CN115233031B - High-performance copper alloy and preparation method thereof - Google Patents
High-performance copper alloy and preparation method thereof Download PDFInfo
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- CN115233031B CN115233031B CN202211003954.9A CN202211003954A CN115233031B CN 115233031 B CN115233031 B CN 115233031B CN 202211003954 A CN202211003954 A CN 202211003954A CN 115233031 B CN115233031 B CN 115233031B
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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
- C22C9/04—Alloys based on copper with zinc as the next major constituent
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- 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
- C22C1/02—Making non-ferrous alloys by melting
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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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Abstract
The invention provides a high-performance copper alloy and a preparation method thereof, belonging to the field of metal material preparation. According to the high-performance copper alloy provided by the invention, the performance of a copper matrix can be similar to that of brass by adding Zn, and precipitated phase particles can be formed in the copper matrix by adding Ni and Si as reinforcing elements, so that the mechanical property of the copper alloy is effectively reinforced and the copper alloy is ensured to have higher conductivity; in addition, the adverse effect of Fe and Pb on the copper alloy can be reduced as much as possible by controlling the contents of Fe and Pb, so that the improvement of the performance of the copper alloy by other strengthening elements is effectively ensured. The results of the examples show that the tensile strength of the copper alloy prepared by the invention can reach 586 to 707MPa, the yield strength can reach 479 to 604MPa, and the electric conductivity can reach 21 to 24 percent IACS.
Description
The application is a divisional application with the application date of 2021, 09/07, and the application number of 202111041817.X, the invention name of a high-performance copper alloy and a preparation method thereof.
Technical Field
The invention relates to the field of metal material preparation, in particular to a high-performance copper alloy and a preparation method thereof.
Background
Brass is one of the most important copper alloy varieties, has high mechanical properties, has the inherent characteristics of electric conduction, heat conduction, easy processing and the like of copper alloy, is relatively cheap and low in production cost, so that the copper alloy with the largest use amount in various fields in China is widely used for heat exchangers, valves, drainage pipelines, radiators, important parts in ships, chemical machinery and electrical instruments, connectors and fittings of electronic and telecommunication equipment and household appliances, interior decoration, clothing ornaments, water tanks for vehicles, batteries and the like.
Among them, H65 brass is one of the most representative ones. However, with the rapid development of the electronic, electrical and power industries, the demand of brass with both excellent mechanical properties and electrical conductivity has increased greatly year by year. Therefore, the existing H65 brass in China cannot meet the higher use requirement of the connector in the field of electric power and electric appliances in the aspects of high strength, high plasticity and good conductivity. The H65 brass is a solid solution alloy, wherein a zinc element is used as a solid solution atom to form an alpha solid solution alloy with a copper base, the H65 brass is adversely affected by reducing or increasing the zinc element, and a precipitated phase is easily formed by adding other alloy elements, so that the brittleness and the mechanical property of the H65 brass are increased, and the electrical conductivity of the H65 brass is greatly reduced.
Therefore, how to balance the mechanical property and the electrical conductivity of the brass to obtain high-performance brass with excellent comprehensive performance becomes a difficult problem to be solved in the prior art.
Disclosure of Invention
The invention aims to provide a high-performance copper alloy and a preparation method thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a high-performance copper alloy which comprises the following components in percentage by mass: zn27.5-29.3%, ni0.08-1.4%, si0.02-0.25%, fe <0.08%, pb <0.06% and the balance Cu; the mass ratio of the Ni to the Si is (4.2-5.8): 1;
the preparation method of the high-performance copper alloy comprises the following steps:
(1) Smelting and casting alloy raw materials in sequence to obtain a casting material;
(2) Sequentially rolling, annealing, solution treatment and aging treatment the cast material obtained in the step (1) to obtain a high-performance copper alloy;
the temperature of the annealing treatment in the step (2) is 280-320 ℃, and the time of the annealing treatment is 60-100 min;
the temperature of the solution treatment in the step (2) is 680-720 ℃, and the time of the solution treatment is 570-630 min;
the temperature of the aging treatment in the step (2) is 390-410 ℃, and the time of the aging treatment is 150-210 min.
Preferably, the paint comprises the following components in percentage by mass: zn28.0-29.0%, ni0.1-1.3%, si0.03-0.2%, fe <0.05%, pb <0.05% and the balance of Cu; the mass ratio of the Ni to the Si is (4.3-5.7): 1.
preferably, the paint comprises the following components in percentage by mass: zn28.3-28.8%, ni0.2-1.1%, si0.04-0.15%, fe <0.03%, pb <0.03% and Cu in balance; the mass ratio of Ni to Si is (4.5-5.5): 1.
the invention also provides a preparation method of the high-performance copper alloy, which comprises the following steps:
(1) Smelting and casting alloy raw materials in sequence to obtain a casting material;
(2) Sequentially carrying out rolling, annealing treatment, solid solution treatment and aging treatment on the cast material obtained in the step (1) to obtain a high-performance copper alloy;
the temperature of the annealing treatment in the step (2) is 280-320 ℃, and the time of the annealing treatment is 60-100 min;
the temperature of the solution treatment in the step (2) is 680-720 ℃, and the time of the solution treatment is 570-630 min;
the temperature of the aging treatment in the step (2) is 390-410 ℃, and the time of the aging treatment is 150-210 min.
Preferably, the heat preservation temperature of the smelting in the step (1) is 1100-1200 ℃, and the heat preservation time of the smelting is 7-15 min.
Preferably, the rolling temperature in the step (2) is 720-880 ℃, the rolling passes are 7-14, the single-pass deformation amount of the rolling is 4-10%, and the total deformation amount of the rolling is 50-90%.
The invention provides a high-performance copper alloy which comprises the following components in percentage by mass: zn27.32 to 29.9 percent, ni0.06 to 1.5 percent, si0.01 to 0.3 percent, fe <0.1 percent, pb <0.08 percent and the balance of Cu; the mass ratio of the Ni to the Si is (4-6): 1. according to the invention, zn is added to enable the copper matrix to obtain the performance similar to that of brass, and meanwhile, ni and Si are added as strengthening elements to form precipitated phase particles in the copper matrix, so that the mechanical property of the copper alloy is effectively strengthened and the copper alloy is ensured to have higher conductivity; in addition, the adverse effect of Fe and Pb on the copper alloy can be reduced as much as possible by controlling the contents of Fe and Pb, so that the improvement of the performance of the copper alloy by other strengthening elements is effectively ensured. The results of the examples show that the copper alloy produced by the present invention can achieve a tensile strength of 586 to 707MPa, a yield strength of 479 to 604MPa, and an electric conductivity of 21 to 24% IACS.
Detailed Description
The invention provides a high-performance copper alloy which comprises the following components in percentage by mass: zn27.32-29.9%, ni0.06-1.5%, si0.01-0.3%, fe <0.1%, pb <0.08% and the balance of Cu;
the mass ratio of the Ni to the Si is (4-6): 1.
the high-performance copper alloy provided by the invention comprises 27.32-29.9% of Zn by mass, preferably 27.5-29.3%, more preferably 28.0-29.0%, and most preferably 28.3-28.8%. According to the invention, the performance of the copper matrix is similar to that of brass by adding Zn, and meanwhile, the Zn content is controlled within the range, so that the copper matrix has good plasticity, and the brittleness of the copper matrix is reduced, thereby being more beneficial to improving the mechanical property of the copper matrix through plastic deformation such as rolling and the like and being not easy to crack.
The high-performance copper alloy provided by the invention comprises 0.06-1.5% of Ni, preferably 0.08-1.4%, more preferably 0.1-1.3%, and most preferably 0.2-1.1% by mass. According to the invention, by adding Ni element and controlling the content of the Ni element within the range, part of Ni can be dissolved in the copper matrix in a solid mode, and meanwhile, part of Ni can be combined with other alloying elements to form fine and uniformly distributed precipitated phase particles in the copper-nickel-tin alloy, so that the mechanical property of the copper alloy is effectively enhanced.
The high-performance copper alloy provided by the invention comprises 0.01-0.3% of Si, preferably 0.02-0.25%, more preferably 0.03-0.2%, and most preferably 0.04-0.15% by mass. According to the invention, by adding the Si element and controlling the content of the Si element within the range, the Si element and the Ni can be combined to form precipitated phase particles, so that the mechanical property of the copper alloy is effectively enhanced and the copper alloy is ensured to have higher conductivity.
In the present invention, the mass ratio of Ni to Si is (4 to 6): 1, preferably (4.2 to 5.8): 1, more preferably (4.3 to 5.7): 1, most preferably (4.5 to 5.5): 1. by controlling the addition ratio of Ni and Si within the range, the intermetallic compound of Ni and Si can be formed in the copper matrix and uniformly precipitated in the copper matrix in a precipitated phase form, so that the mechanical property of the copper alloy is effectively enhanced and the high conductivity of the copper alloy is ensured.
The high performance copper alloy provided by the present invention comprises, in mass%, fe <0.1%, preferably <0.06%, more preferably <0.05%, most preferably <0.03%. In the present invention, the Fe is present as an impurity in the high performance copper alloy. According to the invention, the content of Fe is controlled within the range, so that the adverse effect of Fe on the copper alloy can be reduced as much as possible, and the improvement of other strengthening elements on the performance of the copper alloy is effectively ensured.
The high performance copper alloy provided by the present invention comprises <0.08% Pb, preferably <0.08%, more preferably <0.05%, most preferably <0.03% by mass. In the present invention, the Pb exists as an impurity in the high-performance copper alloy. By controlling the content of Pb within the range, the adverse effect of Pb on the copper alloy can be reduced as much as possible, so that the improvement of the performance of the copper alloy by other strengthening elements is effectively ensured.
According to the mass percentage, the high-performance copper alloy provided by the invention comprises the balance of copper. According to the invention, copper is taken as a matrix, zn, ni and Si strengthening elements are added, and the contents of Fe and Pb are controlled, so that the strength and the conductivity of the copper matrix can be effectively improved.
The high-performance copper alloy provided by the invention can effectively improve the strength and the conductivity of a copper matrix by adding Zn, ni and Si strengthening elements, controlling the addition ratio of Ni and Si and controlling the contents of Fe and Pb.
The invention also provides a preparation method of the high-performance copper alloy, which comprises the following steps:
(1) Smelting and casting alloy raw materials in sequence to obtain a casting material;
(2) And (2) sequentially carrying out rolling, annealing treatment, solution treatment and aging treatment on the cast material obtained in the step (1) to obtain the high-performance copper alloy.
The invention carries out smelting and casting on alloy raw materials in sequence to obtain a casting material.
In the present invention, the alloy raw material is preferably electrolytic copper, pure zinc, pure nickel and pure silicon. In the invention, the purities of the electrolytic copper, the pure zinc, the pure nickel and the pure silicon are preferably more than or equal to 99.99%.
In the present invention, the temperature of the melting is preferably 1500 to 1600 ℃, more preferably 1550 to 1600 ℃. The invention is more beneficial to quickly melting all the raw materials to form a melt by smelting at a higher temperature, and avoids the problems of oxidation, burning loss and the like caused by long-time semi-melting state of all the raw materials.
In the invention, the heat preservation temperature of the smelting is preferably 1100-1200 ℃, more preferably 1130-1180 ℃, and most preferably 1150-1160 ℃; the heat preservation time for the smelting is preferably 7-15 min, more preferably 9-13 min, and most preferably 10-12 min. The invention can fully and uniformly diffuse each alloy element in the melt by keeping the temperature at the lower temperature than the melting temperature and controlling the temperature and the time in the above range, thereby being more beneficial to reducing element segregation and obtaining casting materials with uniform components.
In the present invention, the casting method is preferably horizontal continuous casting, semi-continuous casting or die casting, more preferably die casting.
After the cast material is obtained, the high-performance copper alloy is obtained by sequentially carrying out rolling, annealing treatment, solid solution treatment and aging treatment on the cast material.
In the invention, the rolling temperature is preferably 720-880 ℃, and more preferably 780-820 ℃; the rolling passes are preferably 7 to 14 times, and more preferably 9 to 12 times; the single-pass deformation of the rolling is preferably 4 to 10 percent, and more preferably 6 to 8 percent; the total deformation of the rolling is preferably 50 to 90%, more preferably 65 to 75%. According to the invention, by controlling the rolling temperature, the rolling pass, the single-pass deformation and the total deformation, the casting defects such as shrinkage porosity and shrinkage cavity in the cast material can be effectively closed, and the conductivity of the copper alloy is effectively improved; meanwhile, more dislocation is obtained in the cast material structure through rolling deformation, crystal grains are refined, the problem that the copper alloy is easy to coarsen through subsequent continuous heat treatment is avoided, and therefore the mechanical property of the copper alloy is effectively improved.
In the invention, the temperature of the annealing treatment is preferably 200-400 ℃, more preferably 230-360 ℃, and most preferably 280-320 ℃; the time of the annealing treatment is preferably 30 to 150min, more preferably 40 to 120min, and most preferably 60 to 100min. According to the invention, through annealing treatment and controlling the temperature and time within the range, the structural stress during rolling deformation can be effectively eliminated, the size of the copper alloy is stabilized, the structure is more uniform, and the mechanical property of the copper alloy is improved.
In the present invention, the cooling method of the annealing treatment is preferably air cooling.
In the present invention, the temperature of the solution treatment is preferably 620 to 780 ℃, more preferably 680 to 720 ℃; the time for the solution treatment is preferably 510 to 690min, and more preferably 570 to 630min. According to the invention, through solution treatment and temperature control within the range, all strengthening elements can be fully dissolved in the copper matrix in a solid manner, so that a uniform supersaturated solid solution structure is formed, and the subsequent aging treatment is more favorable for precipitating fine precipitated phases, so that the strength of the copper alloy is enhanced and the copper alloy has higher conductivity.
In the present invention, the solution treatment is preferably performed by water cooling.
In the invention, the temperature of the aging treatment is preferably 370-430 ℃, and more preferably 390-410 ℃; the time for the aging treatment is preferably 150 to 210min, and more preferably 170 to 190min. According to the invention, through aging treatment and controlling the temperature and time within the range, the strengthening elements in the supersaturated solid solution can form fine and uniformly distributed precipitated phase particles, so that the strength of the copper alloy is effectively enhanced and the copper alloy has high conductivity.
In the present invention, the cooling method of the aging treatment is preferably air cooling.
According to the preparation method of the high-performance copper alloy, uniform and fine precipitated phase particles are more favorably precipitated through a heat treatment mode of rolling, annealing, solid solution and aging after smelting and casting, so that the mechanical property of the copper alloy is effectively enhanced, and the copper alloy has high conductivity; meanwhile, the preparation method is simple and easy to control, safe, effective and low in cost.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The high-performance copper alloy prepared in the embodiment comprises the following components in percentage by mass: zn27.8%, ni0.52%, si0.01%, fe0.05%, pb0.05% and the balance of Cu; the mass ratio of Ni to Si is 4.7:1.
the preparation method of the high-performance copper-nickel-tin alloy comprises the following steps:
(1) Adding alloy raw materials of electrolytic copper, pure nickel and pure silicon with the purity of more than or equal to 99.99 percent, and smelting and casting in sequence to obtain a cast material; wherein the smelting temperature is 1600 ℃, the heat preservation temperature is 1150 ℃, the heat preservation time is 13min, and the casting adopts horizontal continuous casting.
(2) Rolling the cast ingot obtained in the step (1) at 790 ℃ in sequence, wherein the rolling pass is 10, the single-pass deformation is 7%, and the total deformation is 70%; and after rolling, carrying out homogenizing annealing at 310 ℃ for 90min, cooling at room temperature, carrying out solution treatment at 710 ℃ for 570min, cooling with water, carrying out aging treatment at 410 ℃ for 210min, and cooling at room temperature to obtain the high-performance copper alloy.
Example 2
The high-performance copper alloy prepared in the embodiment comprises the following components in percentage by mass: zn28.4%, ni0.8%, si0.16%, fe0.05%, pb0.04% and the balance of Cu; the mass ratio of Ni to Si is 5.0:1.
the preparation method of the high-performance copper-nickel-tin alloy comprises the following steps:
(1) Sequentially adding alloy raw materials of electrolytic copper, pure nickel and pure silicon with the purity of more than or equal to 99.99 percent, and sequentially smelting and casting to obtain a casting material; wherein the smelting temperature is 1600 ℃, the heat preservation temperature is 1160 ℃, the heat preservation time is 11min, and the casting adopts semi-continuous casting.
(2) Sequentially rolling the cast ingot obtained in the step (1) at 820 ℃, wherein the rolling pass is 8, the single-pass deformation is 10%, and the total deformation is 80%; and after rolling, carrying out homogenizing annealing at 310 ℃ for 70min, cooling at room temperature, carrying out solution treatment at 710 ℃ for 630min, cooling with water, carrying out aging treatment at 390 ℃ for 170min, and cooling at room temperature to obtain the high-performance copper alloy.
Example 3
The high-performance copper alloy prepared in the embodiment comprises the following components in percentage by mass: zn28.7%, ni1.3%, si0.3%, fe0.04%, pb0.04% and the balance of Cu; the mass ratio of Ni to Si is 4.3:1.
the preparation method of the high-performance copper-nickel-tin alloy comprises the following steps:
(1) Sequentially adding alloy raw materials of electrolytic copper, pure nickel and pure silicon with the purity of more than or equal to 99.99 percent, and sequentially smelting and casting to obtain a casting material; wherein the smelting temperature is 1600 ℃, the heat preservation temperature is 1160 ℃, the heat preservation time is 11min, and the casting adopts die casting.
(2) Rolling the cast ingot obtained in the step (1) at 800 ℃ in sequence, wherein the rolling pass is 10, the single-pass deformation is 7%, and the total deformation is 70%; and after rolling, carrying out homogenizing annealing at 300 ℃ for 60min, cooling at room temperature, carrying out solution treatment at 700 ℃ for 600min, cooling with water, carrying out aging treatment at 400 ℃ for 120min, and cooling at room temperature to obtain the high-performance copper alloy.
Comparative example 1
A commercially available conventional H65 brass was used as the copper alloy sample of comparative example 1.
Performance detection
The copper alloys prepared in examples 1 to 3 and comparative example 1 were tested for yield strength and tensile strength, the test standard adopted the GB/T228.1-2010 metal material tensile test, and the test results are shown in table 1.
The copper alloys prepared in examples 1 to 3 and comparative example 1 were tested for conductivity according to the test method of GBT11007-2008 conductivity meter, and the test results are shown in table 1.
Table 1 test results of yield strength, tensile strength and electric conductivity of copper alloys prepared in examples 1 to 3 and comparative example 1
| Alloy (I) | Tensile strength | Yield strength | Electrical conductivity of |
| Comparative example 1 | 373 | 156 | 16 |
| Example 1 | 586 | 479 | 24 |
| Example 2 | 642 | 556 | 23 |
| Example 3 | 707 | 604 | 21 |
According to the table 1, the copper alloy prepared by the invention can effectively improve the yield strength and the tensile strength without causing the conductivity to be obviously reduced, so that the mechanical property of the copper nickel tin alloy can be effectively improved while the copper nickel tin alloy meets the use requirement of the conductivity.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and amendments can be made without departing from the principle of the present invention, and these modifications and amendments should also be considered as the protection scope of the present invention.
Claims (6)
1. A high-performance copper alloy comprises the following components in percentage by mass: zn27.5-29.3%, ni0.08-1.4%, si0.02-0.25%, fe <0.08%, pb <0.06% and the balance Cu; the mass ratio of the Ni to the Si is (4.2-5.8): 1;
the preparation method of the high-performance copper alloy comprises the following steps:
(1) Smelting and casting alloy raw materials in sequence to obtain a casting material;
(2) Sequentially rolling, annealing, solution treatment and aging treatment the cast material obtained in the step (1) to obtain a high-performance copper alloy;
the temperature of the annealing treatment in the step (2) is 280-320 ℃, and the time of the annealing treatment is 60-100 min;
the temperature of the solution treatment in the step (2) is 680-720 ℃, and the time of the solution treatment is 570-630 min;
the temperature of the aging treatment in the step (2) is 390-410 ℃, and the time of the aging treatment is 150-210 min.
2. The high performance copper alloy of claim 1, comprising the following components in mass percent: zn28.0-29.0%, ni0.1-1.3%, si0.03-0.2%, fe <0.05%, pb <0.05% and the balance of Cu; the mass ratio of the Ni to the Si is (4.3-5.7): 1.
3. the high performance copper alloy of claim 1 or 2, comprising the following components in mass percent: zn28.3-28.8%, ni0.2-1.1%, si0.04-0.15%, fe <0.03%, pb <0.03% and Cu in balance; the mass ratio of the Ni to the Si is (4.5-5.5): 1.
4. the method for producing a high-performance copper alloy as claimed in any one of claims 1 to 3, comprising the steps of:
(1) Smelting and casting alloy raw materials in sequence to obtain a casting material;
(2) Sequentially carrying out rolling, annealing treatment, solid solution treatment and aging treatment on the cast material obtained in the step (1) to obtain a high-performance copper alloy;
the temperature of the annealing treatment in the step (2) is 280-320 ℃, and the time of the annealing treatment is 60-100 min;
the temperature of the solution treatment in the step (2) is 680-720 ℃, and the time of the solution treatment is 570-630 min;
the temperature of the aging treatment in the step (2) is 390-410 ℃, and the time of the aging treatment is 150-210 min.
5. The preparation method according to claim 4, wherein the holding temperature for melting in the step (1) is 1100-1200 ℃, and the holding time for melting is 7-15 min.
6. The preparation method according to claim 4, wherein the rolling temperature in the step (2) is 720-880 ℃, the number of passes of the rolling is 7-14, the single-pass deformation of the rolling is 4-10%, and the total deformation of the rolling is 50-90%.
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