WO2015192279A1 - Matériau d'alliage à faible teneur en cuivre résistant au fluage de résistance mécanique élevée et application de celui-ci - Google Patents

Matériau d'alliage à faible teneur en cuivre résistant au fluage de résistance mécanique élevée et application de celui-ci 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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English (en)
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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Publication of WO2015192279A1 publication Critical patent/WO2015192279A1/fr

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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

La présente invention concerne un matériau d'alliage à faible teneur en cuivre résistant au fluage de résistance mécanique élevée, la composition en pourcentages massiques de celui-ci comprenant : Cu : 4 ~ 10 % en masse, Mg : 0,01 ~ 0,5 % en masse, Mn : 0,01 ~ 2,0 % en masse, Ti : 0,01 ~ 1,0 % en masse, et le reste étant constitué de Zn et des impuretés inévitables. La composition de phase de la structure brute de coulée du matériau d'alliage à faible teneur en cuivre comprend un substrat Zn, une phase CuZn5 en forme de chrysanthème équiaxe et un composé Zn-Cu-Ti-Mg-Mn présentant un réseau en forme de bande. L'alliage présente une excellente résistance au fluage. Dans des conditions de 100 oC et de contrainte de charge de fluage de 100 MPa, la vitesse de fluage est de (1,18 – 8,87) x 10-6 s-1, l'allongement est de 10-20 %, la résistance à la traction est de 400 à 550 MPa et la dureté HV5 est de 100 à 150. Le matériau d'alliage peut être utilisé comme substitut de laiton dans l'industrie des connecteurs de communication, et peut également être utilisé dans d'autres industries en tant que substitut de certains composants d'alliage de cuivre.
PCT/CN2014/001135 2014-06-17 2014-12-17 Matériau d'alliage à faible teneur en cuivre résistant au fluage de résistance mécanique élevée et application de celui-ci WO2015192279A1 (fr)

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CN104073685B (zh) * 2014-06-17 2016-08-17 宁波博威合金材料股份有限公司 一种高强度抗蠕变低铜合金材料及其应用
CN104328313B (zh) * 2014-10-29 2016-09-14 宁波博威合金材料股份有限公司 一种高强度的变形锌基合金材料
CN105543561A (zh) * 2015-12-11 2016-05-04 滁州市品诚金属制品有限公司 一种锌合金材料及其制备方法
CN105543562A (zh) * 2016-01-20 2016-05-04 广西丛欣实业有限公司 防盗窗用锌合金
CN106521241B (zh) * 2016-10-21 2018-03-27 宁波博威合金材料股份有限公司 一种可冷镦的变形锌合金及其应用
CN109735744B (zh) * 2019-01-28 2020-05-26 东北大学 一种具有室温超塑性的锌基合金棒材/板材及其制备方法
CN110343901A (zh) * 2019-08-27 2019-10-18 天长市华海电子科技有限公司 一种高韧性低应力锻造件及其生产工艺
CN114293039B (zh) * 2021-12-27 2022-07-12 江苏中矿大正表面工程技术有限公司 一种热喷涂用Zn-Cu-Ti-Mg合金的制备方法

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EP0899349A1 (fr) * 1997-08-13 1999-03-03 MITSUI MINING & SMELTING CO., LTD. Alliage de zinc thermorésistant et article moulé en celui-ci
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GB1194289A (en) * 1967-12-15 1970-06-10 Centre Nat Rech Metall Zinc Based Alloys having High Resistance to Breaking Load
FR2083866A5 (en) * 1970-03-07 1971-12-17 Metallgesellschaft Ag Castable zinc alloy
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