CN113755716A - High-performance copper-nickel-tin alloy and preparation method thereof - Google Patents
High-performance copper-nickel-tin alloy and preparation method thereof Download PDFInfo
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- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
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Abstract
The invention provides a high-performance copper-nickel-tin alloy and a preparation method thereof, belonging to the field of metal material preparation. The high-performance copper-nickel-tin alloy provided by the invention comprises the following components in percentage by mass: ni 14-16%, Sn 7-9%, V0.45-0.55% and the balance of copper. According to the invention, by adding Ni, Sn and V and jointly regulating and controlling the addition amount of Ni, Sn and V, the mechanical property of the copper-nickel-tin alloy can be improved, and the conductivity of the copper-nickel-tin alloy can meet the use requirement, so that the copper-nickel-tin alloy has good comprehensive performance. The results of the examples show that the tensile strength of the high-performance copper-nickel-tin alloy prepared by the invention can reach 1026MPa, the hardness can reach 375HV, and the electric conductivity can reach 8.2 percent IACS.
Description
Technical Field
The invention relates to the field of metal material preparation, in particular to a high-performance copper-nickel-tin alloy and a preparation method thereof.
Background
The Cu-Ni-Sn alloy belongs to one of high-strength high-elasticity conductive copper alloys, has high strength, hardness and elasticity, excellent electric and thermal conductivity, wear resistance, corrosion resistance and other properties, is widely applied to the fields of precision instruments, electronic appliances, aerospace and the like, and particularly has high elasticity, so that the Cu-Ni-Sn alloy becomes an indispensable material for manufacturing electronic connecting pieces such as contact springs, leaf springs, current-carrying elastic elements, relay switches and the like in precision instruments and meters. In recent years, with the rise and development of the electronic industry, electronic and electrical equipment and instruments and devices have been developed to be light in weight, miniaturized, precise, integrated and high in performance, and the demand for the elastic conductive copper alloy as a core material has been greatly increased, and higher requirements for the performance stability have been made. However, in the current Cu-Ni-Sn alloy series, for example, the Cu-15Ni-8Sn alloy seriously affects the strength of the alloy due to the precipitation reaction of discontinuous precipitation during the aging process, and reduces the stability of the alloy. Therefore, for the precipitation strengthening Cu-15Ni-8Sn alloy, the method has the important effect of inhibiting discontinuous precipitation reaction in the aging process and improving the mechanical property and the comprehensive stability of the alloy.
At present, for Cu-Ni-Sn alloy, the prior art mainly obtains an aging peak value by adjusting aging temperature and aging time so as to obtain an optimal heat treatment system; in addition, the mechanical property of the alloy can be improved by cold deformation treatment before aging. However, the aim of inhibiting discontinuous precipitation cannot be achieved from the viewpoint of heat treatment or deformation process alone, which still has great limitation on further improving the comprehensive stability of the alloy. Meanwhile, for the precipitation strengthening Cu-Ni-Sn alloy, new alloy elements are added, so that not only can the alloy form a new precipitation phase in the aging process, the crystal boundary brittleness can be caused, and the mechanical property of the alloy is seriously reduced, but also the copper content in the copper-based alloy is reduced and the electrical conductivity of the copper-based alloy is also reduced due to the addition of the alloy elements. Therefore, it is difficult to control the discontinuous precipitation reaction from the viewpoint of the composition design, and the mechanical properties and conductivity of the alloy are more likely to be lowered.
In conclusion, the improvement of the strength and the electrical conductivity of the Cu-Ni-Sn alloy still faces a larger challenge at present. Therefore, it is highly desirable to provide a high performance copper-nickel-tin alloy to meet the requirements of the electronic components on the use of copper-nickel-tin alloy.
Disclosure of Invention
The invention aims to provide a high-performance copper-nickel-tin 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-nickel-tin alloy which comprises the following components in percentage by mass: 14-16% of Ni, 7-9% of Sn, 0.45-0.55% of V and the balance of copper.
Preferably, the high-performance copper-nickel-tin alloy comprises the following components in percentage by mass: 14.5-15.5% of Ni, 7.5-8.5% of Sn, 0.48-0.52% of V and the balance of copper.
Preferably, the high-performance copper-nickel-tin alloy comprises the following components in percentage by mass: 15% of Ni, 8% of Sn, 0.50% of V and the balance of copper.
The invention also provides a preparation method of the high-performance copper-nickel-tin alloy, which comprises the following steps:
(1) sequentially smelting and casting alloy raw materials to obtain a cast ingot;
(2) carrying out homogenizing annealing, solution treatment, quenching and aging treatment on the ingot obtained in the step (1) in sequence to obtain a high-performance copper-nickel-tin alloy; the temperature of the solution treatment is 800-900 ℃, and the time of the solution treatment is 1-3 h.
Preferably, the heat preservation temperature of the smelting in the step (1) is 1500-1650 ℃, and the heat preservation time of the smelting is 20-30 min.
Preferably, the temperature for casting in the step (1) is 1200-1350 ℃.
Preferably, the mold used for casting in step (1) is a graphite mold.
Preferably, the temperature of the homogenizing annealing in the step (2) is 800-900 ℃, and the time of the homogenizing annealing is 2-6 h.
Preferably, the quenching manner in the step (2) is water quenching.
Preferably, the temperature of the aging treatment in the step (2) is 400-550 ℃, and the time of the aging treatment is 1-15 h.
The invention provides a high-performance copper-nickel-tin alloy which comprises the following components in percentage by mass: 14-16% of Ni, 7-9% of Sn, 0.45-0.55% of V and the balance of copper. According to the invention, more precipitated phases can be formed in the copper-nickel-tin alloy by adding Ni and Sn, so that the crystal grains of the copper-nickel-tin alloy are effectively refined, and the mechanical formation of the copper-nickel-tin alloy is improved; meanwhile, the V element is added, so that the precipitation behavior of each precipitated phase in the copper-nickel-tin alloy can be effectively regulated and controlled, namely Ni can be precipitated on crystal boundaries and in crystal grains3The V stable phase particles can exist in the crystal boundary and in the crystal grain of the copper-nickel-tin alloy at the same time, effectively inhibit nucleation of discontinuous precipitation on the crystal boundary, pin the crystal boundary to prevent the growth of the discontinuous precipitation, and finally improve the mechanical property of the alloy; in addition, the addition amounts of Ni, Sn and V are jointly regulated and controlled, so that the mechanical property of the copper-nickel-tin alloy is improved, and the conductivity of the copper-nickel-tin alloy is not deteriorated, so that the copper-nickel-tin alloy has high strength and excellent conductivity. The results of the examples show that the high performance copper nickel tin alloy prepared by the inventionThe tensile strength can reach 1002-1026 MPa, the hardness can reach 372-376 HV, and the electric conductivity can reach 8.1-8.4% IACS.
Detailed Description
The technical scheme of the invention provides a high-performance copper-nickel-tin alloy which comprises the following components in percentage by mass: 14-16% of Ni, 7-9% of Sn, 0.45-0.55% of V and the balance of copper.
According to the mass percentage, the high-performance copper-nickel-tin alloy provided by the invention comprises 14-16% of Ni, preferably 14.5-15.5%, and more preferably 15%. 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, 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 nucleation of discontinuous precipitates on grain boundaries is effectively inhibited, the grain boundaries are pinned to prevent the growth of the discontinuous precipitates, and finally, the comprehensive mechanical properties of the alloy are improved.
According to the mass percentage, the high-performance copper-nickel-tin alloy provided by the invention comprises 7-9% of Sn, preferably 7.5-8.5%, and more preferably 8%. According to the invention, the mechanical property of the copper matrix can be effectively enhanced by adding the Sn element, and the tendency of Sn segregation can be reduced by controlling the content of the Sn element within the range, so that the strength of the copper matrix can be improved.
According to the mass percentage, the high-performance copper-nickel-tin alloy provided by the invention comprises 0.45-0.55% of V, preferably 0.48-0.52%, and most preferably 0.50%. The invention can combine with partial Ni in the copper alloy to form Ni by adding V element3The content of V element is controlled in the range, so that the precipitation behavior of each precipitated phase in the copper-nickel-tin alloy can be effectively regulated and controlled, namely Ni can be precipitated on grain boundaries and in the grains3The V stable phase particles can exist in the grain boundary and in the grain of the copper-nickel-tin alloy stably, so that nucleation of discontinuous precipitates on the grain boundary is effectively inhibited, the grain boundary is pinned to prevent the growth of the discontinuous precipitates, and the mechanical property of the alloy is finally improved.
According to the mass percentage, the high-performance copper-nickel-tin alloy provided by the invention comprises the balance of copper. The invention takes copper as a matrix, and improves the performance of the copper matrix by adding Ni, Sn and V as strengthening elements, so that the copper matrix has high strength, high hardness and excellent conductivity.
According to the high-performance copper-nickel-tin alloy provided by the invention, by adding Ni, Sn and V and jointly regulating and controlling the addition amounts of Ni, Sn and V, the mechanical property of the copper-nickel-tin alloy can be effectively improved, and the conductivity of the copper-nickel-tin alloy is not influenced, so that the copper-nickel-tin alloy has high strength, high hardness and excellent conductivity.
The invention also provides a preparation method of the high-performance copper-nickel-tin alloy, which comprises the following steps:
(1) sequentially smelting and casting alloy raw materials to obtain a cast ingot;
(2) carrying out homogenizing annealing, solution treatment, quenching and aging treatment on the ingot obtained in the step (1) in sequence to obtain a high-performance copper-nickel-tin alloy; the temperature of the solution treatment is 800-900 ℃, and the time of the solution treatment is 1-3 h.
The alloy raw materials are sequentially smelted and cast to obtain the cast ingot.
In the present invention, the alloy raw material preferably includes electrolytic copper, electrolytic nickel, pure tin, and pure vanadium. In the invention, the purities of the electrolytic copper, the electrolytic nickel, the pure tin and the pure vanadium are preferably more than or equal to 99.95 percent.
In the present invention, the alloy raw materials are preferably fed in the order of adding the raw materials of Cu, Ni, Sn, and V in this order. According to the invention, the raw materials with low content are added later by feeding according to the feeding sequence, so that the raw materials with low content are mixed more uniformly in the melt, the element segregation is reduced more favorably, and the copper-nickel-tin alloy with uniform structure is obtained, thereby being more favorable for improving the strength and hardness of the copper-nickel-tin alloy and enabling the copper-nickel-tin alloy to have higher conductivity.
In the invention, the heat preservation temperature of the smelting is preferably 1500-1650 ℃, more preferably 1550-1600 ℃, and most preferably 1580 ℃; the heat preservation time of the smelting is preferably 20-30 min, more preferably 25-30 min, and most preferably 30 min. By controlling the smelting temperature and the smelting time within the range, the invention can ensure that all elements are uniformly distributed in the melt and reduce the burning loss of the elements, thereby effectively enhancing the strength, the hardness and the conductivity of the copper-nickel-tin alloy by all strengthening elements within the set range.
In the invention, the casting temperature is preferably 1200-1350 ℃, more preferably 1250-1300 ℃, and most preferably 1280 ℃. The invention can lead the melt to obtain proper cooling rate by controlling the casting temperature in the range, lead the solidification structure to be more uniform and the crystal grains to be finer, and simultaneously reduce the casting defects of shrinkage porosity, shrinkage cavity and the like.
In the present invention, the mold used for the casting is preferably a graphite mold. According to the invention, the graphite mold is selected, so that the melt can obtain a proper heat dissipation rate, namely, the melt can obtain a proper cooling rate, and the graphite mold is more favorable for demolding the copper-nickel-tin alloy.
After the ingot is obtained, the ingot is sequentially subjected to homogenizing annealing, solid solution treatment, quenching and aging treatment to obtain the high-performance copper-nickel-tin alloy.
In the invention, the temperature of the homogenizing annealing is preferably 800-900 ℃, more preferably 820-880 ℃, and most preferably 840-860 ℃; the time of the homogenizing annealing is preferably 2-6 h, more preferably 3-5 h, and most preferably 4 h. According to the invention, through carrying out uniform annealing and controlling the temperature and time within the range, the structural stress after casting of the cast ingot can be eliminated, so that the crack deformation and the crack tendency are reduced; meanwhile, the element segregation is reduced, and the uniformity of the ingot casting structure can be effectively improved.
In the present invention, the cooling method of the homogenization annealing is preferably furnace cooling.
In the invention, the temperature of the solid solution treatment is 800-900 ℃, preferably 820-880 ℃, and more preferably 840-860 ℃; the time of the solution treatment is 1 to 3 hours, preferably 1.5 to 2.5 hours, more preferably 1.8 to 2.2 hours, and most preferably 2 hours. According to the invention, all strengthening elements can be fully dissolved in the copper matrix through solution treatment, 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 and hardness of the copper-nickel-tin alloy are enhanced, and the copper-nickel-tin alloy has higher conductivity.
In the present invention, the quenching method is preferably water quenching. According to the invention, a larger cooling rate can be obtained by selecting a quenching mode of water quenching, so that a supersaturated solid solution subjected to solid solution treatment cannot form a precipitated phase in advance, and thus, tissue preparation is made for aging treatment.
In the invention, the temperature of the aging treatment is preferably 400-550 ℃, more preferably 420-520 ℃, and most preferably 450-500 ℃; the time of the aging treatment is preferably 1-15 h, more preferably 2-10 h, and most preferably 3-6 h. 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 and hardness of the copper-nickel-tin alloy are effectively enhanced, and the copper-nickel-tin alloy has high conductivity.
In the present invention, the cooling method of the aging treatment is preferably tapping air cooling.
The preparation method of the high-performance copper-nickel-tin alloy provided by the invention is more beneficial to precipitation of Ni through a heat treatment mode of annealing, solid solution and aging after smelting and casting3The V stabilizes phase particles, stably exists in a crystal boundary and crystal grains, inhibits nucleation of discontinuous precipitation on the crystal boundary, pins the crystal boundary to prevent growth of the discontinuous precipitation, thereby effectively regulating and controlling precipitation behavior of a precipitated phase, and enables the nickel-tin alloy to have high conductivity, high strength and high hardness.
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-nickel-tin alloy prepared in the embodiment comprises the following components in percentage by mass: 15% of Ni, 8% of Sn, 0.45% of V and the balance of copper.
The preparation method of the high-performance copper-nickel-tin alloy comprises the following steps:
(1) sequentially adding alloy raw materials of electrolytic copper, electrolytic nickel, pure tin and pure vanadium with the purity of more than or equal to 99.95 percent, and sequentially smelting and casting to obtain cast ingots; wherein the smelting heat preservation temperature is 1600 ℃, the heat preservation time is 20min, the casting temperature is 1300 ℃, and the casting mould is a graphite mould.
(2) And (2) carrying out homogenizing annealing on the ingots obtained in the step (1) at 850 ℃ for 4h in sequence, cooling along with the furnace, carrying out solution treatment at 850 ℃ for 120min, then immediately carrying out water quenching to room temperature, finally carrying out aging treatment at 400 ℃ for 240min, and carrying out air cooling after discharging to obtain the high-performance copper-nickel-tin alloy.
Example 2
The high-performance copper-nickel-tin alloy prepared in the embodiment comprises the following components in percentage by mass: 15% of Ni, 8% of Sn, 0.50% of V and the balance of copper.
The preparation method of the high-performance copper-nickel-tin alloy comprises the following steps:
(1) sequentially adding alloy raw materials of electrolytic copper, electrolytic nickel, pure tin and pure vanadium with the purity of more than or equal to 99.95 percent, and sequentially smelting and casting to obtain cast ingots; wherein the smelting heat preservation temperature is 1600 ℃, the heat preservation time is 20min, the casting temperature is 1300 ℃, and the casting mould is a graphite mould.
(2) And (2) carrying out homogenizing annealing on the ingots obtained in the step (1) at 850 ℃ for 4h in sequence, cooling along with the furnace, carrying out solution treatment at 850 ℃ for 120min, then immediately carrying out water quenching to room temperature, finally carrying out aging treatment at 400 ℃ for 240min, and carrying out air cooling after discharging to obtain the high-performance copper-nickel-tin alloy.
Example 3
The high-performance copper-nickel-tin alloy prepared in the embodiment comprises the following components in percentage by mass: 15% of Ni, 8% of Sn, 0.55% of V and the balance of copper.
The preparation method of the high-performance copper-nickel-tin alloy comprises the following steps:
(1) sequentially adding alloy raw materials of electrolytic copper, electrolytic nickel, pure tin and pure vanadium with the purity of more than or equal to 99.95 percent, and sequentially smelting and casting to obtain cast ingots; wherein the smelting heat preservation temperature is 1600 ℃, the heat preservation time is 20min, the casting temperature is 1300 ℃, and the casting mould is a graphite mould.
(2) And (2) carrying out homogenizing annealing on the ingots obtained in the step (1) at 850 ℃ for 4h in sequence, cooling along with the furnace, carrying out solution treatment at 850 ℃ for 120min, then immediately carrying out water quenching to room temperature, finally carrying out aging treatment at 400 ℃ for 240min, and carrying out air cooling after discharging to obtain the high-performance copper-nickel-tin alloy.
Example 4
The solution treatment temperature in the embodiment 2 is replaced by 820 ℃, the solution treatment time is replaced by 3h, and the other technical characteristics are the same as those of the embodiment 2.
Example 5
The solution treatment temperature in the embodiment 2 is replaced by 880 ℃, the solution treatment time is replaced by 1h, and the other technical characteristics are the same as those of the embodiment 2.
Example 6
The aging treatment temperature in the embodiment 2 is replaced by 425 ℃, the aging treatment time is replaced by 2h, and the other technical characteristics are the same as those in the embodiment 2.
Example 7
The aging treatment temperature in the embodiment 2 is replaced by 450 ℃, the aging treatment time is replaced by 2h, and the other technical characteristics are the same as those in the embodiment 2.
Comparative example 1
The copper-nickel-tin alloy prepared by the comparative example comprises the following components in percentage by mass: 15% of Ni, 8% of Sn and the balance of copper, and preparing the copper-nickel-tin alloy according to the preparation scheme of the embodiment 1, wherein the raw materials in the preparation method are electrolytic copper, electrolytic nickel and pure tin with the purity of more than or equal to 99.95%.
Performance detection
The hardness and the tensile strength of the copper-nickel-tin alloy prepared in the embodiment 1-7 and the comparative example 1 are detected, wherein a Vickers hardness test adopts an MH-50 Vickers hardness tester to test, the loading force is 300g, the loading time is 15s, the surface of each sample is measured for 5 times, and finally, an average value is taken; the tensile test was performed on an MTS tensile tester at a tensile rate of 0.5mm/min, the same state sample was stretched three times, and finally the average was taken, and the test results are shown in table 1.
Conductivity of the Copper-nickel-tin alloy prepared in examples 1 to 7 and comparative example 1 was measured, a conductivity tester (Sigmascope SMP 350) for eddy current testing of nonferrous metals, which is a hand-held tester manufactured by Fischer of germany, was used to perform conductivity testing at room temperature, a standard sample was used to calibrate the tester before each test, each sample was tested 5 times and then averaged, and the conductivity of the alloy measured by the apparatus was expressed by international Annealed Copper standard% iacs (international Annealed Copper standard), and the measurement results are shown in table 1.
Table 1 test results of hardness, tensile strength and conductivity of copper-nickel-tin alloys prepared in examples 1 to 7 and comparative example 1
According to the table 1, the copper-nickel-tin alloy prepared by the invention can effectively improve the tensile strength, simultaneously has higher hardness, does not cause the electrical conductivity to be obviously reduced, and can still reach more than 8.1% IACS (intrinsic chemical industry standard), 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 electrical 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 decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A high-performance copper-nickel-tin alloy comprises the following components in percentage by mass: ni 14-16%, Sn 7-9%, V0.45-0.55% and the balance of copper.
2. The high-performance copper-nickel-tin alloy according to claim 1, comprising the following components in percentage by mass: 14.5-15.5% of NiNi, 7.5-8.5% of SnS, 0.48-0.52% of V and the balance of copper.
3. The high-performance copper-nickel-tin alloy according to claim 2, comprising the following components in percentage by mass: ni 15%, Sn 8%, V0.50% and the balance of copper.
4. The method for preparing the high-performance copper-nickel-tin alloy according to any one of claims 1 to 3, comprising the following steps:
(1) sequentially smelting and casting alloy raw materials to obtain a cast ingot;
(2) carrying out homogenizing annealing, solution treatment, quenching and aging treatment on the ingot obtained in the step (1) in sequence to obtain a high-performance copper-nickel-tin alloy; the temperature of the solution treatment is 800-900 ℃, and the time of the solution treatment is 1-3 h.
5. The preparation method according to claim 4, wherein the heat preservation temperature for smelting in the step (1) is 1500-1650 ℃, and the heat preservation time for smelting is 20-30 min.
6. The method according to claim 4, wherein the temperature of the casting in the step (1) is 1200 to 1350 ℃.
7. The method according to claim 4, wherein the mold used for casting in step (1) is a graphite mold.
8. The preparation method according to claim 4, wherein the temperature of the homogenizing annealing in the step (2) is 800-900 ℃, and the time of the homogenizing annealing is 2-6 h.
9. The production method according to claim 4, wherein the quenching in the step (2) is performed by water quenching.
10. The preparation method according to claim 4, wherein the temperature of the aging treatment in the step (2) is 400-550 ℃, and the time of the aging treatment is 1-15 h.
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| CN114561568A (en) * | 2022-02-23 | 2022-05-31 | 山西尼尔耐特机电技术有限公司 | Component design of high-performance copper-nickel-tin-molybdenum alloy, and preparation method and application thereof |
| CN116287856A (en) * | 2023-02-23 | 2023-06-23 | 昆明理工大学 | High-strength high-elasticity quaternary copper-nickel-tin-chromium alloy and preparation method thereof |
| CN117127058A (en) * | 2023-05-06 | 2023-11-28 | 江西省科学院应用物理研究所 | High-strength high-hardness copper-based alloy and preparation process thereof |
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