WO2019148304A1 - 析出强化型铜合金及其应用 - Google Patents

析出强化型铜合金及其应用 Download PDF

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WO2019148304A1
WO2019148304A1 PCT/CN2018/000074 CN2018000074W WO2019148304A1 WO 2019148304 A1 WO2019148304 A1 WO 2019148304A1 CN 2018000074 W CN2018000074 W CN 2018000074W WO 2019148304 A1 WO2019148304 A1 WO 2019148304A1
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copper alloy
alloy
precipitation
weight
strength
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English (en)
French (fr)
Inventor
李建刚
杨泰胜
赵红彬
杨朝勇
周耀华
黄强
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Ningbo Powerway Alloy Material Co Ltd
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Ningbo Powerway Alloy Material Co Ltd
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Priority to EP18903347.5A priority Critical patent/EP3748023A4/en
Priority to US16/490,562 priority patent/US11486029B2/en
Publication of WO2019148304A1 publication Critical patent/WO2019148304A1/zh
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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
    • 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
    • C22C9/02—Alloys based on copper with tin as the next major constituent
    • 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
    • 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
    • C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
    • 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
    • C22F1/002—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working by rapid cooling or quenching; cooling agents used therefor
    • 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

Definitions

  • the invention relates to the technical field of copper alloys, in particular to a precipitation strengthening copper alloy with high strength and application thereof.
  • the miniaturization and flaking require the strength and elastic properties of the material to be improved, and the complexity of the shape of the part requires improvement in the press workability and bending workability of the material, an increase in the amount of electricity per unit sectional area, and an increase in the speed of the electric signal.
  • the conductivity is improved.
  • some products have increased requirements for Sn, Au, Ag, etc., and some products have increased requirements for soldering. Therefore, there is a high requirement for plating adhesion or solderability of materials. In some areas of the connector where the ambient temperature is required, the stress relaxation resistance of the material must also be met.
  • materials commonly used in electrical and electronic equipment such as connectors, terminals, relays, switches, etc. are brass (C28000), phosphor bronze (C51900, C52100), beryllium bronze (C17200, C17530), and copper nickel silicon.
  • Copper alloys such as copper alloys (C19010, C70250, C70350) can meet the requirements of copper alloys in different fields. Taking C28000 brass as an example, its tensile strength is about 450MPa, and the electrical conductivity is about 25% IACS, which can meet the performance requirements of common connectors and terminals, but in some pairs of strength, electrical conductivity, especially stress resistance. In areas where slack performance is highly demanding, the lack of comprehensive performance of brass is evident.
  • Phosphor bronze is a copper alloy widely used in connectors and terminals. Phosphorus contained in phosphor bronze has solid solution strengthening effect, and cold deformation hardening makes phosphor bronze have higher strength, but Sn affects the conductivity of phosphor bronze. The conductivity of phosphor bronze is generally below 20% IACS, and the price of Sn is relatively high. Therefore, the application of phosphor bronze is limited.
  • the barium contained in beryllium bronze is toxic, and beryllium bronze is expensive, and is generally only used in certain fields where high elastic properties and strength are required.
  • copper-nickel-silicon alloy is developed to replace beryllium bronze, but its processing cost is high, and it is usually applied to the field of high-end connectors which require high strength and electrical conductivity.
  • the technical problem to be solved by the present invention is to provide a precipitation-strengthened copper alloy excellent in overall performance including yield strength, electrical conductivity, bending workability, and stress relaxation resistance, and an application thereof, in view of the deficiencies of the prior art.
  • a precipitation strengthened copper alloy the weight percentage composition of the copper alloy includes: Cu: 80 wt% to 95 wt%, Sn: 0.05 wt% to 4.0 wt%, Ni: 0.01 wt. % to 3.0 wt%, Si: 0.01 wt% to 1.0 wt%, the balance being Zn and unavoidable impurities.
  • the present invention adds Ni, Si, and Sn elements, and on the one hand, enhances the strength of the alloy by solid solution strengthening, and on the other hand, enhances the strength of the alloy while increasing the strength of the alloy by precipitation of NiSi phase.
  • the bending processability meets the requirements, and has the stress relaxation resistance comparable to tin phosphor bronze; the overall performance of the alloy of the invention is superior to C51900 tin phosphor bronze, and at the same time, the alloy of the invention is added with elements such as Zn and Sn. In addition to cost savings, it has obvious advantages in welding and plating.
  • the effect of adding Sn to the copper alloy of the present invention is to improve the strength and elasticity of the alloy, and to improve the stress relaxation resistance (heat resistance) of the alloy in an environment of about 150 ° C. Therefore, Sn is a useful additive element for materials for electric components.
  • Sn content is less than 0.05% by weight, the effect of improving the properties of the alloy is not satisfactory; when the content of Sn exceeds 4.0% by weight, the electrical conductivity of the alloy is greatly lowered, and therefore, the present invention controls the Sn content to be 0.05 wt% to 4.0 wt%.
  • the Zn element is added to the copper alloy of the present invention, and on the one hand, Zn has a solid solution strengthening effect, and the strength of the substrate can be improved. On the other hand, Zn improves solder wettability and tin plating adhesion which are necessary for electrical and electronic component materials. Has a significant effect.
  • Zn is less expensive than other elements and can be used as a raw material source of Zn in the copper alloy of the present invention with inexpensive brass scrap. If the content of Zn is too low, the effect of solid solution strengthening is not significant, and the recycling of brass scrap is limited, and if the content of Zn is too high, the electrical conductivity, bending workability and stress corrosion resistance of the alloy are lowered.
  • the copper alloy of the present invention can also recycle other scraps, such as nickel-plated scrap for connectors such as personal computers and mobile phones, tin-plated scrap for automotive-oriented connectors, and tin-plated yellow for automotive applications. Copper scrap, etc.
  • the use of the above-mentioned scraps in the copper alloy of the present invention can effectively reduce the alloy preparation cost and promote the recycling of waste materials.
  • Ni is added to the copper matrix, and Ni can enhance the strength of the matrix by solid solution strengthening.
  • the more important role of Ni in the copper alloy of the present invention is to form a NiSi phase with Si, which does not lower the electrical conductivity while improving the strength of the alloy. If the Ni content is less than 0.01% by weight, the improvement of the strength of the alloy is not obvious; when the Ni content exceeds 3.0% by weight, the NiSi phase cannot be completely precipitated, thereby affecting the electrical conductivity of the alloy and is disadvantageous for bending performance.
  • the Ni content is controlled to be 0.01 wt% to 3.0 wt%.
  • the effect of the addition of Si in the present invention is mainly to form a NiSi compound with Ni to enhance the strength of the alloy, since excess Si reduces the electrical conductivity of the alloy. Therefore, the present invention controls the Si content to 0.01 to 1 wt%, so that Si is as The form of the NiSi phase exists.
  • the copper alloy of the present invention contains a NiSi phase, and the amount of the NiSi phase having a particle diameter of 50 nm or less in the NiSi phase after aging is ⁇ 75%.
  • a small amount of Ni and Si added to the alloy of the present invention can form a NiSi phase precipitate, and precipitation of the NiSi phase can significantly increase the yield strength of the alloy.
  • the inventors of the present application have found through a large number of experiments that the finer the dispersion phase is, the higher the strength of the alloy is; the precipitate phase is coarse, and the weak interface is easy to occur, which causes the alloy strip to be cracked and cracked; the precipitate phase is too segregated, which tends to cause local stress concentration. It also causes cracking when the alloy strip is bent. Further, the inventors of the present application have found that the fine dispersion of NiSi is advantageous in bending workability with respect to the alloy strip, and at the same time hinders the dislocation motion in the stress relaxation process, thereby improving the stress relaxation resistance of the alloy strip.
  • the amount of NiSi phase having a particle diameter of 50 nm or less after aging of the copper alloy of the present invention accounts for more than 75% of the total amount of the NiSi phase, and the distribution is dispersed, thereby ensuring that the yield strength of the alloy strip of the present invention is above 600 MPa, and the electrical conductivity is above 20% IACS.
  • the value of the 90° bending workability of the copper alloy strip in the GW direction is R/t ⁇ 1, and the value R/t ⁇ 2 in the BW direction.
  • the X-ray diffraction crystal plane of the copper alloy strip of the present invention in the range of 0 ⁇ 2 ⁇ 90° mainly includes ⁇ 111 ⁇ , ⁇ 200 ⁇ , ⁇ 220 ⁇ and ⁇ 311 ⁇ , ⁇ 111 ⁇ , ⁇ 200 ⁇ , ⁇ 220 ⁇ .
  • the X-ray diffraction intensity of the ⁇ 311 ⁇ crystal plane is related to the state of the strip. After the strip is cold-rolled, the diffraction intensity of the ⁇ 111 ⁇ , ⁇ 220 ⁇ crystal plane will gradually increase, and the diffraction intensity of the ⁇ 200 ⁇ and ⁇ 311 ⁇ crystal plane will gradually decrease.
  • the diffraction intensity of the ⁇ 200 ⁇ and ⁇ 311 ⁇ planes will gradually increase, while the diffraction intensity of the ⁇ 111 ⁇ and ⁇ 220 ⁇ planes will gradually decrease.
  • the increase of the diffraction intensity of the ⁇ 111 ⁇ and ⁇ 220 ⁇ crystal faces is conducive to the increase of the strength of the strip, but it is not favorable for the bending workability of the strip; the increase of the diffraction intensity of the ⁇ 200 ⁇ and ⁇ 311 ⁇ planes is beneficial to the bending.
  • the workability is improved, but when the crystal face diffraction intensity is large, the strength of the alloy strip is low.
  • the yield strength of the alloy of the present invention is to be more than 600 MPa, it is necessary to apply cold rolling deformation to the alloy after aging, but to ensure good bending workability of the strip (90° bending test, the value R/t ⁇ in the GW direction) 1, the value in the BW direction R / t ⁇ 2), the amount of rolling deformation of the alloy strip after the aging is controlled, the inventors of the present application found through a large number of experiments: ⁇ 111 ⁇ , ⁇ 220 ⁇ , ⁇ 200 ⁇ and ⁇ 311
  • the crystal plane diffraction intensity is one of the key control points affecting the yield strength and bending workability of the alloy.
  • the rolled surface of the copper alloy strip has a ⁇ 111 ⁇ crystal plane X in the range of 0 ⁇ 2 ⁇ 90°.
  • the ray diffraction intensity is denoted by I ⁇ 111 ⁇
  • the X-ray diffraction intensity of the ⁇ 200 ⁇ crystal plane is denoted by I ⁇ 200 ⁇
  • the X-ray diffraction intensity of the ⁇ 220 ⁇ crystal plane is denoted by I ⁇ 220 ⁇ , ⁇ 311 ⁇ crystal plane
  • the X-ray diffraction intensity is recorded as I ⁇ 311 ⁇ .
  • the present invention limits I ⁇ 111 ⁇ , I ⁇ 200 ⁇ , I ⁇ 220 ⁇ , and I ⁇ 311 ⁇ to satisfy: 0.5 ⁇ ( I ⁇ 111 ⁇ +I ⁇ 220 ⁇ )/(I ⁇ 200 ⁇ +I ⁇ 311 ⁇ ) ⁇ 10.
  • the alloy of the present invention may further contain Co: 0.01% by weight to 2.0% by weight.
  • Co and Si are simultaneously added to form a cobalt-silicon intermetallic compound, which is precipitated as a compound by a solid solution aging process, and is dispersed and distributed on the substrate to further increase the strength of the alloy without lowering the electrical conductivity.
  • the Co content exceeds 2.0% by weight, the hot workability of the material deteriorates, and when the Co content is less than 0.01% by weight, a sufficient amount of precipitated phase cannot be formed to improve the material properties. Therefore, the present invention controls the Co content to 0.01 wt%. 2.0wt%.
  • the alloy of the present invention may further contain Fe: 0.01% by weight to 2.0% by weight and/or P: 0.001% by weight to 1.0% by weight.
  • the role of Fe is to refine the alloy grains. A trace amount of Fe can also increase the strength of the alloy. When the Fe content is too large, the conductivity of the alloy is adversely affected. Therefore, the present invention controls the Fe content to be 0.01 wt% to 2.0 wt%.
  • the present invention controls the content of P to be 0.001 wt% to 1.0 wt%.
  • the weight percentage composition of the copper alloy may further include at least one element of Mg, B, Re, Cr, and Mn in a total amount of not more than 2.0% by weight, wherein Mg: 0.005 wt% to 1.5 wt%, B: 0.0005 From wt% to 0.3 wt%, Re: 0.0001 wt% to 0.1 wt%, Cr: 0.01 wt% to 1.5 wt%, and Mn: 0.001 wt% to 0.8 wt%.
  • Mg, B, and Re can inhibit the grain boundary reaction, reduce the number of nickel silicon and cobalt silicon precipitates distributed on the grain boundary, reduce the hardness of the alloy after solution treatment, and improve the cold workability of the subsequent channels.
  • B can also improve the alloy's resistance to dezincification and improve corrosion resistance.
  • B, Mg can also improve the stress relaxation resistance of the alloy and improve the hot and cold processing properties of the alloy.
  • Re can remove impurities and deoxidize during smelting, improve the purity of the metal, and the melting point of the rare earth is high. It can be used as the core of crystallization during smelting, reduce the columnar crystal content in the ingot, increase the content of equiaxed crystals, and improve the material. Thermal processing properties.
  • the control ranges of Mg, B and Re in the present invention are respectively : Mg: 0.005 wt% to 1.5 wt%, B: 0.0005 wt% to 0.3 wt%, and Re: 0.0001 wt% to 0.1 wt%.
  • the present invention has a controlled amount of Cr of 0.01 wt% to 1.5 wt%.
  • Mn can deoxidize during the smelting process, improve the purity of the alloy, improve the hot workability of the alloy, improve the basic mechanical properties of the alloy, and reduce the elastic modulus of the alloy.
  • the Mn content of less than 0.001% by weight does not play the above-mentioned role, and Mn is more than 0.8% by weight, which seriously deteriorates the electrical conductivity and the elastic modulus, and cannot satisfy the use requirements of the alloy.
  • the alloy of the present invention is kept at 150 ° C for 1000 hours, and the residual stress is 70% or more.
  • the stress relaxation resistance is also a key factor in evaluating the overall performance of the alloy.
  • the C28000 brass with poor stress relaxation resistance is a Cu-Zn matrix. After 1000 h incubation at 150 ° C, the residual stress is about 35%. After the tin phosphor bronze C51900 is kept at 150 ° C for 1000 h, the residual stress is About 60%.
  • the amount of the NiSi phase having a particle diameter of 50 nm or less in the NiSi phase after controlling the aging is ⁇ 75%, and the presence of the precipitate of the NiSi phase acts as a pinning barrier to the dislocation motion in the stress relaxation process, and the NiSi phase
  • the dispersion distribution of the precipitates can improve the stability of the stress relaxation resistance of the alloy and impart more excellent stress relaxation resistance to the alloy of the present invention.
  • the copper alloy of the invention can be processed into strips, bars, wires and the like according to different application requirements, and is applied to the electrical and electronic industry.
  • the copper alloy of the invention can be processed into strips, bars, wires and the like according to different application requirements.
  • the preparation method can adopt any one of the following two methods.
  • Method 1 batching ⁇ melting ⁇ hot rolling ⁇ milling surface ⁇ primary cold rolling ⁇ one aging ⁇ secondary cold rolling ⁇ secondary aging ⁇ pre-cold rolling ⁇ low temperature annealing ⁇ cleaning ⁇ striping ⁇ packaging.
  • Method 2 batching ⁇ horizontal continuous casting ⁇ milling surface ⁇ one cold rolling ⁇ solution treatment ⁇ secondary cold rolling ⁇ aging treatment ⁇ pre-cold rolling ⁇ low temperature annealing ⁇ cleaning ⁇ striping ⁇ packaging.
  • the melting temperature is 1080 ° C ⁇ 1280 ° C
  • the casting method is semi-continuous casting or horizontal continuous casting.
  • Hot rolling In order to ensure the re-dissolution of the coarse precipitates existing in the ingot, the hot rolling temperature of the alloy is controlled at 750 ° C ⁇ 900 ° C, and the holding time is 1 h ⁇ 6 h. The alloy can be homogenized under this process. In order to minimize the precipitation of phase particles after hot rolling, the final rolling temperature of the alloy is controlled to be above 650 ° C, and is cooled by on-line water after hot rolling. The rolling reduction rate is controlled to be more than 85%.
  • Milling surface After hot rolling, the surface oxide scale is thicker, and the lower milling surface of the hot rolled sheet is 0.5mm ⁇ 1.0mm.
  • One-time cold rolling The total reduction ratio of cold rolling is controlled to be more than 80%, which is beneficial to the later solution treatment and forms an ideal recrystallized structure.
  • One-time treatment the first-stage aging can achieve the purpose of precipitation of the second phase and softening of the tissue.
  • the temperature is controlled at 400 ° C ⁇ 600 ° C, and the time is 3 h ⁇ 20 h.
  • the rolling ratio is controlled at 60% to 85%. Applying cold deformation after solid solution is beneficial to the precipitation of the NiSi phase, which can significantly increase the strength of the alloy. If the amount of deformation is too small, it is not conducive to the completion of recrystallization in the post-aging microstructure, which is disadvantageous for the bending process of the strip.
  • Secondary aging temperature controlled at 350 ° C ⁇ 550 ° C.
  • Aging treatment is the key process for the precipitation strengthening of the alloy.
  • the high temperature is conducive to the complete recrystallization of the microstructure and the precipitation of the second phase.
  • the aging temperature is too high and the overaging problem is easy to occur, which is not conducive to the strength increase of the alloy.
  • Low temperature aging is not conducive to the recrystallization of the strip or the precipitation of the second phase, and has a great influence on the bending process of the strip. Therefore, the aging temperature of the alloy of the present invention is controlled at 350 ° C to 550 ° C.
  • Cold rolling before forming The rolling rate is controlled to be below 40%. Applying cold deformation to the alloy after aging is beneficial to the further improvement of the strength of the strip, but the deformation amount should not be too large, and too large may cause the recrystallized structure to be completely broken, which is not conducive to the bending processing energy of the strip.
  • Low temperature annealing The temperature is 150 ° C ⁇ 300 ° C.
  • low temperature annealing after cold deformation is beneficial to the improvement of strength, especially the increase of yield strength, and also release certain residual stress.
  • the low temperature annealing temperature is controlled at 150 °C ⁇ 300 °C. If the temperature is too high, the purpose of strengthening will not be achieved.
  • the alloy of the present invention is mainly directed to the insufficiency of the comprehensive performance of the copper alloy and the high cost and low electrical conductivity of the phosphor bronze.
  • the present invention adds Ni, Si, and Sn elements, on the one hand, through solid solution. Strengthening, strengthening the strength of the alloy, on the other hand, by strengthening the NiSi phase strengthening, the influence of the strength of the alloy is small while the strength of the matrix is increased, the bending processing performance meets the requirements, and the stress relaxation resistance comparable to that of the tin phosphor bronze is comparable.
  • the comprehensive performance of the alloy of the invention is superior to C51900 tin phosphor bronze, and at the same time, the alloy of the invention is added with elements such as Zn and Sn, and has obvious advantages in welding and electroplating, in addition to cost saving;
  • the present invention controls the diffusion distribution of the NiSi phase, and controls the critical control point of the NiSi phase having a particle size of 50 nm or less in the NiSi phase to account for ⁇ 75%, thereby realizing the copper alloy including yield strength, conductivity, Excellent overall performance including bending workability and stress relaxation resistance;
  • the copper alloy of the present invention can achieve a yield strength of 600 MPa or more and a conductivity of 20% IACS or more after aging, cold rolling deformation, and low temperature annealing; the 90° bending workability of the copper alloy strip is: GW direction value R /t ⁇ 1, the value of BW direction R / t ⁇ 2; holding at 150 ° C for 1000 hours, residual stress of 70% or more, excellent stress relaxation resistance;
  • the alloy of the present invention can solve various utilization problems of waste materials such as brass scrap, nickel-plated scrap for connectors such as personal computers and mobile phones, tin-plated scrap for automotive-oriented connectors, and plating for automotive use. Tin brass scrap, etc., is conducive to energy saving, reducing alloy preparation costs, and promoting recycling of waste materials;
  • the alloy of the invention can be processed into products such as rods and strips, and is widely used in electrical and electronic industry products such as connectors and connectors.
  • Example 1 is a TEM photograph (10000 ⁇ ) of a strip sample of Example 1.
  • Hot rolling heating temperature 780 ° C, heat preservation 5h, hot rolling to 16.5mm;
  • Milling surface up and down milling surface to 15mm;
  • Low temperature annealing low temperature annealing temperature 210 ° C, holding time 6 h, to obtain strip samples.
  • the room temperature tensile test is carried out in accordance with GB/T 228.1-2010 Metallic Material Tensile Test Part 1: Room Temperature Test Method on an electronic universal performance test machine, using a lead sample with a width of 12.5 mm and a tensile speed of 5 mm/ Min.
  • the stress relaxation resistance test is based on the JCBA T309:2004 copper and copper alloy sheet bending stress relaxation test method, sampled parallel to the rolling direction, the sample width is 10mm, the length is 100mm, and the initial loading stress value is 0.2% of the yield strength. %, test temperature is 150 ° C, time is 1000h.
  • the bending performance test was carried out on the bending test machine according to GBT 232-2010 Metal Material Bending Test Method, and the sample width was 5 mm and the length was 50 mm.
  • composition and performance test results of the respective examples and comparative examples are shown in Table 1.
  • a TEM photograph of the strip sample of Example 1 is shown in FIG.

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Abstract

一种析出强化型铜合金，重量百分比组成包括：Cu：80wt％～95wt％，Sn：0.05wt％～4.0wt％，Ni：0.01wt％～3.0wt％，Si：0.01wt％～1.0wt％，余量为Zn和不可避免的杂质。该合金通过固溶强化和析出强化改善综合性能，保持导电率，强度提升，弯曲加工性及耐应力松弛性良好，应用于连接器、接插件等电子电气行业产品。

Description

析出强化型铜合金及其应用 技术领域
本发明涉及铜合金技术领域，具体涉及一种具有高强度的析出强化型铜合金及其应用。
背景技术
近年来随着电子、电气行业的发展，各种各样的机械电气配线复杂化、高集成化，连接器、继电器、开关等电气电子部件进一步轻量化和提升可靠性的要求越来越被重视。特别是平板电脑和手机等使用的连接器、插座等，省空间化和高性能化同时进行，要求铜合金板带材的厚度朝向薄片化的趋势发展，对铜合金的弹性特性和可靠性等性能提出了更高的要求。具体来说，小型化、薄片化要求材料的强度和弹性特性提高，零件形状的复杂化要求材料的冲压加工性和弯曲加工性提高，单位截面积通电量的增加以及电信号的高速化要求材料的导电率提高，此外，根据用途的不同，有些产品对镀Sn、Au、Ag等的要求增加，有些产品对焊接的要求增加，因此，对材料的电镀附着性或焊接性也有较高要求。而在某些对工作环境温度有要求的连接器领域，材料的耐应力松弛性能也必须得到满足。
目前，在连接器、端子、继电器、开关等用于电气电子设备的零部件中常用的材料有黄铜(C28000)、磷青铜(C51900、C52100)、铍青铜(C17200、C17530)以及铜镍硅系铜合金(C19010、C70250、C70350)等铜合金，可以实现不同领域对铜合金性能的要求。以C28000黄铜为例，其抗拉强度为450MPa左右，导电率在25％IACS左右，可以满足普通连接器、端子对材料的性能要求，但在某些对强度、导电，特别是对耐应力松弛性能有较高要求的领域，黄铜综合性能的不足就十分明显。磷青铜是目前连接器、端子等领域广泛使用的铜合金，磷青 铜中含有的Sn具有固溶强化作用，加之冷变形硬化，使磷青铜具有较高的强度，但Sn影响磷青铜的导电率，磷青铜的导电率一般在20％IACS以下，且Sn的价格较高，因此，磷青铜的应用受到一定的限制。铍青铜中含有的铍有毒，且铍青铜价格昂贵，一般仅应用于某些对弹性性能和强度要求较高的领域。铜镍硅合金作为一种时效析出强化型合金，以替代铍青铜而开发，但其加工成本高，通常应用于对强度、导电性等要求较高的高端连接器领域。
发明内容
本发明所要解决的技术问题是：针对现有技术的不足，提供一种包括屈服强度、导电性、弯曲加工性、耐应力松弛性能在内的综合性能优异的析出强化型铜合金及其应用。
本发明解决上述技术问题所采用的技术方案为：析出强化型铜合金，该铜合金的重量百分比组成包括：Cu：80wt％～95wt％，Sn：0.05wt％～4.0wt％，Ni：0.01wt％～3.0wt％，Si：0.01wt％～1.0wt％，余量为Zn和不可避免的杂质。
在铜合金的基体上，本发明添加Ni、Si、Sn元素，一方面通过固溶强化，提升合金的强度，另一方面通过析出NiSi相强化，在提升基体强度的同时对合金导电率的影响较小，弯曲加工性能满足要求，并具有与锡磷青铜相媲美的耐应力松弛性能；本发明合金的综合性能比C51900锡磷青铜优异，同时，本发明合金中添加有Zn、Sn等元素，除了节省成本外，在焊接、电镀等方面具有明显优势。
本发明铜合金中添加Sn的作用是提高合金强度和弹性，同时改善合金150℃左右环境下的耐应力松弛性能(耐热性)，因此Sn对于电气元件用材料是有益的添加元素。但是，Sn含量不足0.05wt％时，改善合金性能的效果不理想； Sn含量超过4.0wt％时，会大幅降低合金导电率，因此，本发明将Sn含量控制在0.05wt％～4.0wt％。
本发明铜合金中添加Zn元素，一方面Zn具有固溶强化作用，可提高基体的强度，另一方面，Zn对于改善作为电气、电子元件材料所必需的焊料润湿性、镀锡附着性也具有明显效果。此外，与其他元素比较，Zn的价格较低，且能够以廉价的黄铜废料作为本发明铜合金中Zn的原料来源。若Zn的含量过低，固溶强化效果不明显，且会限制黄铜废料的回收利用，而若Zn含量过高，则会降低合金的导电率、弯曲加工性和耐应力腐蚀性。
除黄铜废料外，本发明铜合金还可以回收利用其他废料，例如，个人电脑和手机等连接器使用的镀镍废料、面向汽车的连接器使用的镀锡废料、面向汽车用途的镀锡黄铜废料等。上述这些废料在本发明铜合金中的利用可以有效降低合金制备成本，促进废料的循环利用。
在铜基体中添加一定量的Ni，Ni可通过固溶强化提升基体强度，但本发明铜合金中Ni更重要的作用是与Si形成NiSi相，在提升合金强度的同时不降低其导电率。若Ni含量在0.01wt％以下，对合金强度的提升不明显；当Ni含量超过3.0wt％时，无法使NiSi相较为完全地析出，从而影响合金的导电率，且对折弯性能不利，因此，本发明中Ni含量控制在0.01wt％～3.0wt％。
本发明添加Si的作用主要是与Ni形成NiSi化合物从而提升合金的强度，因多余的Si会降低合金的导电率，因此，本发明将Si含量控制在0.01～1wt％，使Si尽可能地以NiSi相的形式存在。
传统的黄铜通过固溶强化增加基体强度，因此其强度提升有限，以C28000为例，其抗拉强度为450MPa左右。而本发明铜合金含有NiSi相，时效后该NiSi 相中粒径50nm以下的NiSi相的数量占比≥75％。本发明合金中添加的少量的Ni、Si可形成NiSi相析出物，NiSi相的析出可显著提高合金的屈服强度。本申请发明人通过大量试验发现：析出相越细小弥散，合金的强度越高；析出相粗大，易出现弱界面，导致合金带材弯曲加工开裂；析出相过于偏聚，易导致局部应力集中，同样致使合金带材弯曲加工时出现开裂现象。此外，本申请发明人还发现，细小弥散的NiSi析出相对合金带材的弯曲加工性能有益，同时对应力松弛过程中的位错运动具有阻碍作用，从而提高合金带材的耐应力松弛性能。本发明铜合金时效后粒径50nm以下的NiSi相数量占NiSi相总数量的75％以上，且分布弥散，确保了本发明合金带材的屈服强度在600MPa以上，导电率在20％IACS以上，同时保证铜合金带材90°弯曲加工性在GW方向的值R/t≤1，在BW方向的值R/t≤2。
本发明铜合金带材在0<2θ<90°范围内的X射线衍射晶面主要有{111}、{200}、{220}和{311}，{111}、{200}、{220}、{311}晶面的X射线衍射强度与带材的状态有关。带材经冷轧变形后，{111}、{220}晶面的衍射强度将逐渐增强，而{200}和{311}晶面的衍射强度将逐渐减弱。带材经热处理后，{200}和{311}晶面的衍射强度将逐渐增强，而{111}、{220}晶面的衍射强度将逐渐减弱。{111}、{220}晶面衍射强度的增加，有利于带材强度的增加，但其对带材的弯曲加工性不利；{200}和{311}晶面衍射强度的增加，有利于弯曲加工性的改善，但其晶面衍射强度较大时，合金带材的强度较低。本发明合金的屈服强度若要达到600MPa以上，需要对合金在时效后施加冷轧变形，但为保证带材具有良好的弯曲加工性(90°折弯试验，在GW方向的值R/t≤1，在BW方向的值R/t≤2)，需控制时效后合金带材的轧制变形量，本申请发明人通过大量试验发现：{111}、 {220}、{200}和{311}晶面衍射强度是影响合金的屈服强度和弯曲加工性的关键控制点之一，将该铜合金的带材的轧制面在0<2θ<90°范围内的{111}晶面的X射线衍射强度记为I {111}，{200}晶面的X射线衍射强度记为I {200}，{220}晶面的X射线衍射强度记为I {220}，{311}晶面的X射线衍射强度记为I {311}，当(I {111}+I{ 220})/(I {200}+I {311})<0.5时，合金的屈服强度在600MPa以下，90°折弯试验中GW方向的值R/t≤1，BW方向的值R/t≤2，当(I {111}+I{ 220})/(I {200}+I {311})>10时，虽然合金的屈服强度在600MPa以上，但90°折弯试验中BW方向的值R/t>2，弯曲加工性达不到要求，因此，为了兼顾屈服强度和弯曲加工性，本发明限定I {111}、I {200}、I {220}和I {311}满足：0.5<(I {111}+I{ 220})/(I {200}+I {311})<10。
本发明合金中还可含有Co：0.01wt％～2.0wt％。
Co和Si同时添加，可以形成钴硅金属间化合物，通过固溶时效工艺，以化合物形式析出，弥散分布在基体上，在进一步提高合金强度的同时而不降低导电率。Co含量超过2.0wt％时，材料的热加工性能恶化，而Co含量低于0.01wt％时，无法形成数量足够的析出相以改善材料性能，因此，本发明将Co含量控制在0.01wt％～2.0wt％。
本发明合金中还可含有Fe：0.01wt％～2.0wt％和/或P：0.001wt％～1.0wt％。
Fe的作用是细化合金晶粒，微量的Fe还可以提高合金强度，当Fe含量过多时反而影响合金的导电性能，因此，本发明将Fe的含量控制在0.01wt％～2.0wt％。
P能够有效地进行脱氧，增加合金熔体的流动性，进一步提高合金的强度、硬度、弹性模量、疲劳强度和耐磨性。但若P过量会严重降低合金电导率，且 易形成Cu 3P低熔点共晶相，造成合金热轧开裂，因此，本发明将P的含量控制在0.001wt％～1.0wt％。
该铜合金的重量百分比组成中还可包括总量不超过2.0wt％的Mg、B、Re、Cr和Mn中的至少一种元素，其中，Mg：0.005wt％～1.5wt％，B：0.0005wt％～0.3wt％，Re：0.0001wt％～0.1wt％，Cr：0.01wt％～1.5wt％，Mn：0.001wt％～0.8wt％。
Mg、B、Re可以抑制晶界反应，减少分布在晶界上的镍硅、钴硅析出相的数量，降低合金固溶处理后的硬度，改善后道冷加工性能。B也可以提高合金的抗脱锌能力，提高耐蚀性。B、Mg还可以提高合金的耐应力松弛性能，改善合金的冷热加工性能。Re在熔炼时可以除杂、除氧，提高金属的纯度，且稀土的熔点高，在熔炼时可以作为结晶的核心，减少铸锭中的柱状晶含量，增加等轴晶的含量，从而改善材料的热加工性能。Re含量低于0.0001wt％时，起不到上述作用，稀土含量超过0.1wt％时，会形成高温氧化物夹杂，使合金性能恶化，因此，本发明中Mg、B和Re的控制范围分别为：Mg：0.005wt％～1.5wt％，B：0.0005wt％～0.3wt％，Re：0.0001wt％～0.1wt％。
Cr可以提高合金的软化温度和高温强度，提升合金的高温稳定性，降低其应力松弛率，当Cr含量小于0.01wt％，其作用不明显，当Cr含量超过1.5wt％时，合金的导电性和加工性能恶化，因此，本发明将Cr的控制量在0.01wt％-1.5wt％。
Mn在熔炼过程中可以起到脱氧作用，提高合金的纯度，还可以改善合金的热加工性能，提高合金的基本力学性能，降低合金的弹性模量。Mn含量小于0.001wt％不能起到上述作用，Mn大于0.8wt％，会严重降低导电率和弹性模量， 无法满足合金的使用需求。
本发明合金在150℃下保温1000小时，残余应力70％以上。作为连接器用铜合金，除了需要满足强度和导电率外，在某些对工作环境温度有要求的情况下，耐应力松弛性能也是评价合金综合性能优劣的关键因素。例如，耐应力松弛性能较差的C28000黄铜，其是Cu-Zn基体，在150℃保温1000h后，其残余应力为35％左右；锡磷青铜C51900在150℃保温1000h后，其残余应力为60％左右。而本发明通过控制时效后NiSi相中粒径50nm以下的NiSi相的数量占比≥75％，该NiSi相析出物的存在对应力松弛过程中的位错运动起到钉扎阻碍作用，NiSi相析出物的弥散分布可以提高合金的耐应力松弛性能的稳定性，赋予本发明合金更加优异的耐应力松弛性能。
本发明铜合金，可以根据不同的应用需求，加工成板带材、棒材、线材等，应用于电子电气行业。
本发明铜合金可以根据不同的应用需求加工成板带材、棒材、线材等。以板带材为例，其制备方法可以采用下面2种方法中的任一种。
方法1：配料→熔炼→热轧→铣面→一次冷轧→一次时效→二次冷轧→二次时效→成前冷轧→低温退火→清洗→分条→包装。
方法2：配料→水平连铸→铣面→一次冷轧→固溶处理→二次冷轧→时效处理→成前冷轧→低温退火→清洗→分条→包装。
其中，熔炼温度为1080℃～1280℃，熔铸方式为半连铸或者水平连铸。
热轧：为保证铸锭中存在的粗大析出相重新回溶，合金的热轧温度控制在750℃～900℃，保温时间1h～6h，此工艺下合金可达均匀化的目的。为尽量减少热轧后相粒子的析出，合金终轧温度控制在650℃以上，热轧后在线水冷却。 轧制压下率控制在85％以上。
铣面：热轧后表面氧化皮较厚，热轧板上下铣面0.5mm～1.0mm。
一次冷轧：冷轧总压下率控制在80％以上，有利于后期固溶处理，形成理想的再结晶组织。
一次时效处理：一级时效可以达到第二相析出和组织软化的目的，温度控制在400℃～600℃，时间为3h～20h。
二次冷轧：轧制率控制在60％～85％。固溶后施加冷变形有利于NiSi相的析出，可显著提高合金的强度。若变形量过小，不利于后期时效组织完成再结晶，对板带材的弯曲加工不利。
二次时效温度：控制在350℃～550℃。时效处理是合金实现析出强化的关键工艺，温度高有利于组织的完全再结晶和第二相的析出，但时效温度过高易出现过时效问题，不利于合金的强度提升。低温时效，既不利于带材的再结晶也不利于第二相的析出，对带材的弯曲加工影响较大，因此，本发明合金的时效温度控制在350℃～550℃。
成前冷轧：轧制率控制在40％以下。对时效后的合金施加冷变形有利于带材强度的进一步提高，但变形量不宜过大，过大易导致再结晶组织完全破碎，不利于带材的弯曲加工能。
低温退火：温度为150℃～300℃。对于含锌量较高的铜合金而言，冷变形后低温退火有利于强度的提高，尤其是屈服强度的提高，此外还可释放一定的残余应力，低温退火温度控制在150℃～300℃之间，若温度过高，达不到强化的目的。
与现有技术相比，本发明的优点在于：
(1)本发明合金主要针对铜合金综合性能的不足以及磷青铜较高的成本和较低的导电性能，在铜合金的基体上，本发明添加Ni、Si、Sn元素，一方面通过固溶强化，提升合金的强度，另一方面通过析出NiSi相强化，在提升基体强度的同时对合金导电率的影响较小，弯曲加工性能满足要求，并具有与锡磷青铜相媲美的耐应力松弛性能；本发明合金的综合性能比C51900锡磷青铜优异，同时，本发明合金中添加有Zn、Sn等元素，除了节省成本外，在焊接、电镀等方面具有明显优势；
(2)本发明通过控制NiSi相的弥散分布，控制时效后NiSi相中粒径50nm以下的NiSi相的数量占比≥75％这一关键控制点，实现了铜合金包括屈服强度、导电性、弯曲加工性、耐应力松弛性能在内的优异的综合性能；
(3)本发明铜合金经时效、冷轧变形、低温退火后可以实现屈服强度600MPa以上，导电率20％IACS以上；该铜合金的带材的90°弯曲加工性为：GW方向的值R/t≤1，BW方向的值R/t≤2；在150℃下保温1000小时，残余应力70％以上，耐应力松弛性能优异；
(4)本发明合金可解决多种废料的利用问题，例如：黄铜废料、个人电脑和手机等连接器使用的镀镍废料、面向汽车的连接器使用的镀锡废料、面向汽车用途的镀锡黄铜废料等，有利于节能降耗，降低合金制备成本，促进废料的循环利用；
(5)本发明合金可以加工成棒线、板带等产品，广泛应用于连接器、接插件等电子电气行业产品。
附图说明
图1为实施例1的带材样品的TEM照片(10000×)。
具体实施方式
以下结合附图实施例对本发明作进一步详细描述。
选取了20个实施例合金和2个对比例合金(C28000黄铜和C51900锡磷青铜)，所添加元素根据各自含量添加到熔炼炉，半连铸浇铸规格170mm×320mm的铸锭，浇铸温度为1150℃。
其他主要制备工艺参数为：
热轧：加热温度780℃，保温5h，热轧至16.5mm；
铣面：上下铣面至15mm；
一次冷轧：15mm冷轧至2mm；
一次时效：时效温度550℃，保温6h；
二次冷轧：2mm冷轧至0.35mm；
二次时效：时效温度380℃，保温时间8h；
三次冷轧：0.35mm冷轧至0.2mm；
低温退火：低温退火温度210℃，保温时间6h，得到带材样品。
对于制备得到的20个实施例合金和2个对比例合金的带材样品，分别测试力学性能、导电率、耐应力松弛性能和折弯性能。
室温拉伸试验按照《GB/T 228.1-2010金属材料拉伸试验第1部分：室温试验方法》在电子万能力学性能试验机上进行，采用宽度为12.5mm的带头试样，拉伸速度为5mm/min。
导电率测试按照《GB/T 3048.2-2007电线电缆电性能试验方法第2部分：金属材料电阻率试验》，本检测仪器为ZFD微电脑电桥直流电阻测试仪，样品宽度为20mm，长度为500mm。
耐应力松弛性能测试按照《JCBA T309：2004铜及铜合金薄板条弯曲应力 松弛试验方法》，沿平行于轧制方向取样，样品宽度10mm，长度100mm，初始加载应力值为0.2％屈服强度的50％，测试温度为150℃，时间为1000h。
折弯性能测试按照《GBT 232-2010金属材料弯曲试验方法》在折弯测试机上进行，样品宽度为5mm，长度50mm。
各实施例及对比例的成分及性能测试结果见表1。实施例1的带材样品的TEM照片见图1。
Figure PCTCN2018000074-appb-000001

Claims (9)

  1. 析出强化型铜合金，其特征在于，该铜合金的重量百分比组成包括：Cu：80wt％～95wt％，Sn：0.05wt％～4.0wt％，Ni：0.01wt％～3.0wt％，Si：0.01wt％～1.0wt％，余量为Zn和不可避免的杂质。
  2. 根据权利要求1所述的析出强化型铜合金，其特征在于，该铜合金含有NiSi相，时效后该NiSi相中粒径50nm以下的NiSi相的数量占比≥75％。
  3. 根据权利要求1所述的析出强化型铜合金，其特征在于，将该铜合金的带材的轧制面在0＜2θ＜90°范围内的{111}晶面的X射线衍射强度记为I {111}，{200}晶面的X射线衍射强度记为I {200}，{220}晶面的X射线衍射强度记为I {220}，{311}晶面的X射线衍射强度记为I {311}，I {111}、I {200}、I {220}和I {311}满足：0.5＜(I {111}+I {220})/(I {200}+I {311})＜10。
  4. 根据权利要求1所述的析出强化型铜合金，其特征在于，该铜合金的重量百分比组成中还包括Co：0.01wt％～2.0wt％。
  5. 根据权利要求1-4中任一项所述的析出强化型铜合金，其特征在于，该铜合金的重量百分比组成中还包括Fe：0.01wt％～2.0wt％和/或P：0.001wt％～1.0wt％。
  6. 根据权利要求5所述的析出强化型铜合金，其特征在于，该铜合金的重量百分比组成中还包括总量不超过2.0wt％的Mg、B、Re、Cr和Mn中的至少一种元素，其中，Mg：0.005wt％～1.5wt％，B：0.0005wt％～0.3wt％，Re：0.0001wt％～0.1wt％，Cr：0.01wt％～1.5wt％，Mn：0.001wt％～0.8wt％。
  7. 根据权利要求1所述的析出强化型铜合金，其特征在于，该铜合金的带材的屈服强度在600MPa以上，导电率在20％IACS以上。
  8. 根据权利要求1所述的析出强化型铜合金，其特征在于，该铜合金的带材的90°弯曲加工性为：GW方向的值R/t≤1，BW方向的值R/t≤2。
  9. 权利要求1-8中任一项所述的析出强化型铜合金在电子电气行业中的应用。
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