WO2021253603A1 - 一种电气化铁路用Cu-Cr-Zr合金绞线及其制造方法 - Google Patents

一种电气化铁路用Cu-Cr-Zr合金绞线及其制造方法 Download PDF

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WO2021253603A1
WO2021253603A1 PCT/CN2020/109357 CN2020109357W WO2021253603A1 WO 2021253603 A1 WO2021253603 A1 WO 2021253603A1 CN 2020109357 W CN2020109357 W CN 2020109357W WO 2021253603 A1 WO2021253603 A1 WO 2021253603A1
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alloy
water
treatment
stranded wire
hours
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PCT/CN2020/109357
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English (en)
French (fr)
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王聪利
庾高峰
吴斌
靖林
张航
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陕西斯瑞新材料股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • 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
    • C22F1/002—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working by rapid cooling or quenching; cooling agents used therefor
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H01B1/026—Alloys based on copper
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H01B13/02—Stranding-up

Definitions

  • the invention relates to the technical field of stranded wire manufacturing, in particular to a Cu-Cr-Zr alloy stranded wire for electrified railways and a manufacturing method thereof.
  • High-speed railways have become the main development trend of electrified railways. With the rapid development of electrified railways, the performance requirements of high-speed electrified twisted wires continue to increase.
  • the generally recognized ideal copper alloy stranded wire material is the age-enhanced Cu-Cr- Zr alloy, high strength and high conductivity are always important indicators of the performance requirements of the stranded wire.
  • For copper alloy stranded wire there has been a contradiction between high strength and high conductivity for a long time.
  • Aging precipitation strengthening can achieve a better combination of the strength and conductivity of copper alloys.
  • the main preparation methods of Cu-Cr-Zr alloy include vacuum induction melting, down-drawing semi-continuous casting, etc. Due to the limitation of the melting environment, the melted Cu-Cr-Zr alloy cannot effectively solve the distribution of the main alloy elements of Cr and Zr in the cast slab. And the problems of uniformity, there are also many problems such as high content of impurities in the cast slab, high content of gas elements, relatively coarse as-cast structure, etc., which reduce the performance of the alloy. The most important thing is that the continuous production of large length and large unit weight cannot be realized, the production efficiency is low, the production process is long, and the production cost is high, which cannot meet the product requirements of electrified railway stranded wires.
  • the present invention provides a method for manufacturing Cu-Cr-Zr alloy stranded wire for electrified railways.
  • the technical scheme of the present invention is: a manufacturing method of Cu-Cr-Zr alloy stranded wire for electrified railway, including the following steps:
  • S3 rolling heat-rolling ⁇ 25-35mm copper rod blanks at a heating temperature of 800-1000°C, multiple passes rolling to obtain ⁇ 10-20mm hot-rolled blanks;
  • step S4 solution heat treatment: the ⁇ 10-20mm hot-rolled billet is subjected to solution heat treatment, the solution temperature is 850-1000°C, the holding time is 1-2 hours, and the water is quenched; the alloy elements are solid-dissolved into the copper matrix through the solution heat treatment, and then passed
  • the aging heat treatment in step S6 causes the second phase solute atoms and compounds to precipitate out to achieve the effect of strengthening the alloy;
  • S7 stranded wire stranding the aged cold-rolled billet of ⁇ 8- ⁇ 10mm is further subjected to multi-pass drawing to obtain a finished product of ⁇ 2.25- ⁇ 3.15mm stranded wire single wire, and ⁇ 2.25- ⁇ 3.15mm multi-wire stranding Obtain finished stranded wire.
  • the manufacturing method of the alloy stranded wire of the present invention is based on the continuous casting of the up-drawing method to prepare Cu-Cr-Zr alloy, and realizes mass production of stranded wire products.
  • the prepared alloy stranded wire has excellent performance and structure, high material utilization rate and energy consumption Small, realized the industrialized production of Cu-Cr-Zr railway strands, and solved the bottleneck problem restricting the development of high-speed railways.
  • the mass percentage of each component of the Cu-Cr-Zr alloy material in the step S1 is: Cr: 0.2%-1.0%, Zr: 0.02%-0.2%, Cu: the balance.
  • the range of each composition is reduced to a narrower range through process optimization to achieve better performance.
  • the actual composition is Cr: 0.8%-0.9%, Zr: 0.08-0.10%, Cu: margin, the actual test tensile strength of the product can reach 540-600Mpa before and after twisting, and the conductivity is 90-94% IACS.
  • each element in the step S2 is specifically: Cr and Zr are added in the form of a cored wire, and Cu is added in the form of an oxygen-free copper rod. Cr and Zr are cored wire and the entire smelting process is carried out in a sealed atmosphere protection environment. With the upward casting process, this method can obtain a material with a very uniform composition, avoiding defects such as oxide inclusions caused by contact with air. Reduce the consumption of alloying elements.
  • the upward casting in the step S2 uses a Cu-Cr-Zr alloy upward device, and the heating element and the crucible of the Cu-Cr-Zr alloy upward device are made of graphite.
  • the graphite material can improve the temperature uniformity and the stability of the casting system. At the same time, it is added in the form of cored wire with the feeding method, which has better casting performance.
  • the upward casting speed of the upward casting in the step S2 is controlled at 800-1400 mm/min.
  • the copper rod blank with good comprehensive performance can be obtained by controlling the upward drawing speed within the above range.
  • the upward casting adopts the method of filling argon to isolate oxygen, and adopts the cooling method of water cooling, the cooling water used is continuously supplied with direct current, the current density is 0.35-0.75A/cm 2 , and the water enters The temperature is controlled at 21-24°C; wherein the cooling water is distilled water containing potassium nitrate with a mass concentration of 1.7-4.3%.
  • the micro current is entrained by the cooling water and the current is effectively passed through through the cooperation of potassium nitrate, which can make the internal crystal orientation of the precipitation hardening alloy more uniform during the upward casting cooling process, and at the same time improve the surface tensile strength and toughness.
  • the water quenching is performed with distilled water containing special preparations, specifically:
  • the annular barrel and the water depth tank are sealed and spliced up and down, and the inner wall of the annular barrel is provided with multiple sets of atomizing nozzles at equal intervals in the circumferential direction.
  • the first liquid storage box and the second liquid storage box of the distilled water, the upper end side wall of the annular barrel is provided with a water pump, one end of the water pump is connected to the first liquid storage box through a pipe, and the other end is hollow in the wall of the annular barrel through a pipe
  • the cavity is connected; the other side wall of the water depth tank is provided with a liquid outlet.
  • the Cu-Cr-Zr alloy with different contents of distilled water of the above-mentioned special preparation is water-quenched to improve the Cu-Cr-Zr
  • the alloy's tensile strength and electrical conductivity and other related properties improve its application effect in railway stranded wires.
  • the special preparation is specifically based on mass fraction: 10-15 parts polyacrylamide, 3-7 parts potassium chloride, 5-10 parts polyvinyl alcohol, 1-3 parts disodium ethylenediaminetetraacetate .
  • the water quenching agent formed by mixing with distilled water in proportion to the special agent in the above ratio can effectively cooperate with the above treatment process to perform water quenching treatment on Cu-Cr-Zr alloy, thereby improving its tensile strength and electrical conductivity And other related performance.
  • the invention also provides a Cu-Cr-Zr alloy stranded wire produced by the above-mentioned method for manufacturing the Cu-Cr-Zr alloy stranded wire for electrified railways.
  • the present invention also provides a method for preparing Cu-Cr-Zr alloy, which includes the following steps:
  • the alloy solution is subjected to an upward casting process to obtain a copper rod blank; among them:
  • the alloy solution contains Cu, Cr and Zr, the Cr and Zr are added to the casting furnace in the form of cored wires, and the Cu is added to the casting furnace in the form of oxygen-free copper rods;
  • step (2) Subject the copper rod blank mentioned in step (1) to hot rolling treatment, solution treatment, cold rolling treatment and aging treatment, that is;
  • the temperature of the aging treatment is 500-650°C.
  • the inert atmosphere may be a conventional inert atmosphere in the art, such as an argon atmosphere.
  • the ratio of Cr, Zr and Cu in the alloy solution can be a conventional ratio in the field, for example: Cr: 0.2%-1.0%, Zr: 0.02%-0.2%, Cu: balance; percentage Refers to weight percentage.
  • the content of Cr may be 0.8-0.9%, such as 0.8%, 0.85% or 0.9%.
  • the content of Zr can be 0.08-0.10%, for example, 0.08%, 0.09% or 0.10%.
  • the ratio of Cr, Zr and Cu in the alloy solution may be Cr: 0.8-0.9%, Zr: 0.08-0.10%, Cu: the balance; for example: Cr: 0.85%, Zr: 0.09%, Cu: the balance Or, Cr: 0.8%, Zr: 0.08%, Cu: balance; or, Cr: 0.9%, Zr: 0.10%, Cu: balance.
  • the Cr cored wire may be a conventional Cr cored wire in the art, such as a pure Cr cored wire.
  • the Zr cored wire may be a conventional Zr cored wire in the art, such as a Cu-Zr master alloy cored wire.
  • the oxygen-free copper rod may be a conventional oxygen-free copper rod in the field, and generally refers to a copper rod with an oxygen content ⁇ 5 ppm.
  • the alloy solution can be obtained by vacuum melting.
  • step (1) the alloy solution can be heat-maintained for 1-2 hours before the upward casting is performed.
  • the upward casting process can be a conventional upward casting process in the field, for example, the following steps are performed: the alloy solution is cooled to obtain a copper rod blank, and the copper rod blank is passed through Pull the traction device of the casting machine upwards, and that's it.
  • the alloy solution can be kept in a carbon-based (for example, graphite) crucible system for heat preservation.
  • a carbon-based (for example, graphite) crucible system for heat preservation.
  • the material of the heating element in the upward casting machine may be graphite.
  • the upward drawing speed of the upward casting may be 800-1400 mm/min, for example, 1200 mm/min.
  • argon gas can be used to insulate oxygen.
  • the cooling method may be a water cooling method.
  • the inlet temperature of the cooling water may be 21-24°C, for example, 23°C.
  • direct current can be passed into the cooling water.
  • the current density of the direct current may be 0.35-0.75 A/cm 2 , for example 0.55 A/cm 2 .
  • the cooling water may contain potassium nitrate, for example, distilled water containing potassium nitrate.
  • the mass concentration of the potassium nitrate may be 1.7-4.3%, for example, 3.7%.
  • step (1) the upward casting process can be operated with reference to the following documents: Qin Xiangzhong, etc., the working principle and influencing factors analysis of upward continuous casting [J], Electrotechnical Materials, 2010(1): 17-19.
  • the present invention refers to the full text of this document.
  • the size of the copper rod blank may be ⁇ 25-35mm.
  • the hot rolling treatment may be a conventional rolling treatment after heating in the art, and the heating temperature may be 800-1000°C (for example, 950°C).
  • the heating temperature may be 800-1000°C (for example, 950°C).
  • hot-rolled blanks of ⁇ 10-20mm can be obtained by continuous rolling multiple passes.
  • the solution treatment may be a conventional solution treatment in the art, for example, after heat preservation treatment, water quenching.
  • the holding temperature in the solution treatment is preferably 850-1000°C, for example, 890°C.
  • the holding time in the solution treatment may be 1-3 hours, for example 1.5 hours.
  • the heat preservation process of the solution treatment can be carried out according to the following steps: heat preservation at 890°C for 1.5 hours, and then water quenching.
  • the water quenching may be conventional water quenching in the field, for example, the blank after the heat preservation treatment is transferred to water for cooling.
  • the water may contain special preparations, and in terms of mass fraction, the composition of the special preparations is: 10-15 parts of polyacrylamide, 3-7 parts of potassium chloride, 5-10 parts of polyvinyl alcohol and 1- 3 parts disodium ethylenediaminetetraacetic acid.
  • the polyacrylamide may be 10 parts, 13 parts and 15 parts.
  • the potassium chloride can be 3 parts, 5 parts and 7 parts.
  • the polyvinyl alcohol may be 5 parts, 7 parts and 10 parts.
  • the disodium ethylenediaminetetraacetic acid can be in 1, 2, and 3 parts.
  • composition of the special preparation can be: 13 parts polyacrylamide, 5 parts potassium chloride, 7 parts polyvinyl alcohol and 2 parts ethylenediaminetetraacetic acid disodium; or, 10 parts polyacrylamide, 3 parts potassium chloride, 5 parts polyvinyl alcohol and 1 part disodium ethylenediaminetetraacetic acid; or 15 parts polyacrylamide, 7 parts potassium chloride, 10 parts polyvinyl alcohol and 3 parts disodium ethylenediaminetetraacetate.
  • the mass concentration of the special preparation in water may be 1.5-5.8%, for example 1.5-2.3% or 4.5-5.8%, and for example 1.9% or 5.3%.
  • the water quenching can be carried out according to the following steps:
  • the fog in the fog area is formed by water containing the special preparation with a mass concentration of 4.5-5.8%;
  • the water contains the special preparation with a mass concentration of 1.5-2.3%.
  • the water quenching adopts a method of sequentially cooling to 350-450°C through the mist zone and cooling to room temperature through water
  • the water quenching can be performed by a water quenching device, and the water quenching device includes the following structure:
  • a ring-shaped bucket and a water depth groove, the ring-shaped bucket and the water depth groove are sealed and spliced up and down;
  • the inner wall of the annular barrel is provided with multiple sets of atomizing nozzles at equal intervals in the circumferential direction;
  • One side wall of the annular barrel is provided with a first liquid storage box for storing distilled water containing special preparations;
  • a water pump is provided on the upper side wall of the annular barrel, one end of the water pump is connected to the first liquid storage box through a pipe, and the other end of the water pump is communicated with the hollow cavity in the barrel wall of the annular barrel through a pipe;
  • One side wall of the water depth tank is provided with a second liquid storage box for storing distilled water containing special preparations; the other side wall of the water depth tank is provided with a liquid outlet.
  • the Cu-Cr-Zr alloy with different contents of distilled water of the above-mentioned special preparation is water-quenched to improve the Cu-Cr-Zr
  • the alloy's tensile strength and electrical conductivity and other related properties improve its application effect in railway stranded wires.
  • the cold rolling treatment can be a conventional cold rolling treatment in the field, and a cold rolled billet with a diameter of 8-10 mm can be obtained through continuous multiple passes of cold rolling or cold drawing.
  • the temperature of the aging treatment is preferably "500-650°C but not 500°C" or 540-600°C, such as 540°C, 550°C or 600°C.
  • the time of the aging treatment is preferably 3-5 hours, such as 3 hours, 4 hours or 5 hours.
  • step (2) when the temperature of the aging treatment is 500°C, the time of the aging treatment is preferably 4-5 hours (for example, 4 hours or 5 hours).
  • the aging treatment is preferably: heat preservation at 500°C for 4 hours or 5 hours, heat preservation at 540°C for 3-5 hours, heat preservation at 550°C for 4 hours, or heat preservation at 600°C for 3 hours.
  • the invention also provides a Cu-Cr-Zr alloy prepared by the above method.
  • the present invention also provides a Cu-Cr-Zr alloy stranded single wire, which can be obtained by drawing the aforementioned Cu-Cr-Zr alloy to obtain a stranded single wire.
  • the drawing may be a multi-pass drawing.
  • the size of the stranded single wire can be ⁇ 2.25-3.15mm.
  • the present invention also provides an alloy stranded wire, in which n single wires of the aforementioned Cu-Cr-Zr alloy stranded wire are twisted, that is, n ⁇ 2.
  • the n can be 19-37, such as 19 or 37.
  • ⁇ refers to diameter
  • room temperature refers to 25°C ⁇ 5°C.
  • the manufacturing method of the alloy stranded wire of the present invention is based on the up-drawing method of continuous casting to prepare Cu-Cr-Zr alloy, and realizes mass production of stranded wire products.
  • the prepared alloy stranded wire has excellent performance and structure, and high material utilization rate. , Low energy consumption, realized the industrialized production of Cu-Cr-Zr railway strands, and solved the bottleneck problem restricting the development of high-speed railways.
  • the method of adding the alloy stranded wire of the present invention is through the cored wire method and the entire smelting process is carried out in a sealed atmosphere protection environment. This method can obtain a material with a very uniform composition and avoids the formation of oxides in contact with air. Inclusions and other defects reduce the consumption of alloying elements.
  • the Cu-Cr-Zr alloy is water-quenched by distilled water with different contents of special preparations through water quenching treatment, and corresponding to annular mist cooling and immersion water cooling, which can improve the tensile strength of Cu-Cr-Zr alloy Strength and electrical conductivity and other related properties, improve its application effect in railway stranded wire.
  • Fig. 1 is a 1 ⁇ 37 schematic diagram of a finished stranded wire end surface structure in a specific embodiment of the present invention.
  • Fig. 2 is a 1 ⁇ 19 schematic diagram of the end surface structure of the finished stranded wire in a specific embodiment of the present invention.
  • Fig. 3 is a schematic diagram of the overall structure of a special water quenching device in a specific embodiment of the present invention.
  • Fig. 4 is a cross-sectional view of the overall structure of a water quenching special device in a specific embodiment of the present invention.
  • 1-ring barrel 11-atomizing nozzle, 12-first liquid storage box, 13-water pump, 14-hollow cavity, 2-water depth tank, 21-second liquid storage box, 22-liquid outlet.
  • a manufacturing method of Cu-Cr-Zr alloy stranded wire for electrified railway including the following steps:
  • the heating element and crucible of the upward casting machine used in upward casting are made of graphite.
  • the upward casting speed of the upward casting is controlled at 1200mm/min. Cooling by water cooling, the temperature of the cooling water used is controlled at 23°C;
  • S4 solution heat treatment the ⁇ 10-20mm hot-rolled billet is subjected to solution heat treatment, the solution temperature is 890°C, the holding time is 1.5 hours, and water quenching;
  • S6 Aging heat treatment the ⁇ 8- ⁇ 10mm cold-rolled billet is subjected to aging heat treatment, the aging temperature is 540°C, and the holding time is 3-5 hours;
  • S7 stranded wire stranding the aged cold-rolled billet of ⁇ 8- ⁇ 10mm is further subjected to multi-pass drawing to obtain a finished product of ⁇ 2.25- ⁇ 3.15mm stranded wire single wire, and ⁇ 2.25- ⁇ 3.15mm multi-wire stranding Obtain the finished stranded wire as shown in Figure 1 or 2.
  • the above-mentioned manufacturing method of alloy stranded wire is based on the continuous casting of up-drawing method to prepare Cu-Cr-Zr alloy, and realizes mass production of stranded wire products.
  • the prepared alloy stranded wire has excellent performance and structure, high material utilization rate and low energy consumption. , Realized the industrialized production of Cu-Cr-Zr railway strands, and solved the bottleneck problem restricting the development of high-speed railways.
  • This embodiment is basically the same as embodiment 1, and the difference is that the mass percentage of each component of the Cu-Cr-Zr alloy material in step S1 is: Cr: 0.8%, Zr: 0.08%, and Cu: the balance.
  • This embodiment is basically the same as embodiment 1, and the difference is that the mass percentage of each component of the Cu-Cr-Zr alloy material in step S1 is: Cr: 0.9%, Zr: 0.10%, and Cu: the balance.
  • This embodiment is basically the same as embodiment 1, and the difference is that the cooling water used in the water cooling method in step S2 is continuously supplied with direct current, the current density is 0.55A/cm 2 , and the inlet water temperature is controlled at 23°C; ,
  • the cooling water is distilled water containing potassium nitrate with a mass concentration of 3.7%.
  • This solution also provides a special device for water quenching in step S4, specifically:
  • the ring barrel 1 and the water depth tank 2 are sealed and spliced up and down, and the inner wall of the ring barrel 1 is provided with multiple sets of atomizing nozzles 11 at equal intervals in the circumferential direction.
  • the ring barrel 1, the water depth tank 2 side wall Each is provided with a first liquid storage box 12 and a second liquid storage box 21 for storing distilled water containing special preparations.
  • the upper side wall of the annular barrel 1 is provided with a water pump 13, and one end of the water pump 13 is connected to the first liquid storage box 12 through a pipe.
  • the other end is connected to the hollow cavity 14 in the barrel wall of the annular barrel 1 through a pipe; a liquid outlet 22 is provided on the other side wall of the water depth tank 2; among them, the above-mentioned water pump 13 is a commercially available water pump and its shape is adjusted to Adapt to the installation requirements of this device.
  • step S4 the water quenching is performed with distilled water containing a special agent, which includes the following steps:
  • the special preparation is specifically: 13 parts polyacrylamide, 5 parts potassium chloride, 7 parts polyvinyl alcohol, 2 parts ethylenediaminetetraacetic acid disodium by mass fraction.
  • the Cu-Cr-Zr alloy can be water-quenched to improve Cu-Cr-Zr.
  • the alloy's tensile strength and electrical conductivity and other related properties improve its application effect in railway stranded wires.
  • Example 5 This example is basically the same as Example 5, and the difference lies in the different formulations of the special preparations, specifically: the special preparations are specifically: 10 parts polyacrylamide, 3 parts potassium chloride, and 5 parts polyethylene in terms of mass fraction. Alcohol, 1 part of disodium ethylenediaminetetraacetic acid.
  • Example 5 This example is basically the same as Example 5, and the difference lies in the different formulations of the special preparations, specifically: the special preparations are specifically: 15 parts polyacrylamide, 7 parts potassium chloride, and 10 parts polyethylene in terms of mass fraction. Alcohol, 3 parts of disodium ethylenediaminetetraacetic acid.
  • Tensile strength select the alloy samples ( ⁇ 8- ⁇ 10mm) and alloy strand samples ( ⁇ 2.25- ⁇ 3.15mm) after Cu-Cr-Zr aging heat treatment of each experimental example, refer to GB228-2002 "Metal Material Room Temperature Tension Test Method", the tensile test was carried out on the WDW-1 electronic universal testing machine.
  • the Cu-Cr-Zr alloy strands were prepared by using the various preparation methods of Examples 1-7, and the experimental groups were successively grouped, which were recorded as Experimental Examples 1-7 in turn;
  • Winding test Refer to GB/T4909.7.
  • the tensile strength of experimental example 1 is relatively higher than that of experimental examples 2 and 3. It can be seen that the composition ratio of different Cu-Cr-Zr alloy strands has a certain effect on the tensile strength. In Example 1, the ratio of Cu, Cr, Zr is the best;
  • the tensile strength of experimental example 4 is relatively higher than that of experimental example 1. It can be seen that adding potassium nitrate to the cooling water and applying a certain weak direct current has a certain influence on the tensile strength, which may be related to quenching cooling. It is related but has little effect. Among them, the Cu-Cr-Zr alloy stranded wire prepared by the method of Example 4 has better tensile strength performance;
  • the tensile strength of experimental example 5 is relatively higher than that of experimental example 4. It can be seen that the above-mentioned water quenching treatment has a certain effect on the tensile strength of Cu-Cr-Zr alloy.
  • the Cu-Cr-Zr alloy stranded wire prepared by the method 5 has better tensile strength performance;
  • experimental example 5 Compared with experimental examples 5-7, the tensile strength of experimental example 5 and experimental examples 6 and 7 is relatively high. It can be seen that different special formulations have a certain influence on the effect of water quenching treatment. Among them, the special formulations in example 5 The distribution ratio of each component is optimal.
  • experimental example 1 Compared with experimental examples 1-3, the conductivity of experimental example 1 is relatively higher than that of experimental examples 2 and 3. It can be seen that the composition ratio of different Cu-Cr-Zr alloy strands has a certain effect on the electrical conductivity. In Example 1, the ratio of Cu, Cr, Zr is the best;
  • experimental example 5 Compared with experimental examples 5-7, the electrical conductivity of experimental example 5 and experimental examples 6 and 7 is relatively high. It can be seen that different special preparation ratios have a certain influence on the effect of water quenching treatment. Among them, the special preparation in example 5 The distribution ratio of each component is optimal.

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Abstract

一种电气化铁路用Cu-Cr-Zr合金绞线的制造方法，S1配料：按照成分选择并准备相应的原料；S2熔炼及铸造：根据各元素的配比及各自特定加入方式将原料装入熔炼炉进行熔炼，保温后开始上引铸造，获得铜杆坯料；S3轧制：将铜杆坯料进行加热轧制，获得热轧坯料；S4固溶热处理：将热轧坯料进行固溶热处理，保温后水淬；S5冷轧：将固溶热处理后的坯料进行多道次冷轧，获得冷轧坯料；S6时效热处理：将冷轧坯料进行时效热处理；S7绞线绞合：将时效后的冷轧坯料进行多道次拉拔获得绞线单线成品，并将多线绞合获得成品绞线。该制备方法所制备的合金绞线性能、组织优异，材料利用率高、能耗小，实现了Cu-Cr-Zr铁路绞线的产业化生产。

Description

一种电气化铁路用Cu-Cr-Zr合金绞线及其制造方法
本申请要求申请日为2020/6/16的中国专利申请202010548176.6的优先权。本申请引用上述中国专利申请的全文。
技术领域
本发明涉及绞线制造技术领域，具体是涉及一种电气化铁路用Cu-Cr-Zr合金绞线及其制造方法。
背景技术
铁路高速化已成为电气化铁路的主要发展趋势，随着电气化铁路的快速发展，高速电气化对绞线的性能要求不断提高，公认的比较理想的铜合金绞线材料是时效强化型的Cu-Cr-Zr合金，高强度和高导电始终是绞线性能要求的重要指标，而对于铜合金绞线，长期以来一直存在着高强度与高导电率之间的矛盾，在各种制备材料的方法中，时效析出强化可以使铜合金的强度和导电性达到较好的结合，到目前为止，世界各国所开发出来的绞线均满足不了高速铁路的发展对绞线材料的要求，而我国高速电气化铁路正在迅速发展，显然绞线有着很大的国内外市场。
目前Cu-Cr-Zr合金主要的制备方法有真空感应熔炼、下引半连续铸造等，受到熔炼环境的限制，熔炼的Cu-Cr-Zr合金不能有效解决铸坯中Cr、Zr主要合金元素分布及均匀性的问题，还存在铸坯杂质含量高、气体元素含量高、铸态组织相对粗大等诸多的问题，降低了合金的性能。最重要的是不能实现大长度大单重的连续生产，生产效率低、生产工艺流程长、生产成本高等，无法满足电气化铁路绞线的产品要求。
鉴于以上，必须尽快地在高起点、高质量的基点上进行新一代绞线产品的研究与开发，现需要开发一种高质量连续铸造Cu-Cr-Zr合金绞线的制备方法以解决上述技术问题。
发明内容
为解决上述技术问题，本发明提供了一种电气化铁路用Cu-Cr-Zr合金绞线的制造方法。
本发明的技术方案是：一种电气化铁路用Cu-Cr-Zr合金绞线的制造方法，包括以下步骤：
S1配料：按照Cu-Cr-Zr合金材料成分要求对各合金元素进行配比，选择并准备相应 的原料；
S2熔炼及铸造：根据各元素的配比及各自特定加入方式将原料装入熔炼炉进行熔炼，送料进入加料区域的同时加热，原料熔炼后铸造机液位控制区域，整个过程充入氩气保护，保温1-2h后开始上引铸造，确保合金溶液在碳基坩埚***的自然脱氧环境中获得足够的保温时间，获得Φ25-35mm的铜杆坯料；
S3轧制：将Φ25-35mm的铜杆坯料进行加热轧制，加热温度800-1000℃，多道次轧制获得Φ10-20mm热轧坯料；
S4固溶热处理：将Φ10-20mm热轧坯料进行固溶热处理，固溶温度850-1000℃，保温时间1-2小时，水淬；通过固溶热处理合金元素固溶到铜基体里面，再通过步骤S6的时效热处理使第二相溶质原子及化合物析出，达到强化合金的效果；
S5冷轧：将固溶热处理后的Φ10-20mm坯料进行多道次冷轧或冷拉拔，获得Φ8-Φ10mm冷轧坯料；
S6时效热处理：将Φ8-Φ10mm冷轧坯料进行时效热处理，时效温度500-600℃，保温时间3-5小时；通过时效热处理使第二相溶质原子及化合物析出，以配合步骤S4固溶热处理处理，达到强化合金的效果；
S7绞线绞合：将时效后的Φ8-Φ10mm冷轧坯料进一步进行多道次拉拔，获得Φ2.25-Φ3.15mm绞线单线成品，并将Φ2.25-Φ3.15mm多线绞合获得成品绞线。
本发明合金绞线的制造方法基于上引法连续铸造对Cu-Cr-Zr合金进行制备，并实现批量生产绞线产品，所制备的合金绞线性能、组织优异，材料利用率高、能耗小，实现了Cu-Cr-Zr铁路绞线的产业化生产，解决了制约高速铁路发展的瓶颈问题。
进一步地，所述步骤S1中Cu-Cr-Zr合金材料各成分质量百分计为：Cr：0.2％-1.0％，Zr:0.02％-0.2％，Cu：余量。上述Cu-Cr-Zr合金配比在满足产品使用必须符合国家标准的前提下，将各个成分范围通过工艺优化等缩小至一个较窄的范围，以达到更优的使用性能，例如，实际成分在Cr：0.8％-0.9％，Zr：0.08-0.10％，Cu：余量，产品实际检测抗拉强度绞前绞后能到540-600Mpa，电导率90-94％IACS。
进一步地，所述步骤S2中各元素的各自特定加入方式具体为：Cr和Zr以包芯线的形式加入，Cu选用无氧铜杆形式加入。Cr、Zr通过包芯线方式并且整个熔炼过程在密封的气氛保护环境下进行，配合上引铸造工艺，这种方式能够获得成分非常均匀的材料，避免了与空气接触产生氧化物夹杂等缺陷，减少合金元素的消耗。
进一步地，所述步骤S2中上引铸造使用Cu-Cr-Zr合金上引设备，所述Cu-Cr-Zr合金上引设备的加热元件及坩埚均采用石墨材质制成。通过石墨材质可以提高温度均匀性 及铸造***稳定性，同时配合加料方式采用包芯线形式加入，具有更优铸造性能。
进一步地，所述步骤S2中上引铸造的上引速度控制在800-1400mm/min。通过上引速度控制在上述范围内能够获得综合性能良好的铜杆坯料。
进一步地，所述步骤S2中上引铸造采用充入氩气方式隔氧，并采用水冷方式冷却，其所用冷却水持续通入直流电，其电流密度为0.35-0.75A/cm 2，并且进水温度控制在21-24℃；其中，所述冷却水为含有质量浓度1.7-4.3％的硝酸钾的蒸馏水。通过冷却水夹带微电流并通过硝酸钾的配合使电流有效通入，可以在上引铸造冷却过程中，使沉淀硬化型合金内部晶向组织更为均匀，同时提高表面抗拉强度及韧性。
进一步地，所述步骤S4中水淬采用含有特制剂的蒸馏水进行水淬处理，具体为：
1)选取含有质量浓度为4.5-5.8％特制剂的蒸馏水，将Φ10-20mm热轧坯料伸入由环形桶制雾形成环形的出雾区，降温至350-450℃；
2)随后将其继续伸入至环形桶下方的水深槽中降至室温，所述水深槽中填充有含有质量浓度为1.5-2.3％特制剂的蒸馏水。
其中，所述环形桶与水深槽上下密封拼接而成，且环形桶内壁周向等间距设有多组雾化喷头，环形桶、水深槽一侧侧壁各设有一个用于存放含特制剂的蒸馏水的第一储液盒、第二储液盒，环形桶上端侧壁设有水泵，所述水泵一端通过管道与第一储液盒连接，其另一端通过管道与环形桶桶壁内中空腔连通；水深槽另一侧侧壁上设有出液口。
通过上述水淬处理，利用环形雾冷包裹一段冷却，再通过浸泡液冷至室温，配合不同含量的上述特制剂的蒸馏水对Cu-Cr-Zr合金进行水淬处理，可以提高Cu-Cr-Zr合金的抗拉强度以及电导率等相关性能，提高其应用于铁路绞线的使用效果。
更进一步地，所述特制剂按质量分数计具体为：10-15份聚丙烯酰胺、3-7份氯化钾、5-10份聚乙烯醇、1-3份乙二胺四乙酸二钠。上述配比下组成的特制剂，其与蒸馏水按比例混合形成的水淬用剂，能够有效配合上述处理工艺，对Cu-Cr-Zr合金进行水淬处理，从而提高其抗拉强度以及电导率等相关性能。
本发明还提供了一种上述电气化铁路用Cu-Cr-Zr合金绞线的制造方法制得的Cu-Cr-Zr合金绞线。
本发明还提供了一种Cu-Cr-Zr合金的制备方法，其包括下述步骤：
(1)在惰性气氛中，将合金溶液经上引铸造工艺制得铜杆坯料；其中：
所述合金溶液中包含Cu、Cr和Zr，所述Cr和所述Zr以包芯线的形式加入到铸造炉中，所述Cu以无氧铜杆的形式加入到铸造炉中；
(2)将步骤(1)中所述铜杆坯料经热轧处理、固溶处理、冷轧处理和时效处理， 即可；其中：
所述时效处理的温度为500-650℃。
步骤(1)中，所述惰性气氛可为本领域常规的惰性气氛，例如氩气气氛。
步骤(1)中，所述合金溶液中Cr、Zr和Cu的比例可为本领域常规的比例，例如：Cr:0.2％-1.0％，Zr:0.02％-0.2％，Cu:余量；百分比是指重量百分比。
其中，所述Cr的含量可为0.8-0.9％，例如0.8％、0.85％或0.9％。
其中，所述Zr的含量可为0.08-0.10％，例如0.08％、0.09％或0.10％。
其中，所述合金溶液中Cr、Zr和Cu的比例可为Cr:0.8-0.9％，Zr:0.08-0.10％，Cu:余量；例如：Cr:0.85％，Zr:0.09％，Cu:余量；或者，Cr:0.8％，Zr:0.08％，Cu:余量；或者，Cr:0.9％，Zr:0.10％，Cu:余量。
步骤(1)中，所述Cr的包芯线可为本领域常规的Cr的包芯线，例如纯Cr包芯线。
步骤(1)中，所述Zr的包芯线可为本领域常规的Zr的包芯线，例如Cu-Zr中间合金包芯线。
步骤(1)中，所述无氧铜杆可为本领域常规的无氧铜杆，一般是指氧含量≤5ppm的铜杆。
步骤(1)中，所述合金溶液可经真空熔炼获得。
步骤(1)中，所述合金溶液可保温处理1-2小时后再进行所述上引铸造。
步骤(1)中，所述上引铸造工艺可为本领域常规的上引铸造工艺，例如按下述步骤进行操作：将所述合金溶液经冷却得铜杆坯料，将所述铜杆坯料经上引铸造机的牵引装置牵出，即可。
其中，所述合金溶液可盛放于碳基(例如石墨)坩埚***中保温。
其中，所述上引铸造机中的加热元件的材质可为石墨材质。
其中，所述上引铸造的上引速度可为800-1400mm/min，例如1200mm/min。
其中，所述上引铸造的过程中可采用充入氩气的方式隔氧。
其中，所述冷却的方式可为水冷方式。
所述水冷方式中，冷却水的进水温度可为21-24℃，例如23℃。
所述水冷方式中，冷却水中可通入直流电。所述直流电的电流密度可为0.35-0.75A/cm 2，例如0.55A/cm 2。
所述水冷方式中，冷却水中可含有硝酸钾，例如含有硝酸钾的蒸馏水。所述硝酸钾的质量浓度可为1.7-4.3％，例如3.7％。
步骤(1)中，所述上引铸造工艺可参照下述文献进行操作：覃向忠等，上引连铸的 工作原理及影响因素分析[J]，电工材料，2010(1):17-19。本发明在此引用该文献全文。
步骤(1)中，所述铜杆坯料的尺寸可为Φ25-35mm。
步骤(2)中，所述热轧处理可为本领域常规的经加热后轧制处理，所述加热的温度可为800-1000℃(例如950℃)。一般地，经连续多道次轧制可获得Φ10-20mm的热轧坯料。
步骤(2)中，所述固溶处理可为本领域常规的固溶处理，例如经保温处理后，水淬。
其中，所述固溶处理中的保温温度优选为850-1000℃，例如890℃。
其中，所述固溶处理中的保温时间可为1-3小时，例如1.5小时。
其中，所述固溶处理的保温过程可按下述步骤进行：890℃保温1.5小时，水淬，即可。
其中，所述水淬可为本领域常规的水淬，例如，将经保温处理后的坯料转入水中冷却，即可。
所述水淬中，水中可含有特制剂，以质量分数计，所述特制剂的组成为：10-15份聚丙烯酰胺、3-7份氯化钾、5-10份聚乙烯醇和1-3份乙二胺四乙酸二钠。所述聚丙烯酰胺可为10份、13份和15份。所述氯化钾可为3份、5份和7份。所述聚乙烯醇可为5份、7份和10份。所述乙二胺四乙酸二钠可为1份、2份和3份。
所述特制剂的组成可为：13份聚丙烯酰胺、5份氯化钾、7份聚乙烯醇和2份乙二胺四乙酸二钠；或者，10份聚丙烯酰胺、3份氯化钾、5份聚乙烯醇和1份乙二胺四乙酸二钠；或者，15份聚丙烯酰胺、7份氯化钾、10份聚乙烯醇和3份乙二胺四乙酸二钠。
所述特制剂在水中的质量浓度可为1.5-5.8％，例如1.5-2.3％或者4.5-5.8％，再例如1.9％或5.3％。
当所述水中含有所述特制剂时，所述水淬可按下述步骤进行：
将所述热轧处理后的坯料依次经雾区降温至350-450℃、经水降温至室温；
所述雾区中的雾由含有质量浓度为4.5-5.8％的所述特制剂的水形成；
所述水中含有质量浓度为1.5-2.3％的所述特制剂。
当所述水淬采用依次经雾区降温至350-450℃、经水降温至室温的方式时，所述水淬可采用一水淬装置进行，所述水淬装置包括下述结构：
一环形桶与一水深槽，所述环形桶与所述水深槽上下密封拼接而成；
所述环形桶内壁周向等间距设有多组雾化喷头；
所述环形桶的一侧侧壁设有一个用于存放含特制剂的蒸馏水的第一储液盒；
所述环形桶上端侧壁设有水泵，所述水泵一端通过管道与第一储液盒连接，其另一 端通过管道与所述环形桶的桶壁内中空腔连通；
所述水深槽的一侧侧壁设有一个用于存放含特制剂的蒸馏水的第二储液盒；所述水深槽另一侧侧壁上设有出液口。
通过上述水淬处理，利用环形雾冷包裹一段冷却，再通过浸泡液冷至室温，配合不同含量的上述特制剂的蒸馏水对Cu-Cr-Zr合金进行水淬处理，可以提高Cu-Cr-Zr合金的抗拉强度以及电导率等相关性能，提高其应用于铁路绞线的使用效果。
步骤(2)中，所述冷轧处理可为本领域常规的冷轧处理，经连续多道次冷轧或冷拉拔可获得Φ8-10mm冷轧坯料。
步骤(2)中，所述时效处理的温度优选为“500-650℃、但不为500℃”或者540-600℃，例如540℃、550℃或600℃。
步骤(2)中，所述时效处理的时间优选为3-5小时，例如3小时、4小时或5小时。
步骤(2)中，当所述时效处理的温度为500℃时，时效处理的时间优选为4-5小时(例如4小时或5小时)。
步骤(2)中，所述时效处理优选为：500℃保温4小时或5小时，540℃保温3-5小时，550℃保温4小时，或者，600℃保温3小时。
本发明还提供了一种采用上述方法制得的Cu-Cr-Zr合金。
本发明还提供了一种Cu-Cr-Zr合金绞线的单线，将如前所述的Cu-Cr-Zr合金经拉拔获得绞线单线，即可。
其中，所述拉拔可为多道次拉拔。
其中，所述绞线单线的尺寸可为Φ2.25-3.15mm。
本发明还提供了一种合金绞线，将n根如前所述的Cu-Cr-Zr合金绞线的单线经绞合，即可，n≥2。
其中，所述n可为19-37，例如19或37。
本发明中，Φ是指直径。
本发明中，室温是指25℃±5℃。
本发明的有益效果是：
(1)本发明合金绞线的制造方法基于上引法连续铸造对Cu-Cr-Zr合金进行制备，并实现批量生产绞线产品，所制备的合金绞线性能、组织优异，材料利用率高、能耗小，实现了Cu-Cr-Zr铁路绞线的产业化生产，解决了制约高速铁路发展的瓶颈问题。
(2)本发明合金绞线制备的加入方式，通过包芯线方式并且整个熔炼过程在密封的气氛保护环境下进行，这种方式能够获得成分非常均匀的材料，避免了与空气接触产生 氧化物夹杂等缺陷，减少合金元素的消耗。
(3)本发明通过水淬处理，通过不同含量特制剂的蒸馏水对Cu-Cr-Zr合金进行水淬处理，并对应配合环形雾冷以及浸泡水冷，可以提高Cu-Cr-Zr合金的抗拉强度以及电导率等相关性能，提高其应用于铁路绞线的使用效果。
附图说明
图1是本发明具体实施例中成品绞线端面结构1×37示意图。
图2是本发明具体实施例中成品绞线端面结构1×19示意图。
图3是本发明具体实施例中水淬专用装置的整体结构示意图。
图4是本发明具体实施例中水淬专用装置的整体结构剖视图。
其中，1-环形桶、11-雾化喷头、12-第一储液盒、13-水泵、14-中空腔、2-水深槽、21-第二储液盒、22-出液口。
具体实施方式
实施例1
一种电气化铁路用Cu-Cr-Zr合金绞线的制造方法，包括以下步骤：
S1配料：按照Cu-Cr-Zr合金材料成分要求对各合金元素进行配比，Cu-Cr-Zr合金材料各成分质量百分计为：Cr：0.85％，Zr：0.09％，Cu：余量，选择并准备相应的原料；
S2熔炼及铸造：根据各元素的配比及各自特定加入方式将原料装入熔炼炉进行熔炼，Cr和Zr以包芯线的形式加入，Cu选用无氧铜杆形式加入，送料进入加料区域的同时加热，原料熔炼后铸造机液位控制区域，整个过程充入氩气保护，保温1-2h后开始上引铸造，确保合金溶液在碳基坩埚***的自然脱氧环境中获得足够的保温时间，获得Φ25-35mm的铜杆坯料；
其中，上引铸造使用的上引铸造机的加热元件及坩埚均采用石墨材质制成，上引铸造的上引速度控制在1200mm/min，上引铸造采用充入氩气方式隔氧，并采用水冷方式冷却，其所用冷却水进水温度控制在23℃；
S3轧制：将Φ25-35mm的铜杆坯料进行加热轧制，加热温度950℃，多道次轧制获得Φ10-20mm热轧坯料；
S4固溶热处理：将Φ10-20mm热轧坯料进行固溶热处理，固溶温度890℃，保温时间1.5小时，水淬；
S5冷轧：将固溶热处理后的Φ10-20mm坯料进行多道次冷轧，获得Φ8-Φ10mm冷 轧坯料；
S6时效热处理：将Φ8-Φ10mm冷轧坯料进行时效热处理，时效温度540℃，保温时间3-5小时；
S7绞线绞合：将时效后的Φ8-Φ10mm冷轧坯料进一步进行多道次拉拔，获得Φ2.25-Φ3.15mm绞线单线成品，并将Φ2.25-Φ3.15mm多线绞合获得如图1或2所示的成品绞线。
上述合金绞线的制造方法基于上引法连续铸造对Cu-Cr-Zr合金进行制备，并实现批量生产绞线产品，所制备的合金绞线性能、组织优异，材料利用率高、能耗小，实现了Cu-Cr-Zr铁路绞线的产业化生产，解决了制约高速铁路发展的瓶颈问题。
实施例2
本实施例与实施例1基本相同，与其不同之处在于，步骤S1中Cu-Cr-Zr合金材料各成分质量百分计为：Cr：0.8％，Zr：0.08％，Cu：余量。
实施例3
本实施例与实施例1基本相同，与其不同之处在于，步骤S1中Cu-Cr-Zr合金材料各成分质量百分计为：Cr：0.9％，Zr：0.10％，Cu：余量。
实施例4
本实施例与实施例1基本相同，与其不同之处在于，步骤S2中水冷方式所用冷却水进行持续通入直流电，其电流密度为0.55A/cm 2，并且进水温度控制在23℃；其中，冷却水为含有质量浓度3.7％的硝酸钾的蒸馏水。
本方案还提供了一种用于步骤S4中水淬专用装置，具体为：
如图3、4所示，环形桶1与水深槽2上下密封拼接而成，且环形桶1内壁周向等间距设有多组雾化喷头11，环形桶1、水深槽2一侧侧壁各设有一个用于存放含特制剂的蒸馏水的第一储液盒12、第二储液盒21，环形桶1上端侧壁设有水泵13，水泵13一端通过管道与第一储液盒12连接，其另一端通过管道与环形桶1桶壁内中空腔14连通；水深槽2另一侧侧壁上设有出液口22；其中，上述水泵13选用市售水泵并对其外形调整以适配本装置的安装需求。
实施例5
本实施例与实施例4基本相同，与其不同之处在于，步骤S4中水淬采用含有特制剂的蒸馏水进行水淬处理，包括以下步骤：
1)选取含有质量浓度为5.3％特制剂的蒸馏水，将Φ10-20mm热轧坯料伸入由环形桶1制雾形成环形的出雾区，降温至420℃；
2)随后将其继续伸入至环形桶1下方的水深槽2中降至室温，水深槽2中填充有含有质量浓度为1.9％特制剂的蒸馏水。
其中，特制剂按质量分数计具体为：13份聚丙烯酰胺、5份氯化钾、7份聚乙烯醇、2份乙二胺四乙酸二钠。
通过上述水淬处理，利用环形雾冷包裹一段冷却，再通过浸泡液冷至室温，配合不同含量的上述特制剂的蒸馏水对Cu-Cr-Zr合金进行水淬处理，可以提高Cu-Cr-Zr合金的抗拉强度以及电导率等相关性能，提高其应用于铁路绞线的使用效果。
实施例6
本实施例与实施例5基本相同，与其不同之处在于特制剂的配组不同，具体为：特制剂按质量分数计具体为：10份聚丙烯酰胺、3份氯化钾、5份聚乙烯醇、1份乙二胺四乙酸二钠。
实施例7
本实施例与实施例5基本相同，与其不同之处在于特制剂的配组不同，具体为：特制剂按质量分数计具体为：15份聚丙烯酰胺、7份氯化钾、10份聚乙烯醇、3份乙二胺四乙酸二钠。
实施例8
本实施例中S6时效处理工艺如下表所示，其余步骤同实施例1。
电导率：选取各个实验例的Cu-Cr-Zr时效热处理后的合金样本(Φ8-Φ10mm)、合金绞线样本(Φ2.25-Φ3.15mm)，参照GB/T3048.2进行导电率测试。
抗拉强度：选取各个实验例的Cu-Cr-Zr时效热处理后的合金样本(Φ8-Φ10mm)、合金绞线样本(Φ2.25-Φ3.15mm)，参照GB228-2002《金属材料室温拉伸试验方法》，在WDW-1电子万能试验机上进行拉伸试验。
表1
Figure PCTCN2020109357-appb-000001
Figure PCTCN2020109357-appb-000002
Cu-Cr-Zr合金绞线性能试验
一、实验样本
选用实施例1-7各个制备方法制备出Cu-Cr-Zr合金绞线，对其进行顺次实验分组，依次记作实验例1-7；
二、实验项目
分别对实验例1-7的抗拉强度以及电导率进行测试，具体如下：
1)抗拉强度：选取各个实验例的Cu-Cr-Zr合金绞线样本，参照GB228-2002《金属材料室温拉伸试验方法》，在WDW-1电子万能试验机上进行拉伸试验，试验结果如下表2所示：
表2 Cu-Cr-Zr合金绞线样本的抗拉强度测试
Figure PCTCN2020109357-appb-000003
2)电导率：选取各个实验例的Cu-Cr-Zr合金绞线样本，参照GB/T3048.2进行导电率测试，实验结果如下表3所示：
表3 Cu-Cr-Zr合金绞线样本的导电率测试
Figure PCTCN2020109357-appb-000004
3)扭转试验：参照GB/T4909.4。
反复弯曲试验：参照GB/T4909.5。
卷绕试验：参照GB/T4909.7。
表4
Figure PCTCN2020109357-appb-000005
三、实验结论
1)由表2测试数据可知，
对比实验例1-3，实验例1与实验例2、3相比其抗拉强度相对较高，可见不同Cu-Cr-Zr合金绞线的成分配比对抗拉强度有一定影响，其中，以实施例1中Cu、Cr、Zr的配比最优；
对比实验例1与4，实验例4与实验例1相比其抗拉强度相对较高，可见对冷却水进行硝酸钾添加并施加一定微弱直流电对抗拉强度有一定影响，可能与淬火冷却有一定关联但影响不大，其中，以实施例4的方法制备的Cu-Cr-Zr合金绞线的抗拉强度性能更优；
对比实验例4与5，实验例5与实验例4相比其抗拉强度相对较高，可见通过上述水淬处理对Cu-Cr-Zr合金的抗拉强度有一定影响，其中，以实施例5的方法制备的Cu-Cr-Zr合金绞线的抗拉强度性能更优；
对比实验例5-7，实验例5与实验例6、7相对其抗拉强度相对较高，可见不同的特制剂配比对水淬处理效果有一定影响，其中，以实施例5中特制剂的各成分配比最优。
2)由表3测试数据可知，
对比实验例1-3，实验例1与实验例2、3相比其导电率相对较高，可见不同Cu-Cr-Zr合金绞线的成分配比对导电率有一定影响，其中，以实施例1中Cu、Cr、Zr的配比最优；
对比实验例1与4，实验例4与实验例1相比其导电率相对较高，可见对冷却水进行硝酸钾添加并施加一定微弱直流电对导电率基本无影响；
对比实验例4与5，实验例5与实验例4相比其导电率相对较高，可见通过上述水淬处理对Cu-Cr-Zr合金的导电率有一定影响，其中，以实施例5的方法制备的Cu-Cr-Zr合金绞线的导电率性能更优；
对比实验例5-7，实验例5与实验例6、7相对其导电率相对较高，可见不同的特制剂配比对水淬处理效果有一定影响，其中，以实施例5中特制剂的各成分配比最优。
虽然以上描述了本发明的具体实施方式，但是本领域的技术人员应当理解，这些仅是举例说明，在不背离本发明的原理和实质的前提下，可以对这些实施方式做出多种变更或修改。因此，本发明的保护范围由所附权利要求书限定。

Claims (19)

  1. 一种Cu-Cr-Zr合金的制备方法，其特征在于，其包括下述步骤：
    (1)在惰性气氛中，将合金溶液经上引铸造工艺制得铜杆坯料；其中：
    所述合金溶液中包含Cu、Cr和Zr，所述Cr和所述Zr以包芯线的形式加入到铸造炉中，所述Cu以无氧铜杆的形式加入到铸造炉中；
    (2)将步骤(1)中所述铜杆坯料经热轧处理、固溶处理、冷轧处理和时效处理，即可；其中：
    所述时效处理的温度为500-650℃。
  2. 如权利要求1所述的Cu-Cr-Zr合金的制备方法，其特征在于，步骤(1)中，所述惰性气氛为氩气气氛；
    和/或，步骤(1)中，所述合金溶液中：Cr:0.2％-1.0％，Zr:0.02％-0.2％，Cu:余量；百分比是指重量百分比；其中，所述Cr的含量可为0.8-0.9％，所述Zr的含量可为0.08-0.10％；
    和/或，步骤(1)中，所述Cr的包芯线为纯Cr包芯线；
    和/或，步骤(1)中，所述Zr的包芯线为Cu-Zr中间合金包芯线；
    和/或，步骤(1)中，所述合金溶液经真空熔炼获得；
    和/或，步骤(1)中，所述合金溶液保温处理1-2小时后再进行所述上引铸造；
    和/或，步骤(1)中，所述上引铸造工艺按下述步骤进行操作：将所述合金溶液经冷却得铜杆坯料，将所述铜杆坯料经上引铸造机的牵引装置牵出，即可，所述冷却的方式可为水冷方式；
    和/或，步骤(1)中，所述铜杆坯料的尺寸为Φ25-35mm；
    和/或，步骤(2)中，所述热轧处理中，加热的温度为800-1000℃；
    和/或，步骤(2)中，所述时效处理的温度为540-600℃，例如540℃、550℃或600℃；
    和/或，步骤(2)中，所述时效处理的时间为3-5小时，例如3小时、4小时或5小时。
  3. 如权利要求2所述的Cu-Cr-Zr合金的制备方法，其特征在于，所述上引铸造工艺中，所述合金溶液盛放于碳基坩埚***中保温；
    和/或，所述上引铸造工艺中，所述上引铸造机中的加热元件的材质为石墨材质；
    和/或，所述上引铸造工艺中，所述上引铸造的上引速度为800-1400mm/min，例如1200mm/min；
    和/或，所述上引铸造的过程中采用充入氩气的方式隔氧；
    和/或，所述水冷方式中，冷却水的进水温度为21-24℃，例如23℃；
    和/或，所述水冷方式中，冷却水中通入直流电，所述直流电的电流密度可为0.35-0.75A/cm 2；
    和/或，所述水冷方式中，冷却水中含有硝酸钾，所述硝酸钾的质量浓度可为1.7-4.3％，例如3.7％；
    和/或，步骤(2)中，所述时效处理的温度和时间为：500℃保温4小时或5小时，540℃保温3-5小时，550℃保温4小时，或者，600℃保温3小时。
  4. 如权利要求1-3中至少一项所述的Cu-Cr-Zr合金的制备方法，其特征在于，步骤(2)中，所述固溶处理的条件为：经850-1000℃保温处理1-3小时后，水淬；
    其中，所述固溶处理中的保温温度可为890℃，所述固溶处理中的保温时间可为1.5小时；
    其中，所述水淬按下述步骤进行：将经保温处理后的坯料转入水中冷却，即可；所述水中可含有特制剂。
  5. 如权利要求4所述的Cu-Cr-Zr合金的制备方法，其特征在于，当所述水中含有所述特制剂时，以质量分数计，所述特制剂的组成为：10-15份聚丙烯酰胺、3-7份氯化钾、5-10份聚乙烯醇和1-3份乙二胺四乙酸二钠；
    和/或，当所述水中含有所述特制剂时，所述特制剂在水中的质量浓度为1.5-5.8％，例如1.5-2.3％或者4.5-5.8％，再例如1.9％或5.3％；
    和/或，当所述水中含有所述特制剂时，所述水淬可按下述步骤进行：将所述热轧处理后的坯料依次经雾区降温至350-450℃、经水降温至室温；所述雾区中的雾由含有质量浓度为4.5-5.8％的所述特制剂的水形成；所述水中含有质量浓度为1.5-2.3％的所述特制剂。
  6. 如权利要求5所述的Cu-Cr-Zr合金的制备方法，其特征在于，当所述水淬采用依次经雾区降温至350-450℃、经水降温至室温的方式时，所述水淬采用一水淬装置进行，所述水淬装置包括下述结构：
    一环形桶与一水深槽，所述环形桶与所述水深槽上下密封拼接而成；
    所述环形桶内壁周向等间距设有多组雾化喷头；
    所述环形桶的一侧侧壁设有一个用于存放含特制剂的蒸馏水的第一储液盒；
    所述环形桶上端侧壁设有水泵，所述水泵一端通过管道与第一储液盒连接，其另一端通过管道与所述环形桶的桶壁内中空腔连通；
    所述水深槽的一侧侧壁设有一个用于存放含特制剂的蒸馏水的第二储液盒；所述水深槽另一侧侧壁上设有出液口。
  7. 一种如权利要求1-6中至少一项所述的Cu-Cr-Zr合金的制备方法制得的Cu-Cr-Zr合金。
  8. 一种Cu-Cr-Zr合金绞线的单线，其特征在于，将如权利要求7所述的Cu-Cr-Zr合金经拉拔获得绞线单线，即可。
  9. 一种合金绞线，其特征在于，将n根如权利要求8所述的Cu-Cr-Zr合金绞线的单线经绞合，即可，n≥2；其中，所述n可为19-37，例如19或37。
  10. 一种电气化铁路用Cu-Cr-Zr合金绞线的制造方法，其特征在于，包括以下步骤：
    S1配料：按照Cu-Cr-Zr合金材料成分要求对各合金元素进行配比，选择并准备相应的原料；
    S2熔炼及铸造：根据各元素的配比及各自特定加入方式将原料装入熔炼炉进行熔炼，期间充入氩气保护，保温一定时间后开始上引铸造，获得Φ25-35mm的铜杆坯料；
    S3轧制：将Φ25-35mm的铜杆坯料进行加热轧制，加热温度800-1000℃，多道次轧制获得Φ10-20mm热轧坯料；
    S4固溶热处理：将Φ10-20mm热轧坯料进行固溶热处理，固溶温度850-1000℃，保温时间1-2小时，水淬；
    S5冷轧：将固溶热处理后的Φ10-20mm坯料进行多道次冷轧，获得Φ8-Φ10mm冷轧坯料；
    S6时效热处理：将Φ8-Φ10mm冷轧坯料进行时效热处理，时效温度500-600℃，保温时间3-5小时；
    S7绞线绞合：将时效后的Φ8-Φ10mm冷轧坯料进一步进行多道次拉拔，获得Φ2.25-Φ3.15mm绞线单线成品，并将Φ2.25-Φ3.15mm多线绞合获得成品绞线。
  11. 如权利要求10所述的一种电气化铁路用Cu-Cr-Zr合金绞线的制造方法，其特征在于，所述步骤S1中Cu-Cr-Zr合金材料各成分质量百分计为：Cr：0.2％-1.0％，Zr:0.02％-0.2％，Cu：余量。
  12. 如权利要求10或11所述的一种电气化铁路用Cu-Cr-Zr合金绞线的制造方法，其特征在于，所述步骤S2中各元素的各自特定加入方式具体为：Cr和Zr以包芯线的形式加入，Cu选用无氧铜杆形式加入。
  13. 如权利要求10-12中至少一项所述的一种电气化铁路用Cu-Cr-Zr合金绞线的制造方法，其特征在于，所述步骤S2中上引铸造使用Cu-Cr-Zr合金上引设备，所述Cu-Cr-Zr 合金上引设备的加热元件及坩埚均采用石墨材质制成。
  14. 如权利要求10-13中至少一项所述的一种电气化铁路用Cu-Cr-Zr合金绞线的制造方法，其特征在于，所述步骤S2中上引铸造的上引速度控制在800-1400mm/min。
  15. 如权利要求10-14中至少一项所述的一种电气化铁路用Cu-Cr-Zr合金绞线的制造方法，其特征在于，所述步骤S2中上引铸造采用充入氩气方式隔氧，并采用水冷方式冷却，其所用冷却水持续通入直流电，其电流密度为0.35-0.75A/cm 2，并且进水温度控制在21-24℃；其中，所述冷却水为含有质量浓度1.7-4.3％的硝酸钾的蒸馏水。
  16. 如权利要求10-15中至少一项所述的一种电气化铁路用Cu-Cr-Zr合金绞线的制造方法，其特征在于，所述步骤S2中Cr和Zr以包芯线的形式加入，Cu选用无氧铜杆形式加入。
  17. 如权利要求10-16中至少一项所述的一种电气化铁路用Cu-Cr-Zr合金绞线的制造方法，其特征在于，所述步骤S4中水淬采用含有特制剂的蒸馏水进行水淬处理，具体为：1)选取含有质量浓度为4.5-5.8％特制剂的蒸馏水，将Φ10-20mm热轧坯料伸入由环形桶制雾形成环形的出雾区，降温至350-450℃；2)随后将其继续伸入至环形桶下方的水深槽中降至室温，所述水深槽中填充有含有质量浓度为1.5-2.3％特制剂的蒸馏水。
  18. 如权利要求17所述的一种电气化铁路用Cu-Cr-Zr合金绞线的制造方法，其特征在于，所述特制剂按质量分数计具体为：10-15份聚丙烯酰胺、3-7份氯化钾、5-10份聚乙烯醇、1-3份乙二胺四乙酸二钠。
  19. 一种如权利要求10-18中至少一项所述的电气化铁路用Cu-Cr-Zr合金绞线的制造方法制得的Cu-Cr-Zr合金绞线。
PCT/CN2020/109357 2020-06-16 2020-08-14 一种电气化铁路用Cu-Cr-Zr合金绞线及其制造方法 WO2021253603A1 (zh)

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