CN110066939B - High-strength high-conductivity copper-chromium-zirconium alloy and low-temperature deformation preparation method thereof - Google Patents
High-strength high-conductivity copper-chromium-zirconium alloy and low-temperature deformation preparation method thereof Download PDFInfo
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- 229910001093 Zr alloy Inorganic materials 0.000 title claims abstract description 21
- QZLJNVMRJXHARQ-UHFFFAOYSA-N [Zr].[Cr].[Cu] Chemical compound [Zr].[Cr].[Cu] QZLJNVMRJXHARQ-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 101
- 239000000956 alloy Substances 0.000 claims abstract description 101
- 239000013078 crystal Substances 0.000 claims abstract description 28
- 239000010949 copper Substances 0.000 claims abstract description 23
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052802 copper Inorganic materials 0.000 claims abstract description 21
- 238000005266 casting Methods 0.000 claims abstract description 9
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- 239000011651 chromium Substances 0.000 abstract description 18
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 12
- 229910000881 Cu alloy Inorganic materials 0.000 abstract description 12
- 229910052804 chromium Inorganic materials 0.000 abstract description 12
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052726 zirconium Inorganic materials 0.000 abstract description 6
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- GXDVEXJTVGRLNW-UHFFFAOYSA-N [Cr].[Cu] Chemical compound [Cr].[Cu] GXDVEXJTVGRLNW-UHFFFAOYSA-N 0.000 description 4
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- C22C9/00—Alloys based on copper
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
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Abstract
The invention relates to the field of copper alloy and application thereof, in particular to a high-strength high-conductivity copper-chromium-zirconium alloy and a low-temperature deformation preparation method thereof. The alloy comprises the following chemical components in percentage by mass: 0.2 to 1.5% of chromium, 0.05 to 0.2% of zirconium, and the balance of copper and inevitable impurities. The typical structure of the alloy is a copper matrix with a nanoscale deformed structure and dispersed chromium particles. The typical nano structure is a deformed twin crystal bundle, the thickness of a twin crystal layer sheet is 20-100 nanometers, and the size of the twin crystal bundle is several micrometers to hundreds of micrometers. The grain diameter of the dispersed chromium particles is 10-100 nanometers. The alloy has the strength of 700MPa, and the conductivity is in the range of 78-82% IACS. The alloy is manufactured by two parts of alloy billet casting hot working and low-temperature deformation. The alloy has the characteristics of high strength, high conductivity, high softening temperature, wear resistance, excellent weldability and the like, and can be applied to the field of the existing copper-chromium-zirconium alloy and the field with higher requirements on strength and conductivity.
Description
Technical Field
The invention relates to a copper alloy and the application field thereof, in particular to a high-strength high-conductivity copper-chromium-zirconium alloy reinforced by a nanometer twin crystal structure and dispersed chromium particles and a manufacturing method mainly characterized by low-temperature deformation.
Background
With the rapid development of industries such as power electronics and high-speed rail transit, higher and higher requirements are put forward on light weight, low energy consumption and the like of conductive parts, which requires that conductive materials used for key conductive parts such as lead frames, high-speed railway contact lines and the like have high conductivity and higher strength. The existing high-strength high-conductivity material mainly comprises copper alloy. The alloy has the characteristics of excellent forming ability, moderate price, higher strength, high toughness, excellent connection performance, high electrical conductivity, high thermal conductivity and the like, and still is one of the most important conductor materials in the future for a long time.
The biggest problem faced in the application of high conductivity pure copper and copper alloys as conductive materials is insufficient strength (the yield strength of high purity copper at room temperature is about 50 MPa). The strength and other mechanical properties of copper can be controlled in a considerable range by alloying, plastic deformation, compositing and other methods, but at present, various ways of strengthening metal materials lead to loss of conductivity to different degrees, namely, the strength is improved while the conductivity is generally reduced remarkably. At present, the main high-strength high-conductivity conductive copper alloy mostly uses a precipitation strengthening system with low alloy content, and alloy elements in solid solution are precipitated in a precipitation phase form through artificial aging treatment of the precipitation strengthening copper alloy, so that the content of the solid solution alloy elements in a copper matrix is reduced, the conductivity is improved, and the precipitation of the precipitation phase improves the alloy strength. The common precipitation strengthening high-strength high-conductivity copper alloy at present comprises Cu-Be, Cu-Fe-P, Cu-Ni-Si, Cu-Cr-Zr and the like. On the premise of keeping higher conductivity, the selection of an alloy system is limited, so that the precipitation strengthening degree is limited, and the strength is still difficult to be continuously improved. For example, the strength of the common C70250 alloy can reach 600MPa, but the conductivity is only 40-50% IACS. The C70350 alloy developed on the basis can improve the strength to 800MPa, but the electric conductivity is still not higher than 50% IACS. The conductivity of the C18200 alloy reaches 80% IACS level, but the strength is only about 400 MPa.
Since the solid solubility of Cr in Cu-Cr and Cu-Cr alloys is extremely low, the Cu-Cr alloy has high electrical conductivity, and the precipitation of a precipitate phase mainly containing Cr can improve a remarkable strengthening effect. The alloy system has good processing performance and welding performance, and is an alloy system with large-scale application potential in the fields of integrated circuits, connectors, contact wires and the like. However, the extremely low solid solubility of Cr in Cu also limits the strength limit due to precipitation strengthening. The tensile strength of the Cu-Cr and Cu-Cr-Zr systems commonly used at present is generally about 400MPa, and the composite strengthening limit obtained by various methods is 550-600 MPa.
The traditional precipitation strengthening copper alloy can generally improve the strengthening effect through plastic deformation before aging treatment, but generally the deformation obtains a microstructure which is micron crystal and high-density dislocation, and the strengthening effect is limited through structure refinement. While the mechanical properties of metallic materials are generally related to the microstructure size, the grain size is most representative of the hardness/tensile strength relationship. The grain size decreases and the hardness/strength of the metal increases. Conventional hot rolling/hot extrusion processes can reduce the grain size of Cu-Cr alloys to hundreds of microns, which can typically reach several microns after cold rolling or cold drawing. After aging treatment, the tensile strength of the alloy can reach 400-500 MPa.
In the severe deformation method developed in recent years, the purpose of reducing the grain size is achieved by repeatedly deforming the metal and accumulating deformation defects in the metal. The Cu-Cr alloy extruded at equal channel angles has the grain size of hundreds of nanometers and the strength of 550-600 MPa. However, such methods do not continue to reduce the grain size and thereby increase the strength of the alloy, since the formation and annihilation of internal defects in the metal are balanced among repeated deformations.
On the other hand, the high-density defect structure (such as high-density dislocation) obtained by deformation and the high-density grain boundary generated along with the reduction of the grain size can also cause the great increase of the scattering cross section in the electron transportation process, namely the alloy strength is improved, the resistivity is obviously improved, and the conductivity is obviously reduced. The paradoxical phenomenon of increasing the defect density while increasing the strength and resistivity limits the development of conductive copper alloys to achieve higher strength and conductivity simultaneously.
Disclosure of Invention
The invention aims to solve the technical problem of providing a nano-structure high-strength high-conductivity copper chromium zirconium alloy with yield strength of more than 600MPa and conductivity of more than 75% IACS and a preparation method thereof, wherein the alloy has simple components and no toxicity, meets the requirement of environmental protection, the main process flow is based on the existing production equipment capacity, the modification cost and the production cost are not remarkably increased, and different mechanical and conductivity combinations can be obtained through relatively simple process adjustment.
The technical scheme for solving the technical problems is as follows:
the high-strength high-conductivity copper-chromium-zirconium alloy comprises the following chemical components in percentage by mass: 0.2 to 1.5, Zr: 0.05 to 0.2% and the balance of copper and inevitable impurities.
The typical microstructure of the high-strength high-conductivity copper-chromium-zirconium alloy is Cr particles which are dispersed and a deformed copper matrix with a nano structure.
The typical structure of the high-strength high-conductivity copper-chromium-zirconium alloy matrix is a deformed twin crystal bundle, the average thickness of twin crystal laminas is 20-100 nanometers, and the size of the twin crystal bundle is 0.5-100 micrometers.
The low-temperature deformation preparation method of the high-strength high-conductivity copper-chromium-zirconium alloy comprises the steps of smelting the alloy in vacuum according to alloy components, preparing an alloy blank through thermal deformation, carrying out pre-aging treatment on the alloy blank, carrying out low-temperature heat preservation on the pre-aged alloy blank, carrying out low-temperature deformation on the low-temperature alloy blank, and finishing the low-temperature deformed alloy blank reaching the designed deformation and size to obtain a finished product.
The low-temperature deformation preparation method of the high-strength high-conductivity copper-chromium-zirconium alloy adopts the following steps of: vacuum melting, ingot casting, hot extrusion or continuous casting and continuous extrusion.
According to the low-temperature deformation preparation method of the high-strength high-conductivity copper-chromium-zirconium alloy, the pre-aging treatment temperature is 600 +/-20 ℃, and the pre-aging treatment time is 20 minutes to 5 hours according to the shape and the size of a blank.
According to the low-temperature deformation preparation method of the high-strength high-conductivity copper-chromium-zirconium alloy, the temperature range of the low-temperature heat preservation link of the alloy blank is between 196 ℃ below zero and 50 ℃ below zero according to the shape and the size of the blank.
According to the low-temperature deformation preparation method of the high-strength high-conductivity copper-chromium-zirconium alloy, the low-temperature deformation of the alloy blank after low-temperature heat preservation is still carried out in a low-temperature environment, and the temperature range is from-196 ℃ to-50 ℃.
The design idea of the invention is as follows:
the invention has the main design idea that based on the traditional CuCrZr alloy production process, the alloy elements are separated out by heat preservation in the hot working link, and the nanometer-sized deformation twin crystals are introduced into the alloy by adding the low-temperature deformation link, so that the artificial aging process after deformation is not needed, or only the simplified annealing process (the time and temperature parameter range is greatly widened) is needed, and the high conductivity is kept under the simple process flow, and the alloy strength is greatly improved.
The main principle is as follows:
on one hand, the twin boundary is a flat two-dimensional interface, the matching degree of crystals on two sides at the interface is high, the interface energy is low, and the two-position low-energy interface has higher stability than the common large-angle grain boundary in the deformation process. Once the twin boundary is formed, the condition that the defect is rapidly annihilated due to the reaction of common high-angle boundary and dislocation is not easy to occur, so that a stable high-density twin structure can be rapidly obtained at a relatively small deformation amount. Suitable low temperature deformation may introduce nano-twinning structures in the copper alloy.
On the other hand, the fine structure strengthens the metal material and brings a large number of interfaces inside the metal. These interfaces act as electron scattering sources when current is passed through them, significantly increasing the resistivity of the metal. Because the mismatching degree of atoms on two sides of the twin boundary interface is extremely low, the interface energy is lower by one order of magnitude than that of the traditional large-angle grain boundary. Studies have shown that twin boundaries in copper bring about an order of magnitude lower resistivity than the normal high angle boundaries. And the twin boundaries have strengthening effects similar to those of ordinary high-angle boundaries with equivalent interface spacing. Therefore, the strength of the copper alloy can be greatly improved on the premise of keeping higher conductivity by utilizing the nano twin crystal reinforced copper alloy.
Compared with the traditional CuCr alloy, the method saves the artificial aging treatment link or greatly widens the artificial aging treatment conditions, improves the alloy strength and shortens the flow of the cold deformation stage.
The invention has the advantages and beneficial effects that:
1. the invention adopts a low-temperature deformation method, and the CuCr alloy is cooled to a lower temperature after being hot-processed. Deformation at this temperature is effective to produce high density deformed twins. It is subjected to limited plastic deformation at this temperature, and a deformed twin bundle represented by the parallel lamellar structure shown in fig. 1 can be obtained. The typical size of the deformed twin crystal bundle is between hundreds of nanometers and tens of micrometers, and the average typical size of the twin crystal lamella spacing is between 20 nanometers and 50 nanometers. The structure ensures that the electric conductivity of the material at room temperature can be simultaneously obtained at the strength of 700MPa level and the electric conductivity of the material at room temperature is higher than 70% IACS level, and the optimized performance is 78% IACS at 700 MPa.
2. The low-temperature environment adopted in the invention is determined by alloy components, the typical temperature range is-196 ℃ to-50 ℃, a plurality of low-temperature means can be used, and the low-temperature environment can be produced in large scale and comprises but is not limited to liquid nitrogen soaking cooling, liquid nitrogen steam cooling, dry ice cooling, compressor refrigeration air medium cooling or other medium cooling. The low-temperature deformation mode is determined by the final shape and size of the product and can be rolling, drawing, forging, extruding, spinning and the like. The existing low-temperature implementation means can be mostly used in the low-temperature link, a special cooling mechanism and a cooling method do not need to be independently researched and developed, and the cost is increased limitedly.
3. The invention carries out heat preservation treatment at 600 ℃ after hot working, so that solid solution elements are dispersed and precipitated, and the purity of a matrix is ensured. The process ensures that the alloy after the subsequent low-temperature deformation does not need the artificial aging process of precise temperature and time control, greatly reduces the production control difficulty and reduces the subsequent flow.
Compared with the traditional CuCrZr alloy, the alloy prepared by the method has the comprehensive performance of high strength-conductivity, does not use a novel deformation mode with a complicated deformation shape, and does not need to introduce novel deformation equipment. On the basis of the traditional production flow, the method can be realized by innovatively introducing a low-temperature environment and changing a heat treatment process. Compared with emerging nano-twin crystal pure copper of high-conductivity pure copper, the nano-twin crystal CuCrZr alloy containing dispersed phases has the advantages of obviously improved strength and improved thermal stability, and has better industrial application value.
Drawings
Fig. 1 is a diagram of a typical nano twin structure.
FIG. 2 is a typical room temperature tensile curve of a low temperature deformation nano twinned CuCrZr alloy.
FIG. 3 is a graph comparing the tensile strength of a typical CuCrZr alloy.
Detailed Description
In the specific implementation process, the high-strength high-conductivity copper-chromium-zirconium alloy comprises the following chemical components in percentage by mass: 0.2 to 1.5% of chromium, 0.05 to 0.2% of zirconium, and the balance of copper and inevitable impurities. The typical structure of the alloy is a copper matrix with a nanoscale deformed structure and dispersed chromium particles. The typical nano structure is a deformed twin crystal bundle, the thickness of a twin crystal layer sheet is 20-100 nanometers, and the size of the twin crystal bundle is several micrometers to hundreds of micrometers. The grain diameter of the dispersed chromium particles is 10-100 nanometers. The alloy has the strength of 700MPa, and the conductivity is in the range of 78-82% IACS. The alloy is manufactured by two parts of alloy billet casting hot working and low-temperature deformation. Wherein, the alloy billet casting hot working part comprises: vacuum casting/hot extrusion or vacuum melting/continuous casting and continuous extrusion, and keeping the temperature at 600 ℃. The low-temperature deformation part comprises pre-cooling, low-temperature deformation and finishing of the alloy blank. The method is based on the existing copper-chromium-zirconium alloy system and the conventional manufacturing method, combines the pre-aging at 600 ℃ with the low-temperature deformation, and achieves the purpose of greatly improving the alloy strength on the premise of keeping high conductivity by introducing a chromium dispersion strengthening phase and a nanometer deformation twin crystal into the alloy. The alloy has the characteristics of high strength, high conductivity, high softening temperature, wear resistance, excellent weldability and the like, and can be suitable for the application field of the existing copper-chromium-zirconium alloy and the field with higher requirements on strength and conductivity. The method is based on the existing alloy system and does not need to add noble metals or rare earth elements. Based on the capability of the existing manufacturing equipment, the method can realize the great improvement of the strength only by introducing the nanometer twin crystal in the low-temperature deformation process, and maintain the high-point conductivity. The method has the advantages of simple manufacturing process, wide process parameter regulation and control range, wide applicable product shape and size range, easy production and the like.
The present invention will be explained in further detail below by way of examples and figures.
Example 1
The copper-chromium alloy comprises the following components in percentage by mass: 98.6% of copper, 1.0% of chromium, 0.1% of zirconium and the balance of inevitable impurities. After the alloy is subjected to vacuum casting, hot extrusion is carried out at 1000 ℃, and the temperature is kept at 600 ℃ for 0.5 hour. After the alloy is soaked in liquid nitrogen after hot extrusion, the alloy is cold forged in a liquid nitrogen environment, and the equivalent strain capacity is 2.0. The typical microstructure of the alloy after deformation is a mixed structure of nano-sized twin crystal bundles and nano-crystals, the average thickness of a nano-twin crystal layer is 30nm, and the average grain size of the nano-crystals is 50 nm. The tensile strength of the alloy at room temperature is 700MPa, and the electrical conductivity is 78% IACS.
Example 2
The copper-chromium alloy comprises the following components in percentage by mass: 98.6% of copper, 1.0% of chromium, 0.1% of zirconium and the balance of inevitable impurities. After the alloy is subjected to vacuum casting, the alloy is subjected to hot extrusion at 1000 ℃ and is cooled by water. And (3) preserving the heat of the hot extruded material for 2 hours at 600 ℃, naturally cooling, soaking in liquid nitrogen, and performing cold forging at-50 ℃. After the alloy is subjected to the process flow, the typical microstructure is a mixed structure of nano-sized twin crystal bundles and nano-crystals, the average thickness of a nano-twin crystal layer is 30nm, and the average size of nano-crystal grains is 100 nm. The tensile strength of the alloy at room temperature is 650MPa, and the electrical conductivity is 80% IACS.
Example 3
The copper-chromium alloy comprises the following components in percentage by mass: 98.6% of copper, 1.0% of chromium, 0.1% of zirconium and the balance of inevitable impurities. After the alloy is subjected to vacuum casting, hot extrusion is carried out at 1000 ℃ and water cooling is carried out. After the hot extrusion, the alloy is subjected to heat preservation for 2 hours at 600 ℃, then is soaked in liquid nitrogen, and is rolled in an environment of 100 ℃ below zero, wherein the total rolling amount is 85%. After the alloy is subjected to the process flow, the typical microstructure is a mixed structure of nano-sized twin crystal bundles and nano-crystals, the average thickness of a nano-twin crystal layer is 30nm, and the average grain size of the nano-crystals is 50 nm. The tensile strength of the alloy at room temperature is 680MPa, and the electrical conductivity is 80% IACS.
Comparative example 1:
the copper-chromium alloy comprises the following components in percentage by mass: 98.6% of copper, 1.0% of chromium, 0.1% of zirconium and the balance of inevitable impurities. After the alloy is vacuum cast, the alloy is hot extruded at 1000 ℃, and is water-cooled and acid-washed. After room temperature extrusion and multi-pass drawing, aging treatment is carried out for 20 minutes at 400 ℃. After the alloy is processed by the process flow, the typical microstructure is a mixed structure of sub-micron dislocation cells and ultra-fine grains. The tensile strength of the alloy at room temperature is 580MPa, and the conductivity is 77% IACS.
Comparative example 2:
and (3) annealing the high-purity copper sample with the purity of 99.99% at 800 ℃ for 2 hours to eliminate the original tissue influence. And performing cold heading treatment at the temperature of 196 ℃ below zero after soaking in liquid nitrogen, wherein the equivalent strain is 2.0. After deformation, the pure copper sample has the strength of 580MPa and the electric conductivity of 96% IACS.
As shown in FIG. 2, as can be seen from the typical room temperature tensile curve of the low temperature deformation nanometer twin crystal CuCrZr alloy, the alloy is obviously strengthened, the yield strength reaches the level of 600MPa, and the tensile strength reaches the level of 700 MPa. The alloy has certain work hardening capacity and certain elongation after fracture.
As shown in FIG. 3, from the comparison of the tensile strength of a typical CuCrZr alloy, the strength of the alloy in the 600 ℃ annealing state is equivalent to the strength of the existing non-hardened CuCrZr alloy for engineering. Compared with the room temperature deformation hardening state of 500MPa level, the low temperature deformation obviously improves the strength of the alloy. Notably, the room temperature conductivity of the alloy is higher than 84% IACS due to near complete precipitation of the Cr element in the alloy by 600 degree c annealing (Cr solubility in Cu is only about 0.07 wt% at 600 degree c according to equilibrium phase diagram). The conductivity of the 700MPa base alloy is still not lower than 78% IACS after low temperature deformation hardening. The peak strength of the CuCrZr alloy subjected to the existing age hardening treatment is only 600MPa, and the electric conductivity is still lower at the moment. The introduction of nano twin strengthening by using low temperature deformation has obvious advantages.
The embodiment result shows that the alloy has the characteristics of high strength and high conductivity, simultaneously keeps the characteristics of high softening temperature, wear resistance, excellent weldability and the like of the CuCr series alloy, can obtain different mechanical and conductive property combinations through process parameter adjustment, and is suitable for the application fields of the traditional CuCr series alloy such as transportation, power and electronic periods, aerospace, weapons and the like and a plurality of new fields with higher requirements on strength and conductivity.
Claims (4)
1. The low-temperature deformation preparation method of the high-strength high-conductivity copper-chromium-zirconium alloy is characterized in that the alloy comprises the following chemical components in percentage by mass: 0.2 to 1.5, Zr: 0.05 to 0.2 percent, and the balance of copper and inevitable impurities; alloy is melted in vacuum according to alloy components, alloy blanks are prepared through thermal deformation, pre-aging treatment is carried out on the alloy blanks, the pre-aging alloy blanks are subjected to low-temperature heat preservation, low-temperature deformation is carried out on the low-temperature alloy blanks, and the low-temperature deformation alloy blanks reaching the designed deformation amount and size are subjected to finishing treatment to obtain finished products;
the pre-aging treatment temperature is 600 +/-20 ℃, and the pre-aging treatment time is 20 minutes to 5 hours according to the shape and the size of the blank;
according to the shape and the size of the blank, the temperature range of the low-temperature heat preservation link of the alloy blank is between 196 ℃ below zero and 50 ℃ below zero;
the low-temperature deformation of the alloy blank after low-temperature heat preservation is still carried out in a low-temperature environment, and the temperature range is from-196 ℃ to-50 ℃.
2. The low-temperature deformation preparation method of the high-strength high-conductivity copper-chromium-zirconium alloy according to claim 1, characterized in that the smelting and hot deformation method adopts, but is not limited to: vacuum melting, ingot casting, hot extrusion or continuous casting and continuous extrusion.
3. The method for preparing the high-strength high-conductivity copper-chromium-zirconium alloy by low-temperature deformation according to claim 1, wherein the typical microstructure of the alloy is dispersed Cr particles and a deformed copper matrix with a nano structure.
4. The low-temperature deformation preparation method of the high-strength high-conductivity copper-chromium-zirconium alloy as claimed in claim 1, wherein the typical structure of the alloy matrix is deformation twin bundles, the average thickness of the twin crystal layer is 20-100 nm, and the size of the twin bundle is 0.5-100 μm.
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| JPH07258805A (en) * | 1994-03-22 | 1995-10-09 | Nikko Kinzoku Kk | Production of high-strength and high-conductivity copper alloy material for electronic equipment |
| JP2012092368A (en) * | 2010-10-25 | 2012-05-17 | Hitachi Cable Ltd | Precipitation hardening copper alloy foil, lithium ion secondary battery negative electrode using it, and manufacturing method of precipitation hardening copper alloy foil |
| CN102839341A (en) * | 2012-09-28 | 2012-12-26 | 合肥工业大学 | Preparation method of high-strength and high-conductivity copper alloy |
| CN105087999A (en) * | 2015-08-31 | 2015-11-25 | 河南科技大学 | High-strength and high-conductivity copper and zirconium alloy and preparation method thereof |
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| JPH07258805A (en) * | 1994-03-22 | 1995-10-09 | Nikko Kinzoku Kk | Production of high-strength and high-conductivity copper alloy material for electronic equipment |
| JP2012092368A (en) * | 2010-10-25 | 2012-05-17 | Hitachi Cable Ltd | Precipitation hardening copper alloy foil, lithium ion secondary battery negative electrode using it, and manufacturing method of precipitation hardening copper alloy foil |
| CN102839341A (en) * | 2012-09-28 | 2012-12-26 | 合肥工业大学 | Preparation method of high-strength and high-conductivity copper alloy |
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