WO2016095288A1 - Matériau déformé d'alliage à base de zinc et son procédé de préparation et son utilisation - Google Patents

Matériau déformé d'alliage à base de zinc et son procédé de préparation et son utilisation Download PDF

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Publication number
WO2016095288A1
WO2016095288A1 PCT/CN2015/000030 CN2015000030W WO2016095288A1 WO 2016095288 A1 WO2016095288 A1 WO 2016095288A1 CN 2015000030 W CN2015000030 W CN 2015000030W WO 2016095288 A1 WO2016095288 A1 WO 2016095288A1
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Prior art keywords
zinc
alloy material
based alloy
phase
deformed
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PCT/CN2015/000030
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English (en)
Chinese (zh)
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孙文声
陈永力
许丁洋
郭俊
王东
余惺
冯振仙
杨澍
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宁波博威合金材料股份有限公司
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Publication of WO2016095288A1 publication Critical patent/WO2016095288A1/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
    • 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
    • C22C18/04—Alloys based on zinc with aluminium 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
    • C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
    • 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

Definitions

  • the invention relates to a zinc-based alloy material and an application field thereof, in particular to a medium-strength, easy-machine-processed deformed zinc-based alloy material, and a preparation method and application thereof, the alloy material can be applied to an AC/DC power plug and an FC communication connection.
  • a zinc-based alloy material and an application field thereof in particular to a medium-strength, easy-machine-processed deformed zinc-based alloy material, and a preparation method and application thereof, the alloy material can be applied to an AC/DC power plug and an FC communication connection.
  • the raw material cost of zinc alloy is 20-30% lower than that of copper alloy, and harmful heavy metal elements such as lead and cadmium are not necessary elements in zinc alloy. Therefore, zinc alloy is a low-cost, green and environmentally friendly alloy.
  • the traditional zinc alloy is mainly cast zinc alloy, and its microstructure contains a brittle intermetallic compound phase, and its solid solubility is relatively low, resulting in low strength of the zinc alloy, especially the disadvantages of subsequent machining.
  • a small number of deformed zinc alloys have been developed, but the general deformed zinc alloys have defects and shortcomings such as high production cost, low yield, poor dimensional stability and poor mechanical properties.
  • elements such as Pb, Bi, and Sb which are advantageous for improving machinability are harmful to the zinc alloy, and are generally controlled as an impurity element in the zinc alloy.
  • the existing deformed zinc The machining performance of gold has been improved to some extent, but the subsequent processing of the deformed zinc alloy has not been fundamentally solved. In practical applications, the requirements for cutting performance of zinc alloys by modern machine tools cannot be met. Therefore, how to make the zinc alloy easy to process while the strength meets the requirements, and even achieve the machinability of the copper alloy, is a problem to be solved by those skilled in the art.
  • the technical problem to be solved by the present invention is to provide an easily machined deformed zinc-based alloy material and a preparation method and application thereof according to the deficiencies of the prior art, the alloy material having medium strength, high plasticity and high electrical conductivity. As an alternative to traditional brass alloys.
  • the technical solution adopted by the present invention to solve the above technical problem is: a deformed zinc-based alloy material, the weight percentage composition of the zinc-based alloy material includes: 3% ⁇ A1 ⁇ 15%, 0.1% ⁇ Cu ⁇ 4.8%, balance For Zn and unavoidable impurities, the microstructure of the zinc-based alloy material comprises an ⁇ phase and an ⁇ phase, wherein the ⁇ phase is a Zn-substituted A1 solid solution based on A1, and the ⁇ phase is based on Zn. Cu and A1 replace the solid solution of Zn.
  • the deformed zinc-based alloy material of the present invention has Zn as a matrix, and a certain amount of Cu is added in addition to the addition of A1 as a strengthening element.
  • the microstructure of the alloy of the present invention comprises two solid solution phases, namely the alpha phase of the FCC structure and the ⁇ phase of the HCP structure.
  • the ⁇ phase is a Zn-substituted A1 solid solution based on A1, and the ⁇ phase has a higher solid solubility than the ⁇ phase. Therefore, the ⁇ phase has higher strength and hardness, but when ⁇ is the same, it also replaces the solid solution, so it has good Plasticity, electrical conductivity.
  • the ⁇ phase of the alloy of the present invention is a solid solution in which Zn is a matrix of Cu and A1 is substituted for Zn, and as a solid solution, the ⁇ phase has good plasticity and electrical conductivity, and is easy to machine and has high electrical conductivity.
  • the alloy of the present invention obtains the above ⁇ phase and ⁇ phase in a reasonable manner by controlling its element ratio, and the most Finally, the machined and moderate strength of the deformed zinc-based alloy material is achieved, and its electrical conductivity is comparable to that of lead brass.
  • the solubility of solute atoms in the ⁇ phase and the ⁇ phase is different, a region having different hardness is formed in the microstructure of the alloy material, so that the internal structure of the alloy generates more interface structure, which is beneficial to the cutting process.
  • the chip breaking improves the machinability of the alloy.
  • the overall deformation coordination ability of the alloy is stronger, which also promotes the subsequent plastic processing of the alloy to be more easily realized.
  • the conductivity of the alloy of the present invention can reach the standard of the conventional brass.
  • an electrical product used for plugs and the like in addition to having good electrical conductivity, it should also have good mechanical properties, machinability and environmental corrosion resistance.
  • the range of addition of A1 should be controlled at 3% ⁇ A1 ⁇ 15%.
  • Cu is present in the zinc matrix in such a manner as to replace the Zn atom, thereby improving the strength and improving the plasticity without affecting the conductivity.
  • the Cu content is more than 4.8%, the excess Cu element will be from the zinc.
  • Precipitation in the matrix is not conducive to machining, and has a certain adverse effect on the electrical conductivity.
  • the Cu content is less than 0.1%, it cannot be strengthened. Therefore, in the present invention, the Cu content is controlled to 0.1% ⁇ Cu ⁇ 4.8%. .
  • the volume fraction of the ⁇ phase is 25-45%, and the volume fraction of the ⁇ phase is 50-75%; the average grain size of the zinc-based alloy material Degree is less than 15um.
  • the alloy of the present invention comprises a Zn-substituted A1 solid solution based on A1, that is, an ⁇ phase, and a solid solution in which Zn is a matrix of Cu and A1 is substituted for Zn, that is, an ⁇ phase.
  • the ⁇ phase of the alloy of the invention has two structures, The invention is referred to as the alpha 1 phase and the alpha 2 phase.
  • the ⁇ 1 phase belongs to the high solid solubility A1 matrix solid solution, that is, the Zn atom replaces the A1 atom in a large amount, the total atom number of the Zn element can account for about 60% of the total solid solution atom, and the low aluminum content ⁇ 1 solid solution often passes.
  • the eutectic reaction is formed and thus has higher strength and hardness.
  • the high aluminum content of ⁇ 2 is formed by eutectoid transformation, and the substitution rate of the Zn atom replacing the A1 atom is about 35%, so the strength and hardness are slightly lower than the ⁇ 1 phase.
  • the ⁇ 2 phase The grain size is smaller than the ⁇ 1 phase.
  • the volume fraction of the ⁇ phase is controlled to 25-45% in the alloy of the present invention, which plays an important role in improving the strength, hardness, plasticity and electrical conductivity of the alloy.
  • the average grain size of the zinc-based alloy material of the present invention is also critical, and by obtaining a uniformly refined microstructure, the average grain size is controlled to 15 ⁇ m or less to ensure the plasticity and strength of the material. Improvement.
  • the ⁇ phase is a main phase composition of the alloy of the present invention, and is a solid solution of an HCP structure obtained by substituting Zn with Zn as a matrix and Cu and A1 atoms.
  • the substitution rate of the A1 atom is about 10%
  • the substitution rate of the Cu element is about 10%
  • the rest is a zinc atom.
  • the alloy of the present invention has a ⁇ phase as a matrix, and the ⁇ 1 phase and the ⁇ 2 phase are dispersed on the ⁇ phase.
  • the volume fraction of the phase in the entire alloy phase composition is controlled at 50-75%. Based on the improvement of ⁇ -alloyability, the synergistic effect is promoted to further improve the plasticity and electrical conductivity of the alloy.
  • the weight percentage composition of the zinc-based alloy material comprises: 3% ⁇ A1 ⁇ 5%, 0.1% ⁇ Cu ⁇ 1.0%, generally, the conductivity is greater than 25.5% IACS, the tensile strength is greater than 360 MPa, and the elongation is greater than 13%, the cutting rate is greater than 62%; or, the weight percentage composition of the zinc-based alloy material includes: 8% ⁇ A1 ⁇ 12%, 1.0% ⁇ Cu ⁇ 4.0%, in general, its conductivity is greater than 25.5% IACS, anti- The tensile strength is greater than 380 MPa, the elongation is greater than 15%, and the cutting rate is greater than 64%; or, the weight percent composition of the zinc-based alloy material includes: 5% ⁇ A1 ⁇ 8%, 1.5% ⁇ Cu ⁇ 4.8%, generally, The electrical conductivity is greater than 26% IACS, the tensile strength is greater than 360 MPa, the elongation is greater than 14%, and the cutting rate is greater than 58%.
  • the electrical conductivity
  • the weight percentage composition of the zinc-based alloy material further comprises 0.001 to 1% of Mg.
  • Mg 0.001 to 1%
  • a trace amount of Mg exists in the phase boundary between the ⁇ phase and the ⁇ phase, and functions to prevent the occurrence of intergranular corrosion and enhance the resistance to environmental corrosion.
  • the Mg content is less than 0.001%, the effect is not obvious.
  • the Mg content is more than 1%, the brittleness of the material is caused, which is disadvantageous for subsequent machining.
  • the weight percentage composition of the zinc-based alloy material may further include 0.001 to 2% of Cr and/or 0.001 to 2% of Mn, or may also include total amount, based on 0.001 to 1% of Mg. It is at least one of Ti, Zr, RE, Ca, Si, Co, Y, and Sc of 0.001-1%.
  • the inclusion of 0.001 to 1% of Mg and 0.001 to 2% of Cr and/or 0.001 to 2% of Mn may also include a total amount of 0.001 to 1% of Ti, Zr, RE, Ca, At least one of Si, Co, Y, and Sc.
  • a small amount of Cr is dissolved in the ⁇ phase, which plays a role in corrosion resistance and high temperature brittleness, and is beneficial to the subsequent machining of the material.
  • the suitable Cr content is 0.001-2%.
  • a small amount of Mn can also be dissolved in the ⁇ phase, which significantly improves the strength and hardness of the alloy. When the Mn content is less than 0.001%, the effect is not obvious. When the Mn content is more than 2%, the strength and hardness of the material are improved, but the plasticity and electrical conductivity are improved. The rate dropped sharply and the overall performance deteriorated.
  • adding a suitable amount of chromium, manganese or magnesium element while increasing the strength and hardness of the alloy, does not reduce the electrical conductivity of the alloy.
  • Ti, Zr, RE, Ca, Si, Co, Y, and Sc may each exist in the matrix of zinc in the form of a small amount of an intermetallic compound phase, and serve to strengthen. Further, zirconium has a function of refining crystal grains and preventing segregation, and the rare earth metal has a function of refining crystal grains and removing oxygen. If the total amount of at least one of Ti, Zr, RE, Ca, Si, Co, Y, and Sc is less than 0.001%, the above effect is not obtained, and if it exceeds 1.0%, the plastic working property of the alloy is caused. The decrease causes difficulty in processing, and therefore, the total amount of the alloy of the present invention is controlled to be 0.001 to 1%.
  • the preparation method of the above deformed zinc-based alloy material comprises the following steps: 1) producing an ingot having a diameter of ⁇ 40-350 mm by hot-top casting, semi-continuous casting or horizontal continuous casting; 2) sawing the ingot after extrusion Cut into a length of 200-1500mm, heated to 180-370 ° C, extruded into a strand of ⁇ 4-45mm diameter by a forward or reverse extruder; 3) After at least two stretching and at least two After the secondary heat treatment, it is processed into a finished product, wherein the heat treatment temperature is 150-350 ° C, and the heat treatment time is 1-10 h.
  • the coarse cast structure can be broken, a uniform fine microstructure can be formed, and the solute content of the best solid solution can be obtained to improve the plasticity. And play a role in improving strength.
  • the above-mentioned deformed zinc-based alloy materials are used in power plugs, communication connectors, and electronic and electrical products.
  • materials for electrical and electronic industries such as power plugs and connectors, in addition to machining performance, it also needs to meet certain performance requirements such as strength, ductility, elongation, and electrical conductivity.
  • the invention further controls the microstructure by controlling the alloy composition, and obtains a deformed zinc-based alloy material which can fully meet the above requirements, and can be applied to electronic and electrical industries such as AC/DC power plugs and FC communication connectors, and can also be applied to other related industries. industry.
  • the solubility of solute atoms in the ⁇ phase and the ⁇ phase is different, a region having different hardness is formed in the microstructure of the alloy material, so that the internal structure of the alloy generates more interface structure, which is favorable for cutting.
  • the chip breaking during processing improves the machining performance of the alloy and makes the alloy have a higher cutting rate.
  • the overall deformation coordination ability of the alloy is stronger, which also promotes the subsequent plasticity of the alloy. The processing becomes easier to realize, and it is possible to realize the molding of various shapes and products of various specifications in the form of wires and bars.
  • the alloy of the invention has medium strength, the tensile strength can reach above 350 MPa, the elongation can reach more than 10%, the electrical conductivity can reach above 25% IACS, and the cutting rate can reach 50-85% of C3604 lead brass. It can fully meet the performance requirements of AC/DC power plugs, FC communication connectors, etc. It can be used as an alternative material for traditional brass alloys.
  • the preparation method of the alloy of the present invention through plastic processing methods such as extrusion and drawing, and reasonable control of the processing processes and parameters such as heat treatment, can break the coarse cast structure, form a uniform and refined microstructure, and obtain the best
  • the solute content of the solid solution is to improve the plasticity and to increase the strength, so that the alloy has a better overall performance.
  • Example 1 is an XRD diffraction photograph of Example 1.
  • ⁇ phase Zn-based solid solution
  • ⁇ phase A1-based solid solution
  • Figure 2 is a scanning electron micrograph of a deformed zinc-based alloy of Example 2 (x4000);
  • Example 3 is a scanning electron micrograph ( ⁇ 8000) of a deformed zinc-based alloy of Example 3, wherein white is ⁇ phase, light black is ⁇ 1 phase, and dark black is ⁇ 2 phase;
  • A1 is 30.27 at%
  • Cu is 1.67 at%
  • Zn is 68.06 at%
  • Example 7 is a graph showing the atomic content detection of the EDS of Example 3 at the spectrum 2, which is calculated by atomic percentage, A1 is 43.80 at%, and Zn is 56.20 at%;
  • Fig. 9 is a graph showing the results of atomic content detection of the EDS of Example 3 at the spectrum 3, which is calculated by atomic percentage, A1 is 34.57 at%, and Zn is 65.43 at%.
  • alloys and 1 comparative alloy were selected.
  • the added elements were added to the melting furnace according to their respective contents, and were produced by hot-top casting, semi-continuous casting or horizontal continuous casting to a diameter of ⁇ 40-350mm.
  • Ingot the ingot is sawn and cut to a length of 200-1500mm, heated to 180-370 ° C, extruded by a forward extruder or a reverse extruder ⁇ 4-45mm, after at least two stretching And after at least two annealing, processing into a finished wire product, the heat treatment temperature is: 150 ° C - 350 ° C, the heat treatment time is 1-10 h, and then straightening.
  • the room temperature tensile test is carried out in accordance with GB/T228.1-2010 Metallic Material Tensile Test Part 1: Room Temperature Test Method on the electronic universal performance test machine.
  • the sample adopts a circular section proportional sample with a proportional coefficient of 12 mm.
  • the stretching speed is 5 mm/min.
  • the experimental conditions are: cutting tool: WC-based super-hard alloy, cutting speed: 122 m / min, cutting depth: 0.5 mm, feed: 0.087 mm circle, cutting state: dry cutting.
  • the specific test results are shown in Table 1.
  • composition and performance test results of the examples, comparative examples are shown in Table 1.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
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Abstract

L'invention concerne un matériau déformé d'alliage à base de zinc et son procédé de préparation et son utilisation. L'alliage comprend (% en poids) : 3 % ≤ Al ≤ 15 % et 0,1 % ≤ Cu ≤ 4,8 %, le reste étant Zn et des impuretés inévitables. La microstructure du matériau d'alliage à base de zinc comprend une phase α et une phase η, la phase α étant une solution solide d'Al-substitué-par-Zn, présentant de l'Al en tant que matrice, et la phase η étant une solution solide de Zn-substitué-par-Cu et d'Al, présentant du Zn en tant que matrice.
PCT/CN2015/000030 2014-12-19 2015-01-19 Matériau déformé d'alliage à base de zinc et son procédé de préparation et son utilisation WO2016095288A1 (fr)

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CN201410797083.1A CN104498773B (zh) 2014-12-19 2014-12-19 一种变形锌基合金材料及其制备方法和应用
CN201410797083.1 2014-12-19

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CN115612901A (zh) * 2022-11-07 2023-01-17 福建省产品质量检验研究院(福建省缺陷产品召回技术中心) 一种半连铸工业化生产高品质Zn-22Al合金管材的方法

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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
KR101910868B1 (ko) * 2017-02-28 2018-10-23 창원대학교 산학협력단 방향성 결정립을 갖는 아연-알루미늄 합금 및 그 제조방법
CN107385279B (zh) * 2017-07-24 2019-02-22 浙江华意拉链有限公司 用于拉链的锌合金及其制备方法
CN108977694A (zh) * 2018-07-13 2018-12-11 安徽省含山县锦华氧化锌厂 一种高致密度锌合金及其制备方法
CN109022917A (zh) * 2018-07-13 2018-12-18 安徽锦华氧化锌有限公司 一种锌合金及其制备方法
CN111607718B (zh) * 2020-05-28 2021-05-25 宁波市佳利来机械制造有限公司 一种锌合金铸件及其制备方法
CN111621672B (zh) * 2020-07-03 2021-08-06 广东省材料与加工研究所 一种锌合金及其制备方法
CN115652143B (zh) * 2022-10-19 2023-12-05 广东省科学院新材料研究所 锌铝合金及其制备方法、应用

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