WO2016023326A1 - 一种高精度锌基合金电极丝及其制备方法 - Google Patents

一种高精度锌基合金电极丝及其制备方法 Download PDF

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WO2016023326A1
WO2016023326A1 PCT/CN2015/000279 CN2015000279W WO2016023326A1 WO 2016023326 A1 WO2016023326 A1 WO 2016023326A1 CN 2015000279 W CN2015000279 W CN 2015000279W WO 2016023326 A1 WO2016023326 A1 WO 2016023326A1
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phase
wire
electrode wire
zinc
heat treatment
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PCT/CN2015/000279
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English (en)
French (fr)
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梁志宁
郭芳林
万林辉
吴桐
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宁波博威麦特莱科技有限公司
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Priority to KR1020177001411A priority Critical patent/KR101873953B1/ko
Priority to US14/772,639 priority patent/US9855617B2/en
Priority to EP15771841.2A priority patent/EP3006152B1/en
Priority to JP2015563189A priority patent/JP6029778B1/ja
Publication of WO2016023326A1 publication Critical patent/WO2016023326A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23H—WORKING OF METAL BY THE ACTION OF A HIGH CONCENTRATION OF ELECTRIC CURRENT ON A WORKPIECE USING AN ELECTRODE WHICH TAKES THE PLACE OF A TOOL; SUCH WORKING COMBINED WITH OTHER FORMS OF WORKING OF METAL
    • B23H7/00—Processes or apparatus applicable to both electrical discharge machining and electrochemical machining
    • B23H7/02—Wire-cutting
    • B23H7/08—Wire electrodes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D21/00—Casting non-ferrous metals or metallic compounds so far as their metallurgical properties are of importance for the casting procedure; Selection of compositions therefor
    • B22D21/002—Castings of light metals
    • B22D21/005—Castings of light metals with high melting point, e.g. Be 1280 degrees C, Ti 1725 degrees C
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C1/00—Manufacture of metal sheets, metal wire, metal rods, metal tubes by drawing
    • B21C1/02—Drawing metal wire or like flexible metallic material by drawing machines or apparatus in which the drawing action is effected by drums
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C23/00—Extruding metal; Impact extrusion
    • B21C23/02—Making uncoated products
    • B21C23/04—Making uncoated products by direct extrusion
    • B21C23/08—Making wire, bars, tubes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D25/00—Special casting characterised by the nature of the product
    • B22D25/02—Special casting characterised by the nature of the product by its peculiarity of shape; of works of art
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23H—WORKING OF METAL BY THE ACTION OF A HIGH CONCENTRATION OF ELECTRIC CURRENT ON A WORKPIECE USING AN ELECTRODE WHICH TAKES THE PLACE OF A TOOL; SUCH WORKING COMBINED WITH OTHER FORMS OF WORKING OF METAL
    • B23H7/00—Processes or apparatus applicable to both electrical discharge machining and electrochemical machining
    • B23H7/22—Electrodes specially adapted therefor or their manufacture
    • B23H7/24—Electrode material
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • 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
    • C22C9/00—Alloys based on copper
    • C22C9/04—Alloys based on copper with zinc as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
    • C22F1/165—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon of zinc or cadmium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/10—Other heavy metals
    • C23G1/103—Other heavy metals copper or alloys of copper
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/24—Cleaning or pickling metallic material with solutions or molten salts with neutral solutions
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/22—Electroplating: Baths therefor from solutions of zinc
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C25D5/50—After-treatment of electroplated surfaces by heat-treatment
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C25D7/0607—Wires

Definitions

  • the invention relates to the technical field of electric spark high-precision wire cutting processing, in particular to a high-precision zinc-based alloy electrode wire and a preparation method thereof.
  • EDM electrospray deposition
  • non-mechanical contact processing Adapted to the requirements of micro-machine manufacturing, and has a high cost performance, it has played an important role in many micro-machinery production fields, and has been rapidly developed.
  • the continuous exploration of EDM high-precision wire-cutting technology at home and abroad has made great progress in the combination and practical application of EDM high-precision wire-cutting.
  • the electrode wire in the prior art generally has one or more cores, and the outermost layer is mostly a shell composed of a copper or ⁇ phase zinc alloy having a significant ⁇ phase, or a biphasic crystal copper-zinc alloy.
  • the phase structure is generally: ⁇ + ⁇ , ⁇ , ⁇ or ⁇ + ⁇ .
  • electrode wires on the market, such as: copper wire, also known as high copper wire, which has a single alpha phase structure, excellent product toughness, very good electrical conductivity, and can withstand the maximum instantaneous height.
  • copper wire also known as high copper wire, which has a single alpha phase structure, excellent product toughness, very good electrical conductivity, and can withstand the maximum instantaneous height.
  • This wire can be used to achieve different tensile strengths through various series of drawing and heat treatment processes to meet different equipment and applications.
  • the strength can reach 1000MPa or more, but the surface of the electrode wire has more copper powder and the geometric error of the cross section is too large, which will lead to the decrease of discharge stability, seriously affect the processing precision and the surface quality of the workpiece, and also pollute the equipment components and increase Loss of equipment; galvanized electrode wire, the core material of the wire is ordinary brass, and the surface is plated with zinc on the surface to make the surface formation remarkable.
  • the shell of the ⁇ phase structure due to the gasification of zinc during the cutting process, helps to improve the rinsing performance during surface cutting.
  • the cutting surface is smoother than ordinary brass wire, but the wire still exists in actual use.
  • coated electrode wire the core material of the wire is mainly brass, copper or other materials, the surface layer is ⁇ phase structure, or ⁇ phase structure, or ⁇ + ⁇ phase mixing Phase structure
  • this kind of wire significantly improves production Efficiency, while improving cutting accuracy and surface quality to a certain extent, but such wire is suitable for processing in complex parts such as mold making, aviation, medical, high-thickness and large-scale parts, and for cutting some small complex parts. Accuracy has not been optimized to the greatest extent, especially with the development and maturity of micromachines, such electrode wires have been unable to meet the precision requirements of this aspect.
  • the electrode wires of the ⁇ phase structure, the ⁇ phase structure or the ⁇ + ⁇ phase shell can improve the cutting efficiency is because they can increase the spark discharge energy, so that the explosive force during discharge is large, the amount of erosion is large and fast, and more It is beneficial to corrode the metal material, so that the cutting efficiency of the electrode wire is significantly improved compared with the common electrode wire.
  • the discharge energy is large and the explosive force is large, so that the surface of the cut material has a large pit. Therefore, it is not conducive to improving the cutting precision and surface finish of the electrode wire.
  • the galvanized electrode wire with significant ⁇ phase is relatively gentle in the cutting discharge, the amount of corrosion is small, and the surface of the cut material is small, which is favorable for improving the cutting precision, but the surface of the electrode wire is basically pure zinc.
  • the melting point of zinc is relatively low, the vaporization enthalpy is relatively small, the rapid gasification takes away less heat, and the effective rinsing effect is poor. If the metal particles are not removed in time, the gap is easily blocked and defects are generated, so when cutting It is necessary to inject a large amount of working fluid for secondary scouring to avoid wire breakage caused by heat accumulation. However, if the scouring is not good or the working fluid is unstable, the machining accuracy will be affected, and the requirements for the washing system of the machine tool will be higher. .
  • the first technical problem to be solved by the present invention is to provide a high-precision zinc-based alloy electrode wire with high cutting precision and high surface finish of a cutting material for the prior art.
  • a second technical problem to be solved by the present invention is to provide a method for preparing the above-mentioned high-precision zinc-based alloy electrode wire.
  • a high-precision zinc-based alloy electrode wire comprising a core material and a shell layer coated on the surface of the core material, the core material being made of brass, characterized in that : The mass percent array of the components in the shell layer becomes:
  • X is any two metals selected from the group consisting of Ni, Ag, Cr, Si, and Zr, and the content of the two metals is 0.01 to 2.0%
  • Y is selected from the group consisting of Ti, Al, Co, B, and P. Any two elements in the range of 0.001 to 0.2%;
  • the shell layer has a thickness of 2 to 4 um, and the shell layer structure has an ⁇ phase content of 80 wt% or more, and the balance is a ⁇ phase or an ⁇ phase, and the ⁇ phase is uniformly distributed on the surface of the core material.
  • the mass percentage array of the components in the shell layer is: mass percentage of each component in the shell layer The array becomes:
  • the shell structure is an ⁇ phase, no other phases, and the ⁇ phase is uniformly distributed on the surface of the core material.
  • Proportioning alloy composition the composition of the mass percentage: copper 57% ⁇ 68%, X: 0.03 ⁇ 4.5%, Y: 0.004 ⁇ 0.5%, the rest is zinc and not brought by raw materials and smelting The impurity is avoided, and the sum of the inevitable impurities is ⁇ 0.5%, wherein X is any two metals selected from the group consisting of Ni, Ag, Cr, Si, and Zr, and the content of the two metals is 0.015 to ⁇ 2.25%, Y is any two elements selected from the group consisting of Ti, Al, Co, B, and P, and the content of the two elements ranges from 0.002 to 0.25%;
  • bus bars having a diameter of 0.5 to 5 mm;
  • the busbar is further degreased-acid washed-washed-galvanized, and the thickness of the zinc plating layer is 0.5-50 um, and the first strand blank is obtained, wherein the plating current is 1500-3000 A and the voltage is 150-220 V;
  • the second wire blank is subjected to alloying heat treatment to obtain a finished electrode wire having a diameter of 0.05 to 0.35 mm.
  • the stretching speed in the step (5) is 500-2000 m/min, the annealing voltage is 10-100 V, and the annealing current is 10-50 A, which easily causes the zinc atoms in the plating layer to diffuse and migrate to the bus bar to form a new crystal structure. Conducive to the subsequent heat treatment process.
  • the heat treatment temperature in the step (6) is 50 to 230 degrees, and the heat treatment time is 3 to 30 hours, which is advantageous for forming a shell layer of the ⁇ phase structure in the finished product.
  • the electrode wire of the invention can quickly provide sufficient positive and negative electrons during cutting, the cutting discharge is moderated, and the effective cutting can be maintained, and the shell layer has a certain copper-zinc alloy layer, which improves the gas.
  • the temperature is favorable to take away more heat, improve the rinsing effect, improve the cutting processing precision, and obtain excellent surface quality.
  • the addition of X and Y elements in the electrode wire of the present invention can increase the dislocation of the copper-zinc alloy atom during the stretching process, the lattice distortion at the grain boundary is large, and the energy is increased, resulting in the shell ⁇ phase during the heat treatment.
  • the zinc atom is easy to diffuse and migrate to the core material ( ⁇ + ⁇ phase), and contributes to the formation of the ⁇ phase structure in the shell layer: the ⁇ phase (80 wt% or more) of the shell electrode has good toughness and is effective against cutting.
  • the wire and the rushing force cause the wire to shake, thereby avoiding the wire
  • the toughness is insufficient and the fracture occurs.
  • the electrode wire has a relatively high melting point, can withstand the instantaneous high pulse current and large cutting current, and the instantaneous discharge gap is short.
  • the surface roughness of the metal workpiece after cutting is higher, and the surface quality is higher. Good, so as to effectively improve the cutting precision, especially suitable for finishing and more than three times of cutting, while adding X, Y elements can reduce the heat treatment temperature and heat treatment time, thereby improving the processing efficiency.
  • the preparation process adopted by the invention is advantageous for forming an ⁇ phase in the finished electrode wire shell layer and avoiding further diffusion of the crystal to form a ⁇ equal phase structure, and the preparation method has the advantages of simple process, strong operability and less preparation steps.
  • the production equipment is simple, it is easy to produce a product that meets the requirements, and it is easy to achieve scale and automated production.
  • FIG. 1 is a schematic cross-sectional view showing a second wire blank in Embodiment 1 of the present invention.
  • FIG. 2 is a cross-sectional view showing the finished electrode wire in the first embodiment of the present invention
  • FIG. 5 are schematic diagrams showing metallographic structures of the electrode wires in Examples 1 to 3;
  • FIG. 6 is a schematic view showing the metallographic structure of the electrode wire in Examples 4, 9, and 10;
  • Figure 7 is a schematic view showing the metallographic structure of the electrode wire in Examples 5, 6, 7, and 8:
  • Proportioning alloy composition the composition of the mass percentage is: Cu: 65%, Ni: 2.0%, Si: 1.2%, Ti: 0.12%, Co: 0.2%, the rest is Zn and brought in by raw materials and during smelting
  • the inevitable impurity, the sum of the inevitable impurities is 0.5%, and the ingredients are mixed and put into an induction furnace for melting, and an alloy wire blank having a diameter of 9 mm is produced by casting.
  • the prepared wire blank is extruded or multi-stretched and annealed to form a bus bar having a diameter of 0.5 mm, and then the prepared bus bar is subjected to degreasing-pickling-washing-galvanizing, and the thickness of the zinc plating layer is 0.5um, the first wire blank is prepared, wherein the plating current is 2000A, the voltage is 200V, and then the first wire blank is continuously pulled and processed to form a second wire blank, as shown in FIG. Core material 1 and plating layer 2, wherein the stretching speed was 600 m/min, the back-off voltage was 20 V, and the annealing current was 15 A.
  • the second wire blank was subjected to alloying heat treatment to obtain a finished electrode wire having a diameter of 0.10 mm and a shell thickness of 2 ⁇ m, the heat treatment temperature was 172 ° C, and the heat treatment time was 11 h, as shown in Fig. 1 and Fig. 2, during the heat treatment, the core material 1 and the plating layer 2 is diffused, the diameter of the core material 1 is decreased and the thickness of the plating layer 2 is increased to form a stable shell layer 3, and finally the finished product obtained after the heat treatment is wound on different shaft types.
  • the chemical composition of the shell layer in the finished electrode wire is: Zn: 70.5%, Cu: 27%, Ni: 1.5%, Si: 0.6%, Ti: 0.1%, Co: 0.1%, and impurity: 0.2%.
  • the dislocations of the copper-zinc alloy in the strand are increased during the atomic stretching process, the lattice distortion at the grain boundary is large, and the energy is increased, resulting in the shell ⁇ phase zinc.
  • Atom in It is easy to diffuse and migrate to the core material ( ⁇ + ⁇ phase) during the heat treatment, which helps to form the ⁇ phase structure in the shell layer.
  • the defects such as atomic dislocations and vacancies caused by stretching are gradually reduced, the dislocation density is also reduced, the diffusion activation energy is reduced, and the melting point of the ⁇ phase structure is relative to the original ⁇ .
  • the phase pure zinc is gradually increased, the bonding force between the atoms is enhanced, and under the heat treatment conditions of the present embodiment, the formation of the ⁇ phase structure of the shell layer is facilitated.
  • the core material in the finished electrode wire is ⁇ + ⁇ phase
  • the content of ⁇ phase in the shell structure is 86wt%
  • the rest is ⁇ phase
  • the ⁇ phase is evenly distributed on the surface of the core material.
  • the elongation was tested on a universal electronic tensile tester, the melting point of the shell layer was tested on a differential thermal analyzer, and the EDM precision of the high-precision zinc-based alloy electrode wire prepared in this example was tested using SKD61 material as a material test. And the cutting speed, the test data are shown in Table 1.
  • Proportioning alloy composition the composition of the mass percentage is: Cu: 66%, Cr: 1.5%, Zr: 1.5%, P: 0.15%, B: 0.06%, the rest is Zn and brought in by raw materials and during smelting
  • the inevitable impurities, the sum of the intrinsic impurities, is 0.3%, and the ingredients are mixed and put into an induction furnace for melting, and an alloy wire blank having a diameter of 8 mm is produced by casting.
  • the prepared strand is extruded or multi-stretched and annealed to form a busbar having a diameter of 3 mm, and the obtained busbar is subjected to degreasing-pickling-washing-galvanizing, and the thickness of the zinc coating is 40 um.
  • the first wire blank is prepared, wherein the plating current is 1500 A, the voltage is 200 V, and then the first wire blank after electroplating is subjected to continuous drawing and retreating to prepare a second wire blank, wherein the drawing speed is 500 m/min, and the drawing speed is 500 m/min.
  • the post voltage is 80V and the annealing current is 50A.
  • the second wire blank was subjected to alloying heat treatment to obtain a finished electrode wire having a diameter of 0.10 mm and a shell thickness of 4 ⁇ m, the heat treatment temperature was 121 ° C, and the heat treatment time was 23 h. Finally, the finished product obtained after the heat treatment was wound on different axial forms.
  • the chemical composition of the shell layer in the finished electrode wire is: Zn: 95%, Cu: 2.5%, Cr: 1.0%, Zr: 1.1%, P: 0.1%, B: 0.03%, and impurity: 0.27%.
  • the dislocations of the copper-zinc alloy in the strand are increased during the atomic stretching process, the lattice distortion at the grain boundary is large, and the energy is increased, resulting in the shell ⁇ phase zinc.
  • the atom is easily diffused and migrated to the core material ( ⁇ + ⁇ phase) during the heat treatment, contributing to the formation of the ⁇ phase structure in the shell layer.
  • the defects such as atomic dislocations and vacancies caused by stretching are gradually reduced, the dislocation density is also reduced, the diffusion activation energy is reduced, and the melting point of the ⁇ phase structure is relative to the original ⁇ .
  • the phase pure zinc is gradually increased, the bonding force between the atoms is enhanced, and under the heat treatment conditions of the present embodiment, the formation of the ⁇ phase structure of the shell layer is facilitated.
  • the core material in the finished electrode wire is ⁇ + ⁇ phase
  • the ⁇ phase content in the shell structure is 92wt%
  • the rest is ⁇ phase
  • the ⁇ phase is evenly distributed on the surface of the core material.
  • the elongation was tested on a universal electronic tensile tester, the melting point of the shell layer was tested on a differential thermal analyzer, and the electric spark machining of the high-precision zinc-based alloy electrode wire prepared in the present example was tested using SKD61 material as a material. Accuracy and cutting speed, the test data are shown in Table 1.
  • Proportioning alloy composition the composition of the mass percentage is: Cu: 60%, Si: 0.12%, Ag: 0.07%, Ti: 0.18%, B: 0.02%, the rest is Zn and brought in by raw materials and smelting
  • the unavoidable impurities, the sum of the inevitable impurities, is 0.3%, and the ingredients are mixed and put into an induction furnace for melting, and an alloy wire blank having a diameter of 10 mm is produced by casting.
  • the prepared wire blank is extruded or multi-stretched and annealed to form a bus bar having a diameter of 4 mm, and the prepared bus bar is subjected to degreasing-pickling-washing-galvanizing, and the thickness of the zinc plating layer is 40 um.
  • the first wire blank is prepared, wherein the plating current is 2500A, the voltage is 150V, and then the first wire blank after electroplating is continuously pulled and processed to form a second wire blank, wherein the drawing speed is 1000m/min, and the drawing speed is 1000m/min.
  • the post voltage is 55V and the annealing current is 30A.
  • the second wire blank was subjected to alloying heat treatment to obtain a finished wire product having a diameter of 0.10 mm and a shell thickness of 3 ⁇ m, a heat treatment temperature of 202 ° C, and a heat treatment time of 5 h. Finally, the finished product obtained after the heat treatment was wound on different axial forms.
  • the chemical composition of the shell layer in the finished electrode wire is: Zn: 75%, Cu: 24.5%, Si: 0.11%, Ag: 0.06%, Ti: 0.15%, B: 0.015%, and impurity: 0.165%.
  • the dislocations of the copper-zinc alloy in the strand are increased during the atomic stretching process, the lattice distortion at the grain boundary is large, and the energy is increased, resulting in the shell ⁇ phase zinc.
  • the atom is easily diffused and migrated to the core material ( ⁇ + ⁇ phase) during the heat treatment, contributing to the formation of the ⁇ phase structure in the shell layer.
  • the defects such as atomic dislocations and vacancies caused by stretching are gradually reduced, the dislocation density is also reduced, the diffusion activation energy is reduced, and the melting point of the ⁇ phase structure is relative to the original ⁇ .
  • the phase pure zinc is gradually increased, the bonding force between the atoms is enhanced, and under the heat treatment condition of the embodiment, the formation of the ⁇ phase structure of the shell layer is facilitated, as shown in FIG. 5, the core material in the finished electrode wire is ⁇ + ⁇ phase.
  • the content of the ⁇ phase in the shell structure is 95% by weight, and the rest is the ⁇ phase, and the ⁇ phase is uniformly distributed on the surface of the core material.
  • the elongation was tested on a universal electronic tensile tester, the melting point of the shell layer was tested on a differential thermal analyzer, and the ESD machining accuracy of the high-precision zinc-based alloy electrode wire prepared in this example was tested using SKD61 material as a material. And the cutting speed, the test data are shown in Table 1.
  • Proportioning alloy composition the composition of the mass percentage is: Cu: 57%, Ni: 2.25%, Cr: 0.9%, Ti: 0.01%, Co: 0.015%, the rest is Zn and brought in by raw materials and during smelting
  • the inevitable impurity, the sum of the inevitable impurities is 0.5%, and the ingredients are mixed and put into an induction furnace for melting, and an alloy wire blank having a diameter of 12 mm is produced by casting.
  • the prepared wire blank is extruded or multi-stretched and annealed to form a bus bar having a diameter of 2 mm, and the prepared bus bar is subjected to degreasing-pickling-washing-galvanizing, and the thickness of the zinc plating layer is 15 um.
  • the first wire blank is prepared, wherein the plating current is 2500A, the voltage is 220V, and then the first wire blank after electroplating is continuously pulled and processed to form a second wire blank, wherein the drawing speed is 1500 m/min, and the drawing speed is 1500 m/min.
  • the post voltage is 10V and the annealing current is 15A.
  • the second wire blank was subjected to alloying heat treatment to obtain a finished electrode wire having a diameter of 0.10 mm and a shell thickness of 3 ⁇ m.
  • the heat treatment temperature was 60 ° C, and the heat treatment time was 26 h.
  • the finished product obtained after the heat treatment was wound on different axial forms.
  • the chemical composition of the shell layer in the finished electrode wire is: Zn: 90%, Cu: 7.5%, Ni: 2%, Cr: 0.3%, Ti: 0.007%, Co: 0.005%, and impurity: 0.188%.
  • the copper and zinc in the wire blank are made.
  • the dislocations increase, the lattice distortion at the grain boundary is larger, and the energy increases, which leads to the easy diffusion of the ⁇ phase zinc atoms in the shell layer to the core material ( ⁇ + ⁇ phase) during the heat treatment.
  • An ⁇ phase structure is formed in the shell layer.
  • the defects such as atomic dislocations and vacancies caused by stretching are gradually reduced, the dislocation density is also reduced, the diffusion activation energy is reduced, and the melting point of the ⁇ phase structure is relative to the original ⁇ .
  • the phase pure zinc is gradually increased, the bonding force between the atoms is enhanced, and under the heat treatment conditions of the present embodiment, the formation of the ⁇ phase structure of the shell layer is facilitated.
  • the core material in the finished electrode wire is ⁇ + ⁇ phase
  • the ⁇ phase content in the shell structure is 98wt%
  • the rest is ⁇ phase
  • the ⁇ phase is evenly distributed on the surface of the core material.
  • the elongation was tested on a universal electronic tensile tester, the melting point of the shell layer was tested on a differential thermal analyzer, and the ESD machining accuracy of the high-precision zinc-based alloy electrode wire prepared in this example was tested using SKD61 material as a material. And the cutting speed, the test data are shown in Table 1.
  • the alloying ingredients are proportioned according to the composition of the mass percentage: Cu 60%, Ni 1.8%, Si 0.1%, P 0.12%, B 0.07%, and the rest are Zn and inevitable impurities brought in by raw materials and during smelting. The sum of the impurities is inevitably 0.4%, and the ingredients are mixed and put into an induction furnace for melting, and an alloy wire blank having a diameter of 15 mm is produced by casting. Then, the prepared wire blank is extruded or multi-stretched and annealed to form a bus bar having a diameter of 1 mm, and then the prepared bus bar is subjected to degreasing-acid washing-water washing-galvanizing, and the thickness of the zinc plating layer is 10 um.
  • the first wire blank is prepared, wherein the plating current is 3000A, the voltage is 220V, and then the first wire blank after electroplating is continuously pulled and processed, and the second wire blank is prepared, wherein the drawing speed is 2000m/min.
  • the back-off voltage is 40V and the annealing current is 20A.
  • the second wire blank was subjected to alloying heat treatment to obtain a finished electrode wire having a diameter of 0.10 mm and a shell thickness of 3 ⁇ m, the heat treatment temperature was 83 ° C, and the heat treatment time was 19 h. Finally, the finished product obtained after the heat treatment was wound on different axial forms.
  • the chemical composition of the shell layer in the finished electrode wire is: Zn: 82%, Cu: 16.4%, Ni: 1.2%, Si: 0.05%, P: 0.07%, B: 0.04%, impurity: 0.24%.
  • the dislocations of the copper-zinc alloy in the strand are increased during the atomic stretching process, the lattice distortion at the grain boundary is large, and the energy is increased, resulting in the shell ⁇ phase zinc.
  • the atom is easily diffused and migrated to the core material ( ⁇ + ⁇ phase) during the heat treatment, contributing to the formation of the ⁇ phase structure in the shell layer.
  • the defects such as atomic dislocations and vacancies caused by stretching are gradually reduced, the dislocation density is also reduced, the diffusion activation energy is reduced, and the melting point of the ⁇ phase structure is relative to the original ⁇ .
  • the phase pure zinc is gradually increased, the bonding force between the atoms is enhanced, and under the heat treatment conditions of the present embodiment, the formation of the ⁇ phase structure of the shell layer is facilitated.
  • the core material in the finished electrode wire is ⁇ + ⁇ phase
  • the ⁇ phase content in the shell structure is almost 100 wt%, and there is no other phase, and the ⁇ phase is uniformly distributed on the surface of the core material.
  • the ⁇ phase content is almost 100wt%, which means that the metallographic structure of the shell layer is ⁇ phase, there is no other phase except ⁇ phase, but it may contain oxides, impurities, etc., and the ⁇ phase content is almost 100wt%. Understanding in other parts of the specification Same as this.
  • the elongation was tested on a universal electronic tensile tester, the melting point of the shell layer was tested on a differential thermal analyzer, and the ESD machining accuracy of the high-precision zinc-based alloy electrode wire prepared in this example was tested using SKD61 material as a material. And the cutting speed, the test data are shown in Table 1.
  • Proportioning alloy composition the composition of the mass percentage is: Cu 68%, Zr 0.8%, Cr 0.04%, Ti 0.016%, Al 0.002%, the rest is Zn and the inevitable impurities brought in by raw materials and smelting The sum of the inevitably impurities was 0.2%, and the ingredients were mixed and put into an induction furnace for melting, and an alloy wire blank having a diameter of 11 mm was produced by casting. Then, the prepared wire blank is extruded or multi-stretched and annealed to form a bus bar having a diameter of 5 mm, and then the prepared bus bar is subjected to degreasing-pickling-washing-galvanizing, and the thickness of the zinc plating layer is 50 ⁇ m.
  • the first wire blank is prepared, wherein the plating current is 3000A, the voltage is 180V, and then the first wire blank after electroplating is continuously pulled and processed to form a second wire blank, wherein the drawing speed is 1500 m/min, and the drawing speed is 1500 m/min.
  • the post voltage is 100V and the annealing current is 10A.
  • the second wire blank was subjected to alloying heat treatment to obtain a finished electrode wire having a diameter of 0.10 mm and a shell thickness of 3.5 um, the heat treatment temperature was 163 ° C, the heat treatment time was 8 h, and finally the finished product obtained after the heat treatment was wound on different axial types. .
  • the chemical composition of the shell layer in the finished electrode wire is: Zn: 80%, Cu: 19.2%, Zr: 0.5%, Cr: 0.02%, Ti: 0.008%, Al: 0.001%, and impurity: 0.271%.
  • the dislocations of the copper-zinc alloy in the strand are increased during the atomic stretching process, the lattice distortion at the grain boundary is large, and the energy is increased, resulting in the shell ⁇ phase zinc.
  • the atom is easily diffused and migrated to the core material ( ⁇ + ⁇ phase) during the heat treatment, contributing to the formation of the ⁇ phase structure in the shell layer.
  • the defects such as atomic dislocations and vacancies caused by stretching are gradually reduced, the dislocation density is also reduced, the diffusion activation energy is reduced, and the melting point of the ⁇ phase structure is relative to the original ⁇ .
  • the phase pure zinc is gradually increased, the bonding force between the atoms is enhanced, and under the heat treatment conditions of the present embodiment, the formation of the ⁇ phase structure of the shell layer is facilitated.
  • the core material in the finished electrode wire is ⁇ + ⁇ phase
  • the ⁇ phase content in the shell structure is almost 100 wt%, and there is no other phase, and the ⁇ phase is uniformly distributed on the surface of the core material.
  • the elongation was tested on a universal electronic tensile tester, the melting point of the shell layer was tested on a differential thermal analyzer, and the ESD machining accuracy of the high-precision zinc-based alloy electrode wire prepared in this example was tested using SKD61 material as a material. And the cutting speed, the test data are shown in Table 1.
  • the alloying ingredients are proportioned according to the composition of the mass percentage: Cu 65%, Ni 2.25%, Si 0.015%, Ti 0.14%, Co 0.25%, and the rest are Zn and inevitable impurities brought in by raw materials and during smelting. The sum of the inevitably impurities was 0.5%, and the ingredients were mixed and put into an induction furnace for melting, and an alloy wire blank having a diameter of 13 mm was produced by casting. Then, the prepared wire blank is extruded or multi-stretched and annealed to form a bus bar having a diameter of 3 mm, and the prepared bus bar is subjected to degreasing-pickling-washing-galvanizing, and the thickness of the zinc plating layer is 30 um.
  • the first wire blank is prepared, wherein the plating current is 2000A, the voltage is 200V, and then the first wire blank is continuously pulled and processed to form a second wire blank, as shown in FIG. 1 , the second wire blank includes the core material 1 and plating 2, wherein the drawing speed was 600 m/min, the back-off voltage was 20 V, and the annealing current was 15 A.
  • the second strand is subjected to alloying heat treatment to have a diameter of 0.10 mm and The finished product has a shell thickness of 2.5 um, the heat treatment temperature is 50 ° C, and the heat treatment time is 30 h. Finally, the finished product obtained after the heat treatment is wound on different shaft types.
  • the chemical composition of the shell layer in the finished electrode wire is: Zn: 78.5%, Cu: 19%, Ni: 1.9%, Si: 0.01%, Ti: 0.12%, Co: 0.2%, impurity: 0.27%.
  • the dislocations of the copper-zinc alloy in the strand are increased during the atomic stretching process, the lattice distortion at the grain boundary is large, and the energy is increased, resulting in the shell ⁇ phase zinc.
  • the atom is easily diffused and migrated to the core material ( ⁇ + ⁇ phase) during the heat treatment, contributing to the formation of the ⁇ phase structure in the shell layer.
  • the defects such as atomic dislocations and vacancies caused by stretching are gradually reduced, the dislocation density is also reduced, the diffusion activation energy is reduced, and the melting point of the ⁇ phase structure is relative to the original ⁇ .
  • the phase pure zinc is gradually increased, the bonding force between the atoms is enhanced, and under the heat treatment conditions of the present embodiment, the formation of the ⁇ phase structure of the shell layer is facilitated.
  • the core material in the finished electrode wire is ⁇ + ⁇ phase
  • the ⁇ phase content in the shell structure is almost 100 wt%, and there is no other phase, and the ⁇ phase is uniformly distributed on the surface of the core material.
  • the elongation was tested on a universal electronic tensile tester, the melting point of the shell layer was tested on a differential thermal analyzer, and the EDM precision of the high-precision zinc-based alloy electrode wire prepared in this example was tested using SKD61 material as a material test. And the cutting speed, the test data are shown in Table 1.
  • the alloying ingredients are proportioned according to the composition of the mass percentage: Cu 60%, Ag 1.0%, Ni 2.1%, Al 0.15%, P 0.09%, and the rest are Zn and inevitable impurities brought in by raw materials and during smelting. The sum of the impurities is inevitably 0.4%, and the ingredients are mixed and put into an induction furnace for melting, and an alloy wire blank having a diameter of 15 mm is produced by casting. Then, the prepared wire blank is extruded or multi-stretched and annealed to form a bus bar having a diameter of 2 mm, and then the prepared bus bar is subjected to degreasing-pickling-washing-galvanizing, and the thickness of the zinc plating layer is 25 um.
  • the first wire blank is prepared, wherein the plating current is 3000A, the voltage is 220V, and then the first wire blank after electroplating is continuously pulled and processed to form a second wire blank, wherein the drawing speed is 2000m/min, and the drawing speed is 2000m/min.
  • the post voltage is 40V and the annealing current is 20A.
  • the second wire blank was subjected to alloying heat treatment to obtain a finished electrode wire having a diameter of 0.10 mm and a shell thickness of 4 ⁇ m, the heat treatment temperature was 230 ° C, and the heat treatment time was 3 h. Finally, the finished product obtained after the heat treatment was wound on different axial forms.
  • the chemical composition of the shell layer in the finished electrode wire is: Zn: 85%, Cu: 12.5%, Ag: 0.7%, Ni: 1.5%, Al: 0.09%, P: 0.06%, impurity: 0.15%.
  • the dislocations of the copper-zinc alloy in the strand are increased during the atomic stretching process, the lattice distortion at the grain boundary is large, and the energy is increased, resulting in the shell ⁇ phase zinc.
  • the atom is easily diffused and migrated to the core material ( ⁇ + ⁇ phase) during the heat treatment, contributing to the formation of the ⁇ phase structure in the shell layer.
  • the defects such as atomic dislocations and vacancies caused by stretching are gradually reduced, the dislocation density is also reduced, the diffusion activation energy is reduced, and the melting point of the ⁇ phase structure is relative to the original ⁇ .
  • the phase pure zinc is gradually increased, the bonding force between the atoms is enhanced, and under the heat treatment conditions of the present embodiment, the formation of the ⁇ phase structure of the shell layer is facilitated.
  • the core material in the finished electrode wire is ⁇ + ⁇ phase
  • the ⁇ phase content in the shell structure is almost 100 wt%, and there is no other phase, and the ⁇ phase is uniformly distributed on the surface of the core material.
  • the elongation was tested on a universal electronic tensile tester, the melting point of the shell layer was tested on a differential thermal analyzer, and the ESD machining accuracy of the high-precision zinc-based alloy electrode wire prepared in this example was tested using SKD61 material as a material. And the cutting speed, the test data are shown in Table 1.
  • the alloying ingredients are proportioned according to the composition of the mass percentage: Cu 64%, Zr 0.02%, Si 1.3%, P 0.15%, Co 0.05%, and the rest are Zn and inevitable impurities brought in by raw materials and during smelting. The sum of the inevitably impurities was 0.5%, and the ingredients were mixed and put into an induction furnace for melting, and an alloy wire blank having a diameter of 12 mm was produced by casting.
  • the prepared wire blank is extruded or multi-stretched and annealed to form a bus bar having a diameter of 1.5 mm, and then the prepared bus bar is subjected to degreasing-acid washing-water washing-galvanizing, and the thickness of the zinc plating layer is 15um, the first wire blank was prepared, wherein the plating current was 2500A, the voltage was 220V, and then the first wire blank after electroplating was continuously pulled and processed to form a second wire blank, wherein the drawing speed was 1500 m/min.
  • the back-off voltage is 10V and the annealing current is 15A.
  • the second wire blank was subjected to alloying heat treatment to obtain a finished wire product having a diameter of 0.10 mm and a shell thickness of 3 ⁇ m, a heat treatment temperature of 140 ° C, and a heat treatment time of 16 h. Finally, the finished product obtained after the heat treatment was wound on different axial forms.
  • the chemical composition of the shell layer in the finished electrode wire is: Zn: 89%, Cu: 10.1%, Zr: 0.012%, Si: 0.8%, P: 0.05%, Co: 0.02%, impurity: 0.018%.
  • the dislocations of the copper-zinc alloy in the strand are increased during the atomic stretching process, the lattice distortion at the grain boundary is large, and the energy is increased, resulting in the shell ⁇ phase zinc.
  • the atom is easily diffused and migrated to the core material ( ⁇ + ⁇ phase) during the heat treatment, contributing to the formation of the ⁇ phase structure in the shell layer.
  • the defects such as atomic dislocations and vacancies caused by stretching are gradually reduced, the dislocation density is also reduced, the diffusion activation energy is reduced, and the melting point of the ⁇ phase structure is relative to the original ⁇ .
  • the phase pure zinc is gradually increased, the bonding force between the atoms is enhanced, and under the heat treatment conditions of the present embodiment, the formation of the ⁇ phase structure of the shell layer is facilitated.
  • the core material in the finished electrode wire is ⁇ + ⁇ phase
  • the ⁇ phase content in the shell structure is 97wt%
  • the rest is ⁇ phase
  • the ⁇ phase is evenly distributed on the surface of the core material.
  • the elongation was tested on a universal electronic tensile tester, the melting point of the shell layer was tested on a differential thermal analyzer, and the ESD machining accuracy of the high-precision zinc-based alloy electrode wire prepared in this example was tested using SKD61 material as a material. And the cutting speed, the test data are shown in Table 1.
  • the alloying ingredients are proportioned according to the composition of the mass percentage: Cu 68%, Zr 0.8%, Ag 0.05%, B 0.08%, Co 0.03%, and the rest are Zn and inevitable impurities brought in by raw materials and during smelting.
  • the ingredients were mixed and put into an induction furnace for melting, and an alloy wire blank having a diameter of 11 mm was produced by casting.
  • the prepared wire blank is extruded or multi-stretched and annealed to form a bus bar having a diameter of 5 mm, and the prepared bus bar is subjected to degreasing-pickling-washing-galvanizing, and the thickness of the zinc plating layer is 45 um.
  • the first wire blank is prepared, wherein the plating current is 3000A, the voltage is 180V, and then the first wire blank after electroplating is continuously connected and processed.
  • the second strand was formed, wherein the drawing speed was 1500 m/min, the back-off voltage was 100 V, and the annealing current was 10 A.
  • the second wire blank was subjected to alloying heat treatment to obtain a finished electrode wire having a diameter of 0.10 mm and a shell thickness of 4 ⁇ m, the heat treatment temperature was 80 ° C, and the heat treatment time was 25 h. Finally, the finished product obtained after the heat treatment was wound on different axial forms.
  • the chemical composition of the shell layer in the finished electrode wire is: Zn: 87%, Cu: 12.2%, Zr: 0.5%, Ag: 0.03%, B: 0.03%, Co: 0.01%, and impurity: 0.23%.
  • the dislocations of the copper-zinc alloy in the strand are increased during the atomic stretching process, the lattice distortion at the grain boundary is large, and the energy is increased, resulting in the shell ⁇ phase zinc.
  • the atom is easily diffused and migrated to the core material ( ⁇ + ⁇ phase) during the heat treatment, contributing to the formation of the ⁇ phase structure in the shell layer.
  • the defects such as atomic dislocations and vacancies caused by stretching are gradually reduced, the dislocation density is also reduced, the diffusion activation energy is reduced, and the melting point of the ⁇ phase structure is relative to the original ⁇ .
  • the phase pure zinc is gradually increased, the bonding force between the atoms is enhanced, and under the heat treatment conditions of the present embodiment, the formation of the ⁇ phase structure of the shell layer is facilitated.
  • the core material in the finished electrode wire is ⁇ + ⁇ phase
  • the ⁇ phase content in the shell structure is 99wt%
  • the rest is ⁇ phase
  • the ⁇ phase is evenly distributed on the surface of the core material.
  • the elongation was tested on a universal electronic tensile tester, the melting point of the shell layer was tested on a differential thermal analyzer, and the ESD machining accuracy of the high-precision zinc-based alloy electrode wire prepared in this example was tested using SKD61 material as a material. And the cutting speed, the test data are shown in Table 1.
  • Proportioning alloy composition the composition of the mass percentage is: 66% Cu, the rest is Zn and the unavoidable impurities brought in by the raw materials and smelting, the sum of the inevitable impurities is 0.3%, and the ingredients are mixed and put into Melting was carried out in an induction furnace, and an alloy wire blank having a diameter of 8 mm was produced by casting. Then, the prepared strand is extruded or multi-stretched and annealed to form a busbar having a diameter of 3 mm, and the obtained busbar is subjected to degreasing-pickling-washing-galvanizing, and the thickness of the zinc coating is 40 um.
  • the first wire blank is obtained, wherein the plating current is 1500 A, the voltage is 200 V, and then the first wire blank after electroplating is subjected to continuous drawing and retreating to form a second wire blank, wherein the drawing speed is 500 m/min, and the back is retracted.
  • the voltage is 80V and the annealing current is 50A.
  • the second wire blank was subjected to alloying heat treatment to obtain a finished wire product having a diameter of 0.10 mm and a shell thickness of 4 ⁇ m, a heat treatment temperature of 208 ° C, and a heat treatment time of 72 h. Finally, the finished product obtained after the heat treatment was wound on different axial forms.
  • the chemical composition of the shell layer in the finished electrode wire is: Zn: 92.1%, Cu: 7.6%, and impurity: 0.3%.
  • the ⁇ phase content in the shell structure was 8 wt%, and the balance was ⁇ phase.
  • Proportioning alloy composition the composition of the mass percentage is: 60% Cu, the rest is Zn and the unavoidable impurities brought in by the raw materials and smelting, the sum of the inevitable impurities is 0.4%, and the ingredients are mixed and cast. Melting is carried out in an induction furnace, and an alloy wire blank having a diameter of 15 mm is produced by casting. Then, the prepared wire blank is extruded or multi-stretched and annealed to form a bus bar having a diameter of 1 mm, and then the prepared bus bar is subjected to degreasing-acid washing-water washing-galvanizing, and the thickness of the zinc plating layer is 10 um.
  • the first wire blank is obtained, wherein the plating current is 3000A, the voltage is 220V, and then the first wire blank after electroplating is continuously pulled and processed to form a second wire blank, wherein the drawing speed is 2000m/min, and the back is retracted.
  • the voltage is 40V and the annealing current is 20A.
  • the second wire blank was subjected to alloying heat treatment to obtain a finished electrode wire having a diameter of 0.10 mm and a shell thickness of 3 ⁇ m, a heat treatment temperature of 105 ° C, and a heat treatment time of 100 h. Finally, the finished product obtained after the heat treatment was wound on different axial forms.
  • the chemical composition of the shell layer in the finished electrode wire is: Zn: 65.2%, Cu: 34.62%, impurity: 0.18%, as shown in Fig. 9, the ⁇ phase content in the shell structure is 10 wt%, and the rest is the ⁇ phase.
  • Proportioning alloy composition the composition of the mass percentage is: Cu60%, Ag1.5%, Ni 0.02%, the rest is Zn and the unavoidable impurities brought by the raw materials and smelting, the sum of the inevitable impurities At 0.3%, the ingredients were mixed and put into an induction furnace for melting, and an alloy wire blank having a diameter of 8 mm was produced by casting. Then, the prepared strand is extruded or multi-stretched and annealed to form a busbar having a diameter of 1 mm, and then the prepared busbar is subjected to degreasing-acid washing-washing-galvanizing, and the thickness of the zinc coating is 15 um.
  • the first wire blank is prepared, wherein the plating current is 1600A, the voltage is 200V, and then the first wire blank after electroplating is continuously pulled and processed to form a second wire blank, wherein the drawing speed is 1000m/min, and the drawing speed is 1000m/min.
  • the post voltage is 50V and the annealing current is 25A.
  • the second wire blank was subjected to alloying heat treatment to obtain a finished wire product having a diameter of 0.10 mm and a shell thickness of 3.5 um, the heat treatment temperature was 190 ° C, the heat treatment time was 60 h, and finally the finished product obtained after the heat treatment was wound on different axial types. .
  • the chemical composition of the shell layer in the finished electrode wire is: Zn: 82.1%, Cu: 16.92%, Ag: 0.6%, Ni: 0.009%, and impurity: 0.371%.
  • the ⁇ phase content in the shell structure was 60% by weight, and the balance was ⁇ phase and ⁇ phase.
  • Proportioning alloy composition the composition of the mass percentage is: Cu 58%, Ti 0.15%, Co 0.004%, the balance is Zn and the unavoidable impurities brought by the raw materials and smelting, the sum of the inevitable impurities At 0.3%, the ingredients were mixed and put into an induction furnace for melting, and an alloy wire blank having a diameter of 10 mm was produced by casting. Then, the prepared wire blank is extruded or multi-stretched and annealed to form a bus bar having a diameter of 1 mm, and then the prepared bus bar is subjected to degreasing-pickling-washing-galvanizing, and the thickness of the zinc plating layer is 12 um.
  • preparing a first wire blank wherein the plating current is 1700A, the voltage is 210V, and then the electroplated wire blank is continuously pulled and processed to form a second wire blank, wherein the drawing speed is 600m/min, the back-off voltage is 10V, and the annealing current is 5A.
  • the second wire blank was subjected to alloying heat treatment to obtain a finished electrode wire having a diameter of 0.10 mm and a shell thickness of 3 ⁇ m.
  • the heat treatment temperature was 135 ° C, and the heat treatment time was 56 h.
  • the finished product obtained after the heat treatment was wound on different axial forms.
  • the chemical composition of the shell layer in the finished electrode wire is: Zn: 80.3%, Cu: 19.448%, Ti 0.06%, Co 0.002%, impurity: 0.19%.
  • the ⁇ phase content in the shell structure was 58 wt%, and the balance was ⁇ phase and ⁇ phase.
  • a galvanized electrode wire consisting of a copper-zinc alloy having a diameter of 0.5 to 5 mm, a core material of 63% Cu, and the others being Zn and inevitable impurities, and the impurity content is inevitably ⁇ 0.3%.
  • the surface of the core material is directly galvanized, the thickness of the coating is 20 um, and then the continuous drawing and retreating processing is performed to prepare a galvanized electrode wire having a diameter of 0.05 to 0.35 mm, and the shell structure is ⁇ phase.
  • the elongation was tested on a universal electronic tensile tester, the melting point of the shell layer was tested on a differential thermal analyzer, and the electric discharge machining accuracy and cutting speed of the galvanized electrode wire were tested with SKD61 material as a material. Table 1 shows.
  • a brass wire is composed of a copper-zinc alloy having a diameter of 0.5 to 5 mm, and the wire is 63% Cu, and the others are Zn and inevitable impurities, and the impurity content is inevitably ⁇ 0.3%.
  • the elongation was tested on a universal electronic tensile tester.
  • the melting point of the shell layer was tested on a differential thermal analyzer.
  • the electric discharge machining accuracy and cutting speed of the brass wire were tested with SKD61 material as the material.
  • the test data was as follows. Table 1 shows.
  • the utility model relates to a high-speed electrode wire, which is composed of a core material with a diameter of 0.5 to 5 mm copper, and then galvanized on the surface of the core material, the thickness of the plating layer is 50 um, the first wire blank is obtained, and the first wire blank is heat-treated, and the temperature of the heat treatment process is 550. °C, the time is 10h, the second wire blank is obtained, and finally the second wire blank after heat treatment is subjected to continuous drawing and retreating to form a high-speed electrode wire having a diameter of 0.05 to 0.35 mm, and the shell structure is a ⁇ phase.
  • the elongation was tested on a universal electronic tensile tester, the melting point of the shell layer was tested on a differential thermal analyzer, and the ESD machining accuracy and cutting speed of the high-speed electrode wire were tested using SKD61 material as a material. As shown in Table 1.
  • a plated electrode wire comprising a core material of a copper-zinc alloy having a diameter of 0.5 to 5 mm, the composition of the core material being the same as that of the core wire in the finished electrode wire of the first embodiment.
  • the surface of the core material is galvanized, the thickness of the coating is 30um, the first strand is heat treated, the temperature of the heat treatment process is 450 ° C, the time is 6h, the second strand is obtained, and finally the second strand after heat treatment is continuously pulled back
  • the film is formed into a coated electrode wire having a diameter of 0.05 to 0.35 mm, and the shell structure is a ⁇ phase.
  • the elongation was tested on a universal electronic tensile tester.
  • the melting point of the shell layer was tested on a differential thermal analyzer.
  • the electric discharge machining accuracy and cutting speed of the coated electrode wire were tested with SKD61 material as the material.
  • the test data are shown in the table. 1 is shown.
  • a composite electrode wire comprising a core material of a copper-zinc alloy having a diameter of 0.5 to 5 mm, the composition of the core material being the same as that of the core wire of the finished electrode wire of the third embodiment.
  • the surface of the core material is galvanized, the thickness of the coating is 40um, the first strand is heat treated, the temperature of the heat treatment process is 600 ° C, and the time is 12h, and the second strand is obtained, and the first strand is continuously processed.
  • a layer of ⁇ phase brass is plated on the surface, and finally, the wire blank is subjected to the second continuous drawing and retreating processing to form a composite electrode wire having a diameter of 0.05-0.35, and the layer structure is ⁇ + ⁇ phase.
  • the elongation was tested on a universal electronic tensile tester.
  • the melting point of the shell layer was tested on a differential thermal analyzer.
  • the electrical discharge machining accuracy and cutting speed of the composite electrode wire were tested with SKD61 material as the material.
  • the test data are shown in the table. 1 is shown.
  • Table 1 shows the shell metallographic structure of the electrode wire, the EDM precision ratio, the cutting speed, the elongation, and the melting point in each of the examples and the comparative examples.
  • the high-precision zinc-based alloy electrode wire of the invention has obvious advantages in electrical discharge machining precision, the cutting speed reaches the level of the same product, and the elongation performance is good and the melting point is relatively high.

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Abstract

一种高精度锌基合金电极丝，所述壳层中各成分的质量百分数组成为：Zn70.5～95％、Cu2.5～27％、X0.02～4.0％、Y0.002～0.4％，其他为由原材料带入的不可避免的杂质；其中，X为选自Ni、Ag、Cr、Si、Zr中的任意两种金属，且该两种金属的含量范围均为0.01～2.0％，Y为选自Ti、Al、Co、B、P中的任意两种元素，且该两种元素的含量范围均为0.001～0.2％；所述壳层结构中ε相含量为80wt％以上，余量为γ相或η相，所述ε相均匀分布在芯材表面；还公开了该电极丝的制备方法。经该电极丝切割处理的金属工件表面光洁度较高，表面质量较好，从而使得切割精度较高，同时该电极丝制备工艺简单，可操作性强，制备步骤少，易于实现规模化和自动化生产。

Description

一种高精度锌基合金电极丝及其制备方法 技术领域
本发明涉及电火花高精度线切割加工技术领域，尤其涉及一种高精度锌基合金电极丝及其制备方法。
背景技术
近年来，随着对微小零件——微小齿轮、微小花键和微小连接器等特殊复杂零件加工的需要，电火花切割高精度加工由于其独特的加工方法，即非机械接触加工的特点，尤其适应微型机械制造的要求，并且具有较高的性价比，因此在许多微型机械生产领域发挥了重要的作用，从而得到了迅速的发展。国内外对电火花高精度线切割加工技术的不断探索，已使电火花高精度线切割加工在与微型机械制造结合及实用化方面取得了较大进步。
影响电火花高精度线切割加工的因素很多，如机床精度、电极丝性能、脉冲电源、走丝系统、控制系统及工艺规划等都会对微小零件的加工精度和表面质量有直接的影响。因此围绕微小复杂零件的电火花高精度线切割加工技术的实现，关键是对电极丝性能及切割加工技术进行研究，从而使其最大限度的满足电火花高精度线切割加工需求。现有技术中的电极丝一般具有一层或多层芯，最外层大多为由具有显著α相的铜或η相锌合金，亦或双相结晶铜锌合金组成的壳层，壳层的相结构一般为：α+β、β、γ或β+γ。目前市场上有多种电极丝，如：紫铜电极丝，也称高铜电极丝，该种电极丝具有单一α相结构，产品韧性极好，具有非常好的导电性能，能够承受最大的瞬间高脉冲电流和大切割电流的能力，但是该种电极丝抗拉强度普遍较低，硬丝的抗拉强度平均也只有400-500MPa左右，只适合特殊机床的特殊加工；黄铜电极丝，是目前市场上最常见的电极丝，具有α和β组成的双相结晶组织，这种电极丝可通过-系列的拉丝和热处理工序来实现不同的拉伸强度从而满足不同的设备和应用场合，拉伸强度可以达到1000MPa以上，但该类电极丝表面铜粉较多，截面几何误差太大等，均会导致放电稳定性下降，严重影响加工精度和工件表面质量，同时也会污染设备部件而加大设备的损耗；镀锌电极丝，该种电极丝的芯材为普通黄铜，制备时在表面镀-层锌，使其表面形成具有显著η相结构的壳层，由于锌在切割过程中的气化作用，有助于改善表面切割时的冲洗性能，切割表面比普通黄铜丝光滑，但在实际使用过程中该种电极丝仍然存在掉粉现象从而阻碍加工精度的进一步提升；镀层电极丝，该种电极丝的芯材主要有黄铜、紫铜或其他材料，表层为β相结构，或γ相结构，亦或β+γ相混合相结构，该种电极丝显著提升生产 效率，同时从一定程度上改善切割精度和表面质量，但这类电极丝适用于在模具制造、航空、医疗等复杂件、高厚度及大型件等加工行业应用，而对于切割一些微小复杂零件加工精度未得到最大优化，特别是随着微型机械的发展与成熟应用，此类电极丝已无法满足这方面精度需求。
β相结构、γ相结构或β+γ相壳层的电极丝之所以能够提升切割效率，是由于它们能够提高电火花放电能量，使得放电时爆炸力大，蚀除量大而快，更有利于腐蚀金属料件，从而使该电极丝的切割效率与普通电极丝相比显著提高，但该种电极丝切割时因放电能量大、爆炸力大，因而切割的料件表面凹坑也较大，所以不利于提高电极丝的切割精度及表面光洁度。虽然具有显著η相的镀锌电极丝在切割放电时比较缓和，腐蚀量较小，切割出来的料件表面凹坑较小，有利于提高切割精度，但该类电极丝表面基本为纯锌，而锌的熔点较低，汽化焓相对较小，迅速气化带走热量较少，有效冲洗效果较差，产生的金属颗粒若未能及时排除，则容易堵住间隙而产生缺陷，因此切割时需要注入大量的工作液进行二次冲刷，从而避免因热量累积而导致的断线，但是若冲刷不佳或工作液不稳定时，会影响加工精度，对机床的冲洗系统的要求也会较高。
发明内容
本发明所要解决的第一个技术问题是针对现有技术而提供一种切割精度高、切割料件表面光洁度高的高精度锌基合金电极丝。
本发明所要解决的第二个技术问题是提供一种上述高精度锌基合金电极丝的制备方法。
本发明解决上述技术问题所采用的技术方案为：一种高精度锌基合金电极丝，包括芯材和包覆在芯材表面的壳层，所述芯材的材质为黄铜，其特征在于：所述壳层中各成分的质量百分数组成为：
Figure PCTCN2015000279-appb-000001
其中，X为选自Ni、Ag、Cr、Si、Zr中的任意两种金属，且该两种金属的含量范围均为0.01～2.0％，Y为选自Ti、Al、Co、B、P中的任意两种元素，且该两种元素的含量范围均为0.001～0.2％；
所述壳层的厚度为2～4um，所述壳层结构中ε相含量为80wt％以上，余量为γ相或η相，所述ε相均匀分布在芯材表面。
作为优选，所述壳层中各成分的质量百分数组成为：所述壳层中各成分的质量百分 数组成为：
Figure PCTCN2015000279-appb-000002
所述壳层结构为ε相，无其他相，且所述ε相均匀分布在芯材表面。
上述高精度锌基合金电极丝的制备方法，其特征在于包括以下步骤：
(1)按比例进行合金配料，其质量百分比的成分组成：铜57％～68％，X：0.03～4.5％，Y：0.004～0.5％，其余为锌和由原材料及熔炼时带入的不可避免的杂质，且不可避免杂质的含量之和≤0.5％，其中，X为选自Ni、Ag、Cr、Si、Zr中的任意两种金属，且该两种金属的含量范围均为0.015～2.25％，Y为选自Ti、Al、Co、B、P中的任意两种元素，且该两种元素的含量范围均为0.002～0.25％；
(2)将配料混合投入感应炉进行熔炼，通过铸造产出直径8～15mm合金线坯：
(3)然后将所制线坯经挤压或多道拉伸和退火制成直径0.5～5mm的母线；
(4)再将所制母线进行除油-酸洗-水洗-镀锌，锌镀层厚度为0.5～50um，制得第一线坯，其中电镀电流为1500～3000A，电压150～220V；
(5)对电镀后的第一线坯进行连拉连退加工，制成第二线坯；
(6)最后对第二线坯进行合金化热处理得直径为0.05～0.35mm的电极丝成品。
所述步骤(5)中拉伸速度为500～2000m/min，退火电压为10～100V，退火电流为10～50A，易使镀层中的锌原子向母线扩散迁移从而形成新的结晶组织，有利于后续的热处理加工。
所述步骤(6)中的热处理温度为50～230度，热处理时间为3～30小时，有利于最终制成的成品中形成ε相组织的壳层。
与现有技术相比，本发明的优点在于：
(1)与普通镀层电极丝相比，本发明的电极丝在切割时能够迅速提供足够的正负电子，切割放电缓和，可保持有效切割，同时壳层具有一定铜锌合金层，提高了气化温度，有利于带走更多热量，改善了冲洗效果，有利于提高切割加工精确度，并且获得优异的表面质量。
(2)本发明的电极丝中加入X、Y元素可使铜锌合金原子在拉伸过程中位错增加，晶界处的晶格畸变较大，能量增高，导致热处理过程中壳层η相锌原子易于向芯材(α+β相)扩散迁移，有助于在壳层形成ε相组织：ε相(80wt％以上)壳层结构的电极丝具有良好的韧性，可有效抵抗因切割时电流和冲洗力造成的电极丝的抖动，从而避免电极丝因 韧性不足而发生断裂，同时该种电极丝具有相对较高的熔点，能承受瞬间高脉冲电流和较大切割电流，瞬间的放电间隙较短，切割处理的金属工件表面光洁度较高，表面质量较好，从而有效提高切割精度，尤其适用于精修以及三次以上的多次切割，同时加入X、Y元素后可降低热处理温度和热处理时间，从而提高加工效率。
(3)本发明所采用的制备工艺有利于成品电极丝壳层中形成ε相且避免晶体进一步扩散而形成γ相等相组织，并且，该制备方法工艺简单，可操作性强，制备步骤少，生产设备简单，易于制得符合要求的产品，且易于实现规模化和自动化生产。
附图说明
图1为本发明实施例1中第二线坯的剖视示意图；
图2为本发明实施例1中电极丝成品的剖视示意图；
图3～图5为实施例1～3中电极丝成品金相结构示意图；
图6为实施例4、9、10中电极丝成品金相结构示意图；
图7为实施例5、6、7、8中电极丝成品金相结构示意图：
图8～图11为比较例1～4中电极丝成品金相结构示意图。
具体实施方式
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：
按比例进行合金配料，其质量百分比的成分组成为：Cu：65％，Ni：2.0％，Si：1.2％，Ti：0.12％，Co：0.2％，其余为Zn和由原材料及熔炼时带入的不可避免的杂质，不可避免杂质的含量之和为0.5％，将配料混合投入感应炉中进行熔炼，通过铸造产出直径为9mm的合金线坯。然后，将所制得的线坯经挤压或多道拉伸和退火制成直径0.5mm的母线，再将所制得的母线进行除油-酸洗-水洗-镀锌，锌镀层厚度为0.5um，制得第一线坯，其中电镀电流为2000A，电压为200V，接着对第一线坯进行连拉连退加工，制成第二线坯，如图1所示，第二线坯中包括芯材1和镀层2，其中拉伸速度为600m/min，退后电压为20V，退火电流为15A。对第二线坯进行合金化热处理得直径为0.10mm且壳层厚度为2um的电极丝成品，热处理温度为172℃，热处理时间为11h，如图1和图2所示，热处理过程中，芯材1和镀层2发生扩散，芯材1的直径减小而镀层2的厚度增加，形成稳定的壳层3，最后将热处理后获得的成品绕在不同轴型上。
电极丝成品中壳层的化学成分为：Zn：70.5％，Cu：27％，Ni：1.5％，Si：0.6％，Ti：0.1％，Co：0.1％，杂质：0.2％。本实施例中加入Ni、Si、Ti及Co后，使得线坯中的铜锌合金原子拉伸过程中位错增加，晶界处的晶格畸变较大，能量增加，导致壳层η相锌原子在 热处理过程中易于向芯材(α+β相)扩散迁移，有助于在壳层形成ε相组织。随着壳层与芯材间原子跃迁，因拉伸造成的原子位错、空位等缺陷逐渐减少，位错密度也随之减少，扩散激活能降低，同时ε相组织的熔点相对于原来的η相纯锌逐渐增高，原子间的结合力增强，且在本实施例的热处理条件下，有利于壳层ε相组织的形成。如图3所示，电极丝成品中芯材为α+β相，壳层结构中ε相含量为86wt％，其余为γ相，并且ε相均匀分布在芯材表面。
在万能电子拉伸仪上测试其延伸率，采用差热分析仪上测试其壳层的熔点，以SKD61材料作为料件测试所制备的本实施例中高精度锌基合金电极丝的电火花加工精度以及切割速度，测试所得数据如表1所示。
实施例2：
按比例进行合金配料，其质量百分比的成分组成为：Cu：66％，Cr：1.5％，Zr：1.5％，P：0.15％，B：0.06％，其余为Zn和由原材料及熔炼时带入的不可避免的杂质，不可避免杂质的含量之和0.3％，将配料混合投入感应炉中进行熔炼，通过铸造产出直径为8mm的合金线坯。然后，将所制得的线坯经挤压或多道拉伸和退火制成直径3mm的母线，再将所制得的母线进行除油-酸洗-水洗-镀锌，锌镀层厚度为40um，制得第一线坯，其中电镀电流为1500A，电压为200V，接着对电镀后的第一线坯进行连拉连退加工，制成第二线坯，其中拉伸速度为500m/min，退后电压为80V，退火电流为50A。对第二线坯进行合金化热处理得直径为0.10mm且壳层厚度为4um的电极丝成品，热处理温度为121℃，热处理时间为23h，最后将热处理后获得的成品绕在不同轴型上。
电极丝成品中壳层的化学成分为：Zn：95％，Cu：2.5％，Cr：1.0％，Zr：1.1％，P：0.1％，B：0.03％，杂质：0.27％。本实施例中加入Cr、Zr、P及B后，使得线坯中的铜锌合金原子拉伸过程中位错增加，晶界处的晶格畸变较大，能量增加，导致壳层η相锌原子在热处理过程中易于向芯材(α+β相)扩散迁移，有助于在壳层形成ε相组织。随着壳层与芯材间原子跃迁，因拉伸造成的原子位错、空位等缺陷逐渐减少，位错密度也随之减少，扩散激活能降低，同时ε相组织的熔点相对于原来的η相纯锌逐渐增高，原子间的结合力增强，且在本实施例的热处理条件下，有利于壳层ε相组织的形成。如图4所示，电极丝成品中芯材为α+β相，壳层结构中ε相含量为92wt％，其余为η相，并且ε相均匀分布在芯材表面。
在万能电子拉伸仪上测试其延伸率，采用差热分析仪上测试其壳层的熔点，以SKD61材料作为料件测试本实施例中所制备的高精度锌基合金电极丝的电火花加工精度以及切割速度，测试所得数据如表1所示。
实施例3：
按比例进行合金配料，其质量百分比的成分组成为：Cu：60％，Si：0.12％，Ag：0.07％，Ti：0.18％，B：0.02％，其余为Zn和由原材料及熔炼时带入的不可避免的杂质，不可避免杂质的含量之和为0.3％，将配料混合投入感应炉中进行熔炼，通过铸造产出直径为10mm的合金线坯。然后，将所制得的线坯经挤压或多道拉伸和退火制成直径4mm的母线，再将所制得的母线进行除油-酸洗-水洗-镀锌，锌镀层厚度为40um，制得第一线坯，其中电镀电流为2500A，电压为150V，接着对电镀后的第一线坯进行连拉连退加工，制成第二线坯，其中拉伸速度为1000m/min，退后电压为55V，退火电流为30A。对第二线坯进行合金化热处理得直径为0.10mm且壳层厚度为3um的电极丝成品，热处理温度为202℃，热处理时间为5h，最后将热处理后获得的成品绕在不同轴型上。
电极丝成品中壳层的化学成分为：Zn：75％，Cu：24.5％，Si：0.11％，Ag：0.06％，Ti：0.15％，B：0.015％，杂质：0.165％。本实施例中加入Si、Ag、Ti及B后，使得线坯中的铜锌合金原子拉伸过程中位错增加，晶界处的晶格畸变较大，能量增加，导致壳层η相锌原子在热处理过程中易于向芯材(α+β相)扩散迁移，有助于在壳层形成ε相组织。随着壳层与芯材间原子跃迁，因拉伸造成的原子位错、空位等缺陷逐渐减少，位错密度也随之减少，扩散激活能降低，同时ε相组织的熔点相对于原来的η相纯锌逐渐增高，原子间的结合力增强，且在本实施例的热处理条件下，有利于壳层ε相组织的形成，如图5所示，电极丝成品中芯材为α+β相，壳层结构中ε相含量为95wt％，其余为γ相，并且ε相均匀分布在芯材表面。
在万能电子拉伸仪上测试其延伸率，采用差热分析仪上测试其壳层的熔点，以SKD61材料作为料件测试本实施例所制备的高精度锌基合金电极丝的电火花加工精度以及切割速度，测试所得数据如表1所示。
实施例：4：
按比例进行合金配料，其质量百分比的成分组成为：Cu：57％，Ni：2.25％，Cr：0.9％，Ti：0.01％，Co：0.015％，其余为Zn和由原材料及熔炼时带入的不可避免的杂质，不可避免杂质的含量之和为0.5％，将配料混合投入感应炉中进行熔炼，通过铸造产出直径为12mm的合金线坯。然后，将所制得的线坯经挤压或多道拉伸和退火制成直径2mm的母线，再将所制得的母线进行除油-酸洗-水洗-镀锌，锌镀层厚度为15um，制得第一线坯，其中电镀电流为2500A，电压为220V，接着对电镀后的第一线坯进行连拉连退加工，制成第二线坯，其中拉伸速度为1500m/min，退后电压为10V，退火电流为15A。对第二线坯进行合金化热处理得直径为0.10mm且壳层厚度为3um的电极丝成品，热处理温度为60℃，热处理时间为26h，最后将热处理后获得的成品绕在不同轴型上。
电极丝成品中壳层的化学成分为：Zn：90％，Cu：7.5％，Ni：2％，Cr：0.3％，Ti：0.007％，Co：0.005％，杂质：0.188％。本实施例中加入Ni、Cr、Ti及Co后，使得线坯中的铜锌 合金原子拉伸过程中位错增加，晶界处的晶格畸变较大，能量增加，导致壳层η相锌原子在热处理过程中易于向芯材(α+β相)扩散迁移，有助于在壳层形成ε相组织。随着壳层与芯材间原子跃迁，因拉伸造成的原子位错、空位等缺陷逐渐减少，位错密度也随之减少，扩散激活能降低，同时ε相组织的熔点相对于原来的η相纯锌逐渐增高，原子间的结合力增强，且在本实施例的热处理条件下，有利于壳层ε相组织的形成。如图6所示，电极丝成品中芯材为α+β相，壳层结构中ε相含量为98wt％，其余为η相，并且ε相均匀分布在芯材表面。
在万能电子拉伸仪上测试其延伸率，采用差热分析仪上测试其壳层的熔点，以SKD61材料作为料件测试本实施例所制备的高精度锌基合金电极丝的电火花加工精度以及切割速度，测试所得数据如表1所示。
实施例5：
按比例进行合金配料，其质量百分比的成分组成为：Cu 60％，Ni 1.8％，Si 0.1％，P 0.12％，B 0.07％，其余为Zn和由原材料及熔炼时带入的不可避免的杂质，不可避免杂质的含量之和0.4％，将配料混合投入感应炉中进行熔炼，通过铸造产出直径为15mm的合金线坯。然后，将所制得的线坯经挤压或多道拉伸和退火制成直径1mm的母线，再将所制得的母线进行除油-酸洗-水洗-镀锌，锌镀层厚度为10um，制得第一线坯，其中电镀电流为3000A，电压为220V，接着对电镀后的第一线坯进行连拉连退加工，制成的第二线坯，其中拉伸速度为2000m/min，退后电压为40V，退火电流为20A。对第二线坯进行合金化热处理得直径为0.10mm且壳层厚度为3um的电极丝成品，热处理温度为83℃，热处理时间为19h，最后将热处理后获得的成品绕在不同轴型上。
电极丝成品中壳层的化学成分为：Zn：82％，Cu：16.4％％，Ni：1.2％，Si：0.05％，P：0.07％，B：0.04％，杂质：0.24％。本实施例中加入Ni、Si、P及B后，使得线坯中的铜锌合金原子拉伸过程中位错增加，晶界处的晶格畸变较大，能量增加，导致壳层η相锌原子在热处理过程中易于向芯材(α+β相)扩散迁移，有助于在壳层形成ε相组织。随着壳层与芯材间原子跃迁，因拉伸造成的原子位错、空位等缺陷逐渐减少，位错密度也随之减少，扩散激活能降低，同时ε相组织的熔点相对于原来的η相纯锌逐渐增高，原子间的结合力增强，且在本实施例的热处理条件下，有利于壳层ε相组织的形成。如图7所示电极丝成品中芯材为α+β相，壳层结构中ε相含量几乎为100wt％，无其他相，并且ε相均匀分布在芯材表面。ε相含量几乎为100wt％是指壳层的金相结构均为ε相，除ε相外无其他相，但可能含有氧化物、杂质等，ε相含量几乎为100wt％在说明书其他部分的理解与此同。
在万能电子拉伸仪上测试其延伸率，采用差热分析仪上测试其壳层的熔点，以SKD61材料作为料件测试本实施例所制备的高精度锌基合金电极丝的电火花加工精度 以及切割速度，测试所得数据如表1所示。
实施例6：
按比例进行合金配料，其质量百分比的成分组成为：Cu 68％，Zr 0.8％，Cr 0.04％，Ti 0.016％，Al 0.002％，其余为Zn和由原材料及熔炼时带入的不可避免的杂质，不可避免杂质的含量之和为0.2％，将配料混合投入感应炉中进行熔炼，通过铸造产出直径为11mm的合金线坯。然后，将所制得的线坯经挤压或多道拉伸和退火制成直径5mm的母线，再将所制得的母线进行除油-酸洗-水洗-镀锌，锌镀层厚度为50um，制得第一线坯，其中电镀电流为3000A，电压为180V，接着对电镀后的第一线坯进行连拉连退加工，制成第二线坯，其中拉伸速度为1500m/min，退后电压为100V，退火电流为10A。对第二线坯进行合金化热处理得直径为0.10mm且壳层厚度为3.5um的电极丝成品，热处理温度为163℃，热处理时间为8h，最后将热处理后获得的成品绕在不同轴型上。
电极丝成品中壳层的化学成分为：Zn：80％，Cu：19.2％，Zr：0.5％，Cr：0.02％，Ti：0.008％，Al：0.001％，杂质：0.271％。本实施例中加入Zr、Cr、Ti及Al后，使得线坯中的铜锌合金原子拉伸过程中位错增加，晶界处的晶格畸变较大，能量增加，导致壳层η相锌原子在热处理过程中易于向芯材(α+β相)扩散迁移，有助于在壳层形成ε相组织。随着壳层与芯材间原子跃迁，因拉伸造成的原子位错、空位等缺陷逐渐减少，位错密度也随之减少，扩散激活能降低，同时ε相组织的熔点相对于原来的η相纯锌逐渐增高，原子间的结合力增强，且在本实施例的热处理条件下，有利于壳层ε相组织的形成。如图7所示，电极丝成品中芯材为α+β相，壳层结构中ε相含量几乎为100wt％，无其他相，并且ε相均匀分布在芯材表面。
在万能电子拉伸仪上测试其延伸率，采用差热分析仪上测试其壳层的熔点，以SKD61材料作为料件测试本实施例所制备的高精度锌基合金电极丝的电火花加工精度以及切割速度，测试所得数据如表1所示。
实施例7：
按比例进行合金配料，其质量百分比的成分组成为：Cu 65％，Ni 2.25％，Si 0.015％，Ti 0.14％，Co 0.25％，其余为Zn和由原材料及熔炼时带入的不可避免的杂质，不可避免杂质的含量之和为0.5％，将配料混合投入感应炉中进行熔炼，通过铸造产出直径为13mm的合金线坯。然后，将所制得的线坯经挤压或多道拉伸和退火制成直径3mm的母线，再将所制得的母线进行除油-酸洗-水洗-镀锌，锌镀层厚度为30um，制得第一线坯，其中电镀电流为2000A，电压为200V，接着对第一线坯进行连拉连退加工，制成第二线坯，如图1所示，第二线坯中包括芯材1和镀层2，其中拉伸速度为600m/min，退后电压为20V，退火电流为15A。对第二线坯进行合金化热处理得直径为0.10mm且 壳层厚度为2.5um的电极丝成品，热处理温度为50℃，热处理时间为30h，最后将热处理后获得的成品绕在不同轴型上。
电极丝成品中壳层的化学成分为：Zn：78.5％，Cu：19％，Ni：1.9％，Si：0.01％，Ti：0.12％，Co：0.2％，杂质：0.27％。本实施例中加入Ni、Si、Ti及Co后，使得线坯中的铜锌合金原子拉伸过程中位错增加，晶界处的晶格畸变较大，能量增加，导致壳层η相锌原子在热处理过程中易于向芯材(α+β相)扩散迁移，有助于在壳层形成ε相组织。随着壳层与芯材间原子跃迁，因拉伸造成的原子位错、空位等缺陷逐渐减少，位错密度也随之减少，扩散激活能降低，同时ε相组织的熔点相对于原来的η相纯锌逐渐增高，原子间的结合力增强，且在本实施例的热处理条件下，有利于壳层ε相组织的形成。如图7所示，电极丝成品中芯材为α+β相，壳层结构中ε相含量几乎为100wt％，无其他相，并且ε相均匀分布在芯材表面。
在万能电子拉伸仪上测试其延伸率，采用差热分析仪上测试其壳层的熔点，以SKD61材料作为料件测试所制备的本实施例中高精度锌基合金电极丝的电火花加工精度以及切割速度，测试所得数据如表1所示。
实施例8：
按比例进行合金配料，其质量百分比的成分组成为：Cu 60％，Ag 1.0％，Ni 2.1％，Al 0.15％，P 0.09％，其余为Zn和由原材料及熔炼时带入的不可避免的杂质，不可避免杂质的含量之和0.4％，将配料混合投入感应炉中进行熔炼，通过铸造产出直径为15mm的合金线坯。然后，将所制得的线坯经挤压或多道拉伸和退火制成直径2mm的母线，再将所制得的母线进行除油-酸洗-水洗-镀锌，锌镀层厚度为25um，制得第一线坯，其中电镀电流为3000A，电压为220V，接着对电镀后的第一线坯进行连拉连退加工，制成第二线坯，其中拉伸速度为2000m/min，退后电压为40V，退火电流为20A。对第二线坯进行合金化热处理得直径为0.10mm且壳层厚度为4um的电极丝成品，热处理温度为230℃，热处理时间为3h，最后将热处理后获得的成品绕在不同轴型上。
电极丝成品中壳层的化学成分为：Zn：85％，Cu：12.5％％，Ag：0.7％，Ni：1.5％，Al：0.09％，P：0.06％，杂质：0.15％。本实施例中加入Ag、Ni、Al及P后，使得线坯中的铜锌合金原子拉伸过程中位错增加，晶界处的晶格畸变较大，能量增加，导致壳层η相锌原子在热处理过程中易于向芯材(α+β相)扩散迁移，有助于在壳层形成ε相组织。随着壳层与芯材间原子跃迁，因拉伸造成的原子位错、空位等缺陷逐渐减少，位错密度也随之减少，扩散激活能降低，同时ε相组织的熔点相对于原来的η相纯锌逐渐增高，原子间的结合力增强，且在本实施例的热处理条件下，有利于壳层ε相组织的形成。如图7所示电极丝成品中芯材为α+β相，壳层结构中ε相含量几乎为100wt％，无其他相，并且ε相均匀分布在芯材表面。
在万能电子拉伸仪上测试其延伸率，采用差热分析仪上测试其壳层的熔点，以SKD61材料作为料件测试本实施例所制备的高精度锌基合金电极丝的电火花加工精度以及切割速度，测试所得数据如表1所示。
实施例9：
按比例进行合金配料，其质量百分比的成分组成为：Cu 64％，Zr 0.02％，Si 1.3％，P 0.15％，Co 0.05％，其余为Zn和由原材料及熔炼时带入的不可避免的杂质，不可避免杂质的含量之和为0.5％，将配料混合投入感应炉中进行熔炼，通过铸造产出直径为12mm的合金线坯。然后，将所制得的线坯经挤压或多道拉伸和退火制成直径1.5mm的母线，再将所制得的母线进行除油-酸洗-水洗-镀锌，锌镀层厚度为15um，制得第一线坯，其中电镀电流为2500A，电压为220V，接着对电镀后的第一线坯进行连拉连退加工，制成第二线坯，其中拉伸速度为1500m/min，退后电压为10V，退火电流为15A。对第二线坯进行合金化热处理得直径为0.10mm且壳层厚度为3um的电极丝成品，热处理温度为140℃，热处理时间为16h，最后将热处理后获得的成品绕在不同轴型上。
电极丝成品中壳层的化学成分为：Zn：89％，Cu：10.1％，Zr：0.012％，Si：0.8％，P：0.05％，Co：0.02％，杂质：0.018％。本实施例中加入Zr、Si、P及Co后，使得线坯中的铜锌合金原子拉伸过程中位错增加，晶界处的晶格畸变较大，能量增加，导致壳层η相锌原子在热处理过程中易于向芯材(α+β相)扩散迁移，有助于在壳层形成ε相组织。随着壳层与芯材间原子跃迁，因拉伸造成的原子位错、空位等缺陷逐渐减少，位错密度也随之减少，扩散激活能降低，同时ε相组织的熔点相对于原来的η相纯锌逐渐增高，原子间的结合力增强，且在本实施例的热处理条件下，有利于壳层ε相组织的形成。如图6所示，电极丝成品中芯材为α+β相，壳层结构中ε相含量为97wt％，其余为η相，并且ε相均匀分布在芯材表面。
在万能电子拉伸仪上测试其延伸率，采用差热分析仪上测试其壳层的熔点，以SKD61材料作为料件测试本实施例所制备的高精度锌基合金电极丝的电火花加工精度以及切割速度，测试所得数据如表1所示。
实施例10：
按比例进行合金配料，其质量百分比的成分组成为：Cu 68％，Zr 0.8％，Ag 0.05％，B 0.08％，Co 0.03％，其余为Zn和由原材料及熔炼时带入的不可避免的杂质，不可避免杂质的含量之和0.2％，将配料混合投入感应炉中进行熔炼，通过铸造产出直径为11mm的合金线坯。然后，将所制得的线坯经挤压或多道拉伸和退火制成直径5mm的母线，再将所制得的母线进行除油-酸洗-水洗-镀锌，锌镀层厚度为45um，制得第一线坯，其中电镀电流为3000A，电压为180V，接着对电镀后的第一线坯进行连拉连退加工，制 成第二线坯，其中拉伸速度为1500m/min，退后电压为100V，退火电流为10A。对第二线坯进行合金化热处理得直径为0.10mm且壳层厚度为4um的电极丝成品，热处理温度为80℃，热处理时间为25h，最后将热处理后获得的成品绕在不同轴型上。
电极丝成品中壳层的化学成分为：Zn：87％，Cu：12.2％，Zr：0.5％，Ag：0.03％，B：0.03％，Co：0.01％，杂质：0.23％。本实施例中加入Zr、Ag、B及Co后，使得线坯中的铜锌合金原子拉伸过程中位错增加，晶界处的晶格畸变较大，能量增加，导致壳层η相锌原子在热处理过程中易于向芯材(α+β相)扩散迁移，有助于在壳层形成ε相组织。随着壳层与芯材间原子跃迁，因拉伸造成的原子位错、空位等缺陷逐渐减少，位错密度也随之减少，扩散激活能降低，同时ε相组织的熔点相对于原来的η相纯锌逐渐增高，原子间的结合力增强，且在本实施例的热处理条件下，有利于壳层ε相组织的形成。如图6所示，电极丝成品中芯材为α+β相，壳层结构中ε相含量为99wt％，其余为η相，并且ε相均匀分布在芯材表面。
在万能电子拉伸仪上测试其延伸率，采用差热分析仪上测试其壳层的熔点，以SKD61材料作为料件测试本实施例所制备的高精度锌基合金电极丝的电火花加工精度以及切割速度，测试所得数据如表1所示。
比较例1：
按比例进行合金配料，其质量百分比的成分组成为：Cu 66％，其余为Zn和由原材料及熔炼时带入的不可避免的杂质，不可避免杂质的含量之和为0.3％，将配料混合投入感应炉中进行熔炼，通过铸造产出直径为8mm的合金线坯。然后，将所制得的线坯经挤压或多道拉伸和退火制成直径3mm的母线，再将所制得的母线进行除油-酸洗-水洗-镀锌，锌镀层厚度为40um，得第一线坯，其中电镀电流为1500A，电压为200V，接着对电镀后的第一线坯进行连拉连退加工，制成第二线坯，其中拉伸速度为500m/min，退后电压为80V，退火电流为50A。对第二线坯进行合金化热处理得直径为0.10mm且壳层厚度为4um的电极丝成品，热处理温度为208℃，热处理时间为72h，最后将热处理后获得的成品绕在不同轴型上。电极丝成品中壳层的化学成分为：Zn：92.1％，Cu：7.6％，杂质：0.3％。如图8所示，壳层结构中ε相含量为8wt％，其余为η相。
在万能电子拉伸仪上测试其延伸率，采用差热分析仪上测试其壳层的熔点，以SKD61材料作为料件测试比较例1所制备的电极丝的电火花加工精度以及切割速度，测试所得数据如表1所示。
比较例2：
按比例进行合金配料，其质量百分比的成分组成为：Cu 60％，其余为Zn和由原材料及熔炼时带入的不可避免的杂质，不可避免杂质的含量之和为0.4％，将配料混合投 入感应炉中进行熔炼，通过铸造产出直径为15mm的合金线坯。然后，将所制得的线坯经挤压或多道拉伸和退火制成直径1mm的母线，再将所制得的母线进行除油-酸洗-水洗-镀锌，锌镀层厚度为10um，得第一线坯，其中电镀电流为3000A，电压为220V，接着对电镀后的第一线坯进行连拉连退加工，制成第二线坯，其中拉伸速度为2000m/min，退后电压为40V，退火电流为20A。对第二线坯进行合金化热处理得直径为0.10mm且壳层厚度为3um的电极丝成品，热处理温度为105℃，热处理时间为100h，最后将热处理后获得的成品绕在不同轴型上。电极丝成品中壳层的化学成分为：Zn：65.2％，Cu：34.62％，杂质：0.18％，如图9所示，壳层结构中ε相含量为10wt％，其余为γ相。
在万能电子拉伸仪上测试其延伸率，采用差热分析仪上测试其壳层的熔点，以SKD61材料作为料件测试比较例2所制备的电极丝的电火花加工精度以及切割速度，测试所得数据如表1所示。
比较例3：
按比例进行合金配料，其质量百分比的成分组成为：Cu60％，Ag1.5％，Ni 0.02％，其余为Zn和由原材料及熔炼时带入的不可避免的杂质，不可避免杂质的含量之和为0.3％，将配料混合投入感应炉中进行熔炼，通过铸造产出直径为8mm的合金线坯。然后，将所制得的线坯经挤压或多道拉伸和退火制成直径1mm的母线，再将所制得的母线进行除油-酸洗-水洗-镀锌，锌镀层厚度为15um，制得第一线坯，其中电镀电流为1600A，电压为200V，接着对电镀后的第一线坯进行连拉连退加工，制成第二线坯，其中拉伸速度为1000m/min，退后电压为50V，退火电流为25A。对第二线坯进行合金化热处理得直径为0.10mm且壳层厚度为3.5um的电极丝成品，热处理温度为190℃，热处理时间为60h，最后将热处理后获得的成品绕在不同轴型上。电极丝成品中壳层的化学成分为：Zn：82.1％，Cu：16.92％，Ag：0.6％，Ni：0.009％，杂质：0.371％。如图10所示，壳层结构中ε相含量为60wt％，其余为γ相和η相。
在万能电子拉伸仪上测试其延伸率，采用差热分析仪上测试其壳层的熔点，以SKD61材料作为料件测试比较例3所制备的电极丝的电火花加工精度以及切割速度，测试所得数据如表1所示。
比较例4：
按比例进行合金配料，其质量百分比的成分组成为：Cu 58％，Ti 0.15％，Co 0.004％，其余为Zn和由原材料及熔炼时带入的不可避免的杂质，不可避免杂质的含量之和为0.3％，将配料混合投入感应炉中进行熔炼，通过铸造产出直径为10mm的合金线坯。然后，将所制得的线坯经挤压或多道拉伸和退火制成直径1mm的母线，再将所制得的母线进行除油-酸洗-水洗-镀锌，锌镀层厚度为12um，制得第一线坯，其中电镀电流为 1700A，电压为210V，接着对电镀后的线坯进行连拉连退加工，制成第二线坯，其中拉伸速度为600m/min，退后电压为10V，退火电流为5A。对第二线坯进行合金化热处理得直径为0.10mm且壳层厚度为3um的电极丝成品，热处理温度为135℃，热处理时间为56h，最后将热处理后获得的成品绕在不同轴型上。电极丝成品中壳层的化学成分为：Zn：80.3％，Cu：19.448％，Ti 0.06％，Co0.002％，杂质：0.19％。如图11所示，壳层结构中ε相含量为58wt％，其余为η相和γ相。
在万能电子拉伸仪上测试其延伸率，采用差热分析仪上测试其壳层的熔点，以SKD61材料作为料件测试比较例4所制备的电极丝的电火花加工精度以及切割速度，测试所得数据如表1所示。
比较例5：
一种镀锌电极丝，由直径为0.5～5mm的铜锌合金组成芯材，芯材中Cu63％，其他为Zn和不可避免杂质，不可避免杂质含量≤0.3％。在芯材表面直接镀锌，镀层厚度为20um，然后再进行连拉连退加工，制成直径为0.05～0.35mm的镀锌电极丝，壳层结构为η相。
在万能电子拉伸仪上测试其延伸率，采用差热分析仪上测试其壳层的熔点，以SKD61材料作为料件测试上述镀锌电极丝的电火花加工精度以及切割速度，测试所得数据如表1所示。
比较例6：
一种黄铜电极丝，由直径为0.5～5mm的铜锌合金组成线坯，线坯中Cu63％，其他为Zn和不可避免杂质，不可避免杂质含量≤0.3％。直接进行连拉连退加工，制成直径为0.05～0.35mm的黄铜电极丝，壳层结构为α+β相。
在万能电子拉伸仪上测试其延伸率，采用差热分析仪上测试其壳层的熔点，以SKD61材料作为料件测试上述黄铜电极丝的电火花加工精度以及切割速度，测试所得数据如表1所示。
比较例7：
一种高速电极丝，由直径为0.5～5mm紫铜组成芯材，然后在芯材表面镀锌，镀层厚度为50um，得到第一线坯，对第一线坯进行热处理，热处理工艺的温度为550℃，时间为10h，得到第二线坯，最后对热处理后的第二线坯进行连拉连退加工，制成直径为0.05～0.35mm的高速电极丝，壳层结构为β相。
在万能电子拉伸仪上测试其延伸率，采用差热分析仪上测试其壳层的熔点，以SKD61材料作为料件测试上述高速电极丝的电火花加工精度以及切割速度，测试所得数 据如表1所示。
比较例8：
一种镀层电极丝，由直径为0.5～5mm的铜锌合金组成芯材，该芯材成分组成与实施例1中的成品电极丝中的芯材同。在芯材表面镀锌，镀层厚度为30um，对第一线坯进行热处理，热处理工艺的温度为450℃，时间为6h，得到第二线坯，最后对热处理后的第二线坯进行连拉连退加工，制成直径为0.05～0.35mm的镀层电极丝，壳层结构为γ相。
在万能电子拉伸仪上测试其延伸率，采用差热分析仪上测试其壳层的熔点，以SKD61材料作为料件测试上述镀层电极丝的电火花加工精度以及切割速度，测试所得数据如表1所示。
比较例9：
一种复合电极丝，由直径为0.5～5mm的铜锌合金组成芯材，该芯材成分组成与实施例3中成品电极丝的芯材同。在芯材表面镀锌，镀层厚度为40um，对第一线坯进行热处理，热处理工艺的温度为600℃，时间为12h，得到第二线坯，对上述线坯进行第一次连拉连退加工，再在表面镀一层γ相黄铜，最后对以上热处理后线坯进行第二次连拉连退加工，制成直径为0.05-0.35的复合电极丝，层结构为β+γ相。
在万能电子拉伸仪上测试其延伸率，采用差热分析仪上测试其壳层的熔点，以SKD61材料作为料件测试上述复合电极丝的电火花加工精度以及切割速度，测试所得数据如表1所示。
表1为各实施例和比较例中电极丝的壳层金相结构、电火花加工精度比、切割速度、延伸率以及熔点。
表1
Figure PCTCN2015000279-appb-000003
注：表1中的各数据均在同等条件下测试获得，其中电极丝的直径均为0.10mm，当然本领域的技术人员可有效调整各实施例中对第一线坯的连拉连退加工条件和对第二线坯的热处理条件，使得各实施例中的成品电极丝的直径在0.05～0.35mm的范围内变化。
以比较例5的电火花加工精度为基准，实施例1～10以及比较例1、2、3、4、6、7、8、9的加工精度与其比值作为体现它们加工精度的性能参数。
综上，本发明中的高精度锌基合金电极丝的电火花加工精度具有明显的优势，切割速度达到同类产品水平，同时延伸性能较好且熔点相对较高。
上述各实施例用来解释说明本发明，而不是对本发明进行限制，在本发明的精神和权利要求的保护范围内，对本发明作出的任何修改和改变，都落入本发明的保护范围中。

Claims (5)

  1. 一种高精度锌基合金电极丝，包括芯材和包覆在芯材表面的壳层，所述芯材的材质为黄铜，其特征在于：所述壳层中各成分的质量百分数组成为；
    Zn：70.5～95％；Cu：2.5～27％；X：0.02～4.0％；Y；0.002～0.4％；
    其他为由原材料带入的不可避免的杂质，且不可避免杂质的含量之和≤0.3％；
    其中，X为选自Ni、Ag、Cr、Si、Zr中的任意两种金属，且该两种金属的含量范围均为0.01～2.0％，Y为选自Ti、Al、Co、B、P中的任意两种元素，且该两种元素的含量范围均为0.001～0.2％；
    所述壳层的厚度为2～4um，所述壳层结构中ε相含量为80wt％以上，余量为γ相或η相，并且所述ε相均匀分布在芯材表面。
  2. 如权利要求1所述的高精度锌基合金电极丝，其特征在于：所述壳层中各成分的质量百分数组成为：所述壳层中各成分的质量百分数组成为：
    Zn：78.5～85％；Cu：12.5～19％；X：0.02～4.0％；Y：0.002～0.4％；
    其他为由原材料带入的不可避免的杂质；
    所述壳层结构为ε相，无其他相，且所述ε相均匀分布在芯材表面。
  3. 一种高精度锌基合金电极丝的制备方法，其特征在于包括以下步骤：
    (1)按比例进行合金配料，其质量百分比的成分组成：铜：57％～68％，X：0.03～4.5％，Y：0.004～0.5％，其余为锌和由原材料及熔炼时带入的不可避免的杂质，且不可避免杂质的含量之和≤0.5％，其中，X为选自Ni、Ag、Cr、Si、Zr中的任意两种金属，且该两种金属的含量范围均为0.015～2.25％，Y为选自Ti、Al、Co、B、P中的任意两种元素，且该两种元素的含量范围均为0.002～0.25％；
    (2)将配料混合投入感应炉进行熔炼，通过铸造产出直径8～15mm合金线坯；
    (3)然后将所制线坯经挤压或多道拉伸和退火制成直径0.5～5mm的母线；
    (4)再将所制母线进行除油-酸洗-水洗-镀锌，锌镀层厚度为0.5～50um，制得第-线坯，其中电镀电流为1500～3000A，电压150～220V；
    (5)对电镀后的第一线坯进行连拉连退加工，制成第二线坯；
    (6)最后对第二线坯进行合金化热处理得制得直径为0.05～0.35mm的电极丝成品。
  4. 如权利要求3所述的高精度锌基合金电极丝的制备方法，其特征在于；所述步骤(5)中拉伸速度为500～2000m/min，退火电压为10～100V，退火电流为10～50A。
  5. 如权利要求3所述的高精度锌基合金电极丝的制备方法，其特征在于：所述步骤(6)中的热处理温度为50～230度，热处理时间3～30小时。
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US20160368070A1 (en) 2016-12-22
KR20170016499A (ko) 2017-02-13
EP3006152A4 (en) 2017-02-22
CN104191056A (zh) 2014-12-10
KR101873953B1 (ko) 2018-07-03
EP3006152B1 (en) 2017-12-13
CN104191056B (zh) 2016-06-29
US9855617B2 (en) 2018-01-02
EP3006152A1 (en) 2016-04-13
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