CN101386925A - Cu-Cr-Zr alloy preparation technology for contact wire - Google Patents

Cu-Cr-Zr alloy preparation technology for contact wire Download PDF

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CN101386925A
CN101386925A CNA2008101212030A CN200810121203A CN101386925A CN 101386925 A CN101386925 A CN 101386925A CN A2008101212030 A CNA2008101212030 A CN A2008101212030A CN 200810121203 A CN200810121203 A CN 200810121203A CN 101386925 A CN101386925 A CN 101386925A
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alloy
deformation
annealing
preparation technology
contact wire
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CN100587091C (en
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张进东
王立天
方攸同
李维源
韩士恩
孟亮
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YANTAI JINHUI COPPER CO Ltd
XINGTAI XINHUI COPPER INDUSTRY SPECIAL WIRE MATERIAL Co Ltd
Zhejiang University ZJU
China Railway Electrification Survey Design and Research Institute Co Ltd
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YANTAI JINHUI COPPER CO Ltd
XINGTAI XINHUI COPPER INDUSTRY SPECIAL WIRE MATERIAL Co Ltd
Zhejiang University ZJU
China Railway Electrification Survey Design and Research Institute Co Ltd
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Abstract

The invention discloses a process for preparing Cu-Cr-Zr alloys applicable to contact lines. The process comprises the following steps that alloys comprising 0.30 to 0.50 percent of Cu, 0.10 to 0.15 percent of Cr, 0.01 to 0.02 percent of Zr and Si are melt in a vacuum induction furnace, wherein alloy elements, namely Cr, Zr and Si, are added by master alloys; fine casting-state crystal grains and oversaturated matrix tissues having secondary dendritic crystal spaces are obtained by controlling solidification velocity and cooling velocity; rolling in fit, drawing deformation and annealing thermal treatment to the fine casting-state crystal grains and oversaturated matrix tissues are carried out so as to control deformation degrees and parameters for the thermal treatment; and the strain-hardening effect and the precipitation strengthening effect are organically combined. Therefore, the alloys have the advantages of excellent tensile strength, electrical conductivity and high-temperature resistant softening capacity and lower cost under the conditions of simplified process and the simpler apparatus and components, and are applicable to industrial production.

Description

Cu-Cr-Zr alloy preparation technology for contact wire
Technical field
The present invention relates to a kind of copper base alloy processing technology, relate in particular to a kind of Cu-Cr-Zr alloy preparation technology for contact wire.
Background technology
Electric railway is to carry electric current by directly contacting to electric locomotive with the electric locomotive pantograph sliding plate sliding friction with the effect of osculatory, required conductor alloy will be operated in conduction of current, hang under the mal-conditions such as tension force, operational shock, temperature variation, such environmental effects and slide plate abrasion, therefore require the osculatory material should have advantages of higher tensile strength and specific conductivity, and have higher high temperature resistance softening power concurrently.Along with the high speed development of railway electrification, transportation by railroad is raised speed again and again, and is more and more higher with the osculatory performance requriements for electric railway.Yet the intensity of conductor alloy and electroconductibility generally are the inverse function relation, and even adopting particular technology to improve intensity is cost to sacrifice specific conductivity often, perhaps then often loses intensity for improving specific conductivity.Therefore, be starved of and adopt particular technology can obtain good intensity and conductivity coupling level simultaneously, to satisfy the use properties of high-speed railway osculatory with alloy.Especially for the high-speed electric train more than the speed per hour 350km, its tensile strength should reach more than the 550MPa, and relative conductivity should be higher than 75%IACS, and the intensity behind 400 ℃ of softening annealing 2h still need remain on more than 90%.
The conductor alloy of high-speed electric train osculatory employing at present mainly contains Cu-Mg, Cu-Sn, Cu-Ag, Cu-Cd, Cu-Sn-Ag, Cu-Ag-Zr, Cu-Cr-Zr and double metallic composite material etc.In these alloys, Cu-Cr-Zr has showed more outstanding intensity and specific conductivity matching relationship.Yet, in the material preparation process, because Cr, Zr alloying element fusing point are significantly higher than Cu, and very easily oxidation under the melted state, volatilization also react with many contact substances, easily air-breathing, segregation of melt and impurity are difficult for factors such as eliminating in addition, cause material preparation difficulty and actual performance to be difficult to reach the perfect match state.In addition, Cu-Cr-Zr is a precipitation strength type alloy, must adopt solid solution treatment process in preparation process, has increased special-purpose Equipment for Heating Processing and has organized burning equivalent risk factor, has further increased material preparation difficulty and cost.
At present aspect the osculatory alloy, patent CN02128927.1, CN200510082133.9, CN200610039986.9 and CN200610048186.3 disclose oxygen free copper respectively, Cu-(0.12~0.3) %Ag-(0.01~0.05) %O, the processing technology of Cu-(0.15~0.35) %Sn-(0.005~0.01) %Zr-(0.005~0.02) %RE and Cu-(0.05~0.35) %Mg-(0.35~0.05) %Sn osculatory alloy.Mainly by melting and cold deformation processing, technological process is fairly simple for these alloys, and required processing units is less, and cost is lower, but mainly relies on solid solution and the reinforcement of processing optimal way, and product performance particularly tensile strength are not high.
CN200410060463.3 and CN200510124589.7 disclose the technology of preparing of Cu-(0.02~0.4) %Zr and two kinds of alloys of Cu-(0.2~0.72) %Cr.All add the Ag of (0.04~0.16) % and (0.07~0.15) % in two kinds of alloys in addition, by melting, casting, thermal distortion, solid solution, cold deformation, timeliness and once more operation such as cold deformation prepare finished product.This technology of preparing must utilize the solid solution process to provide condition for ageing strengthening, and needs the follow-up cold deformation processing stage of control to cooperate technology and required equipment more complicated with it.CN200410025886.1, CN200510017889.5, CN200510043073.X and CN200510096378.7 have increased a certain amount of rare earth element again in above-mentioned alloy system, further improved microstructure and material property, but still needed the high temperature solid solution process and mate suitable cold deformation.In addition, all contain expensive Ag element in these alloys, and need the extra rare earth element that adds, improved the complicacy of material cost and composition.CN200610019238.4 has added (0.02~0.08) %Nd rare earth element in Cu-(0.4~1.1) %Cr alloy, in the course of processing, need not special solution treatment, but Cr content is higher, and needs during melting add in pure Cr mode, and homogeneity of ingredients is difficult to guarantee.
For the Cu-Cr-Zr alloy system, CN03135758.X discloses the employing rapid solidification flour, pressed compact, sintering, extruding obtains Cu-(0.01~2.5) %Cr-(0.01~2.0) %Zr-(0.01~2.0) % (Y, La, Sm) preparation method of alloy bar material or sheet material, can obtain favorable conductive, heat conduction, hot strength and softening resistance energy, but owing to be subjected to the restriction of processing technology characteristics, moreover alloying element content is higher, only be applicable to products such as resistance welding electrode that manufacturing dimension is less and lead frame, can't be on making practical application in the long osculatory of km.CN200610017523.2 and CN02148648. disclose Cu-(0.05~0.40) %Cr-(0.05~0.20) %Zr-≤0.20% (Ce+Y) and two kinds of alloying constituents of Cu-(0.01~1.0) %Cr-(0.01~0.6) %Zr-(0.05~1.0) %Zn-(0.01~0.30) % (La+Ce) and technology of preparing respectively, can obtain higher intensity and specific conductivity, thermotolerance and high abrasion resistance, but need the extra rare earth element that adds to purify alloy and improve tissue, wherein a kind of alloy is except that adding in addition the Zn, also to further add Co, Fe, auxiliary element guaranteed performances such as Ti, complex chemical composition.In addition, two kinds of alloys all need special solution treatment.
Some United States Patent (USP)s have also related to the technology of preparing of Cu-Cr-Zr alloy.US6679955 discloses the technology of preparing of Cu-(3~20) %Ag-(0.5~1.5) %Cr-(0.05~0.5) %Zr alloy, this alloy relies on rapid solidification to obtain supersaturated solid solution through the thermomechanical treatment precipitation hardening, but the combined action of Ag element need be arranged, moreover what pay attention to is the raising of heat-conductive characteristic and do not relate to conductivity.US7172665 discloses the technology of preparing of Cu-(2~6) %Ag-(0.5~0.9) %Cr alloy, this alloy also can add (0.05~0.2) %Zr again, comprise complex processes such as homogenizing processing, thermal distortion and solution treatment in the technology, expensive Ag element is arranged equally, what also pay attention to is heat-conductive characteristic, but does not relate to conductivity.US6881281 provides a kind of high-strength highly-conductive Cu-(0.05~1.0) %Cr-(0.05~0.25) %Zr alloy with good fatigue and middle warm nature energy, the Zr and the Cu-Zr compound particles that wherein contain certain size, these particles can combine with impurity S and reduce crystal boundary S concentration, and then have improved alloy 250~550 ℃ grain-boundary strength.Yet this alloy is except that the needs solution treatment, and the strict control solution treatment parameter of still needing is to regulate the concentration of S.US5210441 and US5341025 have announced a kind of circuit lead frame Cu-(0.1~1) %Cr-(0.01~0.5) %Zr alloy, Zr particle precipitation has mainly been proposed and the control that distributes, described technology is only applicable to prepare section bars such as band or foil, is not suitable for preparation osculatory section bar.US40677501 provides the complete processing of improving Cu-(0.05~1.25) %Cr-(0.01~1.0) %Zr-(0.01~1.0) %V alloy strength and specific conductivity, rely on hot rolling and solid solution to improve the solute solubility of Cu matrix, be convenient to follow-up distortion and the timeliness process produces effective strengthening effect, but need the rational Match of heat, cold deformation and bigger deflection to come the guaranteed performance level, be only applicable to equally produce sheet material and be unsuitable for producing wire rod.US2002/0189729A1 (notification number) has proposed the dynamic recrystallization crystal grain thinning technology of number of C u alloy, comprising Cu-(0.02~0.40) %Cr-(0.1~0.25) %Zr alloy, can obtain the dynamic recrystallization close grain of diameter by stress relief annealing cold rolling and subsequently less than 1 μ m, higher intensity and good unit elongation are arranged, produce band and foil and be unsuitable for producing wire rod but this technology also only is applicable to, and do not relate to conductivity and high temperature softening resistance energy.US6767643 and US6093499 disclose the technology of preparing of Cu-(0.01~2.0) %Cr-(0.01~1.0) %Zr and Cu-(0.01~0.4) %Cr-(0.01~0.2) %Zr-(0.02~2.0) %Zn, and the latter still looks actual needs also will add Fe, Ti again, Ni, Sn, In, Mn, P, Mg, Al, B, As, Cd, Co, Te, auxiliary element such as Ag and Hf, only be suitable for preparing the foil that stratified composite uses, the excessive or more complicated of alloying element content scope, performance are difficult to control, and specific conductivity is also lower, only about 50%IACS.
Summary of the invention
The object of the invention is to provide a kind of Cu-Cr-Zr alloy preparation technology for contact wire.Interaction by links such as reasonable control melting, cold deformation and annealing, can prepare have good strength, specific conductivity and softening resistance can Cu-(0.30~0.50) %Cr-(0.10~0.15) %Zr-(0.01~0.02) %Si alloy wire, alloying constituent is simple, omitted solution treatment, facility investment is less, be easy to suitability for industrialized production, cost is lower.
The present invention's technical scheme that is adopted that achieves the above object is as follows:
By prepared alloying constituent mass percent batching, wherein Cr content is (0.30~0.50) % with electrolysis Cu and Cu-Cr, Cu-Zr, Cu-Si master alloy, and Zr content is (0.10~0.15) %, and Si content is (0.01~0.02) %, and all the other are Cu.
The master alloy constituent content that is adopted is respectively: Cu-(4~10) %Cr, Cu-(12~20) %Zr, Cu-(15~20) %Si.
Earlier electrolysis Cu is placed vacuum induction furnace, under 0.01~0.1Pa normal atmosphere, melt, after leaving standstill degasification under 1250 ℃, in stove, fill Ar to 30kPa, add the Cu-Cr master alloy, add Cu-Zr and Cu-Si master alloy after the fusing again, induction stirring evenly and leave standstill 5~15min.
Adopt water cooled copper mould at 1200 ℃ of casting ingot-formings, control solidification rate 〉=3 ℃/s, post solidification cooling rate 〉=2 ℃/s
After the defective top layer is removed in the ingot casting surfacing cut, rolling deformation under the normal temperature, deformation extent η=ln (A 0/ A) characterize A wherein 0Being respectively distortion front and back sample cross with A amasss.The passage deformation extent is controlled at η〉0.3, total rolling deformation degree is η=1.8.
Adopt two kinds of technologies to carry out following process to the alloy behind the rolling deformation:
(1) annealing-drawing process: drawing deformation η=2.0~3.0 behind 450~500 ℃ of annealing 1~4h, the passage deformation extent is controlled at η=0.3~0.5.
(2) drawing-annealing-drawing process: drawing deformation η=2.0 at normal temperatures, the passage deformation extent is controlled at η=0.3~0.5, at 400~450 ℃ of annealing 1~2h, continues drawing deformation η=0.6~1.2, and the passage deformation extent is controlled at η<0.2.
Strength of alloy through above-mentioned prepared can reach 580~640MPa, and relative conductivity can reach (77~84) %IACS.Intensity still can remain on 〉=540MPa behind 400 ℃ of softening annealing 2h.
The present invention compares the beneficial effect that has with background technology:
(1) adopts rapid solidification and cooling under the control condition, caused tiny as cast condition crystal grain and secondary dendrite arm spacing, avoided separating out in advance of inferior looks particle, optimized as-cast microstructure, and provide supersaturation matrix condition for precipitation strength.
(2) the supersaturation matrix is directly annealed, form the precipitation strength effect of similar ageing treatment, omitted common solid solution process.
(3) before and after annealing, use the drawing deformation control techniques and combine, further improved the motivating force that the disperse of supersaturation organization internal is separated out, suitable strain hardening effect is provided simultaneously, strengthened thermal effectiveness, help wire forming with annealing process.
(4) simplifying under technology and equipment and the simple condition of composition systematic comparison, can obtain the electric train osculatory alloy material that intensity and specific conductivity have high coupling level, cost is lower, and is suitable for suitability for industrialized production.
Embodiment
Following is that the unified of embodiment 1~6 described:
Melting and pour into a mould Cu-Cr, Cu-Zr and Cu-Si master alloy ingot casting in vacuum induction furnace, composition is respectively Cu-(4~10) %Cr, Cu-(12~20) %Zr and Cu-(15~20) %Si.
By prepared alloying constituent mass percent batching, wherein Cr content is (0.30~0.50) % with electrolysis Cu and Cu-Cr, Cu-Zr, Cu-Si master alloy, and Zr content is (0.10~0.15) %, and Si content is (0.01~0.02) %, and all the other are Cu.
Earlier electrolysis Cu is placed vacuum induction furnace, under 0.01~0.1Pa normal atmosphere, melt, after leaving standstill degasification under 1250 ℃, in stove, fill Ar to 30kPa, add the Cu-Cr master alloy, add Cu-Zr and Cu-Si master alloy after the fusing again, induction stirring evenly and leave standstill 5~15min.
Adopt water cooled copper mould at 1200 ℃ of casting ingot-formings, control solidification rate 〉=3 ℃/s, post solidification cooling rate 〉=2 ℃/s
After the defective top layer is removed in the ingot casting surfacing cut, rolling deformation under the normal temperature.The passage deformation extent is controlled at η〉0.3, total rolling deformation degree is η=1.8.
Adopt dual mode to carry out following process to the alloy behind the rolling deformation.
First kind of mode is annealing-drawing process, parameter such as following table:
The second way is drawing-annealing-drawing process, parameter such as following table:
Above-mentioned 6 used alloys of embodiment under the used processing condition of embodiment, all reach following performance mean value all according to Cu-(0.30~0.50) %Cr-(0.10~0.15) %Zr-(0.01~0.02) %Si proportioning components:
Sequence number Tensile strength MPa Relative conductivity %IACS 400 ℃/2h annealing back tensile strength MPa
Embodiment 1 640 77.0 550
Embodiment 2 635 82.5 545
Embodiment 3 590 78.6 540
Embodiment 4 635 77.6 550
Embodiment 5 595 80.6 565
Embodiment 6 580 84.0 545

Claims (7)

1. Cu-Cr-Zr alloy preparation technology for contact wire is characterized in that:
1) with electrolysis Cu and Cu-Cr, Cu-Zr, Cu-Si master alloy by prepared alloying constituent mass percent batching, wherein Cr content is (0.30~0.50) %, Zr content is (0.10~0.15) %, Si content is (0.01~0.02) %, all the other are Cu;
2) electrolysis Cu is placed vacuum induction furnace, under 0.01~0.1Pa normal atmosphere, melt, after leaving standstill degasification under 1250 ℃, in stove, fill Ar to 30kPa, add the Cu-Cr master alloy, add Cu-Zr and Cu-Si master alloy after the fusing again, induction stirring evenly and leave standstill 5~15min;
3) adopt water cooled copper mould at 1200 ℃ of casting ingot-formings;
4) after the defective top layer is removed in the ingot casting surfacing cut, rolling deformation under the normal temperature;
5) adopt annealing-drawing or drawing-annealing-drawing process to carry out following process to the alloy behind the rolling deformation.
2. a kind of Cu-Cr-Zr alloy preparation technology for contact wire according to claim 1 is characterized in that: the master alloy constituent content that is adopted is respectively Cu-(4~10) %Cr, Cu-(12~20) %Zr and Cu-(15~20) %Si.
3. a kind of Cu-Cr-Zr alloy preparation technology for contact wire according to claim 1 is characterized in that: 1200 ℃ of casting solidification speed 〉=3 ℃/s, and post solidification cooling rate 〉=2 ℃/s.
4. a kind of Cu-Cr-Zr alloy preparation technology for contact wire according to claim 1, it is characterized in that: after the defective top layer is removed in the ingot casting surfacing cut, the passage deformation extent of rolling deformation is controlled at η at normal temperatures〉0.3, total rolling deformation degree is η=1.8.
5. the Cu-Cr-Zr alloy preparation technology for contact wire of a kind of high-performance coupling according to claim 1, it is characterized in that: adopt the technological process of annealing-drawing to be to alloy behind the rolling deformation: drawing deformation η=2.0~3.0 behind 450~500 ℃ of annealing 1~4h, the passage deformation extent is controlled at η=0.3~0.5.
6. a kind of Cu-Cr-Zr alloy preparation technology for contact wire according to claim 1, it is characterized in that: adopt the technological process of drawing-annealing-drawing to be: drawing deformation η=2.0 at normal temperatures alloy behind the rolling deformation, the passage Deformation control is in η=0.3~0.5, at 400~450 ℃ of annealing 1~2h, continue drawing deformation η=0.6~1.2, the passage deformation extent is controlled at η<0.2.
7. a kind of Cu-Cr-Zr alloy preparation technology for contact wire according to claim 1, it is characterized in that: the strength of alloy that stands described prepared can reach 580~640MPa, relative conductivity can reach (77~84) %IACS, and intensity still can remain on 〉=540MPa behind 400 ℃ of softening annealing 2h.
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CN101531149B (en) * 2009-04-09 2011-04-20 中铁电气化局集团有限公司 Preparation method of overlength Cu-Cr-Zr alloyed contact line
CN101613808B (en) * 2009-07-08 2011-05-04 苏州有色金属研究院有限公司 Non-vacuum production method for CuCrZr alloy wire rod
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CN105039883A (en) * 2015-06-30 2015-11-11 昆明理工大学 Preparation method of Cu-Cr-Zr alloy contact wire
CN106591753A (en) * 2016-12-08 2017-04-26 北京科技大学 Short-flow preparing and processing process for copper-chromium-zirconium alloy high-speed rail contact wire
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CN101613808B (en) * 2009-07-08 2011-05-04 苏州有色金属研究院有限公司 Non-vacuum production method for CuCrZr alloy wire rod
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CN104658631A (en) * 2015-02-12 2015-05-27 邢台鑫晖铜业特种线材有限公司 CuCrZr alloy stranded wire and production process thereof
CN104928603A (en) * 2015-06-29 2015-09-23 烟台金晖铜业有限公司 Thermo-mechanical treatment process of great-length Cu-Cr-Zr-Si alloy contact line
CN105039883A (en) * 2015-06-30 2015-11-11 昆明理工大学 Preparation method of Cu-Cr-Zr alloy contact wire
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CN110629139A (en) * 2018-06-25 2019-12-31 南京理工大学 Preparation method of Cu-Cr-Zr alloy
CN109158562A (en) * 2018-09-30 2019-01-08 烟台金晖铜业有限公司 A kind of dedicated contact line of rigid contact net and preparation method thereof
CN111575525A (en) * 2020-04-16 2020-08-25 陕西斯瑞新材料股份有限公司 Method for manufacturing Cu-Cr-Zr alloy contact line for electrified railway
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CN113943874A (en) * 2021-10-23 2022-01-18 福州大学 Copper alloy material for 5G base station power connector and preparation method thereof

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