount of the components, the strength of the alloy is improved, and the conductivity of the alloy is ensured.
The Cr element added to the copper alloy material of the present invention has a solid solubility in Cu of only 0.7% at 1076 ℃ and rapidly decreases in solid solubility with a decrease in temperature, and therefore, can be added to a copper alloy as a precipitation strengthening alloying element. 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. The precipitation of the Cr-rich phase in the copper matrix enables the strength and the conductivity of the alloy to be simultaneously improved. Meanwhile, when Zr element exists in the alloy, Cr and Cu can be generated simultaneously in the aging process5Two fine precipitated phases of Zr greatly improve the strength of the alloy, and simultaneously improve the creep resistance and the fatigue resistance of the Cu-Cr alloy. Therefore, the Cr element has a significant strengthening effect on the copper alloy and also meets the requirement of the conductivity of the copper alloy, when the content of the Cr element is less than 0.3wt%, the strength of the copper alloy is too low due to insufficient precipitated phase, and when the content of the Cr element is more than 0.8wt%, the conductivity of the alloy is too low due to excessive elements dissolved in the copper matrix, so that the content of the Cr element is set to 0.3 to 0.8 wt%.
Both Fe and Ti elements can be present in the copper alloy in the form of binary alloys. Fe element is 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 Cu4In the form of Ti and in spinodal decomposition in copper alloys, Cu-Ti binary alloys, as a substitute for Cu-Be alloys, have very high strength but low electrical conductivity. Fe and Ti elements capable of forming Fe2Ti phase, which improves both tensile mechanical properties and electrical conductivity of the alloy, so Fe and Ti elements are the next major alloying elements in the present 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; and when the content of Fe element is more than 0.5wt%, it may cause 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 Ti elementWhen the content is higher than 0.3wt%, excessive Ti element is caused to be dissolved in the copper 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 is called as Laves phase, but the content of Cr element in the Laves phase is small, generally between 0.001-0.003 wt%, which not only can improve the strength of the alloy, but also can greatly improve the conductivity of the alloy.
Preferably, in the composition of the copper alloy material in percentage by weight, the content of Ni, Fe and Ti in percentage by weight satisfies: 0.35Ni +0.4Fe > Ti. Ti element dissolved in the matrix has adverse effect on the conductivity of the alloy, and in the alloy design system of the invention, when the content of the elements of Ni, Fe and Ti satisfies the formula, the Ti element is Ni3Sum of Ti and (Cr, Fe)2The Ti phase is precipitated in a large amount to improve the conductivity of the alloy, and the Ni and Fe elements are also precipitated in a large amount along with the Ti element, so that the conductivity and yield strength of the alloy are improved, and the bending property of the alloy is obviously improved. If the contents of the added Ti, Fe, and Ni elements do not satisfy the above requirements, the desired strength and conductivity cannot be obtained, and the bendability of the alloy is adversely affected.
Microscopic observation and analysis of the cross section of the strip made of the copper alloy material by an electron microscope revealed that (Cr, Fe) having an average size of 100 to 500nm, respectively, existed in the microscopic structure2Ti precipitated phase, 100 to 400nm Ni3A Ti phase and a large amount of spherical Cr elementary substances with the particle size of 1-10 nm. Wherein the density of the Cr simple substance is 3.75 multiplied by 108Per mm2Above, Ni3The density of Ti phase is 5X 105Per mm2Above, (Cr, Fe)2The density of Ti phase is 8X 105～4.4×106Per mm2. In addition, other precipitated phases such as CrFe exist in the microstructure with different sizes, and the density is 2.0X 105/mm2One below.
The size and number of the precipitated phase particles reflect the effectiveness of the aging treatment. Average size of 10nm or lessThe Cr elemental precipitated phase particles are the most main strengthening phases of the alloy, and the density of the Cr elemental precipitated phase particles is 3.75 multiplied by 108Per mm2As described above, the strength of the alloy can be significantly improved, and the conductivity and bendability of the alloy can be advantageously improved. Ni with an average size of 100 to 400nm3The Ti phase can effectively improve the strength and the bending property of the alloy, and the density of the Ti phase is controlled to be 5 multiplied by 105Per mm2The above. (Cr, Fe) having an average size of 100 to 500nm2Although Ti phase particles can also improve the strength of the alloy, when the grain size of the precipitated phase is increased, the improvement of the bending property of the alloy is not remarkable, and the density is controlled to be 8X 105～4.4×106Per mm2. The other precipitated phases such as CrFe are inferior in strengthening effect and large in phase size, and the positions of the precipitated phases are likely to be the origins of crack generation and cause a reduction in bending workability of the alloy, so that the density of the other phases such as CrFe should be controlled to 2.0X 105Per mm2The following.
The processing mode of the copper alloy strip mainly comprises stamping, bending and the like, and the bending property of the strip has great influence on bending processing. The copper alloy strip belongs to polycrystal, under the action of external stress, plastic deformation of different crystals (grains) in the copper alloy strip is superposed to form the plastic deformation of the copper alloy strip, and the area ratios of different textures of the rolled surface of the copper alloy have important influence on the plastic deformation of the alloy. In order to further improve the bending property of the alloy, the area ratios of different orientations of the rolling surface of the alloy strip are controlled, specifically, the area ratio of a Copper texture of the strip made of the Copper alloy material is 15-30%, the area ratio of an S texture is 20-40%, the sum of the area ratios of the Copper texture and the S texture is 40-60%, and the area ratio of the S texture is larger than that of the Copper texture. The copper alloy texture is generated in the thermomechanical treatment process to a great extent and is converted from each other, and different texture types and contents determine the bending property of the strip product to a certain extent. The alloy strip mainly controls two texture types of a Copper texture and an S texture, and the area ratio of the S texture is higher than that of the Copper texture. When the area ratio sum of the two textures is higher than 60%, although the bending performance of the alloy strip is good, the alloy has very obvious anisotropy, so that the alloy fails in the service process; when the area ratio of the two textures is less than 40%, the bending property of the alloy is poor. Therefore, the area ratio of the Copper texture of the strip made of the Copper alloy material is controlled to be 15-30%, the area ratio of the S texture is controlled to be 20-40%, and the sum of the area ratio and the S texture is controlled to be 40-60%.
Except by controlling the type and the area ratio of the texture in the strip, the shape of alloy grains, the size and the distribution of precipitated phases influence the bending property of the strip to a certain extent. According to the method, after solid solution, a strip is subjected to cold deformation with large deformation, and then high-temperature recrystallization annealing treatment is carried out at 750-850 ℃ for 20-45 s, so that elongated and distorted grains are partially recrystallized in the cold deformation process, a cubic texture generated in the solid solution process is regulated and controlled, and a small amount of Cr elementary substance strengthening phase, (Cr, Fe) is precipitated2Ti phase and Ni3A Ti phase; then, cold rolling with small deformation is carried out again to provide precipitation kinetic energy and a channel for primary aging treatment, and then primary aging treatment is carried out at 380-480 ℃ for 6-8 h, and all second phases can be precipitated in the primary aging treatment process; finally, cold deformation treatment (cold finish rolling) with the deformation not higher than 50% is carried out, extra precipitation power and channels are provided for the secondary aging treatment, and then the secondary aging treatment is carried out for 6-8 hours at 300-360 ℃ so that the Cr simple substance and the Ni are subjected to simple substance treatment3Ti phase and (Cr, Fe)2Ti is continuously precipitated, and the strength and the conductivity of the alloy are improved. The temperature of the secondary aging treatment is controlled to be 300-360 ℃, a better strengthening effect can be obtained in the range, and the improvement degree of the alloy strength is limited when the temperature exceeds the range, so that the secondary aging treatment is carried out for 6-8 hours at the temperature of 300-360 ℃. In the invention, the Goodway 90-degree bend R of the strip is controlled by controlling the texture type, the area ratio, the grain size, the grain deformation degree and the precipitated phase size10/t does not crack, and is bent at Badway90 DEG R2No crack is generated when the/t is less than or equal to 1.
Preferably, the copper alloy material further comprises 0.05-0.15 wt% of Sn in percentage by weight. Sn element can be used as an alloying element together with Ni element in the copper alloy to form a Ni — Sn compound. 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 copper 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 alloy conductivity is lowered due to an excessive amount of the Sn element solid-dissolved in the matrix.
Preferably, the copper alloy material further comprises 0.05-0.3 wt% 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 little influence on the conductivity of the alloy. Ag is different from alloying elements in other copper alloys, and excessive addition of Ag causes strong lattice distortion in the copper alloy, so that the scattering effect of electrons is enhanced, and the conductivity of the alloy is reduced. When a small amount of Ag element is added, the alloy is solid-solution strengthened and has a small influence on the conductivity 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 is extremely limited; when the content is more than 0.3wt%, the lattice distortion of the alloy by 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 700MPa or more and an electrical conductivity of more than 55% IACS.
Preferably, the Goodway90 DEG bend R of the strip made of copper alloy material10/t does not crack, and is bent at Badway90 DEG R2No crack is generated when the/t is less than or equal to 1.
Preferably, the copper alloy material further comprises 0.01-0.5 wt% of an X element in percentage by weight, wherein the X element is any one or more selected from Mg, Al, P, Co and Zr. The addition of one or more elements selected from Mg, Al, P, Co 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, Al, P, Co, and Zr can promote the aging strengthening effect, so that the copper alloy has good strength, conductivity, and bendability. The above-mentioned effects are exhibited when the content of any one or more of Mg, Al, P, Co and Zr is 0.01 wt% or more, but if the content exceeds 0.5wt%, the solubility limit of Ti, Cr and Fe is lowered, coarse precipitated phase particles tend to precipitate in the alloy, and the strength is improved, but the bendability is lowered. Therefore, the content of any one or more elements of Mg, Al, P, Co and Zr is controlled to be 0.01-0.5 wt%.
The preparation process of the strip of the copper alloy material with excellent bending property comprises the following steps: vacuum casting → first surface milling → hot rolling → second surface milling → first cold rolling → solution treatment → second cold rolling → recrystallization annealing treatment → third cold rolling → first aging treatment → cold finish rolling → second aging treatment, wherein the temperature of the recrystallization annealing treatment is 750-850 ℃, the time is controlled within 20-45 s, and the water cooling is carried out at room temperature. Preferably, the temperature of the primary aging treatment is 380-480 ℃, the heating rate is more than 250 ℃/s, and the heat preservation time is 6-8 hours; the temperature of the secondary aging treatment is 300-360 ℃, and the heat preservation time is 6-8 hours. 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 all the raw materials are melted, so that Ti element is protected from being oxidized in the casting process, the content of Ti element is ensured, and Ni can be separated out in the subsequent thermomechanical treatment process3Ti phase and (Cr, Fe)2A 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 precipitated 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, in order to reduce precipitation of phase particles after hot rolling as much as possible, the finish rolling temperature of the alloy is controlled to be above 750 ℃, the cooling speed is controlled to be above 200 ℃/s, and the rolling rate is controlled to be above 85%.
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. The cold working rate of more than 80 percent can provide enough strain energy for the Copper alloy strip, so that the alloy is promoted to form more than 40 percent of cubic texture in the solution quenching process, and the texture type and the area ratio are optimally regulated and controlled in the subsequent deformation heat treatment process, so that the final alloy is mainly in a Copper texture and an S texture. When the cold rolling rate is less than 80%, a sufficient amount of cubic texture cannot be obtained due to low strain energy, and the amount of texture that can be controlled is low, resulting in a decrease in the bending property of the strip.
7) Solution treatment: in order to realize sufficient re-dissolution of phase particles to improve the supersaturation degree of a matrix and promote the alloy strip to generate more than 40% of cubic texture, the solid solution temperature is controlled between 950 ℃ and 1050 ℃, the temperature rise speed is 30-60 ℃/s, the heat preservation is 30-200 s, and the cooling speed is more than 200 ℃/s.
In the solid solution process, coarse precipitated phases in an original casting structure and precipitated phases in the hot rolling cooling process fully dissolve a matrix, and are rapidly cooled to room temperature under the condition that the cooling rate is more than 200 ℃/S, so that a supersaturated solid solution is ensured to be obtained, the precipitation of a strengthening phase in the cooling process is reduced, the rotation of crystal grain orientation in the subsequent cold rolling process is facilitated, and a Copper texture and an S texture with sufficient content are obtained. When the temperature rising speed of the strip is lower than 30 ℃/s, the crystal grains of the alloy can be coarsened; when the temperature rise rate of the strip is more than 60 ℃/S, the development of the Copper texture and the S texture is insufficient.
8) Secondary cold rolling: the secondary cold rolling aims to provide more energy and channels for precipitation of precipitated phases, and enable the structure after solid solution to generate orientation rotation in the secondary cold rolling process, so as to achieve the purpose of regulating and controlling the transformation of the cubic texture to the Copper texture and the S texture. The rolling rate should be controlled between 20-60%. When the secondary cold rolling quantity is less than 20%, sufficient internal energy cannot be provided for the primary aging, insufficient precipitation can be caused, and the strength of the final product is low; when the secondary cold rolling amount is more than 60%, the cubic texture in the texture is transformed into a brass texture instead of a Copper texture and an S texture, thereby causing a reduction in the bending formability of the alloy.
9) Recrystallization annealing treatment: the recrystallization annealing is aimed at recrystallizing crystal grains elongated and twisted due to cold deformation, refining the crystal grains to some extent, and converting brass texture and rotational texture in the texture into Copper texture and S texture; on the other hand, when the recrystallization annealing temperature is 750-850 ℃, a large amount of Ni is precipitated from the alloy3Ti phase, the yield strength, hardness and the like of the alloy are sufficiently improved, and Ni is used3The Ti phase can still keep smaller grain size when the heat preservation is carried out at higher temperature, so the high temperature resistance of the alloy is obviously improved. When the time of recrystallization annealing is controlled to be less than 20s, Ni3Insufficient Ti phase precipitation and insufficient improvement effect of alloy properties, and Ni in the case of more than 45s3The Ti phase will be transformed into NiTi2And the phase reduces the elastoplasticity of the alloy, and simultaneously, other precipitated phases excessively grow up to cause adverse effects on the strength and the bending property of the alloy, so that the recrystallization time is controlled to be 20-45 s.
10) And (3) cold rolling for three times: the cold rolling quantity of the third cold rolling is controlled to be 15-35%, so that the texture type and the content are not influenced, and sufficient kinetic energy and channels can be provided for the subsequent first-stage aging. When the cold rolling quantity is less than 15%, the first-stage aging effect is poor, precipitation is insufficient, and the improvement of the alloy conductivity is greatly influenced; when the cold rolling amount is higher than 35%, the content of the Copper texture and the S texture regulated and controlled by the previous thermomechanical treatment process is reduced, and the bending property of the alloy is reduced.
11) Primary aging treatment: the primary 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, and the precipitation temperature is required to meet the condition that all precipitated phases can be precipitated in large quantity and grow after precipitationThe precipitation speed of a precipitated phase is increased by an excessively high temperature, the growth speed after precipitation is also increased, and the strengthening effect of the precipitation with an excessively large size relative to the strength of the alloy is poor; the lower aging temperature needs a very long time to precipitate the strengthening phase, and because the kinetic energy limited precipitation is insufficient and the strength and the conductivity of the alloy are affected, the primary aging temperature is controlled to be 380-480 ℃, the temperature rise rate is more than 250 ℃/s, and the alloy is air-cooled after heat preservation for 6-8 hours. In the primary aging treatment process, the elementary substances Cr and Ni are subjected to higher temperature3Ti phase, (Cr, Fe)2Ti phase is fully precipitated, the effect of overaging is achieved, and the alloy is ensured to have higher conductivity.
12) Cold finish rolling: the alloy after the primary aging treatment has reached an overaged state, and obtains higher conductivity, the precipitation power and the channel are consumed, if the secondary aging treatment is carried out immediately at the moment, the strengthening phase can not be precipitated from the matrix, and the strengthening phase precipitated in the primary aging process can continue to grow, so that the performance of the alloy is reduced. 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 precipitation power and precipitation channels are provided for the secondary aging treatment, and the strength of the strip is further improved. When the rolling rate is lower than 20 percent and the rolling pass is less than 5, the work hardening effect and the redistribution effect of precipitated phases under the action of shear stress are poor, and meanwhile, the energy and precipitation channels provided for the secondary aging treatment are too few, and the secondary aging treatment can reduce the strength of the alloy. When the rolling rate is more than 55%, the excessive cold deformation causes defects such as cracks and the like at the hard precipitated phase in the alloy deformation process, the alloy structure is cracked, the large-angle grain boundary is forced to increase, the dislocation density is reduced, the processing softening result occurs, and the strength of the alloy is further reduced. In addition, the Copper texture and the S texture regulated at the early stage are transformed and the content is reduced in the cold deformation process, so that the bending property of the alloy is reduced. Therefore, the rolling rate of the cold finish rolling treatment is controlled to be 20-55%, and the rolling pass is more than 5.
13) Secondary aging treatment: the secondary aging treatment is performedThe effect of stress relief annealing can further precipitate a strengthening phase. Although the alloy reaches an overaged state in the primary aging treatment stage, after cold working deformation, an additional precipitation passage and power are provided for the aging treatment, a small amount of elements dissolved in the matrix can be further precipitated, and Cr and Ni are further improved3The precipitation amount of Ti improves the conductivity and strength of the alloy. When the temperature of the secondary aging treatment is lower than 300 ℃, the alloy can not be continuously precipitated due to the fact that the alloy releases internal stress due to too low temperature, meanwhile, the strength and the conductivity of the alloy are reduced, when the temperature of the secondary aging treatment is higher than 360 ℃, the existing precipitation strengthening phase can rapidly grow up due to too high temperature, the strength of the alloy can be greatly reduced, therefore, the temperature of the secondary aging treatment is not too high, and the alloy is cooled after heat preservation is carried out for 6-8 hours at 300-360 ℃.
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, Ni and the like and a thermomechanical treatment process combining two-stage aging and recrystallization annealing.
(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 bending property, the yield strength and the electrical conductivity of the alloy is further favorably realized.
(3) The average size of Cr elementary substance precipitated in the strip made of the copper alloy material is 1-10 nm, and the density of the Cr elementary substance is 3.75 multiplied by 108Per mm2Above, Ni3The Ti phase has an average size of 100 to 400nm and a density of 5X 105Per mm2Above, (Cr, Fe)2The Ti phase has an average size of 100 to 500nm and a density of 8X 105～4.4×106Per mm2Under these conditions, the effects of strengthening the alloy and improving the bendability and conductivity of the alloy are achieved.
(4) The yield strength of the strip made of the copper alloy material is more than 700MPa, the electric conductivity is more than 55% IACS, and the Goodway 90-degree bending R10/t does not crack, and is bent at Badway90 DEG R2No cracking when t is less than or equal to 1And has excellent bending property.
(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 TEM test result of the Cu alloy material of example 4, in which the particles are Ni3Ti precipitated phase;
FIG. 2 is a transmission electron microscope test result II of the copper alloy material of example 4, in which the particles are Cr elemental precipitate phases.
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, preserving the heat of the plate subjected to the primary cold rolling for 30-200 s at 950-1050 ℃ for solution treatment; secondly, carrying out secondary cold rolling on the plate subjected to the solution treatment at a rolling rate of 20-60%, then carrying out recrystallization annealing treatment at 750-850 ℃ for 20-45 s on the plate subjected to the secondary cold rolling, then carrying out tertiary cold rolling at a rolling rate of 15-35%, then carrying out primary aging treatment at 380-480 ℃ for 6-8 h, and then carrying out cold finish rolling at a processing rate of 20-55% for more than 5 times; and finally, carrying out secondary aging treatment at 300-360 ℃ 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.
The bending properties of the tapes of the examples and comparative examples were tested using JCBA T307-2007 Test method of band formability for sheets and strips of tapes of examples and comparative examples (evaluated by whether or not the Goodway90 DEG R/T is 0 and the Badwway 90 DEG R/t.ltoreq.1 bend cracked), and the width of the Test tapes was 10 mm.
And analyzing the texture type and the area ratio of the strip by adopting EBSD, wherein the texture ratio refers to the ratio of the area within 15 degrees of deviation angle of each orientation to the measured area.
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. FIGS. 1 and 2 are TEM (transmission electron microscopy) results of the Cu alloy material of example 4 at different magnifications.
According to the embodiment, the copper alloy in the embodiment of the invention realizes the yield strength of more than or equal to 700MPa, the electric conductivity of more than or equal to 55% IACS and the Goodway 90-degree bending R10/t does not crack, and is bent at Badway90 DEG R2No crack is generated when the/t is less than or equal to 1. Meanwhile, the comparative examples 1 to 3 show that the yield strength and the conductivity of the alloy are affected to different degrees when the element content does not satisfy the specified range, the comparative example 4 shows that the yield strength and the bendability of the alloy do not achieve the ideal effect when no Ni element is added to the alloy, and the comparative example 5 shows that the bendability of the alloy cannot be improved when the element content of Ni, Fe and Ti does not satisfy the formula.
Claims (11)
1. The copper alloy material with excellent bending property is characterized by comprising the following components in percentage by weight: 0.05 to 0.25wt% of Ni, 0.3 to 0.8wt% of Cr, 0.05 to 0.5wt% of Fe, 0.05 to 0.3wt% of Ti, and the balance of Cu and unavoidable impurities; in the weight percentage composition of the copper alloy material, the weight percentage content of Ni, Fe and Ti satisfies: 0.35Ni +0.4Fe > Ti.
2. The copper alloy material with excellent bendability according to claim 1, wherein a Cr elemental phase, Ni elemental phase, is present in a microstructure of a cross section of a strip made of the copper alloy material under an electron microscope3Ti phase and (Cr, Fe)2Ti phase, wherein the average size of Cr elementary phase is 1-10 nm, and the density is 3.75 multiplied by 108/mm2The above; ni3The average size of Ti phase is 100-400 nm, and the density is 5 × 105/mm2The above; (Cr, Fe)2The Ti phase has an average size of 100 to 500nm and a density of 8.0X 105 to 4.6X 106 phases/mm2。
3. The Copper alloy material with excellent bendability according to claim 1, wherein the area ratio of the Copper texture of the strip made of the Copper alloy material is 15 to 30%, the area ratio of the S texture is 20 to 40%, the sum of the area ratios of the Copper texture and the S texture is 40 to 60%, and the area ratio of the S texture is greater than the area ratio of the Copper texture, wherein the area ratio of the texture is a ratio of an area within 15 ° of each orientation deviation angle divided by a measured area.
4. The copper alloy material with excellent bendability according to claim 1, wherein the copper alloy material further comprises 0.05 to 0.15 wt% of Sn in terms of a composition of weight percent.
5. The copper alloy material with excellent bendability according to claim 1, wherein the composition of the copper alloy material further includes 0.05 to 0.3wt% of Ag.
6. A copper alloy material with excellent bendability according to claim 1, wherein a strip made of the copper alloy material has a yield strength of 700MPa or more and an electric conductivity of more than 55% IACS.
7. A copper alloy material with excellent bendability according to claim 1, wherein the strip made of the copper alloy material is not cracked at a Goodway90 ° bend R1/t ═ 0 and is not cracked at a Badway90 ° bend R2/t ≦ 1.
8. The copper alloy material with excellent bending property of claim 1, wherein the composition of the copper alloy material in percentage by weight further comprises 0.01-0.5 wt% of an element X, wherein the element X is selected from one or more of Mg, Al, P, Co and Zr.
9. The method for producing a copper alloy material having excellent bendability according to any one of claims 1 to 8, wherein the production flow of the strip of the copper alloy material is: vacuum casting → first surface milling → hot rolling → second surface milling → first cold rolling → solution treatment → second cold rolling → recrystallization annealing treatment → third cold rolling → first aging treatment → cold finish rolling → second aging treatment, wherein the temperature of the recrystallization annealing treatment is 750-850 ℃, and the time is controlled within 20-45 s.
10. The method for producing a copper alloy material having excellent bendability according to claim 9, wherein the temperature of the primary aging treatment is 380 to 480 ℃, the rate of temperature rise is more than 250 ℃/s, and the holding time is 6 to 8 hours; the temperature of the secondary aging treatment is 300-360 ℃, and the heat preservation time is 6-8 hours.
11. Use of the copper alloy material having excellent bendability according to any one of claims 1 to 8 in large scale integrated circuit lead frames and folding screens.
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