CN113718128B - Copper-chromium-zirconium alloy and preparation method thereof - Google Patents
Copper-chromium-zirconium alloy and preparation method thereof Download PDFInfo
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
- B21C1/00—Manufacture of metal sheets, metal wire, metal rods, metal tubes by drawing
- B21C1/02—Drawing metal wire or like flexible metallic material by drawing machines or apparatus in which the drawing action is effected by drums
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/001—Continuous casting of metals, i.e. casting in indefinite lengths of specific alloys
- B22D11/004—Copper alloys
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/005—Continuous casting of metals, i.e. casting in indefinite lengths of wire
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/06—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of rods or wires
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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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- 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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
Abstract
The invention discloses a copper-chromium-zirconium alloy which is characterized by comprising the following components in percentage by mass: cr: 0.3 to 0.5 wt%, Zr: 0.03-0.05 wt%, Ni: 0.04-0.08 wt%, Si: 0.01 to 0.02 wt%, Fe: 0.01 to 0.02 wt%, and the balance of Cu and unavoidable impurities. According to the invention, Cr, Zr, Ni, Si and Fe are added into the copper alloy, the respective addition amounts are controlled, the Cr and Zr enhance the strength of a matrix and simultaneously improve the high-temperature softening resistance of the material, the Ni and Si do not affect the conductivity of the matrix obviously while improving the strength of the matrix, a trace amount of Fe element refines the crystal grains of the matrix and improves the strength of the material, and the elements cooperate with each other to realize that the conductivity of the copper-chromium-zirconium alloy is 90-95% IACS, and the hardness is HRB 75-78. The strength and the conductivity of the aluminum plate can meet the requirement of passing of large current, and the aluminum plate is wear-resistant, long in service life and suitable for the aluminum plate resistance spot welding industry.
Description
Technical Field
The invention belongs to the technical field of copper alloy, and particularly relates to a copper-chromium-zirconium alloy and a preparation method thereof.
Background
Compared with the traditional steel, the aluminum alloy has the advantages of low density, high specific strength, corrosion resistance, good formability, easiness in recycling and the like, and becomes the most used material in a plurality of light-weight alternative materials.
In the production of motor vehicles, the assembly of different components is involved, most commonly resistance spot welding. Resistance spot welding is a method of welding different workpieces by joining them, applying pressure to them by electrodes, and using resistance heat generated by electric current passing through contact surfaces and adjacent areas. Because the aluminum alloy has higher electrical conductivity and thermal conductivity, the required welding current and electrode pressure are generally 3 times and 2 times of those of the traditional steel plate spot welding, the self heat productivity of the electrode is increased due to the large current required by welding, and the electrode is easily softened and abraded due to the high pressure, so that the service life of the electrode is only about 1/4 of that of the traditional steel plate during welding.
At present, the materials actually used for the preparation of electrode caps are mainly chromium zirconium copper (C18150) and zirconium copper (C15000). The conductivity of the C18150 is generally 80% IACS, the hardness HRB is about 80, and the alloy is widely applied to the field of traditional steel plate welding, but when an aluminum plate is welded, the alloy is easy to generate heat and soften due to large current and high self-resistance, so that the service life is short. Compared with C18150, C15000 has a conductivity of 90% IACS, but has a hardness HRB of only about 65, and although its self-resistance is low, its low hardness is susceptible to wear during welding and has a short service life.
In the expected future, the demand of high-service-life copper materials in the aluminum plate resistance spot welding industry is increasing, and the materials in the current market cannot meet the demands of downstream customers. Therefore, it is urgent to develop a copper alloy bar suitable for resistance spot welding of aluminum plates.
Disclosure of Invention
The invention aims to solve the first technical problem of providing a copper chromium zirconium alloy with high hardness and high conductive combination.
The technical scheme adopted by the invention for solving the first technical problem is as follows: the copper chromium zirconium alloy is characterized by comprising the following components in percentage by mass: cr: 0.3 to 0.5 wt%, Zr: 0.03-0.05 wt%, Ni: 0.04-0.08 wt%, Si: 0.01-0.02 wt%, Fe: 0.01 to 0.02 wt%, and the balance of Cu and unavoidable impurities.
Pure copper has high conductivity (> 99% IACS) but low hardness (hard state HRB45 or so) and is used as a copper alloyThe electrode material has a short service life. If an appropriate amount of Cr or Zr, for example, C18200 (Cr: 0.6-1.2 wt%), C15000 (Zr: 0.1-0.2 wt%), C18150 (Cr: 0.5-1.5 wt%, Zr: 0.05-0.25 wt%) is added to pure copper, Cr or Cu is formed in the copper matrix by solution, cold working and aging treatment 3Zr and the like precipitate, the electric conductivity can reach 75-90% IACS, the hardness HRB can reach 65-80, the electric conductivity of a sacrificial part is improved, and the electrode material is still low in service life when used for welding an aluminum plate. This is because the conductivity and the hardness are in reciprocal relation, that is, the material with high conductivity corresponds to lower hardness, and the material with high hardness corresponds to lower conductivity, for example, the conductivity of C15000 can reach 90% IACS, but the hardness HRB is only about 65; the hardness HRB of the C18150 can reach about 80, but the conductivity is only 80% IACS. As an electrode material for welding an aluminum plate, the electrode material firstly needs to have higher conductivity and higher hardness so as to achieve the service life when a steel plate is welded.
The inventor finds that the addition of Cr: 0.3 to 0.5 wt%, Zr: 0.03-0.05 wt%, and then obtaining higher conductivity and hardness through solution treatment, cold working and aging treatment, wherein compared with materials such as C18200 (Cr: 0.6-1.2 wt%), C15000 (Zr: 0.1-0.2 wt%), C18150 (Cr: 0.5-1.5 wt%, Zr: 0.05-0.25 wt%), the contents of Cr and Zr designed by the inventor are lower, and Cr and Cu precipitated after solution treatment, cold working and aging treatment are lower 3The Zr quantity is relatively lower, so the scattering ability to the electron is lower, and the conductivity is above 95% IACS. And adding a trace amount of Ni: 0.04-0.08 wt%, Si: 0.01-0.02 wt%, and a trace amount of NiSi phase can be generated in the matrix after heat treatment, and the ratio of the NiSi phase to the Fe phase is as follows: 0.01 to 0.02 wt% of the material, and the hardness HRB of the material can reach 75 to 78. The effect generated by the coupling of the elements enables the material to achieve the performances of 90-95% of electrical conductivity IACS and HRB 75-78 hardness, the hardness is improved as much as possible while the electrical conductivity is sacrificed, and the material has high electrical conductivity and hardness and is suitable for preparing electrode materials for welding aluminum plates.
Preferably, the mass addition ratio of Cr to Zr is 8-15: 1; n is a radical of hydrogeni. The mass addition ratio of Si is 3-5: 1. the Cr and the Zr can improve the strength of the material, but have the main effect of improving the high-temperature softening resistance of the material, but the Zr has a large influence on the conductivity, so the mass addition ratio of the Cr to the Zr is controlled to be 8-15. The mass addition ratio of Ni to Si is 3-5: 1, the ratio of Ni and Si can be changed to Ni by appropriate heat treatment2Si is precipitated in a form, the hardness of the material is improved, and meanwhile, the problem that the conductivity of the material is reduced because Ni and Si are dissolved in a copper matrix in a solid solution mode is avoided.
Preferably, the grain size of the copper chromium zirconium alloy is 0.005-0.020 mm. The grain size is beneficial to improving the strength of the material and simultaneously does not influence the conductivity of the material.
Preferably, the copper-chromium-zirconium alloy has an electrical conductivity of 90 to 95% IACS and a hardness of HRB75 to 78. The strength and the conductivity of the alloy not only meet the passing of large current, but also are wear-resistant and have long service life.
The second technical problem to be solved by the invention is to provide a preparation method of the copper-chromium-zirconium alloy.
The technical scheme adopted by the invention for solving the second technical problem is as follows: the preparation method of the copper-chromium-zirconium alloy is characterized in that the process flow comprises continuous casting → first cold deformation → recrystallization heat treatment → second cold deformation → solution treatment → third cold deformation → aging → finished product cold deformation.
The invention adopts continuous casting production to realize continuous production, has high efficiency, high yield and low cost, but the microstructure of the continuous casting material is thick columnar crystal with the grain size of about 0.200mm, and is not suitable for processing and preparing electrode products. Cold working and recrystallization before solid solution cause the coarse structure to be broken, and then relatively fine isometric crystals are formed, so that the finished product is fine crystal grains.
Preferably, the deformation rate of the first cold deformation is 30-40%, the temperature of the recrystallization heat treatment is controlled to be 800-900 ℃, and the heat preservation time is 1-5 hours.
Preferably, the deformation rate of the second cold deformation is 25-40%, the temperature of the solution treatment is controlled to be 940-980 ℃, and the heat preservation time is 0.5-1.5 h.
Preferably, the deformation rate of the third cold deformation is 25-35%, the aging temperature is controlled at 400-500 ℃, and the heat preservation time is 1-7 h.
Preferably, the deformation rate of the cold deformation of the finished product is 5-15%.
Preferably, the process of the first cold deformation → the recrystallization heat treatment is repeated for 1 to 3 times according to different wire blank specifications in order to further improve the hardness of the material and refine the structure of the material.
Compared with the prior art, the invention has the advantages that:
1) according to the invention, Cr, Zr, Ni, Si and Fe are added into the copper alloy, the respective addition amounts are controlled, the Cr and Zr enhance the strength of a matrix and simultaneously improve the high-temperature softening resistance of the material, the Ni and Si do not affect the conductivity of the matrix obviously while improving the strength of the matrix, a trace amount of Fe element refines the crystal grains of the matrix and improves the strength of the material, and the elements cooperate with each other to realize that the conductivity of the copper-chromium-zirconium alloy is 90-95% IACS, and the hardness is HRB 75-78. The strength and the conductivity of the aluminum plate can meet the requirement of passing of large current, and the aluminum plate is wear-resistant, long in service life and suitable for the aluminum plate resistance spot welding industry.
2) The technological process of the copper-chromium-zirconium alloy comprises continuous casting → first cold deformation → recrystallization heat treatment → second cold deformation → solution treatment → third cold deformation → aging → finished product cold deformation. The ingot is continuously cast, coarse structures in the ingot are crushed through cold machining and recrystallization before solid solution, then fine isometric crystals are formed, the finished product is fine crystal grains, the grain size is below 0.02mm, continuous production is realized, the efficiency is high, the yield is high, and the cost is low.
Drawings
FIG. 1 is a metallographic photograph showing a photograph taken in example 1 of the present invention.
Detailed Description
The invention is described in further detail below with reference to the following examples of the drawings.
The invention provides 3 examples and 2 comparative examples, the specific compositions of which are shown in Table 1.
Example 1
The preparation method of the copper-chromium-zirconium alloy comprises the following steps:
step 1: the copper alloy wire blank is prepared by a continuous casting method, and the diameter of the wire blank is 35 mm.
And 2, step: first cold deformation: carrying out drawing processing with 36% deformation on the copper alloy wire blank obtained in the step 1;
and step 3: carrying out recrystallization annealing on the wire blank subjected to cold machining in the step 2, controlling the temperature at 800 ℃, and keeping the temperature for 5 hours;
and 4, step 4: repeating the step 2;
And 5: repeating the step 3;
and 6: and (3) cold deformation for the second time: drawing the wire blank subjected to recrystallization annealing in the step 5 by 30% of deformation;
and 7: carrying out solid solution treatment on the wire blank subjected to cold machining in the step 6, controlling the solid solution temperature at 940 ℃, and keeping the temperature for 1.5 h;
and 8: and (3) cold deformation for the third time: cold working the wire blank subjected to solid solution in the step 7 by 30% of deformation;
and step 9: carrying out aging treatment on the cold-processed wire blank in the step 8, controlling the aging temperature at 450 ℃, and keeping the temperature for 5 hours;
step 10: and (3) cold deformation of a finished product: and (4) drawing the wire blank aged in the step (9) to the specification of a finished product by 12% of deformation.
Example 2
The preparation method of the copper-chromium-zirconium alloy comprises the following steps:
step 1: the copper alloy wire blank is prepared by a continuous casting method, and the diameter of the wire blank is 30 mm.
Step 2: first cold deformation: drawing the copper alloy wire blank obtained in the step 1 by 30% of deformation;
and step 3: carrying out recrystallization annealing on the wire blank subjected to cold machining in the step 2, controlling the temperature at 900 ℃, and keeping the temperature for 1 h;
and 4, step 4: repeating the step 2;
and 5: repeating the step 3;
step 6: and (3) cold deformation for the second time: drawing the wire blank subjected to recrystallization annealing in the step 5 by 36% of deformation;
And 7: carrying out solution treatment on the cold-processed wire blank in the step 6, controlling the solution temperature at 980 ℃ and keeping the temperature for 0.5 h;
and step 8: and (3) cold deformation for the third time: cold working with 25% deformation is carried out on the wire blank subjected to solid solution in the step 7;
and step 9: carrying out aging treatment on the cold-processed wire blank in the step 8, controlling the aging temperature to be 485 ℃, and keeping the temperature for 3 hours;
step 10: and (3) cold deformation of a finished product: and (4) drawing the wire blank aged in the step (9) by 7% of deformation to reach the specification of a finished product.
Example 3
The preparation method of the copper-chromium-zirconium alloy comprises the following steps:
step 1: the copper alloy wire blank is prepared by a continuous casting method, and the diameter of the wire blank is 25 mm.
Step 2: first cold deformation: drawing the copper alloy wire blank obtained in the step 1 by 30% of deformation;
and step 3: carrying out recrystallization annealing on the wire blank subjected to cold machining in the step 2, controlling the temperature at 840 ℃, and keeping the temperature for 4 hours;
and 4, step 4: and (3) cold deformation for the second time: drawing the wire blank subjected to recrystallization annealing in the step 3 by 32% of deformation;
and 5: carrying out solid solution treatment on the wire blank subjected to cold machining in the step 4, controlling the solid solution temperature to be 960 ℃, and keeping the temperature for 1 h;
step 6: and (3) cold deformation for the third time: cold working the wire blank subjected to solid solution in the step 5 by 32% of deformation;
And 7: carrying out aging treatment on the cold-processed wire blank in the step 6, controlling the aging temperature at 500 ℃, and keeping the temperature for 1 h;
and step 8: and (3) cold deformation of a finished product: and (4) drawing the wire blank aged in the step (7) by 9% of deformation to reach the specification of a finished product.
Examples and comparative examples were tested for hardness, conductivity, softening temperature and service life.
Hardness: according to GB/T230.1-2018 part 1 of Rockwell hardness test of metal materials: test methods ″.
Conductivity: and (3) testing according to the standard of GB/T351-2019 'measuring method of metal material resistivity'.
Softening temperature: the method is used for testing according to the standard of GB/T33370-2016 method for measuring the softening temperature of copper and copper alloy.
Electrode life: in order to evaluate the life of the material when used for welding aluminum plates, the material was processed into an electrode cap, and the aluminum plates were welded under the same welding parameters, with the critical point when the welding strength decreased to 80% of the initial point, and the number counted at this time as the electrode life. The welding parameters are as follows: the thickness of the aluminum plate is 1mm, the welding time is 3s, the welding current is 20KA, and the loading pressure is 5 KN.
TABLE 1 Components of inventive and comparative examples
TABLE 2 Properties of the materials of the examples of the invention and of the comparative examples
Claims (7)
1. The preparation method of the copper chromium zirconium alloy is characterized in that the copper chromium zirconium alloy comprises the following components in percentage by mass: cr: 0.3 to 0.5 wt%, Zr: 0.03-0.05 wt%, Ni: 0.04-0.08 wt%, Si: 0.01 to 0.02 wt%, Fe: 0.01 to 0.02 wt%, and the balance of Cu and unavoidable impurities; the process flow comprises continuous casting → first cold deformation → recrystallization heat treatment → second cold deformation → solution treatment → third cold deformation → aging → finished product cold deformation; the deformation rate of the first cold deformation is 30-40%, the temperature of the recrystallization heat treatment is controlled to be 800-900 ℃, and the heat preservation time is 1-5 hours; the copper chromium zirconium alloy has the electric conductivity of 90-95% IACS and the hardness of HRB 75-78.
2. The method of claim 1, wherein the method comprises: the mass addition ratio of Cr to Zr is 8-15: 1; the mass addition ratio of Ni to Si is 3-5: 1.
3. the method of claim 1, wherein the method comprises: the grain size of the copper-chromium-zirconium alloy is 0.005-0.020 mm.
4. The method of claim 1, wherein the method comprises: the deformation rate of the second cold deformation is 25-40%, the temperature of the solution treatment is controlled to be 940-980 ℃, and the heat preservation time is 0.5-1.5 h.
5. The method for preparing a copper-chromium-zirconium alloy according to claim 1, wherein: the deformation rate of the third cold deformation is 25-35%, the aging temperature is controlled to be 400-500 ℃, and the heat preservation time is 1-7 h.
6. The method for preparing a copper-chromium-zirconium alloy according to claim 1, wherein: the deformation rate of the finished product in cold deformation is 5-15%.
7. The method for preparing a copper-chromium-zirconium alloy according to claim 1, wherein: and repeating the processes of the first cold deformation → the recrystallization heat treatment for 1 to 3 times according to different specifications of the wire blank.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63149344A (en) * | 1986-12-12 | 1988-06-22 | Nippon Mining Co Ltd | High strength copper alloy having high electrical conductivity |
| JPH09291323A (en) * | 1996-04-26 | 1997-11-11 | Nikko Kinzoku Kk | Metallic substrate material for semiconductor packaging |
| CN103695825A (en) * | 2013-12-31 | 2014-04-02 | 上海电缆研究所 | Preparation method of high-conductivity high-strength copper chromium zirconium alloy thin line conductor |
| CN111519116A (en) * | 2020-04-23 | 2020-08-11 | 宁波金田铜业(集团)股份有限公司 | Preparation method of large-length solderless copper-chromium-zirconium contact line |
| CN112981170A (en) * | 2021-02-05 | 2021-06-18 | 宁波金田铜业(集团)股份有限公司 | Chromium-zirconium-copper alloy for cold heading and preparation method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63149344A (en) * | 1986-12-12 | 1988-06-22 | Nippon Mining Co Ltd | High strength copper alloy having high electrical conductivity |
| JPH09291323A (en) * | 1996-04-26 | 1997-11-11 | Nikko Kinzoku Kk | Metallic substrate material for semiconductor packaging |
| CN103695825A (en) * | 2013-12-31 | 2014-04-02 | 上海电缆研究所 | Preparation method of high-conductivity high-strength copper chromium zirconium alloy thin line conductor |
| CN111519116A (en) * | 2020-04-23 | 2020-08-11 | 宁波金田铜业(集团)股份有限公司 | Preparation method of large-length solderless copper-chromium-zirconium contact line |
| CN112981170A (en) * | 2021-02-05 | 2021-06-18 | 宁波金田铜业(集团)股份有限公司 | Chromium-zirconium-copper alloy for cold heading and preparation method thereof |
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