WO2015192279A1 - High-strength creep-resistant low-copper alloy material and application thereof - Google Patents

High-strength creep-resistant low-copper alloy material and application thereof Download PDF

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WO2015192279A1
WO2015192279A1 PCT/CN2014/001135 CN2014001135W WO2015192279A1 WO 2015192279 A1 WO2015192279 A1 WO 2015192279A1 CN 2014001135 W CN2014001135 W CN 2014001135W WO 2015192279 A1 WO2015192279 A1 WO 2015192279A1
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copper alloy
creep
alloy material
content
low
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PCT/CN2014/001135
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French (fr)
Chinese (zh)
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孙文声
陈永力
许丁洋
周宏渤
张明
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宁波博威合金材料股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C18/00—Alloys based on zinc
    • C22C18/02—Alloys based on zinc with copper as the next major constituent
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R13/00—Details of coupling devices of the kinds covered by groups H01R12/70 or H01R24/00 - H01R33/00
    • H01R13/02—Contact members
    • H01R13/03—Contact members characterised by the material, e.g. plating, or coating materials

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  • the invention relates to the technical field of low copper alloy materials, in particular to a high-strength creep-resistant low-copper alloy material and an application thereof, which can be applied to the communication connector industry.
  • Copper and copper alloys are one of the most widely used and largest non-ferrous metals, accounting for more than half of the electronics and electrical industry. Although the demand for copper is strong, China's copper resources are in short supply, the domestic resource supply rate is less than 25%, and copper prices continue to remain high. Moreover, the copper content of copper alloy is relatively high, generally above 55%, and the price of copper raw materials usually accounts for 85-90% of the price of copper alloy. Therefore, the impact of copper price on the capital flow of copper processing enterprises and the relationship between market supply and demand is very serious. . The growing shortage of copper resources and the continuing high copper prices have forced people to accept the fact that copper and copper alloys have become scarce materials. Therefore, in order to cope with the complex and ever-changing world economic situation, the development of new low-cost alloy materials to replace copper alloys has become the future development trend of non-ferrous metals and processing industries.
  • Zinc is an important non-ferrous metal with good electrical conductivity, calendering and wear resistance.
  • zinc is used in the field of non-ferrous metals second only to copper and aluminum. It can be combined with various metals to make physical and chemical properties. A more excellent alloy.
  • zinc-based alloys have gradually replaced brass in various industries.
  • the communication connector is generally made of a copper alloy, and the creep resistance of the copper alloy under working conditions is good, and the stable transmission of the signal can be ensured.
  • the existing ordinary zinc alloy has poor creep resistance and strength.
  • the tensile strength of conventional copper alloy products such as HPb59-1 can reach 420 MPa or more, while the tensile strength of die-cast zinc alloy such as No. 3 zinc is only 280 MPa. If applied to a communication connector, any slight strain will cause work. The change of state leads to the change of the tightness of the connector and affects the transmission of the signal. Therefore, the poor creep resistance and strength of the existing zinc alloy cause great restrictions on the further application of the zinc-based alloy.
  • Metal creep refers to the slow dimensional change of a metal that occurs at a certain temperature and stress.
  • Zinc has a melting point of only 420 ° C, and creep occurs at room temperature. For example, at room temperature, if 0.2% deformation is allowed within 100 hours, the stress allowed on the No. 5 die-cast zinc alloy is only 120 MPa, and the stress allowed on the No. 3 zinc alloy is only 80 MPa.
  • Patent No. ZL201010246298.6 a Cr-containing creep-resistant extruded zinc alloy and a preparation method thereof, the alloy composition is as follows: Cr 0.05-3.0%, Cu 0.5-2.5%, Ti 0.1-0.3%, and the rest is Zn and a total amount of impurities not more than 0.05%, the alloy composition may also contain Al 0.1-1.0% by mass. This specification describes that the alloy has more excellent creep resistance and comprehensive properties by adding Cr. The tensile strength of the alloy is 280 MPa. Patent No.
  • the alloy composition is as follows: Cu 0.5-3.0%, Mn 0.01-2.0%, Ti 0.05-0.3%, The balance is Zn and impurities in a total amount of less than 0.05%.
  • the alloy may further contain X 0.01-0.5%, and its composition is at least one of Al and a rare earth element (Ce+La).
  • the tensile strength of the alloy is 230 MPa.
  • the technical problem to be solved by the present invention is to provide a high-strength creep-resistant low-copper alloy material which can be applied to the communication connector industry in view of the deficiencies of the prior art.
  • the technical solution adopted by the present invention to solve the above technical problems is: a high-strength creep-resistant low-copper alloy material, the weight percentage composition thereof including: Cu: 4 to 10 wt%, Mg: 0.01 to 0.5 wt%, Mn: 0.01 to 2.0wt%, Ti: 0.01-1.0wt%, the balance is Zn and unavoidable impurities.
  • the phase composition of the as-cast microstructure of the low-copper alloy material includes the matrix Zn, the equiaxed chrysanthemum-like CuZn 5 phase and the ribbon network Zn. -Cu-Ti-Mg-Mn compound.
  • the content of Cu in the low copper alloy of the invention is 4.0-10.0% by weight.
  • Mg, Mn and Ti elements the strength of the alloy is enhanced by Mg 2 Zn 11 , MnZn 9 or TiZn 15 and the creep is improved. Insufficient performance.
  • Mg, Mn and Ti are added in combination, a large amount of Mg 2 Zn 11 , MnZn 9 and TiZn 15 can be simultaneously formed as a crystal core to promote nucleation and refine the grain structure remarkably.
  • Mg, Mn and Ti are combined with each other to form a high-melting complex intermetallic compound Zn-Cu-Ti-Mg-Mn.
  • strip-shaped elongated compounds appear in the dendrite gap of the primary phase and the grain boundary of the matrix, and are connected. Forming a network shape can effectively inhibit the rapid growth of CuZn 5 dendrites, and form a uniform volume equimolar chrysanthemum with a high volume fraction of CuZn 5 phase.
  • these compounds exist in the form of strips in the grain boundary of the matrix, which can increase the activation energy of the grain boundary diffusion, hinder the sliding of the grain boundary, and increase the surface energy of the grain boundary crack surface.
  • the creep limit of the inventive alloy and the reduction of the steady state creep rate have significant effects.
  • Copper can be solid-solubilized in the low-copper alloy matrix of the present invention to produce solid solution strengthening, and a small amount of Cu solid-solubilized in the low-copper alloy matrix is beneficial for improving the elongation properties of the low-copper alloy. Since the solid solubility of copper in the low copper alloy matrix is not large at normal temperature, the excess copper forms a high melting point intermetallic compound ⁇ phase (ie CuZn 5 ) with zinc, so an appropriate increase in the amount of copper added can increase the second. The amount of phase precipitation plays a role in hardening and strengthening the alloy, and is beneficial for improving the creep resistance of the low copper alloy.
  • the strength of the alloy can be controlled to a higher level: when the amount of copper added is less than 4.0%, the ratio of the ⁇ phase is too low, and the hardening and strengthening effect is not obvious, and The creep properties of the alloy are not improved much.
  • the amount of copper added exceeds 10% by weight, the plasticity of the alloy sharply decreases due to a sharp increase in the ⁇ phase, which is difficult to be hot and cold processed. Therefore, the content of copper in the low copper alloy of the present invention is controlled to be 4 to 10% by weight.
  • the solid solubility of Mg in the low copper alloy matrix of the present invention is extremely small, and the maximum solid solubility is only 0.15 to 0.16 wt%. As the temperature is lowered, the solid solubility of Mg in the low copper alloy matrix is further lowered, and is only 0.005 wt% at room temperature. The excess Mg and Zn undergo eutectic reaction at 364 ° C to form a solid solution of Mg in Zn and a cubic lattice intermetallic compound Mg 2 Zn 11 , and the micro-nano-scale fine-layered sheet-like eutectic structure formed by the two is uniform.
  • the ground is distributed on the grain boundary of the low copper alloy matrix, which can effectively pin the dislocation motion and the grain boundary sliding, significantly improve the strength and hardness of the low copper alloy, and improve the creep resistance of the alloy.
  • the Mg content is more than 0.5% by weight, the impact toughness of the alloy is significantly reduced, resulting in problems in the production and processing of the alloy; and when the Mg content is less than 0.01% by weight, there is no significant strengthening and creep resistance. . Therefore, the low copper alloy of the present invention has a magnesium content of from 0.01 to 0.5% by weight.
  • Mn has a metamorphism effect on the low copper alloy of the present invention, and adding Mn to the low copper alloy can refine the alloy structure and improve the overall mechanical properties. Adding an appropriate amount of Mn to the low copper alloy can improve the strength and hardness of the low copper alloy without affecting the elongation. In addition, Mn forms a high-melting zinc-manganese compound on the grain boundary of the low-copper alloy matrix, which can increase the diffusion activation energy at the grain boundary, reduce the diffusion rate of the atom, and improve the creep resistance.
  • the amount of Mn added in the low copper alloy of the present invention is from 0.01 to 2.0% by weight.
  • Ti is mainly present in the form of an intermetallic compound in the low copper alloy of the present invention.
  • Ti is added, and in the crystallization process, Ti promotes nucleation as a crystal core in the form of a TiZn 15 phase, and effectively prevents grain growth and refines the structure.
  • the micron-sized TiZn 15 phase particles distributed on the grain boundary of the matrix and the crystal grains with the core as the core play an important role in hindering dislocation motion, grain boundary slip and coordinated deformation.
  • the proper amount of Ti can improve the recrystallization of the alloy.
  • the content of Ti is controlled to be 0.01 to 1.0% by weight.
  • the phase composition of the as-cast microstructure of the low-copper alloy material of the invention comprises a matrix Zn, an equiaxed chrysanthemum-like CuZn5 phase and a ribbon network of Zn-Cu-Ti-Mg-Mn compound, and the as-cast microstructure is broken after plastic deformation processing.
  • the microstructure of the alloy is refined, and the Zn-Cu-Ti-Mg-Mn compound of the ribbon network also breaks to form a finer band structure, so that the alloy exhibits better plasticity and greatly improves the creep resistance of the alloy.
  • the volume ratio of the CuZn 5 phase in the phase composition is 30 to 70%.
  • the alloy is hardened and strengthened while ensuring the plasticity of the alloy.
  • the weight percentage composition of the low copper alloy material of the present invention further comprises M: 0.001 to 1.0 wt%, and the M is at least at least Zr, Cr, Fe, Mo, Ni, Si, Co, Al, V, and RE.
  • An element. Zr, Cr, Fe, Mo, Ni, Si, Co, Al, V, and RE are respectively present in the low-copper alloy matrix in the form of a small amount of an intermetallic compound phase, and serve to strengthen.
  • Zr also has the effect of refining crystal grains and preventing segregation
  • RE also has the functions of refining crystal grains and removing oxygen.
  • the content of Zr, Cr, Fe, Mo, Ni, Si, Co, Al, V, RE is less than 0.001% by weight, the above effect is not obtained, and if it exceeds 1.0% by weight, the plastic working property of the alloy is remarkably lowered.
  • the content of Zr is 0.001-0.1 wt%
  • the content of Cr is 0.001-0.1 wt%
  • the content of Fe is 0.001-0.1 wt%
  • the content of Mo is 0.001.
  • the content of Ni is 0.001-0.1 wt%
  • the content of Si is 0.001-0.1 wt%
  • the content of Co is 0.001-0.1 wt%
  • the content of Al is The content of V is 0.001 to 0.1% by weight
  • the content of V is 0.001 to 0.1% by weight
  • the content of RE is 0.001 to 0.1% by weight.
  • the low copper alloy material of the invention has a tensile strength of 400-550 MPa, a hardness of 100-150 HV5, an elongation of 10-20%, and a creeping shift rate at a temperature of 100 ° C and a creep loading stress of 100 MPa (1.18- 8.87) ⁇ 10 -6 s -1 .
  • the high strength creep resistant low copper alloy material of the present invention is used in the communication connector industry.
  • the invention has the advantages that the low copper alloy provided by the invention has excellent creep resistance, and the creep rate can reach at 100 ° C and the creep loading stress is 100 MPa (1.18-8.87).
  • ⁇ 10 -6 s -1 which is one order of magnitude smaller than the conventional zinc-copper-titanium alloy of 7.58 ⁇ 10 -5 s -1 , the elongation can reach 10-20%, the tensile strength is 400-550MPa, and the hardness is HV5.
  • the alloy of the present invention can be used as a substitute for lead brass in the telecommunications connector industry, and can also be used as an alternative to some copper alloy components in other industries.
  • FIG. 1 is a SEM image ( ⁇ 600) of a typical as-cast microstructure of the present invention, which contains a matrix Zn, an equiaxed chrysanthemum CuZn 5 phase, and a ribbon network of Zn-Cu-Ti-Mg-Mn compound;
  • Figure 2 is a SEM picture (x 2500) of a typical as-cast microstructure of the present invention
  • FIG. 4 is an energy spectrum diagram of the Zn-Cu-Ti-Mg-Mn compound of FIG. 2.
  • Comparative Example 1 was alloyed according to ZL201010246298.6, Comparative Example 2 was alloyed according to ZL201010245802.0), and processed into ⁇ 11.3 by the same process.
  • Finished product The cast slab is made by continuous casting or die casting, hot extruded into a bar at a temperature of 180 ° C - 380 ° C, and finally processed into a finished product of ⁇ 11.3 by cold drawing.
  • the SEM images of the typical as-cast microstructure of the low-copper alloy material of the present invention are shown in Fig. 1 ( ⁇ 600) and Fig. 2 ( ⁇ 2500), and the as-cast microstructure contains the matrix Zn, the equiaxed chrysanthemum CuZn 5 phase and the ribbon.
  • the energy spectrum analysis results of the Zn-Cu-Ti-Mg-Mn compound and Zn-Cu-Ti-Mg-Mn compound of the network are shown in Fig. 3.
  • the energy spectrum of the Zn-Cu-Ti-Mg-Mn compound is shown in Fig. 3. 4 is shown.
  • the room temperature tensile test is carried out according to GB/T 228.1-2010 "Metal material tensile test Part 1: room temperature test method" on the electronic universal performance test machine, and the scale factors are used for both Examples 1-25 and Comparative Examples 1-2.
  • the sample having a circular cross section of 11.3 has a tensile speed of 5 mm/min.
  • the high temperature creep test method refers to GB/T 2039-2012 "Metal material uniaxial tensile creep test method", and applies an initial force of not more than 10% of the total test force to the sample before heating, and is maintained by an electronic control adjustment system.
  • the load during the loading process is constant.
  • the high temperature creep test was carried out on an RWS50 electronic creep relaxation tester with a creep loading stress of 100 MPa and a test temperature of 100 °C.
  • the sample heating furnace has the function of automatically adjusting the temperature. During the whole creep test, the temperature fluctuations in the upper, middle and lower sections of the furnace are controlled at ⁇ 3 °C to ensure constant temperature loading.
  • the two-sided axial extensometer was taken out from the furnace and the deformation displacement was measured using an extension clamp fixed to the sample. The whole process is controlled and data collected by computer, and the axial tension, deformation displacement and other data are recorded in real time.
  • composition and performance test results of the examples, comparative examples are shown in Table 1.

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Abstract

A high-strength creep-resistant low-copper alloy material, the weight percentage composition thereof comprising: Cu: 4 ~ 10 wt%, Mg: 0.01 ~ 0.5 wt%, Mn: 0.01 ~ 2.0 wt%, Ti: 0.01 ~ 1.0 wt%, and the remainder being Zn and unavoidable impurities. The phase composition of the as-cast structure of the low-copper alloy material comprises a substrate Zn, an equiaxed chrysanthemum-shaped CuZn5 phase and a Zn-Cu-Ti-Mg-Mn compound having a strip-shaped network. The alloy has excellent creep resistance. At conditions of 100oC and a creep loading stress of 100 MPa, the creep rate is (1.18 - 8.87) x 10-6s-1, the elongation is 10 - 20%, the tensile strength is 400 - 550 MPa and the hardness HV5 is 100 - 150. The alloy material may be used as a substitute for lead brass in the communication connector industry, and may also be used in other industries as a substitute for certain copper alloy components.

Description

一种高强度抗蠕变低铜合金材料及其应用High-strength creep-resistant low-copper alloy material and application thereof 技术领域Technical field
本发明涉及低铜合金材料技术领域，具体涉及一种高强度抗蠕变低铜合金材料及其应用，该合金材料可应用于通讯连接器行业。The invention relates to the technical field of low copper alloy materials, in particular to a high-strength creep-resistant low-copper alloy material and an application thereof, which can be applied to the communication connector industry.
背景技术Background technique
铜及铜合金是应用最广、用量最大的有色金属之一，在电子电器工业中的用量占一半以上。虽然对铜的需求旺盛，但我国铜资源严重短缺，国内资源供给率不足25％，铜价也持续保持高位。并且，铜合金的含铜量较高，一般在55％以上，而铜原料价格通常占铜合金售价的85-90％，因此铜价对铜加工企业的资金流动和市场供求关系的影响十分严重。铜资源的日益短缺和持续的高铜价使人们不得不接受这一事实：铜及铜合金已成为稀缺材料。因此，为应对复杂多变的世界经济形势，开发新型的低成本合金材料替代铜合金已成为有色金属及加工等行业的未来发展趋势。Copper and copper alloys are one of the most widely used and largest non-ferrous metals, accounting for more than half of the electronics and electrical industry. Although the demand for copper is strong, China's copper resources are in short supply, the domestic resource supply rate is less than 25%, and copper prices continue to remain high. Moreover, the copper content of copper alloy is relatively high, generally above 55%, and the price of copper raw materials usually accounts for 85-90% of the price of copper alloy. Therefore, the impact of copper price on the capital flow of copper processing enterprises and the relationship between market supply and demand is very serious. . The growing shortage of copper resources and the continuing high copper prices have forced people to accept the fact that copper and copper alloys have become scarce materials. Therefore, in order to cope with the complex and ever-changing world economic situation, the development of new low-cost alloy materials to replace copper alloys has become the future development trend of non-ferrous metals and processing industries.
锌是一种重要的有色金属，具有良好的导电性、压延性及耐磨性，目前锌在有色金属领域的使用量仅次于铜及铝，可以与多种金属组合制成物理及化学性能更加优良的合金。随着铜资源的日益短缺，锌基合金已逐步替代黄铜应用于各行业。Zinc is an important non-ferrous metal with good electrical conductivity, calendering and wear resistance. Currently, zinc is used in the field of non-ferrous metals second only to copper and aluminum. It can be combined with various metals to make physical and chemical properties. A more excellent alloy. With the increasing shortage of copper resources, zinc-based alloys have gradually replaced brass in various industries.
目前通讯连接器一般由铜合金制造，铜合金工作状态下的抗蠕变性能较好，可确保信号的稳定传输。现有的普通锌合金的抗蠕变性能和强度较差，常规的铜合金产品如HPb59-1的抗拉强度可达420MPa以上，而压铸锌合金如3号锌其抗拉强度仅为280MPa，若应用于通讯连接器，其任何微小应变都会引起工作 状态的改变，导致连接器的密闭性发生变化，影响信号的传输，因此现有锌合金较差的抗蠕变性能和强度对锌基合金的进一步推广应用造成了较大制约。At present, the communication connector is generally made of a copper alloy, and the creep resistance of the copper alloy under working conditions is good, and the stable transmission of the signal can be ensured. The existing ordinary zinc alloy has poor creep resistance and strength. The tensile strength of conventional copper alloy products such as HPb59-1 can reach 420 MPa or more, while the tensile strength of die-cast zinc alloy such as No. 3 zinc is only 280 MPa. If applied to a communication connector, any slight strain will cause work. The change of state leads to the change of the tightness of the connector and affects the transmission of the signal. Therefore, the poor creep resistance and strength of the existing zinc alloy cause great restrictions on the further application of the zinc-based alloy.
金属的蠕变是指金属在一定温度及一定应力下发生的缓慢的尺寸变化的性能。锌的熔点仅有420℃，在室温的条件下即会发生蠕变现象。如在室温条件下，100小时内，若允许发生0.2％的变形，则5号压铸锌合金所允许承受的应力仅为120MPa，3号锌合金允许承受的应力只有80MPa。Metal creep refers to the slow dimensional change of a metal that occurs at a certain temperature and stress. Zinc has a melting point of only 420 ° C, and creep occurs at room temperature. For example, at room temperature, if 0.2% deformation is allowed within 100 hours, the stress allowed on the No. 5 die-cast zinc alloy is only 120 MPa, and the stress allowed on the No. 3 zinc alloy is only 80 MPa.
专利号为ZL201010246298.6，一种含Cr的抗蠕变挤压锌合金及其制备方法，该合金组分如下：Cr 0.05-3.0％，Cu 0.5-2.5％，Ti 0.1-0.3％，其余为Zn及总量不大于0.05％的杂质，合金组成按质量百分比还可以含有Al 0.1-1.0％。该说明书介绍到通过加Cr使合金具有更加优异的抗蠕变性能及综合性能，合金的抗拉强度为280MPa。专利号为ZL201010245802.0，一种含Mn的抗蠕变轧制锌合金板带材及制备方法，该合金组分如下：Cu 0.5-3.0％，Mn 0.01-2.0％，Ti 0.05-0.3％，其余为Zn和总量小于0.05％的杂质。合金还可含有X 0.01-0.5％，其组成为Al、稀土元素(Ce+La)中其中的至少一种。合金的抗拉强度为230MPa。上述两件专利给出的锌合金虽然具有一定的抗蠕变性能，但其强度分别仅为280MPa和230MPa，远不能满足替代黄铜的需要。Patent No. ZL201010246298.6, a Cr-containing creep-resistant extruded zinc alloy and a preparation method thereof, the alloy composition is as follows: Cr 0.05-3.0%, Cu 0.5-2.5%, Ti 0.1-0.3%, and the rest is Zn and a total amount of impurities not more than 0.05%, the alloy composition may also contain Al 0.1-1.0% by mass. This specification describes that the alloy has more excellent creep resistance and comprehensive properties by adding Cr. The tensile strength of the alloy is 280 MPa. Patent No. ZL201010245802.0, a Mn-containing creep-resistant rolled zinc alloy plate strip and a preparation method thereof, the alloy composition is as follows: Cu 0.5-3.0%, Mn 0.01-2.0%, Ti 0.05-0.3%, The balance is Zn and impurities in a total amount of less than 0.05%. The alloy may further contain X 0.01-0.5%, and its composition is at least one of Al and a rare earth element (Ce+La). The tensile strength of the alloy is 230 MPa. Although the zinc alloys given by the above two patents have certain creep resistance, their strengths are only 280 MPa and 230 MPa, respectively, which is far from meeting the needs of replacing brass.
发明内容Summary of the invention
本发明所要解决的技术问题是，针对现有技术的不足，提供一种高强度抗蠕变低铜合金材料，该合金材料可应用于通讯连接器行业。The technical problem to be solved by the present invention is to provide a high-strength creep-resistant low-copper alloy material which can be applied to the communication connector industry in view of the deficiencies of the prior art.
本发明解决上述技术问题所采用的技术方案为：一种高强度抗蠕变低铜合金材料，其重量百分比组成包括：Cu：4～10wt％，Mg：0.01～0.5wt％，Mn：0.01～2.0wt％，Ti：0.01～1.0wt％，余量为Zn和不可避免的杂质，该低铜合金材料铸态 组织的相组成包括基体Zn、等轴菊花状CuZn5相和带状网络的Zn-Cu-Ti-Mg-Mn化合物。The technical solution adopted by the present invention to solve the above technical problems is: a high-strength creep-resistant low-copper alloy material, the weight percentage composition thereof including: Cu: 4 to 10 wt%, Mg: 0.01 to 0.5 wt%, Mn: 0.01 to 2.0wt%, Ti: 0.01-1.0wt%, the balance is Zn and unavoidable impurities. The phase composition of the as-cast microstructure of the low-copper alloy material includes the matrix Zn, the equiaxed chrysanthemum-like CuZn 5 phase and the ribbon network Zn. -Cu-Ti-Mg-Mn compound.
本发明低铜合金中Cu的含量为4.0-10.0wt％，在此基础上，通过复合添加Mg、Mn和Ti元素，克服单纯以Mg2Zn11、MnZn9或TiZn15增强合金强度、提高蠕变性能的不足。复合添加Mg、Mn和Ti，在合金凝固过程中，可以同时形成大量的Mg2Zn11、MnZn9和TiZn15作为结晶核心而促进形核，显著细化晶粒组织。同时，Mg、Mn和Ti又彼此结合形成高熔点的复杂多元金属间化合物Zn-Cu-Ti-Mg-Mn，这些带状长条形化合物出现在初生相的枝晶间隙和基体晶界，连接形成网络状，可有效抑制CuZn5枝晶的快速生长，使高体积比分数的CuZn5相形成尺寸均匀的等轴菊花状。另一方面，这些化合物在基体晶界中以带状长条的形式存在，既能增加晶界扩散激活能，阻碍晶界滑动，又可增大晶界裂纹面的表面能，因而对提高本发明合金的蠕变极限、降低稳态蠕变速率具有显著的效果。The content of Cu in the low copper alloy of the invention is 4.0-10.0% by weight. On the basis of the addition of Mg, Mn and Ti elements, the strength of the alloy is enhanced by Mg 2 Zn 11 , MnZn 9 or TiZn 15 and the creep is improved. Insufficient performance. When Mg, Mn and Ti are added in combination, a large amount of Mg 2 Zn 11 , MnZn 9 and TiZn 15 can be simultaneously formed as a crystal core to promote nucleation and refine the grain structure remarkably. At the same time, Mg, Mn and Ti are combined with each other to form a high-melting complex intermetallic compound Zn-Cu-Ti-Mg-Mn. These strip-shaped elongated compounds appear in the dendrite gap of the primary phase and the grain boundary of the matrix, and are connected. Forming a network shape can effectively inhibit the rapid growth of CuZn 5 dendrites, and form a uniform volume equimolar chrysanthemum with a high volume fraction of CuZn 5 phase. On the other hand, these compounds exist in the form of strips in the grain boundary of the matrix, which can increase the activation energy of the grain boundary diffusion, hinder the sliding of the grain boundary, and increase the surface energy of the grain boundary crack surface. The creep limit of the inventive alloy and the reduction of the steady state creep rate have significant effects.
铜可以固溶于本发明低铜合金基体中产生固溶强化，微量的Cu固溶于低铜合金基体中对改善低铜合金的延伸性能有益。由于在常温下铜在低铜合金基体中的固溶度不大，多余的铜会与锌形成高熔点的金属间化合物ε相(即CuZn5)，因此适当增加铜的添加量可以提高第二相析出量，起到硬化和强化合金的作用，同时对于提升低铜合金的抗蠕变性能有益。当铜的含量大于4.0％时，合金的强度能控制在一个较高的水平：铜的添加量小于4.0％时，ε相的比例过低，其起到的硬化和强化效果不明显，并且对合金的蠕变性能改善也不大。但当铜添加量超过10wt％以后，由于ε相急剧增加会导致合金的塑性急剧下降，不易冷热加工。因此本发明低铜合金中铜的含量控制在4-10wt％。 Copper can be solid-solubilized in the low-copper alloy matrix of the present invention to produce solid solution strengthening, and a small amount of Cu solid-solubilized in the low-copper alloy matrix is beneficial for improving the elongation properties of the low-copper alloy. Since the solid solubility of copper in the low copper alloy matrix is not large at normal temperature, the excess copper forms a high melting point intermetallic compound ε phase (ie CuZn 5 ) with zinc, so an appropriate increase in the amount of copper added can increase the second. The amount of phase precipitation plays a role in hardening and strengthening the alloy, and is beneficial for improving the creep resistance of the low copper alloy. When the content of copper is more than 4.0%, the strength of the alloy can be controlled to a higher level: when the amount of copper added is less than 4.0%, the ratio of the ε phase is too low, and the hardening and strengthening effect is not obvious, and The creep properties of the alloy are not improved much. However, when the amount of copper added exceeds 10% by weight, the plasticity of the alloy sharply decreases due to a sharp increase in the ε phase, which is difficult to be hot and cold processed. Therefore, the content of copper in the low copper alloy of the present invention is controlled to be 4 to 10% by weight.
Mg在本发明低铜合金基体中的固溶度极小，最大固溶度仅为0.15-0.16wt％。随着温度降低，Mg在低铜合金基体中的固溶度进一步降低，室温时仅为0.005wt％。多余的Mg与Zn在364℃时发生共晶反应，形成Mg在Zn中的固溶体以及立方晶格的金属间化合物Mg2Zn11，两者形成的微纳米级的细小层片状共晶组织均匀地分布于低铜合金基体的晶界上，能够有效地钉扎位错的运动和晶界的滑动，显著提高低铜合金的强度、硬度，并改善合金的抗蠕变性能。但是当Mg含量大于0.5wt％时，合金的冲击韧性产生明显的降低，导致合金的生产和加工出现问题；而当Mg含量低于0.01wt％时，不具有显著的强化作用和抗蠕变作用。因此本发明低铜合金确定的镁的含量为0.01-0.5wt％。The solid solubility of Mg in the low copper alloy matrix of the present invention is extremely small, and the maximum solid solubility is only 0.15 to 0.16 wt%. As the temperature is lowered, the solid solubility of Mg in the low copper alloy matrix is further lowered, and is only 0.005 wt% at room temperature. The excess Mg and Zn undergo eutectic reaction at 364 ° C to form a solid solution of Mg in Zn and a cubic lattice intermetallic compound Mg 2 Zn 11 , and the micro-nano-scale fine-layered sheet-like eutectic structure formed by the two is uniform. The ground is distributed on the grain boundary of the low copper alloy matrix, which can effectively pin the dislocation motion and the grain boundary sliding, significantly improve the strength and hardness of the low copper alloy, and improve the creep resistance of the alloy. However, when the Mg content is more than 0.5% by weight, the impact toughness of the alloy is significantly reduced, resulting in problems in the production and processing of the alloy; and when the Mg content is less than 0.01% by weight, there is no significant strengthening and creep resistance. . Therefore, the low copper alloy of the present invention has a magnesium content of from 0.01 to 0.5% by weight.
Mn对本发明低铜合金具有变质作用，在低铜合金中加入Mn，可以细化合金组织，提高综合力学性能。在低铜合金中加入适量的Mn，可以在不影响延伸率的情况下，改善低铜合金的强度和硬度。此外，Mn会在低铜合金基体的晶界上生成高熔点的锌锰化合物，能够增大晶界上的扩散激活能，降低原子的扩散速度，从而提高抗蠕变性能。本发明低铜合金中Mn的添加量为0.01-2.0wt％。Mn has a metamorphism effect on the low copper alloy of the present invention, and adding Mn to the low copper alloy can refine the alloy structure and improve the overall mechanical properties. Adding an appropriate amount of Mn to the low copper alloy can improve the strength and hardness of the low copper alloy without affecting the elongation. In addition, Mn forms a high-melting zinc-manganese compound on the grain boundary of the low-copper alloy matrix, which can increase the diffusion activation energy at the grain boundary, reduce the diffusion rate of the atom, and improve the creep resistance. The amount of Mn added in the low copper alloy of the present invention is from 0.01 to 2.0% by weight.
Ti在固态合金中的固溶度极小，300℃时只有0.007-0.015wt％，因此Ti在本发明低铜合金中主要以金属间化合物的形式存在。本发明低铜合金中加入Ti，在结晶过程中Ti以TiZn15相的形式作为结晶核心促进形核，并有效阻止晶粒的长大而细化组织。同时，分布于基体晶界上的微米级TiZn15相颗粒和以其为核心的晶粒在阻碍位错运动、晶界滑移及协调变形方面起重要作用，适量的Ti可以提高合金的再结晶温度，从而改善其高温抗蠕变性能。当Ti的含量小于0.01wt％时，细化晶粒的效果不显著，不能有效提高合金的强度及抗蠕变性能；而当Ti元素含量过高，会形成大尺寸的块状中间相，导致合金的塑性加工能力出现 下降的情况，为实现合金优越的综合性能，本发明低铜合金中Ti的含量控制在0.01-1.0wt％。The solid solubility of Ti in a solid alloy is extremely small, and is only 0.007 to 0.015 wt% at 300 ° C. Therefore, Ti is mainly present in the form of an intermetallic compound in the low copper alloy of the present invention. In the low copper alloy of the present invention, Ti is added, and in the crystallization process, Ti promotes nucleation as a crystal core in the form of a TiZn 15 phase, and effectively prevents grain growth and refines the structure. At the same time, the micron-sized TiZn 15 phase particles distributed on the grain boundary of the matrix and the crystal grains with the core as the core play an important role in hindering dislocation motion, grain boundary slip and coordinated deformation. The proper amount of Ti can improve the recrystallization of the alloy. Temperature, thereby improving its high temperature creep resistance. When the content of Ti is less than 0.01% by weight, the effect of refining crystal grains is not significant, and the strength and creep resistance of the alloy cannot be effectively improved; and when the content of Ti element is too high, a large-sized block-shaped mesophase is formed, resulting in In the case where the plastic working ability of the alloy is degraded, in order to achieve superior overall properties of the alloy, the content of Ti in the low copper alloy of the present invention is controlled to be 0.01 to 1.0% by weight.
本发明低铜合金材料铸态组织的相组成包括基体Zn、等轴菊花状CuZn5相和带状网络的Zn-Cu-Ti-Mg-Mn化合物，经塑性变形加工后，铸态组织发生破裂，合金组织细化，带状网络的Zn-Cu-Ti-Mg-Mn化合物也发生断裂形成更细小的带状组织，从而合金表现出更好的塑性，使合金的抗蠕变性能大幅提升。The phase composition of the as-cast microstructure of the low-copper alloy material of the invention comprises a matrix Zn, an equiaxed chrysanthemum-like CuZn5 phase and a ribbon network of Zn-Cu-Ti-Mg-Mn compound, and the as-cast microstructure is broken after plastic deformation processing. The microstructure of the alloy is refined, and the Zn-Cu-Ti-Mg-Mn compound of the ribbon network also breaks to form a finer band structure, so that the alloy exhibits better plasticity and greatly improves the creep resistance of the alloy.
优选地，所述的相组成中CuZn5相的体积比为30～70％。对合金起到硬化和强化效果的同时，可保证合金的塑性。Preferably, the volume ratio of the CuZn 5 phase in the phase composition is 30 to 70%. The alloy is hardened and strengthened while ensuring the plasticity of the alloy.
优选地，本发明低铜合金材料的重量百分比组成还包括M：0.001～1.0wt％，所述的M为Zr、Cr、Fe、Mo、Ni、Si、Co、Al、V和RE中的至少一种元素。Zr、Cr、Fe、Mo、Ni、Si、Co、Al、V和RE分别以少量的金属间化合物相的形式存在于低铜合金基体中，起到强化的作用。Zr还具有细化晶粒、防止偏析的作用，RE还具有细化晶粒、除氧的作用。Zr、Cr、Fe、Mo、Ni、Si、Co、Al、V、RE的含量若不足0.001wt％，则达不到上述效果，反之若超过1.0wt％，则合金的塑性加工性能会显著下降，导致加工困难，因此本发明低铜合金中，优选含有以总量计为0.001-1.0wt％的上述元素中的至少一种。作为优选，所述的Zr的含量为0.001-0.1wt％，所述的Cr的含量为0.001-0.1wt％，所述的Fe的含量为0.001-0.1wt％，所述的Mo的含量为0.001-0.1wt％，所述的Ni的含量为0.001-0.1wt％，所述的Si的含量为0.001-0.1wt％，所述的Co的含量为0.001-0.1wt％，所述的Al的含量为0.001-0.1wt％，所述的V的含量为0.001-0.1wt％，所述的RE的含量为0.001-0.1wt％。Preferably, the weight percentage composition of the low copper alloy material of the present invention further comprises M: 0.001 to 1.0 wt%, and the M is at least at least Zr, Cr, Fe, Mo, Ni, Si, Co, Al, V, and RE. An element. Zr, Cr, Fe, Mo, Ni, Si, Co, Al, V, and RE are respectively present in the low-copper alloy matrix in the form of a small amount of an intermetallic compound phase, and serve to strengthen. Zr also has the effect of refining crystal grains and preventing segregation, and RE also has the functions of refining crystal grains and removing oxygen. If the content of Zr, Cr, Fe, Mo, Ni, Si, Co, Al, V, RE is less than 0.001% by weight, the above effect is not obtained, and if it exceeds 1.0% by weight, the plastic working property of the alloy is remarkably lowered. In the low copper alloy of the present invention, it is preferable to contain at least one of the above elements in an amount of 0.001 to 1.0% by weight based on the total amount. Preferably, the content of Zr is 0.001-0.1 wt%, the content of Cr is 0.001-0.1 wt%, the content of Fe is 0.001-0.1 wt%, and the content of Mo is 0.001. -0.1 wt%, the content of Ni is 0.001-0.1 wt%, the content of Si is 0.001-0.1 wt%, the content of Co is 0.001-0.1 wt%, and the content of Al is The content of V is 0.001 to 0.1% by weight, the content of V is 0.001 to 0.1% by weight, and the content of RE is 0.001 to 0.1% by weight.
本发明低铜合金材料的抗拉强度为400-550MPa，硬度为100-150HV5，延 伸率为10-20％，在100℃、蠕变加载应力为100Mpa的条件下的蠕变速率为(1.18-8.87)×10-6s-1。The low copper alloy material of the invention has a tensile strength of 400-550 MPa, a hardness of 100-150 HV5, an elongation of 10-20%, and a creeping shift rate at a temperature of 100 ° C and a creep loading stress of 100 MPa (1.18- 8.87) × 10 -6 s -1 .
优选地，本发明高强度抗蠕变低铜合金材料在通讯连接器行业的应用。Preferably, the high strength creep resistant low copper alloy material of the present invention is used in the communication connector industry.
与现有技术相比，本发明的优点在于：本发明提供的低铜合金具有优异的抗蠕变性能，在100℃、蠕变加载应力为100MPa的条件下蠕变速率可达到(1.18-8.87)×10-6s-1，与常规锌铜钛合金的7.58×10-5s-1相比缩小了一个数量级，延伸率可达到10-20％，抗拉强度为400-550MPa，硬度HV5可达到100-150。本发明合金可作为通讯连接器行业中铅黄铜的替代品，也可应用于其他行业的一些铜合金零部件的替代。Compared with the prior art, the invention has the advantages that the low copper alloy provided by the invention has excellent creep resistance, and the creep rate can reach at 100 ° C and the creep loading stress is 100 MPa (1.18-8.87). ×10 -6 s -1 , which is one order of magnitude smaller than the conventional zinc-copper-titanium alloy of 7.58×10 -5 s -1 , the elongation can reach 10-20%, the tensile strength is 400-550MPa, and the hardness is HV5. Can reach 100-150. The alloy of the present invention can be used as a substitute for lead brass in the telecommunications connector industry, and can also be used as an alternative to some copper alloy components in other industries.
附图说明DRAWINGS
图1为本发明的典型铸造态组织的SEM图片(×600)，该铸造态组织中含有基体Zn、等轴菊花状CuZn5相和带状网络的Zn-Cu-Ti-Mg-Mn化合物；1 is a SEM image (×600) of a typical as-cast microstructure of the present invention, which contains a matrix Zn, an equiaxed chrysanthemum CuZn 5 phase, and a ribbon network of Zn-Cu-Ti-Mg-Mn compound;
图2为本发明的典型铸造态组织的SEM图片(×2500)；Figure 2 is a SEM picture (x 2500) of a typical as-cast microstructure of the present invention;
图3为图2中Zn-Cu-Ti-Mg-Mn化合物的能谱分析结果；3 is a result of energy spectrum analysis of the Zn-Cu-Ti-Mg-Mn compound of FIG. 2;
图4为图2中Zn-Cu-Ti-Mg-Mn化合物的能谱图。4 is an energy spectrum diagram of the Zn-Cu-Ti-Mg-Mn compound of FIG. 2.
具体实施方式detailed description
以下结合附图实施例对本发明作进一步详细描述。The invention will be further described in detail below with reference to the embodiments of the drawings.
选取了25个实施例合金和2个对比例合金(对比例1按照ZL201010246298.6进行合金配比，对比例2按照ZL201010245802.0进行合金配比)，采用相同的工艺方法分别加工成Φ11.3的成品：采用连续铸造或硬模铸造的方法制成铸坯，在180℃-380℃温度下热挤压成棒材，最后经过冷拉加工制成Φ11.3的成品。25 alloys and 2 comparative alloys were selected (Comparative Example 1 was alloyed according to ZL201010246298.6, Comparative Example 2 was alloyed according to ZL201010245802.0), and processed into Φ11.3 by the same process. Finished product: The cast slab is made by continuous casting or die casting, hot extruded into a bar at a temperature of 180 ° C - 380 ° C, and finally processed into a finished product of Φ 11.3 by cold drawing.
本发明低铜合金材料的典型铸造态组织的SEM图片如图1(×600)和图2 (×2500)所示，该铸造态组织中含有基体Zn、等轴菊花状CuZn5相和带状网络的Zn-Cu-Ti-Mg-Mn化合物，Zn-Cu-Ti-Mg-Mn化合物的能谱分析结果如图3所示，Zn-Cu-Ti-Mg-Mn化合物的能谱图如图4所示。The SEM images of the typical as-cast microstructure of the low-copper alloy material of the present invention are shown in Fig. 1 (×600) and Fig. 2 (×2500), and the as-cast microstructure contains the matrix Zn, the equiaxed chrysanthemum CuZn 5 phase and the ribbon. The energy spectrum analysis results of the Zn-Cu-Ti-Mg-Mn compound and Zn-Cu-Ti-Mg-Mn compound of the network are shown in Fig. 3. The energy spectrum of the Zn-Cu-Ti-Mg-Mn compound is shown in Fig. 3. 4 is shown.
对实施例1-25及对比例1-2合金成品分别进行室温拉伸力学性能和高温蠕变性能检测。The alloys of Examples 1-25 and Comparative Examples 1-2 were tested for tensile properties at room temperature and high temperature creep properties, respectively.
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，对实施例1-25和对比例1-2均采用比例系数为11.3的圆截面比例试样，拉伸速度为5mm/min。The room temperature tensile test is carried out according to GB/T 228.1-2010 "Metal material tensile test Part 1: room temperature test method" on the electronic universal performance test machine, and the scale factors are used for both Examples 1-25 and Comparative Examples 1-2. The sample having a circular cross section of 11.3 has a tensile speed of 5 mm/min.
高温蠕变试验方法参照GB/T 2039-2012《金属材料单轴拉伸蠕变试验方法》，在升温前对试样施加不超过总试验力10％的初始力，并通过电子控制调节***保持加载过程的载荷恒定。高温蠕变试验在RWS50电子蠕变松弛试验机上进行，蠕变加载应力为100MPa，试验温度为100℃。试样加热炉具有自动调节温度的功能，在整个蠕变试验过程中炉内上、中、下三段的温度波动控制在±3℃，保证恒温加载。采用固定在试样上的引长夹具，将双侧轴向引伸计从加热炉中引出并测量形变位移。用计算机对整个过程进行控制与数据采集，实时记录轴向拉力、形变位移等数据。The high temperature creep test method refers to GB/T 2039-2012 "Metal material uniaxial tensile creep test method", and applies an initial force of not more than 10% of the total test force to the sample before heating, and is maintained by an electronic control adjustment system. The load during the loading process is constant. The high temperature creep test was carried out on an RWS50 electronic creep relaxation tester with a creep loading stress of 100 MPa and a test temperature of 100 °C. The sample heating furnace has the function of automatically adjusting the temperature. During the whole creep test, the temperature fluctuations in the upper, middle and lower sections of the furnace are controlled at ±3 °C to ensure constant temperature loading. The two-sided axial extensometer was taken out from the furnace and the deformation displacement was measured using an extension clamp fixed to the sample. The whole process is controlled and data collected by computer, and the axial tension, deformation displacement and other data are recorded in real time.
实施例、对比例的成分及性能测试结果见表1。 The composition and performance test results of the examples, comparative examples are shown in Table 1.
Figure PCTCN2014001135-appb-000001
Figure PCTCN2014001135-appb-000001
Figure PCTCN2014001135-appb-000002
Figure PCTCN2014001135-appb-000002

Claims (6)

  1. 一种高强度抗蠕变低铜合金材料，其特征在于，其重量百分比组成包括：Cu：4～10wt％，Mg：0.01～0.5wt％，Mn：0.01～2.0wt％，Ti：0.01～1.0wt％，余量为Zn和不可避免的杂质，该低铜合金材料铸态组织的相组成包括基体Zn、等轴菊花状CuZn5相和带状网络的Zn-Cu-Ti-Mg-Mn化合物。A high-strength creep-resistant low-copper alloy material characterized in that the weight percentage composition thereof comprises: Cu: 4 to 10 wt%, Mg: 0.01 to 0.5 wt%, Mn: 0.01 to 2.0 wt%, Ti: 0.01 to 1.0 Wt%, the balance is Zn and unavoidable impurities, the phase composition of the as-cast microstructure of the low-copper alloy material includes the matrix Zn, the equiaxed chrysanthemum CuZn 5 phase and the ribbon network Zn-Cu-Ti-Mg-Mn compound .
  2. 根据权利要求1所述的一种高强度抗蠕变低铜合金材料，其特征在于所述的相组成中CuZn5相的体积比为30～70％。A high-strength creep-resistant low-copper alloy material according to claim 1, wherein a volume ratio of the CuZn 5 phase in said phase composition is from 30 to 70%.
  3. 根据权利要求1或2所述的一种高强度抗蠕变低铜合金材料，其特征在于还包括M：0.001～1.0wt％，所述的M为Zr、Cr、Fe、Mo、Ni、Si、Co、Al、V和RE中的至少一种元素。A high-strength creep-resistant low-copper alloy material according to claim 1 or 2, which further comprises M: 0.001 to 1.0% by weight, said M being Zr, Cr, Fe, Mo, Ni, Si At least one of Co, Al, V, and RE.
  4. 根据权利要求3所述的一种高强度抗蠕变低铜合金材料，其特征在于所述的Zr的含量为0.001-0.1wt％，所述的Cr的含量为0.001-0.1wt％，所述的Fe的含量为0.001-0.1wt％，所述的Mo的含量为0.001-0.1wt％，所述的Ni的含量为0.001-0.1wt％，所述的Si的含量为0.001-0.1wt％，所述的Co的含量为0.001-0.1wt％，所述的Al的含量为0.001-0.1wt％，所述的V的含量为0.001-0.1wt％，所述的RE的含量为0.001-0.1wt％。A high-strength creep-resistant low-copper alloy material according to claim 3, wherein said Zr is contained in an amount of 0.001 to 0.1% by weight, and said Cr is contained in an amount of 0.001 to 0.1% by weight. The content of Fe is 0.001-0.1 wt%, the content of Mo is 0.001-0.1 wt%, the content of Ni is 0.001-0.1 wt%, and the content of Si is 0.001-0.1 wt%. The content of Co is 0.001-0.1 wt%, the content of Al is 0.001-0.1 wt%, the content of V is 0.001-0.1 wt%, and the content of RE is 0.001-0.1 wt. %.
  5. 根据权利要求1所述的一种高强度抗蠕变低铜合金材料，其特征在于该低铜合金材料的抗拉强度为400-550MPa，硬度为100-150HV5，延伸率为10-20％，在100℃、蠕变加载应力为100Mpa的条件下的蠕变速率为(1.18-8.87)×10-6s-1。 The high-strength creep-resistant low-copper alloy material according to claim 1, wherein the low-copper alloy material has a tensile strength of 400-550 MPa, a hardness of 100-150 HV5, and an elongation of 10-20%. The creep speed at 100 ° C and the creep loading stress of 100 MPa is (1.18-8.87) × 10 -6 s -1 .
  6. 权利要求1所述的一种高强度抗蠕变低铜合金材料在通讯连接器行业的应用。 The use of a high strength creep resistant low copper alloy material as claimed in claim 1 in the telecommunications connector industry.
PCT/CN2014/001135 2014-06-17 2014-12-17 High-strength creep-resistant low-copper alloy material and application thereof WO2015192279A1 (en)

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