WO2018072052A1 - Deformable zinc alloy capable of being cold headed and application thereof - Google Patents

Deformable zinc alloy capable of being cold headed and application thereof Download PDF

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Publication number
WO2018072052A1
WO2018072052A1 PCT/CN2016/000609 CN2016000609W WO2018072052A1 WO 2018072052 A1 WO2018072052 A1 WO 2018072052A1 CN 2016000609 W CN2016000609 W CN 2016000609W WO 2018072052 A1 WO2018072052 A1 WO 2018072052A1
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zinc alloy
phase
cold
deformed
alloy
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PCT/CN2016/000609
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French (fr)
Chinese (zh)
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孙文声
唐宁
冯振仙
郭俊
陈永力
郜晓彬
向紫琪
傅红青
肖金锋
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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
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R4/00—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation
    • H01R4/58—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation characterised by the form or material of the contacting members

Definitions

  • the invention relates to the field of zinc alloy and its application technology, in particular to a deformed zinc alloy having a single-phase matrix structure, which can be subjected to cold deformation processing such as cold heading, and can be specifically applied to various power plugs, binding posts and the like. .
  • Cold heading technology is a high-speed deformation cold-processing technology that rapidly processes metal rod wires into various complex structural parts through various molds. Compared with the traditional turning technology, cold heading can improve the utilization rate of materials, reduce the loss, improve the labor efficiency, and the cold and cold product organization is uniform and compact. It has been widely used in various standard parts, so cold heading becomes metal material processing. An important means of molding.
  • Cold heading requires high performance of metal materials. Metal materials are required to have good structural uniformity, fluidity and formability. At the same time, high hardness, yield strength and toughness of metal materials are required, and the product structure is more complicated. The higher the overall performance requirements of the material.
  • the common metal materials used for cold heading are: iron alloy, stainless steel, aluminum alloy, copper and titanium alloy.
  • the cold heading properties, plasticity, shear strength and microstructure of metallic materials are closely related.
  • plasticity of the material is good, the deformation ability of the material itself is relatively strong, and cracks are not easily generated during the cold deformation process; when the shear strength of the material is high, the shear deformation resistance is good, and the cold deformation zone is good.
  • the grains of the bifurcation site are less prone to fracture when subjected to shear stress. Therefore, good plasticity and ideal shear deformation resistance are the prerequisites for ensuring that zinc-based alloys do not crack during cold heading and large deformation.
  • the deformation processing of cold heading products often has to be processed by multiple molds, multiple passes, and large deformation.
  • the material with less obvious work hardening is more suitable for the cold heading processing technology
  • the zinc alloy belongs to the material which is not obvious in the process of processing and deformation, and the copper alloy, steel and the like are work hardened materials, so Compared to materials such as copper alloys and steel, zinc alloys have a natural advantage for cold heading.
  • Zinc is an important non-ferrous metal with good electrical conductivity, calendering and wear resistance. Although zinc is currently used in the field of non-ferrous metals second only to copper and aluminum, the use of zinc at this stage is mostly concentrated in copper. In alloys or aluminum alloys. In recent years, the industry has also developed a deformed zinc alloy.
  • CN104498773A discloses a deformed zinc alloy whose weight percentage composition includes: 3% ⁇ Al ⁇ 15%, 0.1% ⁇ Cu ⁇ 4.8%, and the balance is Zn and not
  • the microstructure of the zinc-based alloy material includes an ⁇ phase and an ⁇ phase, the ⁇ phase is a Zn-substituted Al solid solution based on Al, and the ⁇ phase is a solid solution of Cu, Al-substituted Zn with Zn as a matrix;
  • the preparation method can obtain the solute content of the best solid solution.
  • the invention improves the comprehensive performance of the alloy by the synergistic promotion of the ⁇ phase and the ⁇ phase.
  • the alloy has medium strength, the tensile strength can reach 350 MPa or more, and the elongation can reach 10% or more.
  • the conductivity can reach 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 plug and FC communication connector, and can be used as an alternative material for traditional brass alloy.
  • CN104328313A discloses a high-strength deformed zinc-based alloy material having a weight percentage composition including: Cu: 5 to 15% by weight, Al: 7 to 20% by weight, Mg: 0.01 to 1.5% by weight, and Cr: 0.01 to 2.0. Wt%, the balance is Zn and unavoidable impurities.
  • the microstructure of the zinc-based alloy material contains fine and uniformly distributed primary phase ⁇ , aluminum-rich Al-Zn-Cu ternary fine eutectoid structure and zinc-rich
  • the Zn-Al-Cu ternary eutectic structure has a tensile strength of 500 MPa or more, an HV hardness of 120 or more, an elongation of 10% or more, a conductivity of 26% IACS or more, and a good machinability.
  • traditional copper alloys especially traditional lead brass, it is used in power plugs, electrical and electronic products and communication connectors.
  • the above deformed zinc alloy does not involve cold heading processing, and its comprehensive performance can not meet the requirements of cold heading processing.
  • due to the high performance requirements of materials for cold heading processing the prior art can be applied to the deformed zinc of cold heading processing. The alloy was not developed.
  • the inventors of the present application have found through extensive research that for the zinc alloy, in order to satisfy the cold heading process, in addition to the requirements of the tensile strength of 280 MPa or more, the elongation of 15% or more, and the hardness of 85 HV5 or more, the shear strength is required. It should reach above 250MPa, and other performance indicators must meet certain requirements, which is crucial for obtaining satisfactory shear properties of zinc alloy and achieving its cold heading processing.
  • the technical problem to be solved by the present invention is to provide a deformed zinc alloy having a single-phase matrix structure, which has excellent comprehensive properties and strength, plasticity, hardness and shear resistance, in view of the deficiencies of the prior art. Coordination, good cold heading performance, cold forming and other cold deformation processing, specifically for a variety of power plugs, binding posts and other products.
  • the technical solution adopted by the present invention to solve the above technical problem is: a cold-formed deformed zinc alloy, the weight percentage composition of the deformed zinc alloy includes: 0.01% ⁇ Cu ⁇ 5.0%, 0.01% ⁇ Al ⁇ 5.0%, 0.001 % ⁇ Mg ⁇ 1.0%, the balance is Zn and unavoidable impurities.
  • the microstructure of the deformed zinc alloy is based on a single-phase ⁇ -phase solid solution structure, and the single-phase ⁇ -phase solid solution structure is in the deformed zinc alloy. The volume fraction in the microstructure is 95 to 99%.
  • a small amount of Cu precipitates to form an ⁇ phase (i.e., CuZn5).
  • Cu can improve the strength, hardness, corrosion resistance and flow properties of the alloy, and reduce the intergranular corrosion sensitivity of the alloy.
  • the maximum solid solubility of copper in zinc is 2.7wt%.
  • the ⁇ phase precipitates.
  • the amount of ⁇ phase precipitates is small and the size is small, and the alloy maintains a small intensity increase.
  • the elongation increases, the hardness remains basically unchanged, and the copper content is appropriately increased, which is advantageous for refining the matrix structure of the zinc-aluminum-based alloy, increasing the density, and reducing the tendency of shrinkage and shrinkage.
  • most of Cu is solid-dissolved in a single-phase ⁇ phase of a matrix structure, and a small amount of Cu is precipitated as a CuZn5 compound.
  • the copper content should not be too high, and when the copper content is too high, a large amount of ⁇ phase will be precipitated, although the strength and hardness are The degree is increased, but the elongation is greatly lowered, so the present invention controls the copper content to be 0.01 to 5.0% by weight.
  • the aluminum content is controlled. 0.01 to 5.0 wt%.
  • the solid solubility of Mg in the zinc alloy matrix of the present invention is extremely small, and 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 , two The fine particles formed uniformly precipitate in the ⁇ phase, significantly increasing the strength and hardness of the deformed zinc alloy, and improving the cold forging property of the alloy.
  • the Mg content exceeds 1.0% by weight, the impact toughness of the alloy is remarkably lowered, causing problems in the production and processing of the alloy; and when the Mg content is less than 0.001% by weight, there is no significant strengthening effect. Therefore, the deformed zinc alloy of the present invention has a magnesium content of 0.001 to 1.0% by weight.
  • the invention adds Cu, Al, Mg, Zn and controls the content of each element, so that Cu, Al and Mg are dissolved as much as possible in the matrix, forming a ⁇ phase with a volume fraction of 95-99%, and the existence of a single phase matrix phase
  • it imparts high elongation and shear strength to the alloy, resulting in an ideal cold heading performance.
  • the microstructure of the deformed zinc alloy comprises a single-phase ⁇ -phase solid solution structure and a precipitated phase, wherein the precipitated phase is CuZn5 ( ⁇ ) and Al ( ⁇ ), and the average grain size of the precipitated phase is ⁇ 5 um.
  • the second phase compound is precipitated in the ⁇ phase, and Cu, Al, and Mg are sufficiently solid-dissolved in the matrix to precipitate CuZn5 ( ⁇ ), Al( ⁇ ), Mg 2 Zn 11 , and the like. These compounds are precipitated in the form of a micron-sized precipitate phase.
  • the average grain size of the present invention is controlled to be no more than 5 um, which further increases the strength of the alloy, has little effect on the elongation, and can improve the impact resistance of the alloy during cold heading. strength.
  • the single-phase ⁇ -phase solid solution structure is equiaxed, and the single-phase ⁇ -phase solid solution structure has a grain size of 5 to 100 ⁇ m.
  • the equiaxed crystals are mainly present in the single-phase alloy, and the properties in all directions are consistent.
  • the produced alloy wires are from a transverse cross section (ie, perpendicular to the machining direction) or a longitudinal cross section (ie, parallel to The microstructured metallographic pictures of the machine direction show that the grain-shaped uniformity of the deformed zinc alloy of the present invention is good, and the grain size ranges from 5 to 100 um.
  • the alloy of the present invention have no macroscopic anisotropy, so that the alloy can be subjected to cold rolling, riveting, and the like from various directions, and has the advantage of being less prone to cracking during processing.
  • the invention controls the grain size of the single-phase ⁇ phase solid solution structure to be 5 to 100 um, and the micro-phase single-phase solid solution makes the grain of the alloy fine, which is advantageous for achieving excellent combination of strength and elongation, and good cold heading effect. .
  • the ratio of the transverse hardness to the longitudinal hardness of the deformed zinc alloy satisfies: 0.9 ⁇ transverse hardness / longitudinal hardness ⁇ 1.1. Since the equiaxed crystals have the same performance in all directions, the ratio of the transverse hardness to the longitudinal hardness is controlled to be 0.9 to 1.1, which ensures the consistency of the material properties.
  • the transverse hardness that is, the surface hardness of the cross section of the wire product made of the deformed zinc alloy
  • the longitudinal hardness that is, the axial surface hardness of the wire product made of the deformed zinc alloy.
  • the weight percent composition of the deformed zinc alloy further comprises 0.01% ⁇ Mn ⁇ 2.0% and/or 0.001% ⁇ Cr ⁇ 1.0%.
  • Mn is solid-solubilized in a copper alloy to enhance the strength, and Mn can also refine the alloy structure. When the Mn content is too low, the strengthening effect is not remarkable. If the Mn content is too high, the elongation is significantly lowered. Therefore, the amount of Mn added in the present invention is controlled to be 0.01 to 2.0% by weight.
  • a small amount of Cr can form a CrZn 17 phase with zinc, and has better deformation coordination with the matrix, and can improve the strength and hardness of the alloy without lowering the plasticity thereof.
  • a suitable Cr content is 0.001 to 1.0%.
  • the weight percent composition of the deformed zinc alloy further includes at least one of Ni, RE, Ca, and Co in a total amount of 0.001 to 1%.
  • Ni is dissolved in the single-phase matrix to achieve dimensional stability, but excessive addition makes the alloy brittle.
  • the rare earth element RE can purify the grain boundary and refine the grain in the zinc alloy, and improve the plasticity.
  • the strength; Ca is hardly dissolved in the solid solution, and is formed in the matrix as a simple substance, thereby increasing the strength of the matrix;
  • Co is a hexagonal structure, and a small amount of Co and Zn matrix forms a subterranean solid solution, which can improve the strength.
  • the total amount of at least one of Ni, RE, Ca, and Co is controlled to be 0.001 to 1%, and the overall performance of the alloy can be further optimized.
  • the deformed zinc alloy has a tensile strength of 280 MPa or more and an elongation of 15% or more.
  • shear resistance is the strength limit at which the external force is perpendicular to the axis of the material and shears the material. In the process of cold heading, the force is vertically downward, which causes shearing effect on the material. If the shearing force of the deformed zinc alloy is insufficient, the material will be distorted during the cold rolling process, and the cold heading performance also needs to satisfy the material. The plasticity, the plasticity is too low, and the material will crack.
  • the invention realizes tensile strength of 280 MPa or more, elongation of 15% or more, and shear strength of 250 MPa or more by a single-phase solid solution matrix, so that the material is subjected to strength without cracking.
  • the preparation method of the cold-formed deformed zinc alloy of the invention comprises the following steps: casting (ingot casting with a diameter of 100-300 mm by hot-top casting, semi-continuous casting or horizontal continuous casting), sawing (saw ingot casting) Cut into the length of 200 ⁇ 1500mm), extrusion (ingot casting 180 ⁇ 370 ° C, through 1000t or more positive and negative extruder extruded into ⁇ 6 ⁇ 20mm strand), stretching, heat treatment (after at least twice After the above stretching and multiple heat treatment, the finished product is obtained, and the heat treatment temperature is 150-350 ° C, and the heat treatment time is 1 ⁇ 10h).
  • the above-described deformed zinc alloy is used in cold heading processing.
  • the above-described deformed zinc alloy is used in a power plug and a terminal.
  • the alloy of the invention has excellent cold heading performance, and can be cold-formed and other cold-deformed processing to satisfy each
  • the production requirements of power plugs and terminal products can be widely used in the electrical and electronic industry.
  • the microstructure of the cold-formed deformed zinc alloy of the present invention is based on a single-phase ⁇ -phase solid solution structure, and the single-phase ⁇ -phase solid solution structure is in the deformation.
  • the volume fraction of the zinc alloy in the microstructure is 95 to 99%, the tensile strength can reach 280 MPa or more, and the elongation can reach 15% or more, which can provide sufficient deformation ability for cold heading processing; the present invention realizes single phase by
  • the matrix structure imparts excellent comprehensive properties to the zinc alloy, and its strength, plasticity, hardness and shear resistance are coordinated, and finally the preferred cold heading performance of the deformed zinc alloy of the present invention is obtained.
  • the microstructure of the deformed zinc alloy includes a small amount of precipitated phases, including CuZn5 ( ⁇ ), Al ( ⁇ ), and Mg 2 Zn 11 , and precipitated phases.
  • the average grain size ⁇ 5um can further improve the strength of the alloy, especially for the improvement of shear strength.
  • the shear strength can reach 250MPa or more, and the high shear strength is more conducive to the realization of cold heading. .
  • the solid solution structure of the single phase of the zinc alloy is equiaxed, and the grain size is controlled to be 5 to 100 um, and the performance of the equiaxed crystals in all directions is uniform.
  • the alloy produced by the transverse section or It is shown from the metallographic photographs of the longitudinal section that the grain size is uniform and the range is 5 to 100 um.
  • This kind of The presence of the axial crystals makes the alloy have no macroscopic anisotropy, so the alloy can be cold-drawn, riveted, etc. from all directions, and the material is not easily cracked during processing.
  • the zinc alloy of the invention has the characteristics of softening of processing, and therefore, the alloy of the invention can be subjected to repeated cold heading processing, and the coldness of the material cannot be caused by work hardening. The situation achieved.
  • the zinc alloy of the present invention can be formed by machining (cutting), riveting, cold forging, etc., but the cold heading can improve the processing efficiency while saving the material cost compared with other processing methods, and thus has obvious advantages.
  • the zinc alloy of the invention can be formed by rods, wires (including round wires, flat wires), etc., and the products obtained through subsequent machining can be widely applied to electronic plugs, binding posts and the like in accordance with the EU and 3C fields. Electrical industry.
  • Example 1 is a microscopic metallographic picture of a cold-form deformable zinc alloy wire of Example 5;
  • Example 2 is a microscopic metallographic picture of the cold-form deformable zinc alloy wire of Example 8 perpendicular to the machine direction;
  • Example 3 is a microscopic metallographic picture of the cold-form deformable zinc alloy wire of Example 8 parallel to the machine direction.
  • alloys and 2 comparative alloys were selected, cast (produced by hot-top casting, semi-continuous casting or horizontal continuous casting into ingots with a diameter of 100-300 mm), sawing (cutting the ingot into 200 ⁇ 1500mm length), extrusion (ingot heating 180 ⁇ 370 ° C, through 1000t or more positive and negative extruder extruded into ⁇ 6 ⁇ 20mm strand), stretching, heat treatment (after at least two times stretching And multiple heat treatment
  • the finished product is obtained by post-processing, and the heat treatment temperature is 150-350 ° C, and the heat treatment time is 1-10 h).
  • the metallographic picture of the wire microstructure of Example 5 is shown in Fig. 1.
  • the microstructure of the wire of Example 8 perpendicular to the machine direction is shown in Fig. 2.
  • the wire of Example 8 is parallel to the microstructure of the machining direction.
  • the picture is shown in Figure 3.
  • the wire products of the alloys of Examples 1 to 20 were tested for transverse hardness and longitudinal hardness according to the GB/T 4340.1-2009 "Metal Vickers Hardness Test” method.
  • the transverse hardness refers to the surface hardness of the cross section of the finished wire product of the alloys of Examples 1 to 20, and the longitudinal hardness refers to the axial surface hardness of the finished wire product of the alloys of Examples 1 to 20, and each set of data is taken 5
  • the test results were averaged, and the transverse hardness and longitudinal hardness of the alloys of Comparative Examples 1 and 2 were examined. Further, the tensile strength and elongation of the alloys of Examples 1 to 20 and Comparative Examples 1 to 2 were examined in accordance with GB T228.1-2010 "Metal Material Room Stretching Method".
  • the tensile strength of the cold-formed deformed zinc alloy of the present invention is 289-375 MPa
  • the elongation is 15 to 33%
  • the transverse hardness HV5 is 90-117
  • the shear strength is 257-340 MPa.
  • the ratio of the transverse hardness to the longitudinal hardness is 0.92 to 1.07
  • the volume fraction of the single phase ⁇ phase solid solution structure in the microstructure of the deformed zinc alloy is 95 to 99%, which satisfies the cold heading processing requirements of the zinc alloy and can be cooled.
  • the products can be specifically applied to the electrical and electronic industries such as power plugs and terminals that comply with the EU and 3C fields.

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Abstract

A deformable zinc alloy capable of being cold headed. The deformable zinc alloy comprises the following components in percentage by weight: 0.01%≤Cu≤5.0%, 0.01%≤Al≤5.0%, and 0.001%≤Mg≤1.0%, with the balance being Zn and inevitable impurities. The microstructure of the deformable zinc alloy uses a single-phase η-phase solid solution structure as a matrix; the volume fraction of the single-phase η-phase solid solution structure in the microstructure of the deformable zinc alloy is 95-99%. The microstructure of the alloy uses a single-phase η-phase solid solution structure as a matrix, the tensile strength of the alloy can reach 280 MPa or more, and the elongation can reach 15% or more, so that sufficient deformability is provided for cold heading processing.

Description

一种可冷镦的变形锌合金及其应用Cold-formed deformed zinc alloy and application thereof 技术领域Technical field
本发明涉及锌合金及其应用技术领域，具体涉及一种具有单相基体组织的变形锌合金，该锌合金可进行冷镦等冷变形加工，具体可应用于各种电源插头、接线柱等产品。The invention relates to the field of zinc alloy and its application technology, in particular to a deformed zinc alloy having a single-phase matrix structure, which can be subjected to cold deformation processing such as cold heading, and can be specifically applied to various power plugs, binding posts and the like. .
背景技术Background technique
冷镦技术是一种高速变形的冷加工技术，通过各种模具将金属棒线材快速加工成各种复杂结构的零件。与传统的车削技术相比较，冷镦可以提高材料的利用率，降低损耗，提高劳动效率，并且冷镦产品组织均匀、致密，已广泛应用于各种标准件产品，因此冷镦成为金属材料加工成型的重要手段。Cold heading technology is a high-speed deformation cold-processing technology that rapidly processes metal rod wires into various complex structural parts through various molds. Compared with the traditional turning technology, cold heading can improve the utilization rate of materials, reduce the loss, improve the labor efficiency, and the cold and cold product organization is uniform and compact. It has been widely used in various standard parts, so cold heading becomes metal material processing. An important means of molding.
冷镦对金属材料的性能要求很高，要求金属材料具备良好的组织均匀性、流动性和成型性，同时对金属材料的硬度、屈服强度和韧性等均有较高要求，且产品结构越复杂对材料的综合性能要求越高。目前常见的用于冷镦的金属材料有：铁合金、不锈钢、铝合金、紫铜及钛合金等。Cold heading requires high performance of metal materials. Metal materials are required to have good structural uniformity, fluidity and formability. At the same time, high hardness, yield strength and toughness of metal materials are required, and the product structure is more complicated. The higher the overall performance requirements of the material. The common metal materials used for cold heading are: iron alloy, stainless steel, aluminum alloy, copper and titanium alloy.
金属材料的冷镦成型性能、塑性、剪切强度及显微组织密切相关。当材料的塑性较好时，材料本身的变形能力比较强，在冷镦大变形过程中不容易产生裂纹；当材料的剪切强度较高时，抗剪切变形能力较好，冷镦变形带分岔部位的晶粒在受到剪切应力的作用时不容易发生断裂。因此良好的塑性和理想的抗剪切变形能力是确保锌基合金在冷镦大变形过程中不产生裂纹的前提基础。冷镦产品的变形加工往往要经过多个模具、多道次、大变形量的加工，如果金属材料的加工硬化率比较高，会出现加工硬化的现象，难以保证最终产品的质量。所以加工硬化不明显的材料更适合于冷镦加工技术，而锌合金属于在加工变形过程中，加工硬化不明显的材料，铜合金、钢铁等属于加工硬化的材料，因此 相比于铜合金和钢铁等材料，锌合金用于冷镦具有天然的优势。The cold heading properties, plasticity, shear strength and microstructure of metallic materials are closely related. When the plasticity of the material is good, the deformation ability of the material itself is relatively strong, and cracks are not easily generated during the cold deformation process; when the shear strength of the material is high, the shear deformation resistance is good, and the cold deformation zone is good. The grains of the bifurcation site are less prone to fracture when subjected to shear stress. Therefore, good plasticity and ideal shear deformation resistance are the prerequisites for ensuring that zinc-based alloys do not crack during cold heading and large deformation. The deformation processing of cold heading products often has to be processed by multiple molds, multiple passes, and large deformation. If the work hardening rate of metal materials is relatively high, work hardening will occur, and it is difficult to guarantee the quality of the final product. Therefore, the material with less obvious work hardening is more suitable for the cold heading processing technology, and the zinc alloy belongs to the material which is not obvious in the process of processing and deformation, and the copper alloy, steel and the like are work hardened materials, so Compared to materials such as copper alloys and steel, zinc alloys have a natural advantage for cold heading.
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，虽然目前锌在有色金属领域的使用量仅次于铜及铝，但是现阶段对锌的使用大多集中在铜合金或铝合金中。近年来业内对变形锌合金也有所研发，例如，CN104498773A公开了一种变形锌合金，其重量百分比组成包括：3％≤Al≤15％，0.1％≤Cu≤4.8％，余量为Zn和不可避免的杂质，该锌基合金材料的微观组织包含α相和η相，α相为以Al为基体的Zn置换Al固溶体，η相为以Zn为基体的Cu、Al置换Zn的固溶体；通过其制备方法可获得最佳的固溶体的溶质含量，该发明通过α相和η相的协同促进改善合金综合性能，合金具有中等强度，其抗拉强度可以达到350MPa以上，延伸率可以达到10％以上，导电率可以达到25％IACS以上，切削率可达C3604铅黄铜的50～85％，完全能够满足AC/DC电源插头、FC通讯连接器等性能需求，可作为传统黄铜合金的替代材料。又如，CN104328313A公开了一种高强度的变形锌基合金材料，其重量百分比组成包括：Cu：5～15wt％，Al：7～20wt％，Mg：0.01～1.5wt％，Cr：0.01～2.0wt％，余量为Zn和不可避免的杂质，该锌基合金材料的微观组织含有细小而均匀分布的初生相ε、富铝的Al-Zn-Cu三元组成的细小共析组织和富锌的Zn-Al-Cu三元共晶组织，其抗拉强度在500MPa以上、HV硬度在120以上、延伸率在10％以上、导电率在26％IACS以上，同时具有良好的机加工性能，可作为传统铜合金尤其是传统铅黄铜的替代品，应用于电源插头、电子电气产品和通讯连接器等行业中。但以上变形锌合金并不涉及冷镦加工，其综合性能也满足不了冷镦加工的要求，而因冷镦加工对材料的高性能要求，目前现有技术中能够应用于冷镦加工的变形锌合金未能得到开发。 Zinc is an important non-ferrous metal with good electrical conductivity, calendering and wear resistance. Although zinc is currently used in the field of non-ferrous metals second only to copper and aluminum, the use of zinc at this stage is mostly concentrated in copper. In alloys or aluminum alloys. In recent years, the industry has also developed a deformed zinc alloy. For example, CN104498773A discloses a deformed zinc alloy whose weight percentage composition includes: 3% ≤ Al ≤ 15%, 0.1% ≤ Cu ≤ 4.8%, and the balance is Zn and not The impurity to be avoided, the microstructure of the zinc-based alloy material includes an α phase and an η phase, the α phase is a Zn-substituted Al solid solution based on Al, and the η phase is a solid solution of Cu, Al-substituted Zn with Zn as a matrix; The preparation method can obtain the solute content of the best solid solution. The invention improves the comprehensive performance of the alloy by the synergistic promotion of the α phase and the η phase. The alloy has medium strength, the tensile strength can reach 350 MPa or more, and the elongation can reach 10% or more. The conductivity can reach 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 plug and FC communication connector, and can be used as an alternative material for traditional brass alloy. For another example, CN104328313A discloses a high-strength deformed zinc-based alloy material having a weight percentage composition including: Cu: 5 to 15% by weight, Al: 7 to 20% by weight, Mg: 0.01 to 1.5% by weight, and Cr: 0.01 to 2.0. Wt%, the balance is Zn and unavoidable impurities. The microstructure of the zinc-based alloy material contains fine and uniformly distributed primary phase ε, aluminum-rich Al-Zn-Cu ternary fine eutectoid structure and zinc-rich The Zn-Al-Cu ternary eutectic structure has a tensile strength of 500 MPa or more, an HV hardness of 120 or more, an elongation of 10% or more, a conductivity of 26% IACS or more, and a good machinability. As a replacement for traditional copper alloys, especially traditional lead brass, it is used in power plugs, electrical and electronic products and communication connectors. However, the above deformed zinc alloy does not involve cold heading processing, and its comprehensive performance can not meet the requirements of cold heading processing. However, due to the high performance requirements of materials for cold heading processing, the prior art can be applied to the deformed zinc of cold heading processing. The alloy was not developed.
本申请发明人经大量研究发现，对锌合金而言，若要满足冷镦加工，除了需要满足抗拉强度在280MPa以上、延伸率在15％以上、硬度在85HV5以上的要求外，剪切强度应达到250MPa以上，并且其他性能指标须达到一定要求，对于获得锌合金的满意的剪切性能并实现其冷镦加工具有至关重要的作用。The inventors of the present application have found through extensive research that for the zinc alloy, in order to satisfy the cold heading process, in addition to the requirements of the tensile strength of 280 MPa or more, the elongation of 15% or more, and the hardness of 85 HV5 or more, the shear strength is required. It should reach above 250MPa, and other performance indicators must meet certain requirements, which is crucial for obtaining satisfactory shear properties of zinc alloy and achieving its cold heading processing.
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，提供一种具有单相基体组织的变形锌合金，该锌合金具有优异的综合性能，其强度、塑性、硬度、抗剪切性能得到协调，冷镦性能较好，可进行冷镦等冷变形加工，具体可应用于各种电源插头、接线柱等产品。The technical problem to be solved by the present invention is to provide a deformed zinc alloy having a single-phase matrix structure, which has excellent comprehensive properties and strength, plasticity, hardness and shear resistance, in view of the deficiencies of the prior art. Coordination, good cold heading performance, cold forming and other cold deformation processing, specifically for a variety of power plugs, binding posts and other products.
本发明解决上述技术问题所采用的技术方案为：一种可冷镦的变形锌合金，该变形锌合金的重量百分比组成包括：0.01％≤Cu≤5.0％，0.01％≤Al≤5.0％，0.001％≤Mg≤1.0％，余量为Zn和不可避免的杂质，该变形锌合金的微观组织以单相的η相固溶体组织为基体，所述的单相的η相固溶体组织在该变形锌合金的微观组织中的体积分数为95～99％。The technical solution adopted by the present invention to solve the above technical problem is: a cold-formed deformed zinc alloy, the weight percentage composition of the deformed zinc alloy includes: 0.01% ≤ Cu ≤ 5.0%, 0.01% ≤ Al ≤ 5.0%, 0.001 %≤Mg≤1.0%, the balance is Zn and unavoidable impurities. The microstructure of the deformed zinc alloy is based on a single-phase η-phase solid solution structure, and the single-phase η-phase solid solution structure is in the deformed zinc alloy. The volume fraction in the microstructure is 95 to 99%.
本发明中加入的Cu除了固溶于单相基体η相外，少量的Cu析出形成ε相(即CuZn5)。Cu可提高合金的强度、硬度、耐蚀性和合金液的流动性能，并降低合金的晶间腐蚀敏感性。铜在锌中的最大固溶度是2.7wt％，随着温度的降低，析出ε相，在铜含量较低的情况下，ε相析出的数量少、尺寸小，合金在保持较小强度增幅下，伸长率增加，硬度基本保持不变，而适当地提高铜含量，有利于细化锌铝基合金的基体组织，提高致密度，减少缩孔缩松倾向。在本发明中，大部分的Cu固溶于单相的基体组织η相，少量的Cu以CuZn5化合物形式析出。但铜含量不宜过高，铜含量过高时会析出大量的ε相，虽然强度、硬 度增高，但延伸率大大下降，因此本发明将铜含量控制在0.01～5.0wt％。In addition to the solid solution of the Cu added in the present invention, a small amount of Cu precipitates to form an ε phase (i.e., CuZn5). Cu can improve the strength, hardness, corrosion resistance and flow properties of the alloy, and reduce the intergranular corrosion sensitivity of the alloy. The maximum solid solubility of copper in zinc is 2.7wt%. As the temperature decreases, the ε phase precipitates. In the case of low copper content, the amount of ε phase precipitates is small and the size is small, and the alloy maintains a small intensity increase. Under the above, the elongation increases, the hardness remains basically unchanged, and the copper content is appropriately increased, which is advantageous for refining the matrix structure of the zinc-aluminum-based alloy, increasing the density, and reducing the tendency of shrinkage and shrinkage. In the present invention, most of Cu is solid-dissolved in a single-phase η phase of a matrix structure, and a small amount of Cu is precipitated as a CuZn5 compound. However, the copper content should not be too high, and when the copper content is too high, a large amount of ε phase will be precipitated, although the strength and hardness are The degree is increased, but the elongation is greatly lowered, so the present invention controls the copper content to be 0.01 to 5.0% by weight.
本发明中大部分的Al固溶于Zn基体中形成η相，起到基体强化的效果，少量Al以Al(α)析出，在合金中主要起强化作用，随着Al含量的提高，合金的强度、硬度提高，但塑性降低。并且适当的Al含量可以改善合金铸造时的流动性，防止氧化，并且改善压力加工性能，但Al含量过高时，会形成网状的富含铝的铝锌铜三元共晶组织，该三元共晶组织使得合金的剪切强度下降，出现开裂现象，而且随着Al含量的增加，化合物含量增加，单相组织减少，影响合金的冷镦性能，因此，本发明中，铝含量控制在0.01～5.0wt％。In the present invention, most of the Al is dissolved in the Zn matrix to form an η phase, which serves as a matrix strengthening effect, and a small amount of Al precipitates as Al(α), which mainly plays a strengthening role in the alloy, and as the Al content increases, the alloy Strength and hardness increase, but plasticity decreases. And the proper Al content can improve the fluidity during alloy casting, prevent oxidation, and improve the press workability, but when the Al content is too high, a network of aluminum-rich aluminum-zinc-copper ternary eutectic structure is formed. The eutectic structure reduces the shear strength of the alloy and causes cracking. As the content of Al increases, the content of the compound increases, and the single-phase structure decreases, which affects the cold heading performance of the alloy. Therefore, in the present invention, the aluminum content is controlled. 0.01 to 5.0 wt%.
Mg在本发明锌合金基体中的固溶度极小，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Mg2Zn11，两者形成的细小颗粒均匀地在η相中析出，显著提高变形锌合金的强度、硬度，并改善合金的冷锻性能。但是当Mg含量超过1.0wt％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0.001wt％时，不具有显著的强化作用。因此本发明变形锌合金确定的镁的含量为0.001～1.0wt％。The solid solubility of Mg in the zinc alloy matrix of the present invention is extremely small, and 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 , two The fine particles formed uniformly precipitate in the η phase, significantly increasing the strength and hardness of the deformed zinc alloy, and improving the cold forging property of the alloy. However, when the Mg content exceeds 1.0% by weight, the impact toughness of the alloy is remarkably lowered, causing problems in the production and processing of the alloy; and when the Mg content is less than 0.001% by weight, there is no significant strengthening effect. Therefore, the deformed zinc alloy of the present invention has a magnesium content of 0.001 to 1.0% by weight.
本发明通过添加Cu、Al、Mg、Zn并控制各元素含量，使得Cu、Al、Mg尽可能固溶于基体中，形成体积分数占到95～99％的η相，单相基体相的存在除了确保合金获得高强度外，更赋予合金高的延伸率和剪切强度，使得合金获得了理想的冷镦性能。The invention adds Cu, Al, Mg, Zn and controls the content of each element, so that Cu, Al and Mg are dissolved as much as possible in the matrix, forming a η phase with a volume fraction of 95-99%, and the existence of a single phase matrix phase In addition to ensuring high strength of the alloy, it imparts high elongation and shear strength to the alloy, resulting in an ideal cold heading performance.
作为优选，该变形锌合金的微观组织包括单相的η相固溶体组织和析出相，所述的析出相为CuZn5(ε)和Al(α)，所述的析出相的平均晶粒度≤5um。本发明除了单相基体固溶体外，在η相中还析出第二相化合物，Cu、Al、Mg 在充分固溶于基体后，析出CuZn5(ε)和Al(α)、Mg2Zn11等，这些化合物以微米级大小析出相形式析出，本发明控制其平均晶粒度不超过5um，在进一步提高合金的强度的同时，对延伸率影响不大，可提高冷镦过程中的合金的耐冲击强度。Preferably, the microstructure of the deformed zinc alloy comprises a single-phase η-phase solid solution structure and a precipitated phase, wherein the precipitated phase is CuZn5 (ε) and Al (α), and the average grain size of the precipitated phase is ≤ 5 um. . In addition to the single-phase matrix solid solution, the second phase compound is precipitated in the η phase, and Cu, Al, and Mg are sufficiently solid-dissolved in the matrix to precipitate CuZn5 (ε), Al(α), Mg 2 Zn 11 , and the like. These compounds are precipitated in the form of a micron-sized precipitate phase. The average grain size of the present invention is controlled to be no more than 5 um, which further increases the strength of the alloy, has little effect on the elongation, and can improve the impact resistance of the alloy during cold heading. strength.
作为优选，所述的单相的η相固溶体组织为等轴晶，所述的单相的η相固溶体组织的晶粒度大小为5～100um。等轴晶主要在单相的合金中存在，沿各个方向的性能一致好，在本发明中，生产加工的合金线材从横向截面(即垂直于机加工方向)或者是从纵向截面(即平行于机加工方向)的微观组织金相图片都显示，本发明变形锌合金的晶粒度一致性好，晶粒度大小的范围为5～100um。这种等轴晶的存在使得本发明合金不存在宏观的各向异性，因此可以从各个方向对合金进行冷镦、铆接等机加工，且具有加工过程中不易开裂的优点。本发明将单相的η相固溶体组织的晶粒度控制在5～100um，该微米级的单相固溶体使得合金的晶粒细小，有利于实现优异的强度和延伸率的结合，冷镦效果好。Preferably, the single-phase η-phase solid solution structure is equiaxed, and the single-phase η-phase solid solution structure has a grain size of 5 to 100 μm. The equiaxed crystals are mainly present in the single-phase alloy, and the properties in all directions are consistent. In the present invention, the produced alloy wires are from a transverse cross section (ie, perpendicular to the machining direction) or a longitudinal cross section (ie, parallel to The microstructured metallographic pictures of the machine direction show that the grain-shaped uniformity of the deformed zinc alloy of the present invention is good, and the grain size ranges from 5 to 100 um. The presence of such equiaxed crystals makes the alloy of the present invention have no macroscopic anisotropy, so that the alloy can be subjected to cold rolling, riveting, and the like from various directions, and has the advantage of being less prone to cracking during processing. The invention controls the grain size of the single-phase η phase solid solution structure to be 5 to 100 um, and the micro-phase single-phase solid solution makes the grain of the alloy fine, which is advantageous for achieving excellent combination of strength and elongation, and good cold heading effect. .
作为优选，该变形锌合金的横向硬度和纵向硬度的比值满足：0.9≤横向硬度/纵向硬度≤1.1。因等轴晶各个方向性能一致，将横向硬度和纵向硬度的比值控制在0.9～1.1，可确保材料性能的一致性。横向硬度，即该变形锌合金制成的线材产品的横截面的表面硬度；纵向硬度，即该变形锌合金制成的线材产品的轴向的表面硬度。Preferably, the ratio of the transverse hardness to the longitudinal hardness of the deformed zinc alloy satisfies: 0.9 ≤ transverse hardness / longitudinal hardness ≤ 1.1. Since the equiaxed crystals have the same performance in all directions, the ratio of the transverse hardness to the longitudinal hardness is controlled to be 0.9 to 1.1, which ensures the consistency of the material properties. The transverse hardness, that is, the surface hardness of the cross section of the wire product made of the deformed zinc alloy; the longitudinal hardness, that is, the axial surface hardness of the wire product made of the deformed zinc alloy.
作为优选，该变形锌合金的重量百分比组成还包括0.01％≤Mn≤2.0％和/或0.001％≤Cr≤1.0％。Mn一方面固溶于铜合金，起到提高强度的作用，同时Mn还可以细化合金组织。Mn含量过低，强化作用不明显，如果Mn含量过高，会造成延伸率的明显下降，因此本发明Mn的添加量控制在0.01～2.0wt％。少量的 Cr可与锌形成CrZn17相，具有较好的与基体的变形协调性，可以提高合金强度和硬度而不降低其塑性，本发明中，适宜的Cr含量为0.001～1.0％。Preferably, the weight percent composition of the deformed zinc alloy further comprises 0.01% ≤ Mn ≤ 2.0% and/or 0.001% ≤ Cr ≤ 1.0%. On the one hand, Mn is solid-solubilized in a copper alloy to enhance the strength, and Mn can also refine the alloy structure. When the Mn content is too low, the strengthening effect is not remarkable. If the Mn content is too high, the elongation is significantly lowered. Therefore, the amount of Mn added in the present invention is controlled to be 0.01 to 2.0% by weight. A small amount of Cr can form a CrZn 17 phase with zinc, and has better deformation coordination with the matrix, and can improve the strength and hardness of the alloy without lowering the plasticity thereof. In the present invention, a suitable Cr content is 0.001 to 1.0%.
作为优选，该变形锌合金的重量百分比组成还包括总量为0.001～1％的Ni、RE、Ca和Co中的至少一种。Ni固溶于单相基体中，起到尺寸稳定性作用，但添加过多，使得合金脆性化明显；稀土元素RE在锌合金中可以起到净化晶界、细化晶粒的作用，提高塑性与强度；Ca几乎不固溶于固溶体，以单质形成存在于基体中，起到提高基体强度的作用；Co为六方结构，少量的Co与Zn基体形成代位式固溶体，能够提高强度。Ni、RE、Ca和Co中的至少一种元素的总量控制在0.001～1％，可进一步优化合金的综合性能。Preferably, the weight percent composition of the deformed zinc alloy further includes at least one of Ni, RE, Ca, and Co in a total amount of 0.001 to 1%. Ni is dissolved in the single-phase matrix to achieve dimensional stability, but excessive addition makes the alloy brittle. The rare earth element RE can purify the grain boundary and refine the grain in the zinc alloy, and improve the plasticity. And the strength; Ca is hardly dissolved in the solid solution, and is formed in the matrix as a simple substance, thereby increasing the strength of the matrix; Co is a hexagonal structure, and a small amount of Co and Zn matrix forms a subterranean solid solution, which can improve the strength. The total amount of at least one of Ni, RE, Ca, and Co is controlled to be 0.001 to 1%, and the overall performance of the alloy can be further optimized.
作为优选，该变形锌合金的抗拉强度为280MPa以上，延伸率为15％以上。冷镦锌合金除材料需要满足强度、塑性、硬度要求外，抗剪切性能对合金的性能同样具有重要的影响。剪切强度是指外力与材料轴线垂直，并对材料呈剪切作用时的强度极限。在冷镦过程中，作用力垂直向下，对材料产生剪切作用，如果变形锌合金的剪切力不够，就会造成材料在冷镦过程中扭曲变形，冷镦性能还需要材料满足较高的塑性，塑性过低，材料会出现开裂。本发明通过单相的固溶体基体实现抗拉强度280MPa以上，延伸率15％以上，剪切强度250MPa以上，使得材料在承受强度的同时，不存在开裂现象。Preferably, the deformed zinc alloy has a tensile strength of 280 MPa or more and an elongation of 15% or more. In addition to the strength, plasticity and hardness requirements of the cold-rolled zinc alloy, the shear resistance also has an important influence on the properties of the alloy. Shear strength is the strength limit at which the external force is perpendicular to the axis of the material and shears the material. In the process of cold heading, the force is vertically downward, which causes shearing effect on the material. If the shearing force of the deformed zinc alloy is insufficient, the material will be distorted during the cold rolling process, and the cold heading performance also needs to satisfy the material. The plasticity, the plasticity is too low, and the material will crack. The invention realizes tensile strength of 280 MPa or more, elongation of 15% or more, and shear strength of 250 MPa or more by a single-phase solid solution matrix, so that the material is subjected to strength without cracking.
本发明可冷镦的变形锌合金的制备方法，包括以下步骤：熔铸(通过热顶铸造、半连铸或水平连铸生产成直径为100～300mm的铸锭)，锯切(将铸锭锯切成200～1500mm的长度)，挤压(铸锭加热180～370℃，通过1000t以上正、反向挤压机挤压成Φ6～20mm的线坯)，拉伸、热处理(经过至少两次以上拉伸和多次热处理后加工得到成品，热处理温度为：150～350℃，热处理时间为1～ 10h)。The preparation method of the cold-formed deformed zinc alloy of the invention comprises the following steps: casting (ingot casting with a diameter of 100-300 mm by hot-top casting, semi-continuous casting or horizontal continuous casting), sawing (saw ingot casting) Cut into the length of 200 ~ 1500mm), extrusion (ingot casting 180 ~ 370 ° C, through 1000t or more positive and negative extruder extruded into Φ6 ~ 20mm strand), stretching, heat treatment (after at least twice After the above stretching and multiple heat treatment, the finished product is obtained, and the heat treatment temperature is 150-350 ° C, and the heat treatment time is 1 ～ 10h).
作为优选，上述变形锌合金在冷镦加工中的应用。Preferably, the above-described deformed zinc alloy is used in cold heading processing.
作为优选，上述变形锌合金在电源插头和接线柱中的应用。Preferably, the above-described deformed zinc alloy is used in a power plug and a terminal.
在变形锌合金作为替代材料过程中，经常需要经过机加工，而冷镦就是冷变形加工加工中的一种，本发明合金具有优异的冷镦性能，可进行冷镦等冷变形加工，满足各种电源插头、接线柱产品的生产需求，加工得到的产品可大量应用于电子电气行业。In the process of deforming zinc alloy as an alternative material, it is often necessary to be machined, and cold heading is one of cold deformation processing. The alloy of the invention has excellent cold heading performance, and can be cold-formed and other cold-deformed processing to satisfy each The production requirements of power plugs and terminal products can be widely used in the electrical and electronic industry.
与现有技术相比，本发明的优点在于：The advantages of the present invention over the prior art are:
(1)区别于普通的Zn-Cu-Al基变形锌合金，本发明可冷镦的变形锌合金的微观组织以单相的η相固溶体组织为基体，单相的η相固溶体组织在该变形锌合金的微观组织中的体积分数为95～99％，其抗拉强度可以达到280MPa以上，延伸率可以达到15％以上，能够为冷镦加工提供足够的变形能力；本发明通过实现单相的基体组织，赋予锌合金优异的综合性能，其强度、塑性、硬度、抗剪切性能得到协调，最终获得了本发明变形锌合金的较好的冷镦性能。(1) Different from the ordinary Zn-Cu-Al-based deformed zinc alloy, the microstructure of the cold-formed deformed zinc alloy of the present invention is based on a single-phase η-phase solid solution structure, and the single-phase η-phase solid solution structure is in the deformation. The volume fraction of the zinc alloy in the microstructure is 95 to 99%, the tensile strength can reach 280 MPa or more, and the elongation can reach 15% or more, which can provide sufficient deformation ability for cold heading processing; the present invention realizes single phase by The matrix structure imparts excellent comprehensive properties to the zinc alloy, and its strength, plasticity, hardness and shear resistance are coordinated, and finally the preferred cold heading performance of the deformed zinc alloy of the present invention is obtained.
(2)进一步地，除了基体组织为单相组成外，该变形锌合金的微观组织中还包括少量的析出相，包括CuZn5(ε)、Al(α)和Mg2Zn11等，析出相的平均晶粒度≤5um，可进一步提高合金强度，特别是对剪切强度的提升具有重要的作用，其剪切强度可以达到250MPa以上，而高的剪切强度的更有利于冷镦加工的实现。(2) Further, in addition to the single-phase composition of the matrix structure, the microstructure of the deformed zinc alloy includes a small amount of precipitated phases, including CuZn5 (ε), Al (α), and Mg 2 Zn 11 , and precipitated phases. The average grain size ≤ 5um can further improve the strength of the alloy, especially for the improvement of shear strength. The shear strength can reach 250MPa or more, and the high shear strength is more conducive to the realization of cold heading. .
(3)该锌合金单相的固溶体组织为等轴晶，且晶粒度控制在5～100um，等轴晶沿各个方向的性能一致好，在本发明中，生产加工的合金从横向截面或者是从纵向截面的金相照片都显示，晶粒度是一致的，范围为5～100um。这种等 轴晶的存在使得合金不存在宏观的各向异性，因此可以从各个方向冷镦、铆接等机加工合金，且加工过程中材料不易开裂。(3) The solid solution structure of the single phase of the zinc alloy is equiaxed, and the grain size is controlled to be 5 to 100 um, and the performance of the equiaxed crystals in all directions is uniform. In the present invention, the alloy produced by the transverse section or It is shown from the metallographic photographs of the longitudinal section that the grain size is uniform and the range is 5 to 100 um. This kind of The presence of the axial crystals makes the alloy have no macroscopic anisotropy, so the alloy can be cold-drawn, riveted, etc. from all directions, and the material is not easily cracked during processing.
(4)相比于传统的铜合金、钢铁等合金，本发明锌合金具有加工软化的特点，因此，本发明合金可进行反复冷镦加工，不会出现因加工硬化而使材料的冷镦无法实现的情况。(4) Compared with the conventional copper alloy, steel and other alloys, the zinc alloy of the invention has the characteristics of softening of processing, and therefore, the alloy of the invention can be subjected to repeated cold heading processing, and the coldness of the material cannot be caused by work hardening. The situation achieved.
(5)本发明锌合金可以采用机加工(切削)、铆接、冷锻等方式成型，但冷镦相比较于其他加工方式，在节省材料成本的同时可提高加工效率，因此具有明显的优势。(5) The zinc alloy of the present invention can be formed by machining (cutting), riveting, cold forging, etc., but the cold heading can improve the processing efficiency while saving the material cost compared with other processing methods, and thus has obvious advantages.
(6)本发明锌合金能够以棒材、线材(包括圆线、扁线)等形式成型，经过后续的机加工得到的产品可广泛应用于符合欧盟、3C领域的电源插头、接线柱等电子电气行业。(6) The zinc alloy of the invention can be formed by rods, wires (including round wires, flat wires), etc., and the products obtained through subsequent machining can be widely applied to electronic plugs, binding posts and the like in accordance with the EU and 3C fields. Electrical industry.
附图说明DRAWINGS
图1为实施例5的可冷镦的变形锌合金线材的微观组织金相图片；1 is a microscopic metallographic picture of a cold-form deformable zinc alloy wire of Example 5;
图2为实施例8的可冷镦的变形锌合金线材垂直于机加工方向的微观组织金相图片；2 is a microscopic metallographic picture of the cold-form deformable zinc alloy wire of Example 8 perpendicular to the machine direction;
图3为实施例8的可冷镦的变形锌合金线材平行于机加工方向的微观组织金相图片。3 is a microscopic metallographic picture of the cold-form deformable zinc alloy wire of Example 8 parallel to the machine direction.
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20个实施例合金和2个对比例合金，熔铸(通过热顶铸造、半连铸或水平连铸生产成直径为100～300mm的铸锭)，锯切(将铸锭锯切成200～1500mm的长度)，挤压(铸锭加热180～370℃，通过1000t以上正、反向挤压机挤压成Φ6～20mm的线坯)，拉伸、热处理(经过至少两次以上拉伸和多次热处理 后加工得到成品，热处理温度为：150～350℃，热处理时间为1～10h)。20 examples of alloys and 2 comparative alloys were selected, cast (produced by hot-top casting, semi-continuous casting or horizontal continuous casting into ingots with a diameter of 100-300 mm), sawing (cutting the ingot into 200 ~ 1500mm length), extrusion (ingot heating 180 ~ 370 ° C, through 1000t or more positive and negative extruder extruded into Φ6 ~ 20mm strand), stretching, heat treatment (after at least two times stretching And multiple heat treatment The finished product is obtained by post-processing, and the heat treatment temperature is 150-350 ° C, and the heat treatment time is 1-10 h).
实施例1～20及对比例1～2合金的成分及性能测试结果见表1。The composition and performance test results of the alloys of Examples 1 to 20 and Comparative Examples 1 and 2 are shown in Table 1.
实施例5的线材微观结构的金相图片见图1，实施例8的线材垂直于机加工方向的微观组织金相图片见图2，实施例8的线材平行于机加工方向的微观组织金相图片见图3。The metallographic picture of the wire microstructure of Example 5 is shown in Fig. 1. The microstructure of the wire of Example 8 perpendicular to the machine direction is shown in Fig. 2. The wire of Example 8 is parallel to the microstructure of the machining direction. The picture is shown in Figure 3.
为了准确表征该材料各个方向的力学性能，对实施例1～20的合金的线材成品，根据GB/T 4340.1-2009《金属维氏硬度试验》方法，分别检测了其横向硬度和纵向硬度，其中横向硬度指的是实施例1～20的合金的线材成品的横截面的表面硬度，纵向硬度指的是实施例1～20的合金的线材成品的轴向的表面硬度，每组数据各取5个点，检测结果取平均值，同时，检测了对比例1～2合金的横向硬度和纵向硬度。此外，根据GB T228.1-2010《金属材料室温拉伸方法》检测了实施例1～20及对比例1～2合金的抗拉强度和延伸率。In order to accurately characterize the mechanical properties of the material in all directions, the wire products of the alloys of Examples 1 to 20 were tested for transverse hardness and longitudinal hardness according to the GB/T 4340.1-2009 "Metal Vickers Hardness Test" method. The transverse hardness refers to the surface hardness of the cross section of the finished wire product of the alloys of Examples 1 to 20, and the longitudinal hardness refers to the axial surface hardness of the finished wire product of the alloys of Examples 1 to 20, and each set of data is taken 5 At the same time, the test results were averaged, and the transverse hardness and longitudinal hardness of the alloys of Comparative Examples 1 and 2 were examined. Further, the tensile strength and elongation of the alloys of Examples 1 to 20 and Comparative Examples 1 to 2 were examined in accordance with GB T228.1-2010 "Metal Material Room Stretching Method".
从表1所列测试结果可见，本发明可冷镦的变形锌合金的抗拉强度在289～375MPa，延伸率在15～33％，横向硬度HV5在90～117，剪切强度在257～340MPa，横向硬度和纵向硬度的比值在0.92～1.07，单相的η相固溶体组织在该变形锌合金的微观组织中的体积分数为95～99％，满足锌合金的冷镦加工要求，可进行冷镦等冷变形加工，生产的产品可具体应用于符合欧盟、3C领域的电源插头、接线柱等电子电气行业。 It can be seen from the test results listed in Table 1 that the tensile strength of the cold-formed deformed zinc alloy of the present invention is 289-375 MPa, the elongation is 15 to 33%, the transverse hardness HV5 is 90-117, and the shear strength is 257-340 MPa. The ratio of the transverse hardness to the longitudinal hardness is 0.92 to 1.07, and the volume fraction of the single phase η phase solid solution structure in the microstructure of the deformed zinc alloy is 95 to 99%, which satisfies the cold heading processing requirements of the zinc alloy and can be cooled.冷 and other cold deformation processing, the products can be specifically applied to the electrical and electronic industries such as power plugs and terminals that comply with the EU and 3C fields.
Figure PCTCN2016000609-appb-000001
Figure PCTCN2016000609-appb-000001

Claims (9)

  1. 一种可冷镦的变形锌合金，其特征在于该变形锌合金的重量百分比组成包括：0.01％≤Cu≤5.0％，0.01％≤Al≤5.0％，0.001％≤Mg≤1.0％，余量为Zn和不可避免的杂质，该变形锌合金的微观组织以单相的η相固溶体组织为基体，所述的单相的η相固溶体组织在该变形锌合金的微观组织中的体积分数为95～99％。A cold-formed deformed zinc alloy characterized in that the weight percentage composition of the deformed zinc alloy comprises: 0.01% ≤ Cu ≤ 5.0%, 0.01% ≤ Al ≤ 5.0%, 0.001% ≤ Mg ≤ 1.0%, and the balance is Zn and unavoidable impurities, the microstructure of the deformed zinc alloy is based on a single-phase η-phase solid solution structure, and the volume fraction of the single-phase η-phase solid solution structure in the microstructure of the deformed zinc alloy is 95 ～ 99%.
  2. 根据权利要求1所述的一种可冷镦的变形锌合金，其特征在于该变形锌合金的微观组织包括单相的η相固溶体组织和析出相，所述的析出相为CuZn5(ε)和Al(α)，所述的析出相的平均晶粒度≤5um。A cold-form deformable zinc alloy according to claim 1, wherein the microstructure of the deformed zinc alloy comprises a single-phase η-phase solid solution structure and a precipitated phase, and the precipitated phase is CuZn5(ε) and Al (α), the average grain size of the precipitated phase is ≤ 5 um.
  3. 根据权利要求1或2所述的一种可冷镦的变形锌合金，其特征在于所述的单相的η相固溶体组织为等轴晶，所述的单相的η相固溶体组织的晶粒度大小为5～100um。A cold-form deformable zinc alloy according to claim 1 or 2, wherein said single-phase η-phase solid solution structure is equiaxed, said single-phase η phase solid solution microstructure crystal grains The degree is 5 to 100 um.
  4. 根据权利要求3所述的一种可冷镦的变形锌合金，其特征在于该变形锌合金的横向硬度和纵向硬度的比值满足：0.9≤横向硬度/纵向硬度≤1.1，其中，横向硬度为该变形锌合金制成的线材产品的横截面的表面硬度，纵向硬度为该变形锌合金制成的线材产品的轴向的表面硬度。A cold-form deformable zinc alloy according to claim 3, wherein the ratio of the transverse hardness to the longitudinal hardness of the deformed zinc alloy satisfies: 0.9 ≤ transverse hardness / longitudinal hardness ≤ 1.1, wherein the transverse hardness is The surface hardness and the longitudinal hardness of the cross section of the wire product made of the deformed zinc alloy are the axial surface hardness of the wire product made of the deformed zinc alloy.
  5. 根据权利要求1所述的一种可冷镦的变形锌合金，其特征在于该变形锌合金的重量百分比组成还包括0.01％≤Mn≤2.0％和/或0.001％≤Cr≤1.0％。A cold-form deformable zinc alloy according to claim 1, wherein the weight percent composition of the deformed zinc alloy further comprises 0.01% ≤ Mn ≤ 2.0% and/or 0.001% ≤ Cr ≤ 1.0%.
  6. 根据权利要求1或5所述的一种可冷镦的变形锌合金，其特征在于该变形锌合金的重量百分比组成还包括总量为0.001～1％的Ni、RE、Ca和Co中的至少一种。 A cold-form deformable zinc alloy according to claim 1 or 5, wherein the weight percent composition of the deformed zinc alloy further comprises at least 0.001 to 1% of a total of 0.001 to 1% of Ni, RE, Ca and Co. One.
  7. 根据权利要求1所述的一种可冷镦的变形锌合金，其特征在于该变形锌合金的抗拉强度为280MPa以上，延伸率为15％以上。A cold-form deformable zinc alloy according to claim 1, wherein the deformed zinc alloy has a tensile strength of 280 MPa or more and an elongation of 15% or more.
  8. 权利要求1-7中任一项所述的一种可冷镦的变形锌合金在冷镦加工中的应用。Use of a cold-form deformable zinc alloy according to any one of claims 1 to 7 in cold heading processing.
  9. 权利要求1-7中任一项所述的一种可冷镦的变形锌合金在电源插头和接线柱中的应用。 Use of a cold-form deformable zinc alloy according to any of claims 1-7 in a power plug and terminal.
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CN106521241A (en) 2017-03-22

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