CN112126815A - Copper-chromium alloy strip and preparation method thereof - Google Patents
Copper-chromium alloy strip and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a copper-chromium alloy strip which is characterized in that the copper-chromium alloy comprises the following components in percentage by mass: 0.2-0.5%, Zr: 0.01-0.1%, Ti: 0.01 to 0.1%, Si: 0.01 to 0.1% and the balance of Cu and unavoidable impurities; at an optional 1000 μm2In the area, the number of precipitated phases with the size of 100nm-1 μm is 100-700, and the number of precipitated phases with the size of more than 1 μm is less than 10. The invention adopts the alloying design of Cr, Zr, Ti, Si and other elements, controls the size and density of precipitated phase, takes a finished strip with the length of 400mm along the rolling direction to be placed on a horizontal test bench, the natural upwarp height of two ends of the strip is less than 35mm, the alloy has lower residual stress, the strip made of the copper alloy material has the tensile strength of more than 480MPa, the electric conductivity of more than 75% IACS and better bending processing performance, the heat conductivity of the alloy can reach more than 300W/(m.K), and the invention can be widely applied to vehicles and semiconductor leadsFrames and electrical and electronic components.
Description
Technical Field
The invention belongs to the technical field of copper alloy, and particularly relates to a copper-chromium alloy strip and a preparation method thereof.
Background
In recent years, with the rapid development of consumer electronics, communication base stations, and electric vehicle technologies, it is necessary to develop precise electrical and electronic components for high current and high voltage conditions. The materials used for these parts are required to have not only high electrical conductivity and high strength but also to cope with high voltage and large current and heat generated from extreme environments (e.g., engine room of automobile), and the copper alloy material used for the large current and high voltage condition is required to have a tensile strength of 480MPa or more and a thermal conductivity of 280W/(m · K) or more, and these performance parameters tend to be gradually improved with the technical development and miniaturization of parts.
Among the existing copper alloys, the copper-chromium alloy has excellent balance between strength and electric conductivity, and can meet the application. In the application process of the copper-chromium alloy, the subsequent application of the material can be directly influenced by the working conditions of the production link besides the application working conditions. The precision electric and electronic parts need to be subjected to high-temperature processes such as packaging, injection molding, soldering and the like in the production process, the temperature can reach 400 ℃ or even higher, the processing time can often reach 2 hours or even higher, the copper-chromium alloy can generate micro deformation after being returned to the room temperature through the temperature, when the requirements of the parts on the material size are not high, the influence of the deformation on the performances of the parts is not obvious, but the service life of the parts can be influenced even if the micro deformation is caused due to the extremely high precision degree of the existing electric and electronic parts. The problems are mainly related to the existence of large residual stress in the alloy, the existing copper-chromium alloy production process usually only pays attention to the strength, the electric conduction and the bending performance of the alloy, but seldom pays attention to the residual stress of the alloy, and the distribution of precipitated phases, particularly the precipitation of large particles, has direct influence on the residual stress.
Therefore, in order to meet the higher requirements of the rapidly developing consumer electronics, communication base stations and electric automobiles on the copper alloy, further improvement is needed for the existing copper-chromium alloy.
Disclosure of Invention
The first technical problem to be solved by the invention is to provide a copper-chromium alloy strip with lower residual stress while meeting the properties of strength, electric conductivity, bending and heat conductivity.
The technical scheme adopted by the invention for solving the first technical problem is as follows: a copper-chromium alloy strip is characterized in that the copper-chromium alloy consists of the following components in percentage by mass: 0.2-0.5%, Zr: 0.01-0.1%, Ti: 0.01 to 0.1%, Si: 0.01 to 0.1% and the balance of Cu and unavoidable impurities; at an optional 1000 μm2In the area, the number of precipitated phases with the size of 100nm-1 μm is 100-700, and the number of precipitated phases with the size of more than 1 μm is less than 10.
Cr is the main component of the alloy of the present invention. At normal temperature, Cr element has low solid solubility in copper, but at high temperature, Cr element has relatively high solid solubility, so Cr is the main precipitation strengthening element in the copper alloy of the present invention. In the copper alloy, the strengthening phase particles of the simple substance Cr can be obtained by heat treatment, and the strengthening effect is formed on a matrix. When Cr is added to the alloy of the present invention, a portion of the Cr forms elemental strengthening phase particles, and a portion of the Cr forms Cr with a small amount of Si and Ti in solid solution in the copper matrix3Si, Cr-Ti-Si compounds. The research finds that the Cr3Si and Cr-Ti-Si compounds are high-temperature stable compound phases and can not be dissolved even at the high temperature of 800 ℃, so that the high-temperature softening capability of the alloy is better, and the alloy can meet the requirements of large current and high temperatureThe requirements of the voltage application conditions. When the content of the Cr element is less than 0.2 wt%, the strength is too low due to insufficient precipitated phases, and when the content of the Cr element is more than 0.5 wt%, the number of primary phases generated in the alloy smelting process is increased, the number of large precipitated phases containing Cr is increased, so that residual stress is concentrated, and the low residual stress copper-chromium alloy required by the invention cannot be obtained. Therefore, the content of Cr element in the alloy of the present invention is set to 0.2 to 0.5 wt%.
Zr is also the main component of the alloy of the present invention. Zr has certain solubility in the copper alloy, can not only improve the recrystallization temperature of the copper matrix and improve the high temperature softening performance of the copper alloy, but also can form Cu with the copper3The Zr intermediate compound has the function of strengthening the copper matrix and simultaneously improves the electrical property of the copper alloy. With Cu3The Zr phase can further refine the sizes of other Cr-containing precipitated phases in the alloy and reduce the number of large Cr-containing precipitated phases. The zirconium content of the alloy is 0.01-0.1 wt%, and if the zirconium content is lower than the range, the zirconium content cannot play a role, and if the zirconium content is higher than the range, the zirconium content can play a role in strengthening the alloy, but the conductivity of the alloy can be greatly reduced, and the comprehensive performance of the alloy is influenced.
Ti is the main component of the alloy of the invention. When Ti is added, the Ti can form precipitates with Cr and Si, the strength of the copper alloy is improved through aging precipitation strengthening, the solid solution amount of the Cr and the Si in a matrix is reduced, and the electrical conductivity of the alloy can be further improved. The alloy of the present invention has a Ti content of 0.01 to 0.10 wt%, and if the Ti content is less than this range, the effect cannot be sufficiently obtained, whereas if the Ti content is more than this range, the conductivity is lowered because excessive Ti cannot be sufficiently precipitated, and the viscosity of the melt is increased due to the increase of the Ti content during the melting process, which is disadvantageous for the production of an ingot, and the production efficiency is lowered. At the same time, the amount of Ti oxide adhering to the furnace wall of the melting furnace increases, which may cause a decrease in quality of an ingot in a casting process, an increase in furnace cleaning, and the like.
The Si element can form a compound with Cr, Ti, or other elements in the copper alloy and precipitate as a strengthening phase. In the design of the invention, Cr element is precipitated as a main strengthening phase, and excessive Cr element can form Cr with Si and Ti elements3Si, Cr-Ti-Si phase fromThe matrix is precipitated, and the strength and the electric conductivity of the alloy are further improved. In the invention, the content of Si element is controlled between 0.01-0.1 wt%. When the Si element content is less than 0.01 wt%, it is not bonded with an excessive amount of Cr element to precipitate from the matrix, thereby lowering the Cr content3Si and Cr-Ti-Si phase contents, which may reduce the strength of the alloy. When the content of the Si element is more than 0.1 wt%, the Si element is excessively increased, thereby lowering the conductivity of the alloy.
The inventor researches and discovers that the size and the density of a precipitation phase of the copper-chromium alloy are directly related to the residual stress of the alloy. The prior art only pays attention to the composition and process of the alloy to obtain enough precipitated phases to achieve the strengthening effect, but neglects the influence of the size and distribution density of the precipitated phases on the residual stress of the alloy. The sizes of precipitated phases of different alloy systems are obviously different, the Ni-Si phase is usually only a few nanometers to a few tens of nanometers, the distribution of the Ni-Si phase has small influence on the residual stress of the alloy, and the size of a chromium-containing precipitated phase contained in the copper-chromium alloy can be from a few nanometers to a few micrometers. When the size of the precipitated phases in the alloy is greater than 100nm, dislocations generated during rolling may be concentrated around the alloy, resulting in stress concentration, which becomes more pronounced as the size of the precipitated phases increases, particularly when the size is greater than 1 μm, and thus the amount of large-sized precipitated phases needs to be strictly controlled, and when the precipitated phases are unevenly distributed, the alloy may have large residual stress. In order to ensure that the precipitated phases can bring about sufficient strengthening effect and also to make the alloy have low residual stress as much as possible, the inventors controlled the number and density distribution of the precipitated phases. The research shows that when the copper-chromium alloy strip meets the requirement of optional 1000 mu m2The number of precipitated phases having a size of 100nm to 1 μm is 100 to 700, and the number of precipitated phases having a size of more than 1 μm is less than 10, whereby the alloy can have sufficient strength, conductivity and bending properties, and the residual stress of the alloy is low. When the number of precipitated phases of 100nm-1 μm is less than 100/1000 μm2The strength of the alloy does not meet the intended requirements of the invention, and the number is more than 700/1000 μm2When the alloy is used, the residual stress of the alloy is large. The precipitated phase with a size of more than 1 μm is copper and chromium generated during alloy smeltingThe primary phase, dislocation generated in the rolling process will gather around the primary phase, and the influence on the alloy residual stress is the largest, so the appearance of the primary phase in the smelting process should be reduced as much as possible, and the position of the precipitated phase is easy to be the origin of crack generation, thereby the bending performance of the alloy is influenced.
Preferably, the brass texture area of the copper-chromium alloy strip within 15-degree deviation angle is 10-30%; setting the area rate of the brass texture on the surface layer of the rolled surface of the strip as B1Setting the area rate of brass texture at 1/2 thickness layer from the rolling surface of the strip as B2，B2/B1The ratio of (A) to (B) is 0.80-1.
The texture of the strip of copper alloy of the invention was tested by EBSD analysis. EBSD is an abbreviation for Electron Backscattered Diffraction (Electron back scattering Diffraction), and is a crystallographic analysis technique that uses Diffraction cuvet line reflection Electron Diffraction generated when an Electron beam is irradiated to an inclined sample surface in a Scanning Electron Microscope (SEM). The alloy strips with the same composition and strength have obvious difference in texture type and proportion, and the texture type and proportion can directly influence the final performance of the alloy. The copper alloy strip is accompanied by a great deal of plastic deformation in the production process, and the proportion of the texture is changed at any time in the plastic deformation process. The inventor researches and discovers that the deformation texture proportion can be used as a judgment basis for the residual stress of the alloy. In the copper-chromium system alloy of the invention, the correlation between brass texture and residual stress is most remarkable. When the brass texture ratio is less than 10%, the alloy strength is low, and when the ratio exceeds 30%, although the alloy strength is high, the bending property is remarkably lowered, and the internal residual stress of the alloy is also large. The reason is that the annealing texture is gradually changed into the deformation texture in the rolling hardening process, and when the work hardening rate is high, the deformation texture proportion of the alloy is too high, the accumulated dislocation density in the alloy is high, and the residual stress is also high. Therefore, the area proportion of the brass texture of the invention meets 10-30%, so that the alloy has enough strength and lower residual stress under the condition of bending performance, and meets the strict requirements of precise parts on product deformation control.
In the cold rolling process, because certain friction force exists between the roller and the surface of the strip, the deformation of the surface layer and the central part of the rolled surface of the strip is inconsistent, the deformation difference can increase the residual stress in the alloy, and the processing amount of a strict cold rolling process is required to reduce the introduction of the residual stress. The inventor finds that when the ratio of the surface layer of the rolled surface of the strip to the texture area ratio of the thickness layer 1/2 of the rolled surface of the strip meets 0.80-1, the residual stress of the alloy is lower.
Preferably, the adding mass of Zr, Ti and Si in the copper-chromium alloy satisfies the following conditions: zr, Ti and Si are more than or equal to 0.05 percent and less than or equal to 0.20 percent. Zr, Ti and Si are important constituent elements forming intermetallic compounds with Cr, and the inventor finds that when the total content of Zr + Ti + Si is less than 0.05%, elements forming a precipitated phase with Cr are insufficient, and the alloy strength cannot meet the expected requirement of the invention. However, when the total Zr + Ti + Si content is not less than 0.20 wt%, the proportion of the elements dissolved in the matrix increases, which affects the conductivity of the alloy and does not reach 75% IACS.
Preferably, the precipitated phase comprises elementary Cr, Cr-Ti-Si and Cr3Si and Cu3Zr, the area content of the precipitated phase is 0.5 to 3.0%. The precipitated phase of the alloy strip comprises elementary substances of Cr, Cr-Ti-Si and Cr3Si and Cu3Zr, the content of precipitated phases is an important factor for controlling the strength and the electric conductivity of the alloy strip according to the invention, and besides the number and the density of the large-grain-size precipitated phases mentioned above for controlling the residual stress of the alloy, other Cr-containing precipitated phases and Cu with a size of less than 100nm are used3The Zr phase is also an important guarantee for realizing the alloy strength, and Cr, Ti, Zr and Si are completely dissolved into the copper matrix after the alloy is subjected to solution treatment to form a supersaturated solid solution, are precipitated from the copper matrix in the subsequent aging process, and are dispersed in the alloy. After the precipitation, the pinning effect is played to the dislocation, so that the strength and the hardness of the copper matrix are improved, and meanwhile, due to the precipitation, the copper matrix becomes pure, the barrier effect on electrons is reduced, the resistivity is reduced, and the conductivity is greatly improved. The area content of the precipitated phase is 0.5-3.0%, when the area is less than 0.5%, the strengthening effect is poor, the strength requirement of the invention cannot be met, and when the area of the precipitated phase is too large, the agglomeration of the precipitated phase is easy to cause, and the residual stress is concentrated.
Preferably, the copper-chromium alloy further comprises 0.01-0.5% by mass of an X element, wherein the X element is at least one selected from Fe, Ag, Co, Mg and Sn. Fe. The addition of Ag, Co, Mg and Sn contributes to grain refinement, and the density of precipitated phase particles can be controlled by performing solution treatment at high temperature, so that the residual stress of the alloy is reduced, and the copper alloy has good strength, electric conductivity and bending workability. The above-mentioned effects are exhibited when the total mass% of Fe, Ag, Co, Mg and Sn is 0.01% or more, but if the content exceeds 0.5%, the solubility limit of Cr, Zr, Ti and Si is lowered, coarse precipitated phase particles tend to precipitate, and the bending workability is lowered although the strength is improved, so that the mass% of the X element is 0.01 to 0.5%.
Preferably, the finished strip of the copper-chromium alloy with the length of 400mm is placed on a horizontal test bench along the rolling direction, and the natural warping height of two ends of the strip is less than 35 mm. The inventor researches and finds that the natural warping height of the finished strip is directly related to the residual stress of the strip, and the stress residual condition in the strip can be easily judged by the method. When the alloy strength, the electric conduction and the bending performance of the copper-chromium alloy strip material reach the expected design, the natural warping height of the strip material is required to be less than 35 mm. When the residual stress of the strip is high, the warping height exceeds the range, and the application requirement cannot be met.
Preferably, the tensile strength of the copper-chromium alloy is not less than 480MPa, the electric conductivity is not less than 75% IACS, the thermal conductivity is not less than 300W/(m.K), and the Badway 90-degree bending R/t is not more than 1.0.
The second technical problem to be solved by the invention is to provide a preparation method of the copper-chromium alloy strip.
The thickness range of the copper-chromium alloy strip is 0.05 mm-2 mm.
The technical scheme adopted by the invention for solving the second technical problem is as follows: a preparation method of a copper-chromium alloy strip is characterized by comprising the following steps: the preparation process of the copper-chromium alloy strip comprises the following steps: batching → casting → homogenizing annealing → hot rolling → quenching → milling → primary cold rolling → primary aging → secondary cold rolling → secondary aging; the primary aging temperature is 420-500 ℃, and the time is 6-10 h; the secondary aging temperature is 380-450 ℃ and the time is 3-5 h.
The gradient aging annealing is beneficial to the dispersion of the second phase distribution, is beneficial to the improvement of the alloy strength, ensures that the alloy strength is more than 480MPa, and simultaneously reduces the uneven stress caused by the agglomeration of precipitated phases. The primary aging temperature is set to 420-500 ℃, the effect of the invention is to cause the supersaturated solid solution to generate solid phase change, and primarily separate out partial precipitated phase particles, thus being beneficial to fully separating out solute atoms to form simple substances of Cr, Cr-Ti-Si and Cr during secondary aging3Si and Cu3Zr and other dispersion strengthening phases reduce the solid solution quantity of the elements in the matrix, and are beneficial to improving the strength, the electric conduction and the heat conductivity of the alloy. When the temperature is lower than 420 ℃, the diffusion speed of solute atoms is slow, and the required quantity of precipitate phases cannot be separated out from the supersaturated solid solution; when the temperature is higher than 500 ℃, precipitation phase particles precipitated by primary aging grow up, so that the quantity of the precipitation phase particles is reduced, and the improvement of mechanical properties is not facilitated. The purpose of the heat preservation time of 6 h-10 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.
When the secondary aging temperature is lower than 380 ℃, the diffusion rate of solute atoms is slow during secondary aging, and a precipitation strengthening phase cannot be effectively precipitated; and when the temperature is low, the proportion of deformation texture represented by brass texture is high, and the residual stress of the alloy cannot be kept at a low level. When the secondary aging temperature is higher than 450 ℃, the precipitated phase precipitated by secondary aging can be coarsened, so that the aging strengthening is weakened, the synergistic strengthening effect between the primary aging precipitated phase particles and the secondary aging precipitated phase particles can not be fully exerted, and the mechanical property of the strip can not reach more than 480MPa due to insufficient deformation texture proportion caused by overhigh temperature. The secondary aging heat preservation time is 2-5 h, and if the heat preservation time is less than 2h, enough secondary aging precipitation phase particles cannot be formed; if the holding time exceeds 5h, the residual stress of the alloy is increased due to excessive growth of precipitation phases separated out by the primary aging and the secondary aging.
Preferably, the slab casting speed in the casting is more than 50 mm/min; the hot rolling temperature of the strip is controlled to be 800-980 ℃, the rolling rate is over 85 percent, and the finish rolling temperature is more than 650 ℃; after the completion of rolling, water-jet quenching cooling treatment is rapidly performed, and quenching is performed at an average cooling rate of 20 ℃/sec or more.
The slab casting speed in casting is more than 50mm/min, and the casting speed of the casting blank is controlled to mainly avoid the formation and growth of large-particle Cr-containing primary phases caused by too low casting speed, and the primary phases are difficult to dissolve back in the subsequent heat treatment processing process to cause the excessive amount of large-particle precipitated phases and be not beneficial to controlling the residual stress of the alloy.
Meanwhile, in order to reduce the precipitation of Cr-containing precipitated phases after alloy hot rolling as much as possible, the hot rolling temperature of the invention is controlled to be more than 800 ℃. When the hot rolling cogging temperature is lower than 800 ℃, the final rolling temperature cannot reach the expected setting, at this time, precipitation of Cr-containing precipitated phases may exist, and at this time, the precipitated second phases may be further coarsened in the subsequent aging treatment process, so that the final performance and the final stress state of the alloy are affected. When the hot rolling temperature is higher than 980 ℃, overheating or overburning may occur, resulting in hot rolling cracking. The rolling rate of hot rolling is controlled to be more than 85%, and the finishing temperature is controlled to be more than 650 ℃. The finishing rolling temperature is controlled to realize the precipitation of Cr, Zr, Ti and Si elements as little as possible, the supersaturation degree of the elements in a matrix is improved, and the driving force for the subsequent element precipitation is increased. When the finishing temperature is lower than 650 ℃, the driving force for dynamic recrystallization of the alloy is insufficient, and the alloy may have a deformation structure, which is not favorable for subsequent rolling deformation with large processing rate. Meanwhile, the proportion of the cubic texture is increased along the rolling direction after hot rolling treatment, and the proportion of the deformation texture is reduced. The transformation is beneficial to improving the shaping of the alloy and facilitating the cold processing in the later period.
After the hot rolling process is finished, the water spray quenching cooling treatment is rapidly carried out, and the quenching is carried out at the average cooling speed of more than 20 ℃/sec, so that Cr, Zr, Ti and Si elements are prevented from being precipitated in the slow cooling process.
Preferably, the total processing rate of the primary cold rolling is 85-95%, and the pass processing rate is 15-30%; the total secondary cold rolling reduction rate is 20-50%.
In order to ensure that enough deformation energy is stored in the copper alloy strip, the primary cold rolling processing rate is required to be more than 85 percent, so that the uniform and full precipitation of compounds in the later aging process is facilitated, and the uniformity of the grain structure in the alloy recrystallization softening process is facilitated to be controlled. If the processing rate of one-time cold rolling is lower than 85 percent, the production efficiency is low, the deformation energy storage is insufficient, and the full precipitation of precipitated phases in the subsequent aging process is influenced. The method requires that the pass processing rate is 15-30%, the single pass processing rate is too low, the probability of uneven alloy deformation is increased, the distribution of alloy stress is influenced, and meanwhile, the ratio of brass texture on the surface and the center of the strip is smaller than 0.80 due to the too low single pass processing rate, so that the residual stress of the alloy is increased. And the single-pass processing rate is too high, the alloy plate shape is difficult to control, the equipment load is increased, and the service life of the equipment is shortened.
In the process of secondary cold rolling, a large number of dislocations are formed by taking the particles primarily precipitated during primary aging as centers, and solute atom diffusion channels are provided for secondary aging of the strip. Meanwhile, as the cold rolling is carried out, the deformation texture proportion along the rolling direction is gradually increased. The rotation of the crystal promotes the increment of dislocation and the disordered arrangement of atoms, the increased energy storage and lattice defects in the material promote the continuous desolventizing and uniform and fine distribution of precipitated phases in the subsequent aging treatment, and the yield strength of the material is improved. Therefore, the secondary cold rolling has a strain amount of 20% or more, and the strain amount is too small, resulting in poor uniform dispersion of precipitated phases and small precipitated phases, which is disadvantageous in the completion of the later-stage complete recrystallization of the aged microstructure and in the bending workability of the final strip. The deformation is too large, the proportion of deformation texture represented by brass texture is increased, the control of the final residual stress of the alloy is not facilitated, and the bending performance of the alloy is also influenced.
Compared with the prior art, the invention has the advantages that:
(1) the invention has low residual stress through the alloying design of Cr, Zr, Ti, Si and other elements and the control of the size and density of a precipitated phase.
(2) According to the copper alloy strip made of the copper alloy, a finished strip with the length of 400mm is placed on a horizontal test bench along the rolling direction, and the natural warping heights of two ends of the strip are smaller than 35 mm.
(3) The strip made of the copper alloy material has the tensile strength of more than 480MPa, the electric conductivity of more than 75% IACS, and better bending processing performance, the thermal conductivity of the alloy can reach more than 300W/(m.K), and the copper alloy material can be widely applied to vehicles, semiconductor lead frames and electric and electronic components.
Drawings
FIG. 1 shows the SEM test results of the copper alloy material of example 5, wherein the particles are precipitated 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 each example and comparative example in the table 1, casting is carried out at 1150-1300 ℃, the thickness of a produced cast ingot is 180mm, the casting speed of the cast ingot is controlled at 100mm/min in the casting process, then the cast ingot is subjected to heat preservation at 870 ℃ for 3h and then is subjected to hot rolling until the thickness is 16.5mm, the final rolling temperature is controlled above 650 ℃, then on-line quenching is directly carried out, then surface milling is carried out, and the thickness of a strip after the upper surface and the lower surface of a hot rolled plate are milled is 15 mm; then, carrying out primary cold rolling, wherein the thickness of the strip after the cold rolling is 1.5mm, and the processing rate of the single-pass cold rolling is controlled to be 20-30%; then, carrying out primary aging treatment at 450 ℃ for 8 hours, and then carrying out cold finish rolling to 0.8 mm; and (3) carrying out secondary aging treatment at 420 ℃, wherein the treatment time is 4 hours, and finally carrying out withdrawal and straightening to obtain a final strip sample.
The finished products of the alloy strips of the examples and the comparative examples are respectively subjected to room-temperature tensile mechanical property, electric conductivity, thermal conductivity, precipitated phase, texture type and area ratio and Badway 90-degree bending detection.
The characteristic evaluation was performed 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.
Thermal conductivity test thermal diffusivity or thermal conductivity, expressed as W/(m.K), was measured according to GB/T22588-2008 flash method.
The bending properties of the tapes of the examples and comparative examples (evaluated as to whether the bend at Badway 90R/T. ltoreq.1.0 cracks) were tested using JCBA T307-2007 Test method of band flexibility for sheets and strips of tapes of the examples and comparative examples, the Test tapes having a width of 10 mm.
And observing the structure of the sample under a scanning electron microscope and a transmission electron microscope when testing the size of the precipitated phase, calculating the average grain diameter of intermetallic compounds precipitated from the alloy according to the observation result, and respectively calculating the number density and the area ratio of the precipitated phase. FIG. 1 shows the SEM test results of the copper alloy material of example 5.
The texture type and the area ratio of the surface layer of the rolled surface of the strip and the layer 1/2 of the thickness away from the rolled surface of the strip in the EBSD analysis embodiment are adopted, and the texture area ratio refers to the ratio of the area within 15 degrees of the deviation angle of the texture divided by the measured area.
According to the embodiment, the copper alloy in the embodiment of the invention realizes the performances of tensile strength not less than 480MPa and electric conductivity not less than 75% IACS, and meets Badway 90 DEG R/t not more than 1.0. After the number and the density of precipitated phases of the alloy strip and the area ratio of the brass texture are analyzed through a scanning electron microscope and EBSD, the numerical values can also meet the requirements of the invention. FIG. 1 is the result of the SEM test of example 5, and the statistics of the number of precipitated phases with different sizes shows that the particle size is 500 μm2The number of precipitated phases having a medium precipitated phase size of 100nm to 1 μm is 73, and the number of precipitated phases having a size larger than 1 μm is 3, and 1000 μm is estimated2The number of the precipitated phases with the particle size of 100nm-1 μm is 146, and the number of the precipitated phases with the particle size of more than 1 μm is 6, thereby meeting the requirements of the invention. Taking a strip with the length of 400mm along the rolling direction, placing the strip on a horizontal test bench, and automatically placing the strip at two endsHowever, the warping heights are less than 35mm, and the warping heights of comparative examples 1 and 2, in which the number and distribution density of precipitated phases do not meet the requirements of the invention, are greater than 35mm, so that the expected design requirements of the invention cannot be met, and the requirements of parts on the residual stress of materials cannot be met.
TABLE 1 ingredients of examples and comparative examples
TABLE 2 microstructures and Properties of examples and comparative examples
Claims (10)
1. A copper-chromium alloy strip is characterized in that the copper-chromium alloy consists of the following components in percentage by mass: 0.2-0.5%, Zr: 0.01-0.1%, Ti: 0.01 to 0.1%, Si: 0.01 to 0.1% and the balance of Cu and unavoidable impurities; at an optional 1000 μm2In the area, the number of precipitated phases with the size of 100nm-1 μm is 100-700, and the number of precipitated phases with the size of more than 1 μm is less than 10.
2. Copper chromium alloy strip according to claim 1, characterized in that: the brass texture area of the copper-chromium alloy strip within 15-degree deviation angle is 10-30%; setting the area rate of the brass texture on the surface layer of the rolled surface of the strip as B1Setting the area rate of brass texture at 1/2 thickness layer from the rolling surface of the strip as B2，B2/B1The ratio of (A) to (B) is 0.80-1.
3. Copper-chromium alloy strip according to claim 1, characterized in that: the adding quality of Zr, Ti and Si in the copper-chromium alloy meets the following requirements: zr, Ti and Si are more than or equal to 0.05 percent and less than or equal to 0.20 percent.
4. Copper chromium alloy strip according to claim 1, characterized in that:the precipitated phase comprises elementary substances of Cr, Cr-Ti-Si and Cr3Si and Cu3Zr, the area content of the precipitated phase is 0.5 to 3.0%.
5. Copper chromium alloy strip according to claim 1, characterized in that: the copper-chromium alloy also comprises 0.01-0.5% of X element by mass, wherein the X element is at least one of Fe, Ag, Co, Mg and Sn.
6. Copper chromium alloy strip according to claim 1, characterized in that: the finished strip with the length of 400mm is placed on a horizontal test bench along the rolling direction, and the natural warping heights of two ends of the strip are smaller than 35 mm.
7. Copper chromium alloy strip according to claim 1, characterized in that: the tensile strength of the copper-chromium alloy is not less than 480MPa, the electric conductivity is not less than 75% IACS, the thermal conductivity is not less than 300W/(m.K), and the Badway 90-degree bending R/t is not more than 1.0.
8. A method of producing a copper chromium alloy strip according to any one of claims 1 to 7, characterized in that: the preparation process of the copper-chromium alloy strip comprises the following steps: batching → casting → homogenizing annealing → hot rolling → quenching → milling → primary cold rolling → primary aging → secondary cold rolling → secondary aging; the primary aging temperature is 420-500 ℃, and the time is 6-10 h; the secondary aging temperature is 380-450 ℃ and the time is 3-5 h.
9. The method of making a copper chromium strip according to claim 8, characterized in that: the slab casting speed in the casting is more than 50 mm/min; the hot rolling temperature is controlled to be 800-980 ℃, the rolling rate is more than 85%, and the finish rolling temperature is more than 650 ℃; after the completion of rolling, water-jet quenching cooling treatment is rapidly performed, and quenching is performed at an average cooling rate of 20 ℃/sec or more.
10. The method for preparing the copper-chromium strip according to claim 8, wherein the total primary cold rolling processing rate is 85-95%, and the pass processing rate is 15-30%; the total secondary cold rolling reduction rate is 20-50%.
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| CN202011024847.5A CN112126815A (en) | 2020-09-25 | 2020-09-25 | Copper-chromium alloy strip and preparation method thereof |
| PCT/CN2021/081490 WO2022062335A1 (en) | 2020-09-25 | 2021-03-18 | Copper-chromium alloy strip and preparation method therefor |
| CN202110820919.5A CN113355554A (en) | 2020-09-25 | 2021-07-20 | Copper-chromium alloy strip and preparation method thereof |
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4640723A (en) * | 1982-12-23 | 1987-02-03 | Tokyo Shibaura Denki Kabushiki Kaisha | Lead frame and method for manufacturing the same |
| CN1856588A (en) * | 2003-09-19 | 2006-11-01 | 住友金属工业株式会社 | Copper alloy and method for production thereof |
| CN102534291A (en) * | 2010-12-09 | 2012-07-04 | 北京有色金属研究总院 | CuCrZr alloy with high strength and high conductivity, and preparation and processing method thereof |
| JP2012214882A (en) * | 2011-03-29 | 2012-11-08 | Kobe Steel Ltd | Copper alloy material for electric and electronic parts, and copper alloy material for plated electric and electronic parts |
| CN105734336A (en) * | 2016-03-11 | 2016-07-06 | 苏州中色华人铜业有限公司 | High-elasticity copper-chromium-zirconium alloy and machining process thereof |
| CN106148753A (en) * | 2015-05-12 | 2016-11-23 | 株式会社神户制钢所 | Copper alloy |
| JP2018159104A (en) * | 2017-03-22 | 2018-10-11 | Ｊｘ金属株式会社 | Copper alloy sheet having excellent strength and conductivity |
| CN110835699A (en) * | 2019-11-05 | 2020-02-25 | 宁波兴业盛泰集团有限公司 | High-strength high-conductivity copper-chromium-zirconium alloy material and preparation method thereof |
| JP2020133000A (en) * | 2019-02-20 | 2020-08-31 | 三菱マテリアル株式会社 | Copper alloy material, commutator segment, and electrode material |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0551673A (en) * | 1991-08-21 | 1993-03-02 | Nikko Kyodo Co Ltd | High-strength and high-conductivity copper alloy for electronic equipment excellent in bendability and stress relaxation property |
| CN1928145A (en) * | 2006-09-20 | 2007-03-14 | 苏州有色金属加工研究院 | Process for preparing Cu-Cr-Zr alloy slat |
| CN105568039B (en) * | 2015-12-22 | 2017-09-05 | 宁波博威合金板带有限公司 | The preparation method of high-intensity high-conductivity copper Cr-Zr alloy and its strip |
| CN107142393A (en) * | 2017-05-11 | 2017-09-08 | 太原晋西春雷铜业有限公司 | A kind of low stress copper chromium titanium silicon band and preparation method thereof |
| CN107619964B (en) * | 2017-09-18 | 2020-05-08 | 宁波兴业盛泰集团有限公司 | High-conductivity copper-silver-tin-chromium alloy plate strip and preparation and processing method thereof |
| CN108754214A (en) * | 2018-06-28 | 2018-11-06 | 湖州好灵通铝业有限公司 | A kind of combarloy silver tin evanohm Strip and its prepare processing method |
| CN109609801A (en) * | 2018-12-06 | 2019-04-12 | 宁波博威合金材料股份有限公司 | High property copper alloy and preparation method thereof |
| CN112126815A (en) * | 2020-09-25 | 2020-12-25 | 宁波博威合金板带有限公司 | Copper-chromium alloy strip and preparation method thereof |
-
2020
- 2020-09-25 CN CN202011024847.5A patent/CN112126815A/en active Pending
-
2021
- 2021-03-18 WO PCT/CN2021/081490 patent/WO2022062335A1/en active Application Filing
- 2021-07-20 CN CN202110820919.5A patent/CN113355554A/en not_active Withdrawn
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4640723A (en) * | 1982-12-23 | 1987-02-03 | Tokyo Shibaura Denki Kabushiki Kaisha | Lead frame and method for manufacturing the same |
| CN1856588A (en) * | 2003-09-19 | 2006-11-01 | 住友金属工业株式会社 | Copper alloy and method for production thereof |
| CN102534291A (en) * | 2010-12-09 | 2012-07-04 | 北京有色金属研究总院 | CuCrZr alloy with high strength and high conductivity, and preparation and processing method thereof |
| JP2012214882A (en) * | 2011-03-29 | 2012-11-08 | Kobe Steel Ltd | Copper alloy material for electric and electronic parts, and copper alloy material for plated electric and electronic parts |
| CN106148753A (en) * | 2015-05-12 | 2016-11-23 | 株式会社神户制钢所 | Copper alloy |
| CN105734336A (en) * | 2016-03-11 | 2016-07-06 | 苏州中色华人铜业有限公司 | High-elasticity copper-chromium-zirconium alloy and machining process thereof |
| JP2018159104A (en) * | 2017-03-22 | 2018-10-11 | Ｊｘ金属株式会社 | Copper alloy sheet having excellent strength and conductivity |
| JP2020133000A (en) * | 2019-02-20 | 2020-08-31 | 三菱マテリアル株式会社 | Copper alloy material, commutator segment, and electrode material |
| CN110835699A (en) * | 2019-11-05 | 2020-02-25 | 宁波兴业盛泰集团有限公司 | High-strength high-conductivity copper-chromium-zirconium alloy material and preparation method thereof |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113355554A (en) * | 2020-09-25 | 2021-09-07 | 宁波博威合金板带有限公司 | Copper-chromium alloy strip and preparation method thereof |
| WO2022062335A1 (en) * | 2020-09-25 | 2022-03-31 | 宁波博威合金板带有限公司 | Copper-chromium alloy strip and preparation method therefor |
| WO2023000510A1 (en) * | 2021-07-19 | 2023-01-26 | 宁波博威合金板带有限公司 | Silicide-reinforced copper-titanium alloy matrix composite material and preparation method therefor |
| CN113913642A (en) * | 2021-09-26 | 2022-01-11 | 宁波博威合金板带有限公司 | Copper alloy strip and preparation method thereof |
| CN115125413A (en) * | 2022-06-30 | 2022-09-30 | 宁波金田铜业(集团)股份有限公司 | Copper alloy strip with excellent comprehensive performance and preparation method thereof |
| CN115198138A (en) * | 2022-07-29 | 2022-10-18 | 宁波博威合金材料股份有限公司 | Copper alloy strip and preparation method thereof |
| CN116970839A (en) * | 2023-09-19 | 2023-10-31 | 宁波兴业盛泰集团有限公司 | Copper-chromium alloy material and preparation method thereof |
| CN116970839B (en) * | 2023-09-19 | 2023-12-19 | 宁波兴业盛泰集团有限公司 | Copper-chromium alloy material and preparation method thereof |
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| CN113355554A (en) | 2021-09-07 |
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