CN114752808A - High-strength high-conductivity copper alloy composite material and preparation method thereof - Google Patents
High-strength high-conductivity copper alloy composite material and preparation method thereof Download PDFInfo
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- CN114752808A CN114752808A CN202210408656.1A CN202210408656A CN114752808A CN 114752808 A CN114752808 A CN 114752808A CN 202210408656 A CN202210408656 A CN 202210408656A CN 114752808 A CN114752808 A CN 114752808A
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- 239000002131 composite material Substances 0.000 title claims abstract description 27
- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 55
- 239000000956 alloy Substances 0.000 claims abstract description 43
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 39
- 239000010949 copper Substances 0.000 claims abstract description 25
- 229910052802 copper Inorganic materials 0.000 claims abstract description 22
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910017813 Cu—Cr Inorganic materials 0.000 claims abstract description 13
- 229910017985 Cu—Zr Inorganic materials 0.000 claims abstract description 12
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 8
- 239000011651 chromium Substances 0.000 claims abstract description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 6
- 239000012535 impurity Substances 0.000 claims abstract description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 14
- 230000006698 induction Effects 0.000 claims description 8
- 238000003723 Smelting Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims 2
- 238000001816 cooling Methods 0.000 abstract description 9
- 229910017526 Cu-Cr-Zr Inorganic materials 0.000 abstract description 8
- 229910017810 Cu—Cr—Zr Inorganic materials 0.000 abstract description 8
- 238000005266 casting Methods 0.000 abstract description 6
- 229910052593 corundum Inorganic materials 0.000 abstract description 4
- 238000002844 melting Methods 0.000 abstract description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 4
- 239000000919 ceramic Substances 0.000 abstract description 3
- 230000008018 melting Effects 0.000 abstract description 3
- 239000002905 metal composite material Substances 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 1
- 238000005728 strengthening Methods 0.000 description 13
- 239000011159 matrix material Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- QZLJNVMRJXHARQ-UHFFFAOYSA-N [Zr].[Cr].[Cu] Chemical compound [Zr].[Cr].[Cu] QZLJNVMRJXHARQ-UHFFFAOYSA-N 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- -1 T1 or T2) Chemical compound 0.000 description 1
- 229910001093 Zr alloy Inorganic materials 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000009617 vacuum fusion Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/10—Alloys containing non-metals
- C22C1/1036—Alloys containing non-metals starting from a melt
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/10—Alloys containing non-metals
- C22C1/1036—Alloys containing non-metals starting from a melt
- C22C1/1047—Alloys containing non-metals starting from a melt by mixing and casting liquid metal matrix composites
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
- C22C32/0015—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides with only single oxides as main non-metallic constituents
- C22C32/0021—Matrix based on noble metals, Cu or alloys thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
- H01B1/026—Alloys based on copper
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Composite Materials (AREA)
- Powder Metallurgy (AREA)
- Manufacture Of Alloys Or Alloy Compounds (AREA)
Abstract
The invention discloses a high-strength and high-conductivity copper alloy composite material and a preparation method thereof, and belongs to the technical field of metal composite materials. The composite material comprises the following components in percentage by mass: 0.1-1.0% of chromium; 0.1-1.0% of zirconium; 0.05-1.5% of alumina ceramic particles; the balance being copper and unavoidable impurities. The preparation method comprises the following steps: compounding material-pure copper, Cu-Cr intermediate alloy and Al2O3Melting ceramic particles, preserving heat, cooling, melting a Cu-Zr intermediate alloy, preserving heat, and casting. The invention improves the mechanical property of the Cu-Cr-Zr alloy material by adding the nanometer micron-sized alumina ceramic particles into the Cu-Cr-Zr alloy, has excellent conductivity, and is suitable for the requirement on the conductivityHigh mechanical performance and high requirement.
Description
Technical Field
The invention relates to the technical field of metal composite materials, in particular to an alumina ceramic particle reinforced high-strength high-conductivity copper alloy composite material and a preparation method thereof.
Background
Although pure copper has good electric and thermal conductivity, it has low strength, poor wear resistance and easy softening and deformation at high temperature, and is limited in application in many occasions. The high-strength high-conductivity copper alloy refers to a copper-based alloy with high strength and high conductivity. The method is widely applied to the aspects of integrated circuit lead frames, high-speed rail contact wires, high-voltage switch electrical contacts, strong magnets, resistance spot welding electrodes, electromagnetic gun guide rails and the like. For copper alloy, the strength and the conductivity are mutually conflicting in nature, and the tensile strength of more than 600MPa and the conductivity of about 80% IACS are generally taken as the performance targets of the high-strength and high-conductivity copper alloy. The copper-chromium-zirconium alloy is a developed third-generation high-strength and high-conductivity copper alloy, and is also a high-strength and high-conductivity copper alloy which is the most widely applied and has the greatest development prospect at present. The copper alloy is a precipitation strengthening type copper alloy, the mechanical property of the copper alloy mainly depends on the nano chromium phase precipitated by aging, the zirconium element not only can refine the crystal grains of the cast sample, but also can refine the chromium precipitated phase and prevent the chromium precipitated phase from growing, and therefore the copper chromium zirconium series alloy shows higher strength.
In addition to this, the matrix can be strengthened by introducing a second phase in the form of particles in the copper matrix. The second-phase strengthening is a method of strengthening an alloy by a second phase present in a matrix, and is a phenomenon in which the second phase exists in a dispersed state of fine particles to strengthen a metal, and is also called dispersion strengthening. According to the theory of electric conduction, the second phase has much smaller scattering effect on electrons than the lattice distortion caused by atoms dissolved in the copper matrix, and thus the second phase is strengthened by the most widely used strengthening method in high-strength and high-conductivity copper alloys. The mechanism of second phase strengthening is related to the size, morphology, amount of second phase and its distribution on the matrix. The second phase particles block dislocation movement and have good thermal stability, so that the strengthening effect is remarkable, the recrystallization can be retarded, and the high-temperature strength of the material is improved. The second phase has a small volume fraction, and therefore has a small detrimental effect on the electrical conductivity. The copper alloy prepared by adopting the traditional strengthening mode has the problems of uncontrollable volume fraction of a second phase, uncontrollable scale and dispersion degree of a strengthening phase, poor conductivity and mechanical property and the like.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides an alumina ceramic particle reinforced high-strength high-conductivity copper alloy composite material with excellent conductivity and mechanical property and a preparation method thereof, so that the composite material can be used in the fields of lead frames, electromagnetic gun guide rails and the like.
The invention is realized by the following technical scheme.
The high-strength high-conductivity copper alloy composite material is characterized by comprising the following components in percentage by mass: 0.1 to 1.0% of chromium, 0.1 to 1.0% of zirconium, 0.05 to 1.5% of alumina ceramic particles, and the balance of copper and inevitable impurities.
Further, the mass percentage of the inevitable impurities is less than or equal to 0.5 percent in total.
Further, the average particle size of the alumina ceramic particles is 10 nm-150 μm.
Further, the average particle size of the alumina ceramic particles is 10 nm-20 μm.
Al2O3The ceramic particles play a second phase strengthening effect in the Cu-Cr-Zr matrix, so that the alloy is subjected to precipitation strengthening and the second phase particles are strengthened together, the mechanical property of the copper-based composite material is improved, and the good conductivity is maintained.
The invention also provides a preparation method of the high-strength high-conductivity copper alloy composite material, which is mainly a preparation process for adding alumina ceramic particles by non-vacuum fusion casting, and comprises the following steps: firstly, weighing pure Cu, Cu-Cr intermediate alloy, Cu-Zr intermediate alloy and alumina ceramic particles according to the proportion, and smelting by using a non-vacuum induction furnace.
The method comprises the following specific steps: (1) preparing materials: taking pure Cu blocks, Cu-Cr intermediate alloy, Cu-Zr intermediate alloy and alumina ceramic particles as raw materials according to the mass ratio, and drying the raw materials and a non-vacuum induction furnace; (2) smelting: placing a pure copper block, alumina ceramic particles and a Cu-Cr intermediate alloy into a graphite crucible to be smelted by adopting a non-vacuum induction furnace, wherein a composite salt covering agent (such as a covering agent for smelting the copper alloy disclosed by patent CN101817066B, and composite salt prepared from a mixture of calcium chloride, potassium chloride and the like is used as the covering agent) is added to be heated to 1200-1300 ℃, the temperature is kept for 1-1.5 h, then the temperature is reduced to 1150-1180 ℃, the Cu-Zr intermediate alloy is added to be kept for 20-45 min, and when the temperature is reduced to 1100-1150 ℃ after the alloy is completely melted, the mixture is cast and molded.
In the present invention, the specifications of the main raw materials used are as follows: pure copper blocks, grade T1 or T2, with purity no less than 99.9 wt.%; the average particle size of the alumina ceramic particles is 10 nm-150 μm, preferably 10 nm-20 μm, and the purity is more than or equal to 99.9 wt.%; Cu-Cr intermediate alloy (preferably Cu-0.1Cr intermediate alloy) and Cu-Zr intermediate alloy (preferably Cu-0.1Zr intermediate alloy) are adopted, and auxiliary raw materials are composite salt covering agents. Cr, Zr and other elements are easy to burn in the air, and the metal burning rate in the smelting process is Cu 3%, Cr 10% and Zr 15%.
Al2O3Has high melting point (2054 ℃) and high boiling point (2980 ℃), ultrahigh thermal stability and mechanical strength, is a very important ceramic material and a very ideal reinforcement, is expected to improve the performance of the composite material when being added into the composite material, and has well-dispersed Al2O3The particles can not only improve the hardness of the copper-based composite material, but also reduce the grain growth rate of the copper-based composite material at the temperature close to the melting point, so the particles can be widely applied to the industrial fields of electronics, automobiles, aerospace (parts of rocket propellers and aircraft engines) and the like.
The invention has the beneficial technical effects that:
compared with the traditional strengthening mode, the preparation method of the invention adopts the preparation process method of the alumina ceramic particle reinforced high-strength high-conductivity copper alloy to strengthen the second phase, and the volume fraction, the scale and the dispersion degree of the strengthening phase are controllable. Compared with the Cu-Cr-Zr alloy material reinforced by the alumina-free ceramic particles, the tensile strength of the adopted alumina-ceramic particle reinforced high-strength high-conductivity Cu-Cr-Zr alloy material is more than 500MPa, the tensile strength of the material is improved by 15-25 percent compared with the tensile strength of the existing material, the elongation is more than 10 percent, and the electric conductivity is more than 70 percent IACS. Compared with the prior art, the mechanical property of the Cu-Cr-Zr alloy material is improved by adding the nano-micron alumina ceramic particles into the Cu-Cr-Zr alloy, and the conductivity is still excellent.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
The production process flow method comprises the following steps:
(1) preparing materials: taking pure copper (such as T1 or T2), Cu-Cr intermediate alloy, Cu-Zr intermediate alloy and alumina ceramic particles according to the mass ratio, wherein the average particle size is 10 nm-150 mu m (preferably 10 nm-20 mu m).
(2) Smelting: putting a pure copper block, a Cu-Cr intermediate alloy and alumina ceramic particles into a non-vacuum induction furnace, heating to 1200-1300 ℃, preserving heat for 1-1.5 h, cooling to 1150-1180 ℃, adding the Cu-Zr intermediate alloy, preserving heat for 20-45 min, cooling to 1100-1150 ℃ after the alloy is completely melted, and then casting and molding.
Example 1
The specific process comprises the following steps: the alumina ceramic particles were mixed according to the composition of Table 1 and had an average particle size of 10 nm.
TABLE 1 composition (wt.%) of a high strength and high conductivity copper alloy composite reinforced with alumina ceramic particles
Putting a pure copper block, a Cu-Cr intermediate alloy and alumina ceramic particles into a non-vacuum induction furnace, heating to 1200 ℃, preserving heat for 1.5h, cooling to 1180 ℃, adding the Cu-Zr intermediate alloy, preserving heat for 20min, cooling to 1150 ℃ after the alloy is completely melted, and then casting and molding. The properties of the finished product prepared are shown in table 2.
Table 2 example properties
Example 2
The specific process is as follows: the alumina particles were formulated according to the ingredients of Table 3 and had an average particle size of 20 μm.
TABLE 3 composition (wt.%) of a high strength and high conductivity copper alloy composite reinforced with alumina ceramic particles
Putting a pure copper block, a Cu-Cr intermediate alloy and alumina ceramic particles into a non-vacuum induction furnace, heating to 1300 ℃, preserving heat for 1h, then cooling to 1150 ℃, adding the Cu-Zr intermediate alloy, preserving heat for 45min, cooling to 1100 ℃ after the alloy is completely melted, and then casting and molding. The properties of the finished product prepared are shown in table 4.
Table 4 example properties
Example 3
The specific process is as follows: the alumina particles were formulated according to the ingredients of Table 5 and had an average particle size of 150 μm.
TABLE 5 composition (wt.%) of a high strength and high conductivity copper alloy composite reinforced with alumina ceramic particles
Putting the pure copper block, the Cu-Cr intermediate alloy and the alumina ceramic particles into a non-vacuum induction furnace, heating to 1250 ℃, preserving heat for 75min, then cooling to 1170 ℃, adding the Cu-Zr intermediate alloy, preserving heat for 35min, cooling to 1125 ℃ after the alloy is completely melted, and then casting and molding. The properties of the finished product prepared are shown in Table 6.
TABLE 6 examples Properties
According to the invention, the nano-sized and micron-sized alumina ceramic particles are added into Cu-Cr-Zr, so that the high-strength and high-conductivity copper alloy composite material with enhanced alumina ceramic particles can be obtained finally, wherein the high-strength and high-conductivity copper alloy composite material is matched with the mechanical property and the conductivity.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention. It should be noted that other equivalent modifications can be made by those skilled in the art in light of the teachings of the present invention, and all such modifications can be made as are within the scope of the present invention.
Claims (7)
1. The high-strength high-conductivity copper alloy composite material is characterized by comprising the following components in percentage by mass: 0.1 to 1.0% of chromium, 0.1 to 1.0% of zirconium, 0.05 to 1.5% of alumina ceramic particles, and the balance of copper and unavoidable impurities.
2. Composite material according to claim 1, characterised in that the mass percentage of the unavoidable impurities amounts to < 0.5%.
3. The composite material according to claim 1, wherein the alumina ceramic particles have an average particle size of 10nm to 150 μm.
4. The composite material according to claim 3, wherein the alumina ceramic particles have an average particle size of 10nm to 20 μm.
5. A method for preparing the high-strength high-conductivity copper alloy composite material as claimed in any one of claims 1 to 4, wherein the method comprises the following steps:
(1) preparing materials: taking pure Cu blocks, Cu-Cr intermediate alloy, Cu-Zr intermediate alloy and alumina ceramic particles as raw materials according to the mass ratio;
(2) smelting: smelting a pure copper block, alumina ceramic particles and a Cu-Cr intermediate alloy by using a non-vacuum induction furnace, wherein the pure copper block, the alumina ceramic particles and the Cu-Cr intermediate alloy are firstly heated to 1200-1300 ℃, are subjected to heat preservation for 1-1.5 h, are cooled to 1150-1180 ℃, are added with the Cu-Zr intermediate alloy, are subjected to heat preservation for 20-45 min, are cooled to 1100-1150 ℃ after the alloy is completely melted, and are then cast and molded.
6. The method of claim 5, wherein the raw materials are as follows: pure copper blocks, grade T1 or T2, with purity no less than 99.9 wt.%; the average particle size of the alumina ceramic particles is 10 nm-150 mu m, and the purity is more than or equal to 99.9 wt.%.
7. The method according to claim 6, wherein the alumina ceramic particles have an average particle size of 10nm to 20 μm.
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| CN202210408656.1A CN114752808A (en) | 2022-04-19 | 2022-04-19 | High-strength high-conductivity copper alloy composite material and preparation method thereof |
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| CN202210408656.1A CN114752808A (en) | 2022-04-19 | 2022-04-19 | High-strength high-conductivity copper alloy composite material and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116024450A (en) * | 2023-02-17 | 2023-04-28 | 有研工程技术研究院有限公司 | Nb-containing aluminum alloy grain refiner and preparation method thereof |
| CN116144972A (en) * | 2023-02-03 | 2023-05-23 | 有研工程技术研究院有限公司 | Damping copper alloy material and preparation method thereof |
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