WO2013149367A1 - Wrought zinc alloy and preparation method and use thereof - Google Patents

Wrought zinc alloy and preparation method and use thereof Download PDF

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Publication number
WO2013149367A1
WO2013149367A1 PCT/CN2012/001396 CN2012001396W WO2013149367A1 WO 2013149367 A1 WO2013149367 A1 WO 2013149367A1 CN 2012001396 W CN2012001396 W CN 2012001396W WO 2013149367 A1 WO2013149367 A1 WO 2013149367A1
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Prior art keywords
zinc
phase
alloy
zinc alloy
deformed
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PCT/CN2012/001396
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French (fr)
Chinese (zh)
Inventor
孙文声
余惺
郭俊
李振宇
张明
谢识才
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Ningbo Powerway Alloy Material Co Ltd
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Ningbo Powerway Alloy Material Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/02Making non-ferrous alloys by melting
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C18/00Alloys based on zinc
    • C22C18/02Alloys based on zinc with copper as the next major constituent
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/16Changing 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
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/16Changing 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
    • C22F1/165Changing 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 of zinc or cadmium or alloys based thereon

Definitions

  • the present invention relates to a deformed zinc alloy and a process for the preparation thereof, and more particularly to a zinc-copper-based deformed zinc alloy which can be used for the manufacture of nuts and nuts for the air-conditioning industry and a method for producing the same. Background technique
  • Air conditioning is a widely used household and office appliance that consists primarily of refrigerant, compressors, piping and various valves.
  • the wrought zinc alloy of the invention is mainly used for replacing the traditional copper alloy, and is used for manufacturing various hexagonal nuts and nuts used in air conditioners. These hex nuts and nuts are mainly used for sealing and connecting the shut-off valve and the four-way valve.
  • Zinc alloys may be a possible alternative, but since metal zinc is a hexagonal crystal structure with less slip, the cast state is a relatively brittle and less rigid metal. Alloying elements such as aluminum, copper, and magnesium are usually added to the zinc matrix to increase the strength of the zinc alloy and improve the overall performance. Commonly used die-casting and gravity-casting zinc alloys are all metal materials with zinc-aluminum as the main alloying element. There is a clear tendency of intergranular corrosion, low electroplating yield, and low creep strength, low temperature brittleness, etc. Used as a structural material, most of it is used as a decorative function or appearance product.
  • "Hot-impregnated surface-formed olive-green zinc alloy coating” disclosed in Japanese Patent Publication No. JP63241132A proposes a zinc alloy containing Mn 0.2-0.8 wt.%, Cu 0.05-1.0 wt%, and the balance being zinc.
  • the zinc herein preferably uses zinc having a purity of >99.99%, and the content of Pb in the zinc alloy is preferably 0.005 wt%.
  • the zinc alloy coating is corrosion resistant and has an olive color. Its main application areas are hot dip coating and surface coating. Further, as disclosed in Chinese Patent Application No.
  • the zinc alloy is composed of the following components by weight: Copper 0.5 ⁇ 3.0%, manganese 0.01 ⁇ 2.0%, titanium 0.05 ⁇ 0.3%, the balance is zinc and the total amount is less than 0.05% impurities.
  • the zinc alloy component may further contain: X 0.01 to 0.5% by mass, and X is at least one of aluminum and a rare earth element (Ce+La).
  • the preparation method is the smelting by the cover protection method, and the alloying elements are added in the form of pure zinc, Zn-Cu, Zn-Ti, Cu-Mn, pure aluminum, Ce+La composite rare earth; the melting temperature is 650-740 ° C; -480 ° C casting; ingots after 350-380 ° C are thickened and annealed for 6-10h; multi-pass hot rolling at 220-280 ° C, total deformation of 60-95%; cold rolling, total deformation The amount is 50-80%; after rolling, it is annealed at 180-200 ° C for 2-3 h, and finally the product of the strip structure is obtained.
  • Bi plays a major role in improving the cutting performance in zinc alloys.
  • Sun Liping in the Journal of Chinese Nonferrous Metals, Vol. 21, No. 7 (2011), reported the microstructure and properties of the free-cutting Zn-Cu-Bi alloy.
  • the main component of the alloy is Zn-Cu-Mn. -Bi-Mg-Ti-Al, which contains aluminum.
  • the cast zinc-based alloy material has good formability, it has poor comprehensive performance indexes such as strength, hardness and workability, and cannot be used as an air-conditioning hex nut or nut. It is mainly used as a die-casting product for appearance parts.
  • Figure 3 shows a metallographic photograph of the Zn-Al-based alloy cast structure. It can be seen from the figure: The coarse HCP structure indicates that the material has obvious brittleness and is not suitable for plastic forming.
  • Table 1 shows the comparison of the mechanical properties of a typical cast alloy Zn-4Al-0.05Mg, the American brand name ZAMAK3# and the lead brass representative C3604.
  • the first technical problem to be solved by the present invention is to provide a deformed zinc alloy for the current state of the art, replacing lead brass at a lower cost for manufacturing nuts and nuts for the air conditioning industry, and solving the problem of lack of copper resources. .
  • a second technical problem to be solved by the present invention is to provide a method for producing a zinc-copper-based deformed zinc alloy of the present invention.
  • the deformed zinc alloy characterized in that the composition by weight is:
  • the balance is zinc and unavoidable impurity elements; the total amount of unavoidable impurity elements is less than 0.01%.
  • the zinc alloy microstructure is mainly composed of a zinc matrix primary phase and an intermetallic compound dispersed between the primary phases; the primary phase is an HCP structure, the intermetallic compound is a fine ZiuCu and Zn 9 Mn; and the volume content of the Zi Cu phase 5%-55%, the volume content of the Zn 9 Mn phase is 0.1%-5%, and the rest is the primary phase; the average grain size of the primary phase is 15 to 35 microns, and the average grain size of the intermetallic compound is 5 ⁇ 15 microns.
  • the average grain size of the intermetallic compound structure refers to the total average grain size of the intermetallic compounds of Zr ⁇ Cu and Zn 9 Mn.
  • the invention adds Cu, Mn to the matrix of zinc, and forms a fine high-strength, high-hardness intermetallic compound dispersed in the matrix of the zinc alloy, thereby improving the strength and increasing the creep resistance;
  • the trace amount of Co is dissolved in the matrix of zinc to form the HCP phase, which can act as a solid solution strengthening.
  • Figure 1 shows the effect of copper content on the strength of Zn( 99 .78 . x )Cu x Mn Q . 2 Co a()2 alloy.
  • Figure 2 shows the copper content versus Zn ( 99.78-x)Cu x Mno. 2 Coo.o2 alloy ductility, table 2 Effect of Mn content (94. 98-x) 5 Mn x Coo.o2 alloy strength, hardness and elongation of the Cu Zn.
  • composition of the above zinc alloy by weight is:
  • the amount of lanthanum is zinc and inevitable impurity elements.
  • the ZmCu phase has a volume content of 10% to 30%, and the Zn 9 Mn phase has a volume content of 1% to 4%.
  • the grain size of the Zn 9 Mn phase is preferably from 1 to 3 ⁇ m.
  • the technical solution adopted by the present invention to solve the above second technical problem is: the method for manufacturing the above-mentioned deformed zinc alloy, characterized in that the Cu, Mn, Co, and zinc are first added as a copper manganese and a copper-zinc intermediate alloy. After casting, a deformed zinc alloy casting blank can be obtained.
  • the heating method of the casting can be a reverberatory furnace, an intermediate frequency heating furnace or a power frequency heating furnace, and the casting temperature is 500 ° C-60 (rC, the crystallization process can be hard mold casting, continuous casting Or semi-continuous casting, the casting rate is 2-5 m / h; the slab is extruded and stretched to obtain a deformed zinc alloy, and the extrusion speed during extrusion is 0.1-3.5 mm/s, the extrusion temperature It is 150 ° C-35 (TC, extrusion ratio is 10-256; the pass processing rate of stretching is 5-15%, and the total processing rate is up to 80%.
  • TC extrusion ratio
  • the pass processing rate of stretching is 5-15%
  • the total processing rate is up to 80%.
  • the invention adopts the method of adding copper-zinc and copper-manganese intermediate alloy to lower the melting point, thereby ensuring the requirement of the alloy composition range and significantly reducing the burning loss of zinc element; at the same time, the copper and manganese elements can be made of metal.
  • the inter-compound enhanced form is present uniformly in the zinc-based alloy matrix.
  • the invention realizes the deformed zinc alloy suitable for the shape and specification of the air conditioner nut nut by hot extrusion, drawing, heat treatment and joint drawing process of the slab, and the characteristic is that the alloy is realized by these treatment processes.
  • the microscopic metallographic structure changes from cast state to processed state, and the material changes from brittle material to ductile material, and the mechanical properties are obviously improved.
  • Fig. 6 shows the metallographic structure of the Zn-Cu-Mn-Co alloy having the chemical composition of the zinc alloy of the present invention in a cast state. It can be seen that the microstructure is coarse, and the intermetallic compound is distributed in the matrix in a coarse needle-like structure.
  • the metallographic structure of the Zn-Cu-Mn-Co zinc alloy of the present invention after hot extrusion and drawing processing is shown in Fig. 7, as can be seen from Fig. 7: Zn after extrusion and drawing
  • the metallographic structure of the -Cu-Mn-Co zinc alloy consists of a hexagonal structure of deformed structure and a dispersed intermetallic compound. The structure is characterized by a certain directionality, and the coarse needle-like structure is refined.
  • Figure 8 shows the distribution of Zi ⁇ Cu and Zn 9 Mn in zinc matrix characterized by scanning electron microscopy.
  • the grain size of HCP primary phase and intermetallic compound Z Cu is relatively large, accounting for a large volume fraction, while Zn 9
  • the grain size of the Mn phase is relatively small, and the volume fraction is small.
  • the microstructure of the deformed zinc alloy of the present invention is mainly composed of a zinc matrix HCP primary phase and a ZmCu phase and a Zn 9 Mn phase which are substantially uniformly dispersed between the primary phases; the volume of the Zi ⁇ Cu phase is 5%-55. The volume content of %, Zn 9 Mn phase is 0.1%-5%, and the rest is primary phase; the average grain size of the primary phase is 15 ⁇ 35 microns, the grain size of Zn 9 Mn phase is smaller, and the ZIL I phase is larger. The total average grain size of the two intermetallic compounds is 5 to 15 microns.
  • the alloy contains cobalt
  • cobalt and zinc are solid-dissolved to form a HCP primary phase, so that the cobalt-containing and cobalt-free deformed zinc alloys have substantially the same metallographic structure.
  • the inventors of the present application have found through extensive experiments that the processing conditions and component contents have an important influence on the metallographic structure, If the composition is not suitable, it is difficult to obtain a deformed zinc alloy having the characteristics of the present invention by changing the processing conditions, and the processing conditions have a direct influence on the metallographic structure of the deformed zinc alloy of the present invention, and finally based on a large number of tests.
  • the composition and processing conditions of the zinc alloy of the present invention were determined.
  • the use of the deformed zinc alloy described above is performed by machining, hot stamping or cold rolling to form a semi-finished product, and the semi-finished product is refined, tapped and then electroplated to form a hexagon for the air conditioning industry. Nut or nut wide mouth;
  • the hot stamping temperature is 200 ⁇ 300 ⁇
  • the cold heading is 3-5 station processing.
  • the forming process of the nut and the nut can be machined, hot forged or cold formed.
  • Zinc alloy hex nuts/nuts can be machined by CNC machine tools, automatic machine tools and special machine tools.
  • the raw materials are linear bars, and coolant is used in the machining process to improve machining efficiency.
  • Hot forging is carried out by using a straight bar, which is heated, stamped into a blank, and then finished by an instrument vehicle. The cold heading adopts the loop line product. After the blanking, after the multi-station is punched into the blank, the finished product is finished with the instrument vehicle.
  • the invention adopts a process of adding zinc-copper and copper-manganese intermediate alloy in the process of casting, so that the casting structure of the zinc-based alloy is refined, and the intermetallic compound can be uniformly distributed in the matrix of the zinc.
  • the brittleness of the material is improved, the subsequent processing is facilitated, the burning of zinc in the high-temperature melting is avoided, and the yield of the material is improved; on the other hand, plastic processing such as extrusion and drawing is performed.
  • the alloy is transformed from a brittle zinc-based alloy into a tough structural state, and the comprehensive performance index of the zinc-based alloy material is significantly improved.
  • the present invention determines a suitable alloy chemical composition, it is processed. After that, a deformed zinc alloy having a specific characteristic metallographic structure can be obtained, and these specific metallographic structures make the overall performance of the deformed zinc alloy of the present invention stably improved and improved.
  • the zinc alloy-based alloy of the present invention does not have the most commonly used alloying element Al in the conventional zinc alloy, the intergranular corrosion which is common in the conventional zinc-aluminum alloy is effectively avoided, and the chemical uniformity and stability of the alloy are improved.
  • FIG. 1 is a graph showing the relationship between the copper content of the present invention and the strength of Zn(99.78-X)CuXMn0.2Co0.02 alloy
  • FIG. 2 is a graph showing the copper content of the present invention for Zn(99.78-X)CuXMn0.2Co0.02 alloy®.
  • FIG. 3 is a metallographic structure of a Zn-Al based casting alloy ZAMAK3# in the background art of the present invention, which is a typical primary dendritic structure, indicating that the material is brittle;
  • Figure 5 is a metallographic structure of a deformed zinc alloy in a 10% oxalic acid medium after 24 hours, and no significant intergranular corrosion is observed;
  • Figure 6 is a metallographic structure of a typical cast zinc alloy having the chemical composition of the zinc alloy of the present invention, the structure of which is coarse, and the intermetallic compound is distributed in the matrix in a coarse needle-like structure;
  • Figure 7 is a metallographic structure of a deformed zinc alloy of the present invention, which is composed of a deformed structure of a hexagonal structure and an intermetallic compound dispersed;
  • Figure 8 is a distribution of Zi ⁇ Cu and Zn 9 Mn characterized by scanning electron microscopy in a deformed zinc alloy matrix of the present invention. detailed description
  • the molten component is Mn: 0.5%, Cu: 2.0%, Co: 0.1%, and the balance of Zn, which is added in the form of pure zinc, zinc-copper intermediate alloy, copper-manganese intermediate alloy, cobalt wire, and a reflection melting furnace of 80 kg capacity is used.
  • the tensile strength of the finished bar product was 400 MPa, the elongation was 16%, and the Vickers hardness was Hvl05.
  • the metallographic structure of the finished product was observed by scanning electron microscopy. Considering the composition of the alloy, the volume content of the Z Cu phase was determined to be 5%, the volume content of the Zn 9 Mn phase was 5%, and the rest was the primary phase.
  • the nuts prepared in this example were tested for their properties under the same test conditions as those of lead brass (C3604) and cast zinc aluminum (ZAMAK3#). The performance parameters are shown in Table 3.
  • the molten component is Mn 0.01%, Cu: 9.5%, Co: 0.02% and the balance of Zn, which is added to the medium-frequency melting furnace of 50 kg capacity in the form of pure zinc and zinc copper, copper-manganese intermediate alloy and cobalt wire.
  • a slab was made using a hard mold with a diameter of 90 mm. After the slab was peeled, it was extruded into a round blank of ⁇ 27.5 mm on an 800T extruder at a pressing speed of 0.1 mm s.
  • the extrusion temperature was 150 ° C, the extrusion ratio was 10; and the finished bar was stretched to ⁇ 19.0 mm, the pass processing rate of the drawing was 8.6%, and the total processing ratio was 52%.
  • the finished bar has been tested to have a tensile strength of 490 MPa, an elongation of 10%, and a Vickers hardness of Hvl35.
  • the metallographic structure of the finished product was observed by scanning electron microscopy. Considering the composition of the alloy, the volume content of the Z Cu phase was determined to be 55%, the volume content of the Zn 9 Mn phase was 0.1%, and the rest was the primary phase.
  • Hot stamping of the finished bar hot stamping temperature of 220 ° C, drilling, shaping, tapping, final plating to make 1.5 pieces of finished nut / nut for air conditioning, the nut / nut resistant to neutral salt spray 1000 More than an hour.
  • Example 3 Hot stamping of the finished bar, hot stamping temperature of 220 ° C, drilling, shaping, tapping, final plating to make 1.5 pieces of finished nut / nut for air conditioning, the nut / nut resistant to neutral salt spray 1000 More than an hour.
  • the molten component is Mn: 0.1%, Cu: 8.0%, Co: 0.05% and the balance of Zn, which is added to the 80-kilometer medium-frequency melting furnace in the form of pure zinc, zinc-copper intermediate alloy, copper-manganese intermediate alloy and cobalt wire. After completely melting at 600 Torr, it was cast into a slab using a die of 170 mm in diameter.
  • the slab After the slab is passed through the flat head and the wagon, it is extruded into a circular blank of ⁇ 15.0 mm on an extruder of 1,250 tons, the extrusion speed is 3.0 mm/s, the extrusion temperature is 300 ° C, and the extrusion ratio is 128; After further stretching to H2.5 mm, the pass pass rate of the drawing was 8.2%, and the total processing rate was 30%. Get the finished circle. After testing, the coil has a tensile strength of 475 MPa, an elongation of 12%, and a Vickers hardness of Hvl25.
  • the metallographic structure of the finished product was observed by scanning electron microscopy.
  • the volume content of the Zn4Cu phase was determined to be 40%, the volume content of the Zn 9 Mn phase was 1.5%, and the rest was the primary phase.
  • Example 4 The above-mentioned coil wire is subjected to cold heading processing, drilling, tapping, cold heading, and 4-station processing, and finally, 1.5 pieces of hexagonal nuts/nuts for air conditioning are electroplated.
  • the hex nut/nut finish is resistant to neutral salt spray for more than 1000 hours.
  • the molten component is Mn: 0.2%, Cu: 6.0% and the balance of Zn. It is added to the medium-frequency melting furnace of 800 kg capacity in the form of pure zinc and zinc-copper intermediate alloy, copper-manganese intermediate alloy, and completely melted at 550 °C. Thereafter, a slab was cast at a rate of 4 m/hr using a horizontal continuous casting having a diameter of 170 mm.
  • the extrusion speed was 3.5 mm/s
  • the extrusion temperature was 350 ° C
  • the extrusion ratio was 61
  • the pass processing rate of the drawing is 5.3%
  • the total processing rate is 33%.
  • the tensile strength of the finished bar product is 455 MPa
  • the elongation is 13%
  • the Vickers hardness is Hvll5.
  • the metallographic structure of the finished product was observed by scanning electron microscopy. Considering the composition of the alloy, the volume content of the ZI14CU phase was determined to be 35%, the volume content of the Zn 9 Mn phase was 2.5%, and the rest was the primary phase.
  • the bar finished product was turned, drilled, tapped and plated to make a hex nut/nut product for air conditioning. After testing, the hex nut/nut finished product was resistant to neutral salt spray for more than 1000 hours.
  • a material having a composition of Mn: 0.3%, Cu: 3.0%, Co: 0.07%, and the balance Zn is added to a 1000 kg capacity power frequency melting furnace in the form of pure zinc and zinc copper, copper manganese intermediate alloy, and cobalt wire. After complete melting at 580 ° C, a cast slab was cast at a speed of 3.5 m/hr using a semi-continuous method of 170 mm diameter.
  • the slab After the slab is passed through the flat head and the wagon, it is extruded into a ⁇ 16.5mm round bar on a 1000 ton extruder with an extrusion speed of 2 mm/s, an extrusion temperature of 200 ° C, and an extrusion ratio of 106;
  • the product was further drawn into a finished bar of ⁇ 16.0 mm, and the pass rate of the pass was 6.0%.
  • the tensile strength of the finished bar is 430 MPa, the elongation is 13%, and the Vickers hardness is ⁇ 110.
  • the metallographic structure of the finished product was observed by scanning electron microscopy.
  • the volume content of the ZI14CU phase was determined to be 10%, and the volume content of the ⁇ 9 ⁇ phase was 3.5%, and the rest was the primary phase.
  • the finished bar is hot-punched, turned, drilled, tapped and plated to produce a finished hex nut/nut for air conditioning.
  • the hex nut/nut is resistant to neutral salt spray for more than 1000 hours.
  • the above hot stamping temperature is 220 °C.
  • the melting composition is Mn: 0.4%, Cu: 3.5%, Co: 0.01% and the balance of Zn, added to the 1500 kg capacity power frequency melting furnace in the form of pure zinc and zinc-copper intermediate alloy, copper-manganese intermediate alloy and cobalt wire.
  • Mn 0.4%
  • Cu 3.5%
  • Co 0.01%
  • Zn the balance of Zn
  • the slab After the slab is cut by a sawing machine, it is extruded into a ⁇ 12.5mm round blank on a 2,500 ton extruder with an extrusion speed of 3.5 mm/s, an extrusion temperature of 250 ° C, and an extrusion ratio of 256; Drawing to a ⁇ 11.7 mm loop product, the pass rate of the pass was 7.1%, and the total processing rate was 13%.
  • the product has a tensile strength of 470 MPa, an elongation of 10%, and a Vickers hardness of Hvl l5.
  • the microstructure of the finished product was observed by metallographic microscope. Considering the composition of the alloy, the volume content of the ZI14CU phase was determined to be 16%, the volume content of the ⁇ 9 ⁇ phase was 3.5%, and the rest was the primary phase.
  • the coiled product is cooled, turned, drilled, tapped and plated to produce a finished hex nut/nut for air conditioning.
  • the nut/nut is resistant to neutral salt spray for more than 1000 hours.
  • the above cold heading is processed by 3 stations.
  • the melting composition is Mn: 0.3%, Cu: 5.0%, Co: 0.0005% and the balance of Zn, added to the 1500 kg capacity power frequency melting furnace in the form of pure zinc and zinc-copper intermediate alloy, copper-manganese intermediate alloy and cobalt wire.
  • a slab was produced at a speed of 5 m / h using a continuous casting method of 200 mm in diameter.
  • Slab blank saw After the bed is discharged, it is extruded into a ⁇ 18.0mm round blank on a 2500 ton extruder with an extrusion speed of 3.5 mm/s, an extrusion temperature of 250 ° C, an extrusion ratio of 123, and a drawing to ⁇ 8.0.
  • the pass rate of the pass is 15.0%, and the total processing rate is 80%.
  • the tensile strength of the coil product is 465 MPa, the elongation is 12%, and the Vickers hardness is observed by scanning electron microscopy.
  • the composition of the alloy is determined by combining the composition of the alloy to determine the volume content of the ZH4CU phase is 30%, ⁇ 9 ⁇ phase. The volume content is 3.5%, and the rest is the primary phase.
  • the coiled product is cooled, turned, drilled, tapped and plated to produce a finished hex nut/nut for air conditioning.
  • the nut/nut is resistant to neutral salt spray for more than 1000 hours.
  • the above cold heading is processed by 5 stations.
  • the total amount of inevitable impurity elements in the alloy components in the above respective examples was less than 0.01%.

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Description

一种变形锌合金及其制造方法和应用  Deformed zinc alloy and manufacturing method and application thereof

技术领域 Technical field

本发明涉及变形锌合金及其制备方法,尤其指一种能够用于制造空调行业用螺母和 螺帽的锌铜基变形锌合金及其制造方法。 背景技术  The present invention relates to a deformed zinc alloy and a process for the preparation thereof, and more particularly to a zinc-copper-based deformed zinc alloy which can be used for the manufacture of nuts and nuts for the air-conditioning industry and a method for producing the same. Background technique

空调是一种广泛使用的家用及办公电器, 主要由冷媒、压缩机、管道和各种阀门组 成。 本发明变形锌合金主要是用于替代传统铜合金, 用于制造空调上使用的各种六角螺 母、 螺帽, 这些六角螺母、 螺帽主要用于截止阀和四通阀的密封与连接。  Air conditioning is a widely used household and office appliance that consists primarily of refrigerant, compressors, piping and various valves. The wrought zinc alloy of the invention is mainly used for replacing the traditional copper alloy, and is used for manufacturing various hexagonal nuts and nuts used in air conditioners. These hex nuts and nuts are mainly used for sealing and connecting the shut-off valve and the four-way valve.

传统的空调螺母、螺帽产品都是由铅黄铜采用车削、热冲等方法制成。 由于铜资源 的紧缺, 随着使用量的增加, 导致铜价上涨。 寻求低成本的铜合金替代材料, 是空调制 冷行业的迫切需求。  Traditional air-conditioning nuts and nut products are made of lead brass by turning and hot punching. Due to the shortage of copper resources, copper prices have risen as usage has increased. The search for low-cost alternatives to copper alloys is an urgent need in the air conditioning refrigeration industry.

锌合金也许是一种可能的替代材料, 但由于金属锌是六方晶体结构, 滑移系较少, 铸造态属于较脆而且硬度比较低的金属。 通常在锌的基体中加入铝、 铜、 镁等合金化元 素来提高锌合金的强度并改善综合使用性能。常用的压铸和重力铸造锌合金都是以锌铝 为主要合金化元素的金属材料, 存在明显的晶间腐蚀倾向, 电镀成品率较低, 并且存在 蠕变强度低, 低温脆性等问题, 不适合作为结构材料使用, 大部分作为装饰功能或外观 产品上使用。  Zinc alloys may be a possible alternative, but since metal zinc is a hexagonal crystal structure with less slip, the cast state is a relatively brittle and less rigid metal. Alloying elements such as aluminum, copper, and magnesium are usually added to the zinc matrix to increase the strength of the zinc alloy and improve the overall performance. Commonly used die-casting and gravity-casting zinc alloys are all metal materials with zinc-aluminum as the main alloying element. There is a clear tendency of intergranular corrosion, low electroplating yield, and low creep strength, low temperature brittleness, etc. Used as a structural material, most of it is used as a decorative function or appearance product.

如: 公开号为 JP63241132A的日本专利公开的 《热浸表面形成橄榄绿锌合金涂层》 提出了一种含 Mn 0.2-0.8wt.%、 Cu 0.05-1.0wt%, 其余为锌的锌合金。 这里的锌最好使 用纯度 >99.99%的锌,并且锌合金中 Pb的含量最好 0.005wt%。该锌合金涂层具有耐蚀 性并具有橄榄色, 其主要应用领域为热浸镀和表面涂层。 又如申请号为 CN201010245802.0的中国专利申请所公开的《一种含 Mn的抗蠕变轧制锌合金板带材及 其制备方法》, 该锌合金按重量百分比由下述组分组成: 铜 0.5〜3.0%, 锰 0.01〜2.0%, 钛 0.05〜0.3 %,其余为锌和总量小于 0.05 %的杂质。该锌合金组分按质量百分比还可以 含有: X 0.01〜0.5 %, X为铝、 稀土元素 (Ce+La)中的至少一种。 其制备方法是采用覆 盖保护法熔炼, 合金元素以纯锌, Zn-Cu, Zn-Ti, Cu-Mn, 纯铝, Ce+La复合稀土的形 式加入;熔炼温度为 650-740°C;在 420-480°C熔铸;铸锭经 350-380°C均勾化退火 6-10h 后; 在 220-280°C进行多道次热轧, 总变形量 60-95%; 再冷轧, 总变形量 50-80%; 轧 制后在 180-200°C退火 2-3h, 最后制得板带结构的产品。 再如公开号为 GB483199A的 英国专利所公开的 《提高机械塑性的锌合金》, 该锌合金中除含有纯度较高的锌外, 还 含有 2-5^%的 Cu、 0.1-1 %的 Bi和 0.1-1^%的 Mn。 其特征是在 Zn-Cu-Mn合金中有For example, "Hot-impregnated surface-formed olive-green zinc alloy coating" disclosed in Japanese Patent Publication No. JP63241132A proposes a zinc alloy containing Mn 0.2-0.8 wt.%, Cu 0.05-1.0 wt%, and the balance being zinc. The zinc herein preferably uses zinc having a purity of >99.99%, and the content of Pb in the zinc alloy is preferably 0.005 wt%. The zinc alloy coating is corrosion resistant and has an olive color. Its main application areas are hot dip coating and surface coating. Further, as disclosed in Chinese Patent Application No. CN201010245802.0, a Mn-containing creep-resistant rolled zinc alloy sheet strip and a preparation method thereof, the zinc alloy is composed of the following components by weight: Copper 0.5~3.0%, manganese 0.01~2.0%, titanium 0.05~0.3%, the balance is zinc and the total amount is less than 0.05% impurities. The zinc alloy component may further contain: X 0.01 to 0.5% by mass, and X is at least one of aluminum and a rare earth element (Ce+La). The preparation method is the smelting by the cover protection method, and the alloying elements are added in the form of pure zinc, Zn-Cu, Zn-Ti, Cu-Mn, pure aluminum, Ce+La composite rare earth; the melting temperature is 650-740 ° C; -480 ° C casting; ingots after 350-380 ° C are thickened and annealed for 6-10h; multi-pass hot rolling at 220-280 ° C, total deformation of 60-95%; cold rolling, total deformation The amount is 50-80%; after rolling, it is annealed at 180-200 ° C for 2-3 h, and finally the product of the strip structure is obtained. Another example is the publication number GB483199A The "Zinc Alloy for Improving Mechanical Plasticity" disclosed in the British Patent, which contains 2-5% of Cu, 0.1-1% of Bi and 0.1-1% of the zinc in addition to the higher purity zinc. Mn. It is characterized by having in Zn-Cu-Mn alloy

Bi 的添加, Bi在锌合金中主要起到改善切削性能的作用。 孙利平等在 《中国有色金属 学报》第 21卷, 第 7期 (2011年), 报道了易切削变形 Zn-Cu-Bi合金显微组织与性能, 其合金的主要成分为 Zn-Cu-Mn-Bi-Mg-Ti-Al, 该合金中含有铝。 With the addition of Bi, Bi plays a major role in improving the cutting performance in zinc alloys. Sun Liping, in the Journal of Chinese Nonferrous Metals, Vol. 21, No. 7 (2011), reported the microstructure and properties of the free-cutting Zn-Cu-Bi alloy. The main component of the alloy is Zn-Cu-Mn. -Bi-Mg-Ti-Al, which contains aluminum.

铸造锌基合金材料虽然有着良好的成型性,但由于强度、硬度及可加工性等综合性 能指标较差, 不能用做空调六角螺母、 螺帽使用, 主要作为外观件的压铸产品使用。 图 3所示为 Zn-Al基合金铸造组织的金相照片, 从图中可以看出: 粗大的 HCP组织表明了 材料具有很明显的脆性, 不适合塑性加工成型。 表 1 给出了典型的铸造合金 Zn-4Al-0.05Mg即美标牌号 ZAMAK3#与铅黄铜的代表 C3604机械性能的对比结果。 由 表 1可见, 无论在强度还是延展性方面锌铝合金与铅黄铜都有很大的差别。 因此在空调 螺母、 螺帽制造领域, 锌铝铸造锌基合金不能作为黄铜的替代品使用。  Although the cast zinc-based alloy material has good formability, it has poor comprehensive performance indexes such as strength, hardness and workability, and cannot be used as an air-conditioning hex nut or nut. It is mainly used as a die-casting product for appearance parts. Figure 3 shows a metallographic photograph of the Zn-Al-based alloy cast structure. It can be seen from the figure: The coarse HCP structure indicates that the material has obvious brittleness and is not suitable for plastic forming. Table 1 shows the comparison of the mechanical properties of a typical cast alloy Zn-4Al-0.05Mg, the American brand name ZAMAK3# and the lead brass representative C3604. It can be seen from Table 1 that there is a big difference between zinc aluminum alloy and lead brass in terms of strength and ductility. Therefore, in the field of air-conditioning nuts and nut manufacturing, zinc-aluminum-cast zinc-based alloys cannot be used as a substitute for brass.

锌铝合金 ZAMAK3#与铅黄铜 C3604的机械性能对比  Comparison of mechanical properties between zinc-aluminum alloy ZAMAK3# and lead brass C3604

Figure imgf000004_0001
Figure imgf000004_0001

可见, 现有铸造锌合金尚无法替代传统铅黄铜, 除非是能对其进行改进。 近年来, 材料工程师通过合理的材料设计来改变强化相的数量,合适的加工方法来得到强化相在 基体中的分布状态, 对于获得高性能多功能的金属材料是一种重要的方法。 金属间化合 物较纯金属元素有较高的熔点和高强度、 高硬度, 但同时大部分的金属间化合物很脆, 金属基体中金属间化合物的数量和分布对金属材料的综合性能有很大的影响, 所以, 如 何获得各方面性能均衡甚至优异的产品并非易事。 发明内容  It can be seen that the existing cast zinc alloy is not a substitute for the traditional lead brass unless it can be improved. In recent years, material engineers have changed the number of strengthening phases by reasonable material design, and the proper processing method to obtain the distribution state of the strengthening phase in the matrix is an important method for obtaining high-performance multifunctional metal materials. Intermetallic compounds have higher melting point and high strength and hardness than pure metal elements, but at the same time most of the intermetallic compounds are very brittle. The amount and distribution of intermetallic compounds in the metal matrix have great comprehensive properties for metal materials. Impact, so how to get a balanced or even superior product in all aspects is not easy. Summary of the invention

本发明所要解决的第一个技术问题是针对现有技术的现状提供一种变形锌合金,以 较低成本地替代铅黄铜用于制造空调行业用螺母和螺帽, 解决铜资源匮乏的问题。  The first technical problem to be solved by the present invention is to provide a deformed zinc alloy for the current state of the art, replacing lead brass at a lower cost for manufacturing nuts and nuts for the air conditioning industry, and solving the problem of lack of copper resources. .

本发明所要解决的第二个技术问题是提供一种本发明锌铜基变形锌合金的制造方 法。  A second technical problem to be solved by the present invention is to provide a method for producing a zinc-copper-based deformed zinc alloy of the present invention.

本发明解决上述技术问题所采用的技术方案为:该变形锌合金,其特征在于以重量 计其组成为:  The technical solution adopted by the present invention to solve the above technical problems is: the deformed zinc alloy, characterized in that the composition by weight is:

Cu 2.0-9.5%  Cu 2.0-9.5%

Mn 0.01-0.5%  Mn 0.01-0.5%

Co 0-0.1%  Co 0-0.1%

余量为锌及不可避免的杂质元素; 不可避免的杂质元素总量小于 0.01%。 该锌合金微观组织主要由锌基体初生相和分散在初生相之间的金属间化合物构成; 所述初生相是 HCP结构, 金属间化合物为细小的 ZiuCu和 Zn9Mn; Zi Cu相的体积含 量为 5%-55%, Zn9Mn相的体积含量为 0.1%-5%, 其余为初生相; 初生相的平均晶粒度 为 15〜35微米, 而金属间化合物组织的平均晶粒度为 5~15微米。 金属间化合物组织的 平均晶粒度指的是 Zr^Cu和 Zn9Mn两种金属间化合物总的平均晶粒度。 The balance is zinc and unavoidable impurity elements; the total amount of unavoidable impurity elements is less than 0.01%. The zinc alloy microstructure is mainly composed of a zinc matrix primary phase and an intermetallic compound dispersed between the primary phases; the primary phase is an HCP structure, the intermetallic compound is a fine ZiuCu and Zn 9 Mn; and the volume content of the Zi Cu phase 5%-55%, the volume content of the Zn 9 Mn phase is 0.1%-5%, and the rest is the primary phase; the average grain size of the primary phase is 15 to 35 microns, and the average grain size of the intermetallic compound is 5~15 microns. The average grain size of the intermetallic compound structure refers to the total average grain size of the intermetallic compounds of Zr^Cu and Zn 9 Mn.

本发明在锌的基体中添加 Cu, Mn后, 会形成细小的高强度、 高硬度的金属间化 合物分散于锌合金的基体中, 起到提高强度, 增加抗蠕变性能的作用; 选择性加入的微 量 Co固溶于锌的基体中形成 HCP相, 能起到固溶强化的作用。  The invention adds Cu, Mn to the matrix of zinc, and forms a fine high-strength, high-hardness intermetallic compound dispersed in the matrix of the zinc alloy, thereby improving the strength and increasing the creep resistance; The trace amount of Co is dissolved in the matrix of zinc to form the HCP phase, which can act as a solid solution strengthening.

发明人做了大量的试验, 来研究铜、锰含量对合金强度、 延展性、硬度等性能的影 响。 图 1 是铜含量对 Zn(99.78.x)CuxMnQ.2Coa()2合金强度的影响, 图 2 是铜含量对 Zn(99.78-x)CuxMno.2Coo.o2合金延展性的影响, 表 2是 Mn含量对 Zn(94.98-x)Cu5MnxCoo.o2合 金强度、 硬度和延伸率的影响。 The inventors have done a lot of experiments to study the effects of copper and manganese content on the properties of alloy strength, ductility and hardness. Figure 1 shows the effect of copper content on the strength of Zn( 99 .78 . x )Cu x Mn Q . 2 Co a()2 alloy. Figure 2 shows the copper content versus Zn ( 99.78-x)Cu x Mno. 2 Coo.o2 alloy ductility, table 2 Effect of Mn content (94. 98-x) 5 Mn x Coo.o2 alloy strength, hardness and elongation of the Cu Zn.

比较图 1、 图 2可明显地看出随铜含量的提高本发明合金的强度明显提高, 而延伸 率却明显下降。 当铜含量低于 2%时抗拉强度在 200MPa左右, 制造的空调螺母扭力达 不到要求, 而当铜含量大于 10%时, 合金的延伸率低于 5%, 变的很脆, 不适合加工成 型。 表 2给出了 Mn含量对 Zn94.98-xCu5MnxCoo.02强度、 硬度和延伸率的影响  Comparing Fig. 1 and Fig. 2, it is apparent that the strength of the alloy of the present invention is remarkably improved as the copper content is increased, and the elongation is remarkably lowered. When the copper content is less than 2%, the tensile strength is about 200MPa, the torque of the manufactured air conditioner nut is not up to the requirement, and when the copper content is more than 10%, the elongation of the alloy is less than 5%, which becomes brittle and unsuitable. Processing and forming. Table 2 shows the effect of Mn content on the strength, hardness and elongation of Zn94.98-xCu5MnxCoo.02.

表 2 Mn含量对 Zn94.98-xCu5MnxCo Q2合金强度、 硬度和延伸率的影响 Table 2 Effect of Mn Content on Strength, Hardness and Elongation of Zn 94 . 98-x Cu 5 Mn x Co Q2 Alloy

Figure imgf000005_0001
Figure imgf000005_0001

从表 2可看出过低的 Mn含量会使合金强度变的很低,而过高的 Mn含量又使材料 变的很脆, 缺乏实用性。  It can be seen from Table 2 that too low a Mn content causes the strength of the alloy to become very low, while an excessively high Mn content makes the material brittle and lacks practicality.

同时, 研究发现, 过高的铜、 锰、 钴含量会使金属间化合物的体积分数过大, 不利 于后续塑性成型的加工, 而铜、 锰、 钴的含量过低, 金属间化合物的体积分数过低, 硬 度和扭力都会达不到空调螺母和螺帽产品的标准要求。 经过大量的试验, 确定 Cu含量 在 2.0-9.5%为宜, Mn含量在 0.01-0.5%为宜, Co含量在 0-0.1%为宜, 这样既能保证合 金的高强度要求, 又能满足空调用六角螺母、 螺帽对材料表面处理、 机械性能和加工性 能的要求。  At the same time, it is found that too high copper, manganese and cobalt content will make the volume fraction of intermetallic compounds too large, which is not conducive to the subsequent plastic forming process, while the content of copper, manganese and cobalt is too low, and the volume fraction of intermetallic compounds Too low, hardness and torque will not meet the standard requirements of air conditioning nuts and nuts. After a large number of tests, it is determined that the Cu content is 2.0-9.5%, the Mn content is 0.01-0.5%, and the Co content is 0-0.1%, which can ensure the high strength requirement of the alloy and satisfy the air conditioner. Requirements for surface treatment, mechanical properties and processability of materials with hex nuts and nuts.

较好的, 上述锌合金以重量计其组成为:  Preferably, the composition of the above zinc alloy by weight is:

Cu 5.0-8.0%  Cu 5.0-8.0%

Mn 0.1-0.4%  Mn 0.1-0.4%

Co 0.0005-0.1%  Co 0.0005-0.1%

佘量为锌和不可避免杂质元素。 优选地, 所述 ZmCu相的体积含量为 10%-30%, Zn9Mn相的体积含量为 1%-4%。 所述 Zn9Mn相的晶粒度优选为 1〜3微米。 The amount of lanthanum is zinc and inevitable impurity elements. Preferably, the ZmCu phase has a volume content of 10% to 30%, and the Zn 9 Mn phase has a volume content of 1% to 4%. The grain size of the Zn 9 Mn phase is preferably from 1 to 3 μm.

本发明解决上述第二个技术问题所采用的技术方案为: 上述变形锌合金的制造方 法, 其特征在于先将所述的 Cu、 Mn、 Co、 锌以铜锰和铜锌中间合金的方式加入, 熔铸 后制得变形锌合金铸坯, 熔铸的加热方式可以是反射炉、 中频加热炉或工频加热炉, 熔 铸温度为 500°C-60(rC, 结晶工艺可采用硬模铸造、 连续铸造或半连续铸造, 铸造速率 为 2-5 米 /小时; 所述铸坯经挤压、 拉伸工艺后即得变形锌合金, 挤压时挤压速度为 0.1-3.5mm/s, 挤压温度为 150°C-35(TC, 挤压比为 10-256; 拉伸的道次加工率为 5-15%, 总的加工率最大为 80%。  The technical solution adopted by the present invention to solve the above second technical problem is: the method for manufacturing the above-mentioned deformed zinc alloy, characterized in that the Cu, Mn, Co, and zinc are first added as a copper manganese and a copper-zinc intermediate alloy. After casting, a deformed zinc alloy casting blank can be obtained. The heating method of the casting can be a reverberatory furnace, an intermediate frequency heating furnace or a power frequency heating furnace, and the casting temperature is 500 ° C-60 (rC, the crystallization process can be hard mold casting, continuous casting Or semi-continuous casting, the casting rate is 2-5 m / h; the slab is extruded and stretched to obtain a deformed zinc alloy, and the extrusion speed during extrusion is 0.1-3.5 mm/s, the extrusion temperature It is 150 ° C-35 (TC, extrusion ratio is 10-256; the pass processing rate of stretching is 5-15%, and the total processing rate is up to 80%.

由于金属铜和锰的熔点,都远高于金属锌的熔点,单质元素很难熔化到锌的溶液中 去。 本发明采用了铜 -锌, 铜 -锰中间合金的方式加入, 降低了熔点, 既保证了合金组分 范围的要求, 又能够明显降低锌元素的烧损; 同时使得铜、 锰元素能够以金属间化合物 强化的形式均匀的存在于锌基合金基体中。  Since the melting points of metallic copper and manganese are much higher than the melting point of metallic zinc, it is difficult for elemental elements to melt into the solution of zinc. The invention adopts the method of adding copper-zinc and copper-manganese intermediate alloy to lower the melting point, thereby ensuring the requirement of the alloy composition range and significantly reducing the burning loss of zinc element; at the same time, the copper and manganese elements can be made of metal. The inter-compound enhanced form is present uniformly in the zinc-based alloy matrix.

本发明通过对铸坯进行热挤压、拉伸、热处理和联合拉拔工艺后制成适合空调螺母 螺帽所需形状和规格的变形锌合金, 其特点是通过这些处理工艺, 实现了合金的微观金 相组织由铸造态向加工态的转变, 材料由脆性材料转变为韧性材料, 各项机械性能得到 明显的提高。  The invention realizes the deformed zinc alloy suitable for the shape and specification of the air conditioner nut nut by hot extrusion, drawing, heat treatment and joint drawing process of the slab, and the characteristic is that the alloy is realized by these treatment processes. The microscopic metallographic structure changes from cast state to processed state, and the material changes from brittle material to ductile material, and the mechanical properties are obviously improved.

图 6给出了具有本发明锌合金化学组成的 Zn-Cu-Mn-Co合金铸造状态的金相组织, 由图可见其组织粗大, 金属间化合物呈粗大的针状组织分布于基体中。 而经过热挤压和 拉拔加工等加工工艺后的本发明 Zn-Cu-Mn-Co锌合金金相组织如图 7所示, 由图 7可 以看出: 经过挤压和拉拔加工的 Zn-Cu-Mn-Co锌合金金相组织由六方结构的变形组织 和弥散分布的金属间化合物组成, 组织特点: 有一定的方向性, 粗大的针状组织得到细 化。  Fig. 6 shows the metallographic structure of the Zn-Cu-Mn-Co alloy having the chemical composition of the zinc alloy of the present invention in a cast state. It can be seen that the microstructure is coarse, and the intermetallic compound is distributed in the matrix in a coarse needle-like structure. The metallographic structure of the Zn-Cu-Mn-Co zinc alloy of the present invention after hot extrusion and drawing processing is shown in Fig. 7, as can be seen from Fig. 7: Zn after extrusion and drawing The metallographic structure of the -Cu-Mn-Co zinc alloy consists of a hexagonal structure of deformed structure and a dispersed intermetallic compound. The structure is characterized by a certain directionality, and the coarse needle-like structure is refined.

图 8给出了用扫描电镜表征的 Zi^Cu和 Zn9Mn在锌基体中的分布状况, HCP初晶 相和金属间化合物 Z Cu的晶粒度比较大, 占体积分数较大, 而 Zn9Mn相的晶粒度比 较小, 所占体积分数较少。 Figure 8 shows the distribution of Zi^Cu and Zn 9 Mn in zinc matrix characterized by scanning electron microscopy. The grain size of HCP primary phase and intermetallic compound Z Cu is relatively large, accounting for a large volume fraction, while Zn 9 The grain size of the Mn phase is relatively small, and the volume fraction is small.

通过扫描电镜观察, 本发明变形锌合金微观组织主要由锌基体 HCP初生相和基本 均匀分散在初生相之间的 ZmCu相和 Zn9Mn相构成; Zi^Cu相的体积含量为 5%-55%, Zn9Mn相的体积含量为 0.1%-5%, 其余为初生相; 初生相的平均晶粒度为 15~35微米, Zn9Mn相的晶粒度较小, ZIL I相较大,两种金属间化合物组织总的平均晶粒度为 5~15 微米。 Observed by scanning electron microscopy, the microstructure of the deformed zinc alloy of the present invention is mainly composed of a zinc matrix HCP primary phase and a ZmCu phase and a Zn 9 Mn phase which are substantially uniformly dispersed between the primary phases; the volume of the Zi^Cu phase is 5%-55. The volume content of %, Zn 9 Mn phase is 0.1%-5%, and the rest is primary phase; the average grain size of the primary phase is 15~35 microns, the grain size of Zn 9 Mn phase is smaller, and the ZIL I phase is larger. The total average grain size of the two intermetallic compounds is 5 to 15 microns.

在合金含钴的情况下, 钴与锌固溶为一体而成 HCP初晶相, 故含钴和不含钴的本 发明变形锌合金, 其金相组织基本相同。  In the case where the alloy contains cobalt, cobalt and zinc are solid-dissolved to form a HCP primary phase, so that the cobalt-containing and cobalt-free deformed zinc alloys have substantially the same metallographic structure.

本申请发明人经大量实验发现, 加工条件、组分含量对金相组织均有重要影响, 组 成成分不合适的话, 很难通过加工条件的改变获得具有本发明特征的变形锌合金, 而加 工条件则对本发明变形锌合金的金相组织更是具有直接的影响, 最终在大量试验的基础 上, 确定了本发明锌合金的组成及加工条件。 The inventors of the present application have found through extensive experiments that the processing conditions and component contents have an important influence on the metallographic structure, If the composition is not suitable, it is difficult to obtain a deformed zinc alloy having the characteristics of the present invention by changing the processing conditions, and the processing conditions have a direct influence on the metallographic structure of the deformed zinc alloy of the present invention, and finally based on a large number of tests. The composition and processing conditions of the zinc alloy of the present invention were determined.

上述变形锌合金的用途,将所述的变形锌合金经过机加工、热冲压或冷镦制成半成 品, 对所述半成品进行精修、 攻牙成型后再电镀, 制成用于空调行业的六角螺母或螺帽 广 Π口;  The use of the deformed zinc alloy described above is performed by machining, hot stamping or cold rolling to form a semi-finished product, and the semi-finished product is refined, tapped and then electroplated to form a hexagon for the air conditioning industry. Nut or nut wide mouth;

其中, 所述热冲压的温度为 200~300Ό, 所述冷镦为 3-5工位加工。  Wherein, the hot stamping temperature is 200~300Ό, and the cold heading is 3-5 station processing.

螺母、螺帽的成型工艺可以为机床加工, 热锻成型或冷镦成型几种方式。锌合金六 角螺母 /螺帽的机床加工可采用数控机床、自动机床及专用机床等,原材料是直线型棒材, 加工过程中使用了冷却液以提高加工效率。热锻成型是采用直线型棒材经过下料,加热, 冲压成毛坯件, 再使用仪表车精整成型。 冷镦成型采用圈线产品, 经过下料后, 多工位 冲压成毛坯件后, 用仪表车精整成品。  The forming process of the nut and the nut can be machined, hot forged or cold formed. Zinc alloy hex nuts/nuts can be machined by CNC machine tools, automatic machine tools and special machine tools. The raw materials are linear bars, and coolant is used in the machining process to improve machining efficiency. Hot forging is carried out by using a straight bar, which is heated, stamped into a blank, and then finished by an instrument vehicle. The cold heading adopts the loop line product. After the blanking, after the multi-station is punched into the blank, the finished product is finished with the instrument vehicle.

与现有技术相比, 本发明一方面通过熔铸过程中使用锌铜、 铜锰中间合金的添加工 艺, 使得锌基合金的铸造组织细化, 金属间化合物可以均匀的分布于锌的基体中, 达到 组织均匀化的目的, 改善了材料的脆性, 有利于后续的加工, 避免了高温熔炼中锌的烧 损, 提高了材料的成品率; 另一方面, 通过挤压和拉制等塑性加工, 使得合金由脆性的 锌基合金铸造组织, 转变为韧性较高的加工态组织, 锌基合金材料的综合性能指标得到 明显的改善; 另外, 由于本发明确定了合适的合金化学组成, 因此在加工后能获得具有 特定特征金相组织的变形锌合金, 而这些特定的金相组织结构使得本发明变形锌合金的 综合性能获得了稳定的提高与改善。同时由于本发明的锌基合金中不存在传统锌合金中 最常用的合金化元素 Al,有效避免了传统锌铝合金中普遍存在的晶间腐蚀,改善了合金 的化学均匀性和稳定性。 上述锌基合金的棒材通过机加工、 热冲或冷镦成型后, 可用于 制造空调用六角螺母 /螺帽, 以替代传统的铜合金空调螺母 /螺帽, 较好地解决了铜资源 缺乏的问题。 附图说明  Compared with the prior art, the invention adopts a process of adding zinc-copper and copper-manganese intermediate alloy in the process of casting, so that the casting structure of the zinc-based alloy is refined, and the intermetallic compound can be uniformly distributed in the matrix of the zinc. To achieve the purpose of homogenization of the structure, the brittleness of the material is improved, the subsequent processing is facilitated, the burning of zinc in the high-temperature melting is avoided, and the yield of the material is improved; on the other hand, plastic processing such as extrusion and drawing is performed. The alloy is transformed from a brittle zinc-based alloy into a tough structural state, and the comprehensive performance index of the zinc-based alloy material is significantly improved. In addition, since the present invention determines a suitable alloy chemical composition, it is processed. After that, a deformed zinc alloy having a specific characteristic metallographic structure can be obtained, and these specific metallographic structures make the overall performance of the deformed zinc alloy of the present invention stably improved and improved. At the same time, since the zinc alloy-based alloy of the present invention does not have the most commonly used alloying element Al in the conventional zinc alloy, the intergranular corrosion which is common in the conventional zinc-aluminum alloy is effectively avoided, and the chemical uniformity and stability of the alloy are improved. After the above-mentioned zinc-based alloy bar is machined, hot-punched or cold-formed, it can be used to manufacture hex nuts/nuts for air conditioners, instead of the traditional copper alloy air-conditioning nuts/nuts, which better solves the shortage of copper resources. The problem. DRAWINGS

图 1为本发明铜含量对 Zn(99.78-X)CuXMn0.2Co0.02合金强度的影响关系图; 图 2为本发明铜含量对 Zn(99.78-X)CuXMn0.2Co0.02合金 ®展性的影响关系图; 图 3 为本发明背景技术中 Zn-Al基铸造合金 ZAMAK3#的金相组织, 其为典型的 初大枝晶组织, 表明材料脆性很大;  1 is a graph showing the relationship between the copper content of the present invention and the strength of Zn(99.78-X)CuXMn0.2Co0.02 alloy; FIG. 2 is a graph showing the copper content of the present invention for Zn(99.78-X)CuXMn0.2Co0.02 alloy®. FIG. 3 is a metallographic structure of a Zn-Al based casting alloy ZAMAK3# in the background art of the present invention, which is a typical primary dendritic structure, indicating that the material is brittle;

图 4为本发明背景技术中 Zn-Al基铸造合金 ZAMAK3#在 10%草酸介质中 24小时 后的金相组织, 表明发生了明显晶间腐蚀现象;  4 is a metallographic structure of a Zn-Al based casting alloy ZAMAK3# in a 10% oxalic acid medium after 24 hours in the background art of the present invention, indicating that significant intergranular corrosion occurs;

图 5为本发明变形锌合金在 10%草酸介质中 24小时后的金相组织, 未观测到明显 的晶间腐蚀; 图 6为具有本发明锌合金化学组成的典型的铸造状态锌合金的金相组织,其组织粗 大, 金属间化合物呈粗大的针状组织分布于基体中; 5 is a metallographic structure of a deformed zinc alloy in a 10% oxalic acid medium after 24 hours, and no significant intergranular corrosion is observed; Figure 6 is a metallographic structure of a typical cast zinc alloy having the chemical composition of the zinc alloy of the present invention, the structure of which is coarse, and the intermetallic compound is distributed in the matrix in a coarse needle-like structure;

图 7为本发明变形锌合金的金相组织,其由六方结构的变形组织和弥散分布的金属 间化合物组成;  Figure 7 is a metallographic structure of a deformed zinc alloy of the present invention, which is composed of a deformed structure of a hexagonal structure and an intermetallic compound dispersed;

图 8为用扫描电镜表征的 Zi^Cu和 Zn9Mn在本发明变形锌合金基体中的分布状况。 具体实施方式 Figure 8 is a distribution of Zi^Cu and Zn 9 Mn characterized by scanning electron microscopy in a deformed zinc alloy matrix of the present invention. detailed description

以下结合附图实施例对本发明作进一步详细描述。 实施例 1 :  The invention will be further described in detail below with reference to the embodiments of the drawings. Example 1

熔化成分为 Mn:0.5%、 Cu:2.0%、 Co:0.1%和余量的 Zn, 以纯锌、 锌铜中间合金、 铜锰中间合金、钴丝的形式加入,使用 80公斤容量的反射熔炼炉在 50CTC下完全熔化后, 使用直径 170毫米的硬模铸造成铸坯。 铸坯经过平头、 车皮后, 在 1250吨的挤压机上, 挤压速度为 1.5mm/s,挤压温度为 180Ό,挤压比为 42,挤压成 S23.2mm的六角型坯料; 再拉伸成 S22.0mm的成品棒材, 拉伸的道次加工率为 5.0%。  The molten component is Mn: 0.5%, Cu: 2.0%, Co: 0.1%, and the balance of Zn, which is added in the form of pure zinc, zinc-copper intermediate alloy, copper-manganese intermediate alloy, cobalt wire, and a reflection melting furnace of 80 kg capacity is used. After completely melting at 50 CTC, it was cast into a cast slab using a die of 170 mm in diameter. After the slab passes through the flat head and the wagon, the extrusion speed is 1.5mm/s on the extruder of 1250 tons, the extrusion temperature is 180Ό, the extrusion ratio is 42, and the hexagonal blank is extruded into S23.2mm; The finished bar of S22.0mm was stretched and the pass rate of the pass was 5.0%.

经检测得知该棒材成品的抗拉强度 400MPa, 延伸率 16%, 维氏硬度 Hvl05。 经扫描电镜观察该成品的金相组织, 并结合考虑合金的成分组成, 确定 Z Cu相 的体积含量为 5%, Zn9Mn相的体积含量为 5%, 其余为初生相。 It was found that the tensile strength of the finished bar product was 400 MPa, the elongation was 16%, and the Vickers hardness was Hvl05. The metallographic structure of the finished product was observed by scanning electron microscopy. Considering the composition of the alloy, the volume content of the Z Cu phase was determined to be 5%, the volume content of the Zn 9 Mn phase was 5%, and the rest was the primary phase.

在自动车床上, 经过车削加工, 钻孔, 攻牙和电镀后制成 1.5匹空调专用六角螺母 /螺帽。 对制得的螺母 /螺帽检进行耐蚀性检测, 测得该螺母 /螺帽耐中性盐雾 1000 小时 以上。  On the automatic lathe, after turning, drilling, tapping and plating, 1.5 hex nuts/nuts for air conditioning are made. The obtained nut/nut was inspected for corrosion resistance, and the nut/nut was measured to have a neutral salt spray for more than 1000 hours.

将本实施例所制得的螺母与铅黄铜 (C3604)和铸造锌铝 (ZAMAK3#)所制得的螺母 在相同的测试条件下测试其性能, 其性能参数如表 3所示。  The nuts prepared in this example were tested for their properties under the same test conditions as those of lead brass (C3604) and cast zinc aluminum (ZAMAK3#). The performance parameters are shown in Table 3.

不同材料制成的空调螺母 (Dg8)的性能比较  Performance comparison of air conditioning nuts (Dg8) made of different materials

Figure imgf000008_0001
Figure imgf000008_0001

由表 3可知, 本实施例中所制得合金的主要机械性能指标与铅黄铜相当。  As can be seen from Table 3, the main mechanical properties of the alloys produced in this example are comparable to those of lead brass.

将 ZAMAK3#基合金和本实施例制造的螺母分别浸泡在 10%草酸介质中 24小时后 的金相照片如图 4和图 5所示, 由图 4可知, ∑八1^八 3#发生了明显的晶间腐蚀现象; 而本实施例则没有出现晶间腐蚀倾向 (图 5)。 这说明本实施例中的合金可作为黄铜的替 代品使用, 用于制作空调用六角螺母 /螺帽, 具有较好的性价比。 下述各实施例所获螺母的性能测试结果均反映主要机械性能指标与铅黄铜相当,在The metallographic photographs of the ZAMAK3# base alloy and the nut produced in this example were immersed in 10% oxalic acid medium for 24 hours, respectively, as shown in Fig. 4 and Fig. 5. As can be seen from Fig. 4, ∑八1^八3# occurred. Significant intergranular corrosion phenomenon; however, there is no tendency for intergranular corrosion in this embodiment (Fig. 5). This shows that the alloy in this embodiment can be used as a substitute for brass, and is used for making hex nuts/nuts for air conditioners, and has a good cost performance. The performance test results of the nuts obtained in the following examples all reflect that the main mechanical performance indicators are comparable to lead brass.

10%草酸介质中 24小时后均未出现明显晶间腐蚀, 不再一一赘述。 实施例 2: No obvious intergranular corrosion occurred in the 10% oxalic acid medium after 24 hours, and will not be repeated. Example 2:

熔化成分为 Mn0.01%、 Cu:9.5%、 Co:0.02%和余量的 Zn, 以纯锌和锌铜、 铜锰中 间合金、钴丝的形式加入到 50公斤容量的中频熔炼炉中, 在 55CTC下完全熔化后, 使用 直径 90 毫米的硬模制造成铸坯, 对铸坯进行剥皮后, 在 800T 的挤压机上挤压成 Φ 27.5mm的圆型坯料, 挤压速度为 0.1mm s, 挤压温度为 150°C, 挤压比为 10; 再拉伸成 Φ 19.0mm的成品棒材, 拉伸的道次加工率为 8.6%, 总加工率为 52%。 经测试, 该成品 棒材的抗拉强度 490MPa, 延伸率 10%, 维氏硬度 Hvl35。  The molten component is Mn 0.01%, Cu: 9.5%, Co: 0.02% and the balance of Zn, which is added to the medium-frequency melting furnace of 50 kg capacity in the form of pure zinc and zinc copper, copper-manganese intermediate alloy and cobalt wire. After completely melting at 55CTC, a slab was made using a hard mold with a diameter of 90 mm. After the slab was peeled, it was extruded into a round blank of Φ 27.5 mm on an 800T extruder at a pressing speed of 0.1 mm s. The extrusion temperature was 150 ° C, the extrusion ratio was 10; and the finished bar was stretched to Φ 19.0 mm, the pass processing rate of the drawing was 8.6%, and the total processing ratio was 52%. The finished bar has been tested to have a tensile strength of 490 MPa, an elongation of 10%, and a Vickers hardness of Hvl35.

经扫描电镜观察该成品的金相组织, 并结合考虑合金的成分组成, 确定 Z Cu相 的体积含量为 55%, Zn9Mn相的体积含量为 0.1%, 其余为初生相。 The metallographic structure of the finished product was observed by scanning electron microscopy. Considering the composition of the alloy, the volume content of the Z Cu phase was determined to be 55%, the volume content of the Zn 9 Mn phase was 0.1%, and the rest was the primary phase.

对该成品棒材热冲压加工, 热冲压温度为 220°C, 钻孔, 整形, 攻牙, 最后电镀制 成 1.5匹空调用成品螺母 /螺帽, 该螺母 /螺帽耐中性盐雾 1000小时以上。 实施例 3 :  Hot stamping of the finished bar, hot stamping temperature of 220 ° C, drilling, shaping, tapping, final plating to make 1.5 pieces of finished nut / nut for air conditioning, the nut / nut resistant to neutral salt spray 1000 More than an hour. Example 3:

熔化成分为 Mn:0.1%、 Cu:8.0%、 Co:0.05%和余量的 Zn, 以纯锌、 锌铜中间合金、 铜锰中间合金和钴丝的形式加入到 80公斤容量的中频熔炼炉中, 在 600Ό下完全熔化 后, 使用直径 170毫米的硬模铸造成铸坯。 铸坯经过平头、 车皮后, 在 1250吨的挤压 机上, 挤压成 Φ 15.0mm的圆型坯料, 挤压速度为 3.0mm/s, 挤压温度为 300°C, 挤压比 为 128; 再拉伸到 H2.5mm, 拉伸的道次加工率为 8.2%, 总加工率为 30%。 得到成品 圈线。 经测试, 该圈线的抗拉强度 475MPa, 延伸率 12%, 维氏硬度 Hvl25。  The molten component is Mn: 0.1%, Cu: 8.0%, Co: 0.05% and the balance of Zn, which is added to the 80-kilometer medium-frequency melting furnace in the form of pure zinc, zinc-copper intermediate alloy, copper-manganese intermediate alloy and cobalt wire. After completely melting at 600 Torr, it was cast into a slab using a die of 170 mm in diameter. After the slab is passed through the flat head and the wagon, it is extruded into a circular blank of Φ 15.0 mm on an extruder of 1,250 tons, the extrusion speed is 3.0 mm/s, the extrusion temperature is 300 ° C, and the extrusion ratio is 128; After further stretching to H2.5 mm, the pass pass rate of the drawing was 8.2%, and the total processing rate was 30%. Get the finished circle. After testing, the coil has a tensile strength of 475 MPa, an elongation of 12%, and a Vickers hardness of Hvl25.

经扫描电镜观察该成品的金相组织, 并结合考虑合金的成分组成, 确定 Zn4Cu相 的体积含量为 40%, Zn9Mn相的体积含量为 1.5%, 其余为初生相。 The metallographic structure of the finished product was observed by scanning electron microscopy. Considering the composition of the alloy, the volume content of the Zn4Cu phase was determined to be 40%, the volume content of the Zn 9 Mn phase was 1.5%, and the rest was the primary phase.

对上述圈线经过 5工位的冷镦加工、 钻孔、 攻牙, 冷镦为 4工位加工, 最后电镀制 成 1.5匹空调用六角螺母 /螺帽成品。该六角螺母 /螺帽成品的耐中性盐雾 1000小时以上。 实施例 4:  The above-mentioned coil wire is subjected to cold heading processing, drilling, tapping, cold heading, and 4-station processing, and finally, 1.5 pieces of hexagonal nuts/nuts for air conditioning are electroplated. The hex nut/nut finish is resistant to neutral salt spray for more than 1000 hours. Example 4:

熔化成分为 Mn:0.2%、 Cu:6.0%和余量的 Zn, 以纯锌和锌铜中间合金、铜锰中间合 金的形式加入到 800公斤容量的中频熔炼炉中, 在 550°C下完全熔化后, 使用直径 170 毫米的水平连续铸造以 4米 /小时的速率铸造成铸坯。 对铸坯平头、 车皮后, 在 1250吨 的挤压机上, 挤压成 S19.5mm的六角型坯料,挤压速度为 3.5mm/s, 挤压温度为 350°C, 挤压比为 61 ; 再拉伸到 S16.0mm的棒材成品, 拉伸的道次加工率为 5.3%, 总加工率为 33% 经测试, 棒材成品的抗拉强度 455MPa, 延伸率 13%, 维氏硬度 Hvll5。 经扫描电镜观察该成品的金相组织, 并结合考虑合金的成分组成, 确定 ZI14CU相 的体积含量为 35%, Zn9Mn相的体积含量为 2.5%, 其余为初生相。 The molten component is Mn: 0.2%, Cu: 6.0% and the balance of Zn. It is added to the medium-frequency melting furnace of 800 kg capacity in the form of pure zinc and zinc-copper intermediate alloy, copper-manganese intermediate alloy, and completely melted at 550 °C. Thereafter, a slab was cast at a rate of 4 m/hr using a horizontal continuous casting having a diameter of 170 mm. After the flat head and the wagon of the cast slab, on a 1,250 ton extruder, extruded into a S19.5 mm hexagonal blank, the extrusion speed was 3.5 mm/s, the extrusion temperature was 350 ° C, and the extrusion ratio was 61; After stretching to a S16.0mm bar finished product, the pass processing rate of the drawing is 5.3%, and the total processing rate is 33%. After testing, the tensile strength of the finished bar product is 455 MPa, the elongation is 13%, and the Vickers hardness is Hvll5. . The metallographic structure of the finished product was observed by scanning electron microscopy. Considering the composition of the alloy, the volume content of the ZI14CU phase was determined to be 35%, the volume content of the Zn 9 Mn phase was 2.5%, and the rest was the primary phase.

对棒材成品进行车削加工、 钻孔、 攻牙和电镀后制成 1 匹空调用六角螺母 /螺帽成 品, 经测试, 六角螺母 /螺帽成品耐中性盐雾 1000小时以上。 实施例 5:  The bar finished product was turned, drilled, tapped and plated to make a hex nut/nut product for air conditioning. After testing, the hex nut/nut finished product was resistant to neutral salt spray for more than 1000 hours. Example 5

向 1000公斤容量的工频熔炼炉中以纯锌和锌铜、 铜锰中间合金、 钴丝的形式加入 组成为 Mn:0.3%、 Cu:3.0%、 Co:0.07%和余量的 Zn的物料, 在 580°C下完全熔化后, 使 用直径 170毫米的半连续方法以 3.5米 /小时的速度铸造成铸坯。 对铸坯经过平头、车皮 后, 在 1000吨的挤压机上, 挤压成 Φ 16.5mm圆型棒材, 挤压速度为 2mm/s, 挤压温度 为 200°C, 挤压比为 106; 再拉伸成 Φ 16.0mm的成品棒材, 拉伸的道次加工率为 6.0%。 成品棒材的抗拉强度 430MPa, 延伸率 13%, 维氏硬度 Ην110。  A material having a composition of Mn: 0.3%, Cu: 3.0%, Co: 0.07%, and the balance Zn is added to a 1000 kg capacity power frequency melting furnace in the form of pure zinc and zinc copper, copper manganese intermediate alloy, and cobalt wire. After complete melting at 580 ° C, a cast slab was cast at a speed of 3.5 m/hr using a semi-continuous method of 170 mm diameter. After the slab is passed through the flat head and the wagon, it is extruded into a Φ 16.5mm round bar on a 1000 ton extruder with an extrusion speed of 2 mm/s, an extrusion temperature of 200 ° C, and an extrusion ratio of 106; The product was further drawn into a finished bar of Φ 16.0 mm, and the pass rate of the pass was 6.0%. The tensile strength of the finished bar is 430 MPa, the elongation is 13%, and the Vickers hardness is Ην110.

经扫描电镜观察该成品的金相组织, 并结合考虑合金的成分组成, 确定 ZI14CU相 的体积含量为 10%, Ζη9Μη相的体积含量为 3.5%, 其余为初生相。 The metallographic structure of the finished product was observed by scanning electron microscopy. Considering the composition of the alloy, the volume content of the ZI14CU phase was determined to be 10%, and the volume content of the Ζη 9 Μη phase was 3.5%, and the rest was the primary phase.

成品棒材经过热冲、 车削加工、 钻孔、 攻牙和电镀制成 1 匹空调用六角螺母 /螺帽 成品, 该六角螺母 /螺帽成品耐中性盐雾 1000小时以上。 上述热冲压温度为 220°C。 实施例 6:  The finished bar is hot-punched, turned, drilled, tapped and plated to produce a finished hex nut/nut for air conditioning. The hex nut/nut is resistant to neutral salt spray for more than 1000 hours. The above hot stamping temperature is 220 °C. Example 6:

熔化成分为 Mn:0.4%、 Cu:3.5%、 Co: 0.01%和余量的 Zn, 以纯锌和锌铜中间合金、 铜锰中间合金和钴丝的形式加入到 1500公斤容量的工频熔炼炉中,在 530Ό下完全熔化 后,使用半连续铸造方法以 2米 /小时的铸造速率制造直径 200毫米的挤压用铸坯。铸坯 经过锯床下料后, 在 2500 吨的挤压机上, 挤压成 Φ 12.5mm 圆型坯料, 挤压速度为 3.5mm/s, 挤压温度为 250°C, 挤压比为 256; 再拉丝到 Φ 11.7mm的圈线产品, 拉伸的 道次加工率为 7.1%, 总加工率为 13%。 该圈线产品的抗拉强度 470MPa, 延伸率 10%, 维氏硬度 Hvl l5。  The melting composition is Mn: 0.4%, Cu: 3.5%, Co: 0.01% and the balance of Zn, added to the 1500 kg capacity power frequency melting furnace in the form of pure zinc and zinc-copper intermediate alloy, copper-manganese intermediate alloy and cobalt wire. Among them, after completely melting at 530 Torr, a 200 mm-diameter billet for extrusion was produced at a casting rate of 2 m/hr using a semi-continuous casting method. After the slab is cut by a sawing machine, it is extruded into a Φ 12.5mm round blank on a 2,500 ton extruder with an extrusion speed of 3.5 mm/s, an extrusion temperature of 250 ° C, and an extrusion ratio of 256; Drawing to a Φ 11.7 mm loop product, the pass rate of the pass was 7.1%, and the total processing rate was 13%. The product has a tensile strength of 470 MPa, an elongation of 10%, and a Vickers hardness of Hvl l5.

经金相显微镜观察该成品的微观组织, 并结合考虑合金的成分组成, 确定 ZI14CU 相的体积含量为 16%, Ζη9Μη相的体积含量为 3.5%, 其余为初生相。 The microstructure of the finished product was observed by metallographic microscope. Considering the composition of the alloy, the volume content of the ZI14CU phase was determined to be 16%, the volume content of the Ζη 9 Μη phase was 3.5%, and the rest was the primary phase.

圈线产品经过冷镦、 车削加工、 钻孔、 攻牙和电镀后制成 1 匹空调用六角螺母 /螺 帽成品, 该螺母 /螺帽成品耐中性盐雾 1000小时以上。 上述冷镦为 3工位加工。 实施例 7:  The coiled product is cooled, turned, drilled, tapped and plated to produce a finished hex nut/nut for air conditioning. The nut/nut is resistant to neutral salt spray for more than 1000 hours. The above cold heading is processed by 3 stations. Example 7

熔化成分为 Mn:0.3%、 Cu:5.0%、 Co: 0.0005%和余量的 Zn, 以纯锌和锌铜中间合 金、铜锰中间合金和钴丝的形式加入到 1500公斤容量的工频熔炼炉中,在 550°C下完全 熔化后,使用直径 200毫米的连续铸造方法以 5米 /小时的速度制造成铸坯。铸坯经过锯 床下料后, 在 2500吨的挤压机上, 挤压成 Φ 18.0mm圆型坯料, 挤压速度为 3.5mm/s, 挤压温度为 250°C, 挤压比为 123 ; 再拉丝到 Φ 8.0mm的圈线产品, 拉伸的道次加工率 为 15.0%, 总加工率为 80%。 该圈线产品的抗拉强度 465MPa, 延伸率 12%, 维氏硬度 经扫描电镜观察该成品的微观组织, 并结合考虑合金的成分组成, 确定 ZH4CU相 的体积含量为 30%, Ζη9Μη相的体积含量为 3.5%, 其余为初生相。 The melting composition is Mn: 0.3%, Cu: 5.0%, Co: 0.0005% and the balance of Zn, added to the 1500 kg capacity power frequency melting furnace in the form of pure zinc and zinc-copper intermediate alloy, copper-manganese intermediate alloy and cobalt wire. After completely melting at 550 ° C, a slab was produced at a speed of 5 m / h using a continuous casting method of 200 mm in diameter. Slab blank saw After the bed is discharged, it is extruded into a Φ 18.0mm round blank on a 2500 ton extruder with an extrusion speed of 3.5 mm/s, an extrusion temperature of 250 ° C, an extrusion ratio of 123, and a drawing to Φ 8.0. For the mm line product, the pass rate of the pass is 15.0%, and the total processing rate is 80%. The tensile strength of the coil product is 465 MPa, the elongation is 12%, and the Vickers hardness is observed by scanning electron microscopy. The composition of the alloy is determined by combining the composition of the alloy to determine the volume content of the ZH4CU phase is 30%, Ζη 9 Μη phase. The volume content is 3.5%, and the rest is the primary phase.

圈线产品经过冷镦、 车削加工、 钻孔、 攻牙和电镀后制成 1 匹空调用六角螺母 /螺 帽成品, 该螺母 /螺帽成品耐中性盐雾 1000小时以上。 上述冷镦为 5工位加工。  The coiled product is cooled, turned, drilled, tapped and plated to produce a finished hex nut/nut for air conditioning. The nut/nut is resistant to neutral salt spray for more than 1000 hours. The above cold heading is processed by 5 stations.

上述各实施例中的合金组分中不可避免的杂质元素总量均小于 0.01%。  The total amount of inevitable impurity elements in the alloy components in the above respective examples was less than 0.01%.

Claims

权 利 要 求 Rights request 1、 一种变形锌合金, 其特征在于以重量计其组成为:  A deformed zinc alloy characterized by the composition of: Cu 2.0-9.5%  Cu 2.0-9.5% Mn 0.01-0.5%  Mn 0.01-0.5% Co 0-0.1%  Co 0-0.1% 余量为锌及不可避免的杂质元素; 不可避免的杂质元素总量小于 0.01%。  The balance is zinc and unavoidable impurity elements; the total amount of unavoidable impurity elements is less than 0.01%. 该锌合金微观组织主要由锌基体初生相和分散在初生相之间的金属间化合物构成; 所述初生相是 HCP结构, 金属间化合物为细小的 Z Cu和 Zn9Mn; Z Cu相的体积含 量为 5%-55%, Zn9Mn相的体积含量为 0.1%-5%, 其余为初生相; 初生相的平均晶粒度 为 15 35微米, 而金属间化合物组织的平均晶粒度为 5~15微米。 The zinc alloy microstructure is mainly composed of a zinc matrix primary phase and an intermetallic compound dispersed between the primary phases; the primary phase is an HCP structure, and the intermetallic compound is fine Z Cu and Zn 9 Mn ; the volume of the Z Cu phase The content is 5%-55%, the volume content of the Zn 9 Mn phase is 0.1%-5%, and the rest is the primary phase; the average grain size of the primary phase is 15 35 microns, and the average grain size of the intermetallic compound is 5~15 microns. 2、 根据权利要求 1所述的变形锌合金, 其特征在于以重量计其组成为:  2. A deformed zinc alloy according to claim 1 wherein the composition is: by weight: Cu 5.0-8.0%  Cu 5.0-8.0% Mn 0.1-0.4%  Mn 0.1-0.4% Co 0.0005-0.1%  Co 0.0005-0.1% 余量为锌和不可避免杂质元素。  The balance is zinc and inevitable impurity elements. 3、 根据权利要求 1或 2所述的变形锌合金, 其特征在于所述 ZiuCu相的体积含量 为 10%-30%, Zn9Mn相的体积含量为 1%-4%。 The wrought zinc alloy according to claim 1 or 2, wherein the ZiuCu phase has a volume content of 10% to 30%, and the Zn 9 Mn phase has a volume content of 1% to 4%. 4、根据权利要求 1或 2或 3所述的变形锌合金, 其特征在于所述 Zn9Mn相的晶粒 度为 1〜3微米。 The wrought zinc alloy according to claim 1 or 2 or 3, wherein the Zn 9 Mn phase has a grain size of 1 to 3 μm. 5、 一种如权利要求 1所述的变形锌合金的制造方法,其特征在于先将所述的 Cu、 Mn、 Co、 锌以铜锰和铜锌中间合金的方式加入, 熔铸后制得变形锌合金铸坯, 熔铸的 加热方式可以是反射炉、 中频加热炉或工频加热炉, 熔铸温度为 500°C-60(TC, 结晶工 艺可采用硬模铸造、连续铸造或半连续铸造,铸造速率为 2-5米 /小时,所述铸坯经挤压、 拉伸工艺后即得变形锌合金,挤压时挤压速度为 0.1-3.5mm/s,挤压温度为 150°C-350°C, 挤压比为 10-256; 拉伸的道次加工率为 5-15%, 总的加工率最大为 80%。  5. A method of producing a deformed zinc alloy according to claim 1, wherein said Cu, Mn, Co, and zinc are first added as a copper-manganese and a copper-zinc intermediate alloy, and are deformed after casting. Zinc alloy slab, the heating method of the casting can be a reverberatory furnace, an intermediate frequency heating furnace or a power frequency heating furnace, and the casting temperature is 500 ° C-60 (TC, the crystallization process can be die casting, continuous casting or semi-continuous casting, casting The rate is 2-5 m / h, the slab is extruded and stretched to obtain a deformed zinc alloy. The extrusion speed is 0.1-3.5 mm/s and the extrusion temperature is 150 ° C-350. °C, the extrusion ratio is 10-256; the pass rate of the pass is 5-15%, and the total processing rate is up to 80%. 6、 一种变形锌合金的用途, 其特征在于: 使用如权利要求 1〜4中任意一项所述的 变形锌合金经过机加工、 热冲压或冷镦制成半成品, 对所述半成品进行精修、 攻牙成型 后再电镀, 制成用于空调行业的六角螺母或螺帽产品; 其中, 所述热冲压的温度为 200 °C-300°C , 所述冷镦为 3-5工位加工。  6. Use of a deformed zinc alloy, characterized in that: the deformed zinc alloy according to any one of claims 1 to 4 is subjected to machining, hot stamping or cold rolling to form a semi-finished product, and the semi-finished product is refined. After repairing and tapping, electroplating is performed to form a hex nut or nut product for the air conditioner industry; wherein the hot stamping temperature is 200 ° C - 300 ° C, and the cold heading is 3-5 stations machining.
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CN102586649B (en) * 2012-04-01 2013-06-05 宁波博威合金材料股份有限公司 Deformation zinc alloy, as well as manufacturing method and application thereof
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE775207A (en) * 1971-11-10 1972-05-10 Centre Rech Metallurgique Zinc-based alloys - with improved hot-creep resistance
BE846899A (en) * 1976-10-01 1977-01-31 ZINC BASED ALLOY, HIGH CREEP RESISTANCE
CN101008058A (en) * 2007-01-26 2007-08-01 宁波博威集团股份有限公司 High density zinc base alloy balance block and methods for manufacturing same
CN101906555A (en) * 2010-08-05 2010-12-08 中南大学 A kind of anti-creep rolling zinc alloy plate and strip containing Mn and its preparation method
CN102586649A (en) * 2012-04-01 2012-07-18 宁波博威合金材料股份有限公司 Deformation zinc alloy, as well as manufacturing method and application thereof

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1010417B (en) * 1988-07-05 1990-11-14 哈尔滨工业大学 High-strength and low-expansion zinc-based wear-resistant alloy
JP4204650B2 (en) * 1996-12-09 2009-01-07 三井金属鉱業株式会社 High strength heat-resistant zinc alloy and molded product

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE775207A (en) * 1971-11-10 1972-05-10 Centre Rech Metallurgique Zinc-based alloys - with improved hot-creep resistance
BE846899A (en) * 1976-10-01 1977-01-31 ZINC BASED ALLOY, HIGH CREEP RESISTANCE
CN101008058A (en) * 2007-01-26 2007-08-01 宁波博威集团股份有限公司 High density zinc base alloy balance block and methods for manufacturing same
CN101906555A (en) * 2010-08-05 2010-12-08 中南大学 A kind of anti-creep rolling zinc alloy plate and strip containing Mn and its preparation method
CN102586649A (en) * 2012-04-01 2012-07-18 宁波博威合金材料股份有限公司 Deformation zinc alloy, as well as manufacturing method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SUN, YANG: "Development and application of high strength zinc-based abrasion resistant alloy with cobalt", MECHANICAL ENGINEER, no. 1, 1987, pages 21 *

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