CN105925923B - The preparation method of copper alloy with high strength and high conductivity as more than 400 kilometers high-speed railway contact wire materials of speed per hour - Google Patents
The preparation method of copper alloy with high strength and high conductivity as more than 400 kilometers high-speed railway contact wire materials of speed per hour Download PDFInfo
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- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 43
- 239000000463 material Substances 0.000 title abstract description 13
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000010949 copper Substances 0.000 claims abstract description 46
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 44
- 239000000956 alloy Substances 0.000 claims abstract description 44
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 27
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 23
- 229910052802 copper Inorganic materials 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000005266 casting Methods 0.000 claims abstract description 17
- 239000006104 solid solution Substances 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 14
- 239000000758 substrate Substances 0.000 claims abstract description 13
- 230000008018 melting Effects 0.000 claims abstract description 10
- 238000002844 melting Methods 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 238000012545 processing Methods 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000005275 alloying Methods 0.000 claims abstract description 6
- 238000010792 warming Methods 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 4
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 4
- 238000013461 design Methods 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 239000000835 fiber Substances 0.000 claims description 43
- 238000000137 annealing Methods 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 8
- 150000001875 compounds Chemical group 0.000 claims description 4
- 230000000737 periodic effect Effects 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 abstract description 3
- 239000005543 nano-size silicon particle Substances 0.000 description 14
- 239000002121 nanofiber Substances 0.000 description 13
- 239000002105 nanoparticle Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 229910052709 silver Inorganic materials 0.000 description 7
- 229910052758 niobium Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910017526 Cu-Cr-Zr Inorganic materials 0.000 description 3
- 229910017810 Cu—Cr—Zr Inorganic materials 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 229910017755 Cu-Sn Inorganic materials 0.000 description 2
- 229910017770 Cu—Ag Inorganic materials 0.000 description 2
- 229910017818 Cu—Mg Inorganic materials 0.000 description 2
- 229910017927 Cu—Sn Inorganic materials 0.000 description 2
- 229910020836 Sn-Ag Inorganic materials 0.000 description 2
- 229910020988 Sn—Ag Inorganic materials 0.000 description 2
- 229910001093 Zr alloy Inorganic materials 0.000 description 2
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910000599 Cr alloy Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007712 rapid solidification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
Classifications
-
- 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
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Conductive Materials (AREA)
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Abstract
The preparation method of copper alloy with high strength and high conductivity as more than 400 kilometers high-speed railway contact wire materials of speed per hour, the copper alloy composition meet this form：CuXY, wherein X are selected from least one of Ag, Nb and Ta, and Y is selected from least one of Cr, Zr and Si；Methods described is：Simple substance and/or intermediate alloy raw material are loaded into vacuum melting furnace according to the alloying component proportioning of design, heating, which is melted and pours to cast from, obtains ingot casting in mould, carry out multi pass drawing at room temperature to ingot casting and be deformed into long bar or line, sample in cross section shrinkage factor is set to reach more than 80%, long bar or line are annealed afterwards, drawing is carried out again to gained alloy afterwards, this stage sample sectional shrinkage is within 50%, liquid nitrogen frozen processing is carried out to gained alloy afterwards, make to remain in the X in Copper substrate or Y solid solution atoms to continue to separate out, room temperature is slowly warming up to afterwards so as to obtain copper alloy.
Description
Technical field
The present invention relates to a kind of preparation method of Cu alloys, especially as high-speed railway particularly 400 kilometers of speed per hour with
The preparation method of the copper alloy of the contact wire material of upper high-speed railway.
Background technology
Substantive rapid development, Beijing-Tianjin are obtained from 2009 Nian Qi China high-speed electric railway (hereinafter referred to as high ferro)
Line, Jing-Hu Railway and Beijing-Guangzhou Railway are in succession open-minded, and high ferro stable operation speed is 300 kilometers/hour.The development of high-speed electric railway
To its critical component-huge market demand of contact line-generation and harsh performance requirement.It is required that the material as contact line
It is provided simultaneously with following characteristic：High intensity, low line density, good electric conductivity, good rub, good corrosion resistance
Deng especially intensity and electrical conductivity are most crucial indexs.
The conductor material that high ferro contact line uses at present mainly has Cu-Mg, Cu-Sn, Cu-Ag, Cu-Sn-Ag, Cu-
The serial Cu alloys such as Ag-Zr, Cu-Cr-Zr, wherein Cu-Cr-Zr show more excellent intensity and electrical conductivity combination property.
Patent CN200410060463.3 and CN200510124589.7 disclose Cu- (0.02 ~ 0.4) %Zr- (0.04 ~ 0.16) %Ag and
The technology of preparing of Cu- (0.2 ~ 0.72) %Cr- (0.07 ~ 0.15) two kinds of alloys of %Ag.By melting, casting, thermal deformation, solid solution,
Cold deformation, timeliness and the technique such as cold deformation prepares finished product again.Patent CN03135758.X disclose using rapid solidification flour,
Pressed compact, sintering, extruding obtain Cu- (0.01 ~ 2.5) %Cr- (0.01 ~ 2.0) %Zr- (0.01 ~ 2.0) % (Y, La, Sm) alloy bar
The preparation method of material or sheet material, good conduction, heat conduction and softening resistant performance can be obtained.Patent CN200610017523.2 is public
Cu- (0.05 ~ 0.40) %Cr- (0.05 ~ 0.2) %Zr- is opened<0.20% (Ce+Y) alloying component and its technology of preparing, by molten
Refining, forging, solid solution, deformation, timeliness obtain high-strength highly-conductive combination property and preferable heat resistance and wearability.Patent
CN02148648.4 discloses Cu- (0.01 ~ 1.0) %Cr- (0.01 ~ 0.6) %Zr- (0.05 ~ 1.0) %Zn- (0.01 ~ 0.30) %
(La+Ce) alloying component and technology of preparing, can be obtained by processes such as melting, hot rolling, solid solution, cold rolling, timeliness, finish to gauges higher
Intensity and electrical conductivity.
United States Patent (USP) US6679955 discloses to be precipitated firmly by quickly solidifying acquisition supersaturated solid solution through thermomechanical treatment
The technology of preparing of Cu- (3 ~ 20) %Ag- (0.5 ~ 1.5) %Cr- (0.05 ~ 0.5) %Zr alloys of change.US7172665 discloses Cu-
The technology of preparing of (2 ~ 6) %Ag- (0.5 ~ 0.9) %Cr alloys, technique include uniformly post processing, thermal deformation and solution treatment and waited
Journey, and (0.05 ~ 0.2) %Zr can be added again.US6881281 provides a kind of high-strength height with excellent tired and middle temperature characteristics
Cu- (0.05 ~ 1.0) %Cr- (0.05 ~ 0.25) %Zr alloys are led, are protected by strictly controlling solution treatment parameter with adjusting S concentration
Hinder superperformance.
With the sustainable development of high-speed electric railway, the especially planning of country 13 clearly proposes to build in the year two thousand twenty
Into high speed rail system of the speed per hour more than 400 kilometers so that matched contact line material property must also improve to
Intensity>680 MPa, electrical conductivity>78%IACS and 400 DEG C of annealing 2h intensity rate of descent<10% level.So harsh performance mark
Standard make it that used Cu-Mg, Cu-Sn, Cu-Ag, Cu-Sn-Ag, Cu-Ag-Zr, Cu-Cr-Zr alloys can not at present
Meet minimum requirements of high speed rail system of the speed per hour more than 400 kilometers to contact wire material performance.New height must be developed
Property alloy is developed with adapting to the lasting speed-raising of high ferro.
The content of the invention
It is an object of the invention to provide a kind of preparation method of copper alloy with high strength and high conductivity, the copper alloy can meet that speed per hour exists
Requirement of more than 400 kilometers of the high speed rail system to contact wire material.
Present invention technical scheme used for achieving the above object is illustrated below.
The invention provides a kind of method for preparing copper alloy, the copper alloy composition meets this form：CuXY, wherein X are selected
From at least one of Ag, Nb and Ta, Y is selected from least one of Cr, Zr and Si；In copper alloy, the total content of X element is more than
0.01 and not higher than 20%, the total content of Y element is more than 0.01 and not higher than 2%, also, Cr content range is 0.01 ~ 1.5%,
Zr content range 0.01 ~ 0.5%, Si content range 0.01 ~ 0.3%；Methods described is：By simple substance and/or middle conjunction
Golden raw material loads vacuum melting furnace according to the alloying component proportioning of design, and heating, which is melted and pours to cast from, obtains ingot casting in mould, right
Ingot casting carries out multi pass drawing and is deformed into long bar or line at room temperature, sample in cross section shrinkage factor is reached more than 80%, right afterwards
Long bar or line are annealed, and the temperature of annealing is chosen at the fiber for forming X element and nodularization fracture does not occur and can make Y element
The scope of nanometer precipitated phase is formed, the time of annealing is chosen at the fiber for forming X element and nodularization fracture does not occur and makes to be more than
50% Y element forms the scope of nanometer precipitated phase, carries out drawing again to gained alloy afterwards, this stage sample cross-sectional constriction
Rate carries out liquid nitrogen frozen processing to gained alloy afterwards within 50%, makes to remain in the X in Copper substrate or Y solid solution atoms continue
Separate out, be slowly warming up to room temperature afterwards so as to obtain copper alloy.
Further, the total content of X element is preferably 3% ~ 12% in copper alloy.
Further, the total content of Y element is preferably 0.1% ~ 1.5% in copper alloy.
Further, described copper alloy is one of following：Cu-12%Ag-0.3%Cr-0.1%Zr-0.05%Si、Cu-12%
Ag-12%Nb-1.3%Cr-0.4%Zr-0.3%Si、Cu-0.1%Ag-0.1%Cr-0.1%Zr、Cu-12%Nb-1%Cr-0.4%Zr-
0.1%Si、Cu-6%Ag-6%Ta-0.1%Cr、Cu-3%Ag-0.8%Cr-0.5%Zr-0.3%Si。
Further, liquid nitrogen frozen processing time is preferably 1 ~ 100 hour.
Further, after carrying out liquid nitrogen frozen processing to alloy, room temperature is preferably warming up to 2 ~ 10 DEG C/min speed.
In the present invention, preparing raw material can be simple substance and/or intermediate alloy, described intermediate alloy can be Cu- (5% ~
50%) Nb, Cu- (3% ~ 20%) Cr, Cu- (4% ~ 15%) Zr, Cu- (5% ~ 20%) Si etc..
Copper alloy obtained by the present invention includes following characteristics：
At ambient temperature, X element exists in the form of pure phase and two kinds of atom of solid solution in the copper alloy, wherein to be dissolved original
The X element content of the form of son is less than 0.5%；Y element is with pure phase and solid solution atom or CuY compounds and the shape of solid solution atom
Formula is present, wherein the content of the Y element in the form of being dissolved atom is less than 0.1%；
The copper alloy exists in the form of long bar or line, wherein, the fibre that the X element of pure phase is arranged with less parallel
Dimension form is inside the copper alloy, and fiber is axially with Copper alloy bar or bobbin to almost parallel, and the diameter of fiber is less than 100
Nm, length are more than 1000 nm, and fiber is smaller than 1000 nm, and the boundary of fiber and Cu matrixes is semicoherent interface, interface
On the misfit dislocation of periodic arrangement is distributed with；It will be appreciated by persons skilled in the art that X fibers are unlikely to be in copper alloy
Absolute " arranged in parallel " in mathematical meaning, fiber is axially with Copper alloy bar or bobbin to being also impossible to be exhausted in mathematical meaning
To " axially in parallel ", more tallied with the actual situation so being used herein as " approximation " and " substantially "；
The Y element of pure phase or compound form is in granular form inside copper alloy, and more than 30% in the copper alloy
For distribution of particles on the boundary of X fibers and Cu matrixes, the diameter of particle is less than 30 nm, is smaller than 200 nm, particle and Cu
The boundary of matrix and particle and X fibers is semicoherent interface or incoherent interface.
This Albatra metal intensity disclosed by the invention reaches 690 more than MPa, and electrical conductivity reaches more than 79%IACS and 400
DEG C annealing 2h intensity rates of descent<10%, reach the high speed rail system of more than 400 kilometers of speed per hour to contacting the requirement of wire material.
Compared with prior art, the invention has the advantages that：
1st, the present invention is handled using liquid nitrogen cryogenics, significantly reduces solid solubility of the alloying element in Copper substrate, is improved precipitation and is become
Gesture, promote remaining solid solution atom to continue to separate out, further purify Copper substrate and improve electrical conductivity.
2nd, copper alloy produced by the present invention has unique structure, and the high density nanofiber formed using X element is had
Effect hinders dislocation motion and produces huge nanofiber and strengthen effect, and lifting alloy bulk strength is horizontal so that copper alloy is strong
Degree can reach 690 more than MPa；
3rd, it is axially axially in parallel with alloy bar or line using fiber, scattering of the electron waves in boundary is reduced, ensures alloy
Electrical conductivity is maintained at higher level, reaches more than 79%IACS；
4th, it is pinned at using nano particle on the boundary of fiber and Copper substrate, prevents nanofiber in annealing process
Nodularization trend, ensure that alloy has very high anti-softening temperature so that its 400 DEG C annealing 2h intensity rates of descent<10%.
Brief description of the drawings
The scanning electron microscope (SEM) photograph for the copper alloy that Fig. 1 is obtained by embodiment 4；
The transmission electron microscope photo of Ag fibers and Cu matrix semicoherent interfaces, interface in the alloy that Fig. 2 is obtained by embodiment 1
On the misfit dislocation of periodic arrangement be present.
The stereoscan photograph of Nb nanofibers in the alloy that Fig. 3 is obtained by embodiment 2；
The transmission electron microscope photo of Cr nano particles in the alloy that Fig. 4 is obtained by embodiment 3.
Embodiment
Technical scheme is described further with specific embodiment below, but protection scope of the present invention is unlimited
In this：
Embodiment 1：
Using pure Cu, pure Ag, pure Cr, pure Zr and pure Si as raw material, heating up to melt and cast using vacuum melting furnace obtains Cu-
12%Ag-0.3%Cr-0.1%Zr-0.05%Si casting rods, carrying out multi pass drawing in room temperature to casting rod reaches its sectional shrinkage
80%.By gained sample be placed in 300 DEG C annealing 24h, after room temperature continue drawing, this stage sectional shrinkage be 50%, finally
Sample, which is placed in liquid nitrogen, to be incubated after 24 h with 10 DEG C/min rate recovery room temperatures, makes gained alloy be received comprising a large amount of fine and closely woven Ag
Rice fiber and Cr, Zr, Si nano-particle.The nm of nanofiber average diameter 50, length are more than 2000 nm, and fiber is smaller than
1000 nm, and the interface of fiber and Copper substrate is semicoherent interface, at interval of 9 Cu's on interface（111）Atomic plane occurs one
Individual misfit dislocation.The nm of average diameter 30 of Cr, Zr, Si nano-particle, is smaller than 200 nm, Cr, Zr, Si nano-particle with
The boundary of Cu matrixes is semicoherent interface, and the boundary with X fibers is incoherent interface.
Embodiment 2：
Using pure Cu, Cu-20%Nb intermediate alloy, Cu-5%Cr intermediate alloys, pure Zr and pure Si as raw material, using vacuum melting
Stove heating, which is melted and cast, obtains Cu-12%Nb-1%Cr-0.2%Zr-0.1%Si casting rods, and multi-pass drawing is carried out in room temperature to casting rod
Pulling out makes its sectional shrinkage reach 85%.Sample is placed in 320 DEG C of 16 h of annealing afterwards, gained sample is subjected to drawing again, this
Stage sectional shrinkage is 30%, and finally sample is placed in liquid nitrogen to be incubated after 100 h to heat up with 5 DEG C/min and recovers room temperature, makes institute
Obtain alloy and include a large amount of fine and closely woven Nb nanofibers and Cr, Zr, Si nano-particle.The nm of nanofiber average diameter 100, length
More than 1000 nm, fiber is smaller than 8000 nm, and the interface of fiber and Copper substrate is semicoherent interface, on interface at interval of
13 Cu's（111）There is a misfit dislocation in atomic plane.The average diameter 25nm of Cr, Zr, Si nano-particle, is smaller than
150 nm, the boundary of Cr, Zr, Si nano-particle and Cu matrixes is semicoherent interface, and the boundary with X fibers is non-coherence circle
Face.
Embodiment 3：
Using pure Cu, pure Ag, Cu-15%Ta intermediate alloy, Cu-3%Cr intermediate alloys as raw material, heated up using vacuum melting furnace
Melt and cast and obtain Cu-6%Ag-6%Ta-0.1%Cr casting rods, carrying out multi pass drawing in room temperature to casting rod makes its cross-sectional constriction
Rate reaches 85%.Sample is placed in 400 DEG C of annealing 8h afterwards, gained sample is subjected to drawing again, this stage sectional shrinkage is
40%, finally sample is placed in liquid nitrogen to be incubated to heat up with 2 DEG C/min after 1h and recovers room temperature, include gained alloy a large amount of fine and closely woven
Ag and Ta nanofibers and Cr nano-particles.The nm of nanofiber average diameter 100, length are more than 1000 nm, fiber spacing
Less than 1000 nm, and the interface of fiber and Copper substrate is semicoherent interface, at interval of 9 Cu's on Cu/Ag interfaces（111）It is former
There is a misfit dislocation in sub- face, at interval of 10 Cu's on Cu/Ta interfaces（111）There is a misfit dislocation in atomic plane.Cr
The nm of average diameter 20 of nano-particle, is smaller than 100 nm.Cr nano-particles Dispersed precipitate is in copper intra-die and fiber circle
Face, the boundary of Cr nano-particles and Cu matrixes is semicoherent interface, and the boundary with X fibers is incoherent interface.
Embodiment 4：
With pure Cu, pure Ag, Cu-50%Nb intermediate alloy, Cu-10%Cr intermediate alloys, Cu-15%Zr intermediate alloys and Cu-5%
Si intermediate alloys are raw material, and heating up to melt and cast using vacuum melting furnace obtains Cu-12%Ag-12%Nb-1.3%Cr-0.4%
Zr-0.3%Si casting rods, carrying out multi pass drawing in room temperature to casting rod makes its sectional shrinkage reach 95%.Sample is placed in afterwards
300 DEG C of annealing 8h, carry out drawing, this stage sectional shrinkage is 30%, and finally sample is placed in liquid nitrogen again by gained sample
Be incubated to heat up with 10 DEG C/min after 200h and recover room temperature, make gained alloy include a large amount of fine and closely woven Ag and Nb nanofibers and Cr,
Zr, Si nano-particle.The nm of nanofiber average diameter 100, length are more than 3000 nm, and fiber is smaller than 800 nm, and fine
Dimension and the interface of Copper substrate are semicoherent interface, at interval of 9 Cu's on Cu/Ag interfaces（111）There is a mispairing in atomic plane
Dislocation, at interval of 13 Cu's on Cu/Nb interfaces（111）There is a misfit dislocation in atomic plane.Cr, Zr, Si nano-particle
Average diameter 25nm, it is smaller than 130 nm.Cr, Zr, Si nano-particle Dispersed precipitate in copper intra-die and fiber interface,
The boundary of Cr, Zr, Si nano-particle and Cu matrixes is semicoherent interface, and the boundary with X fibers is incoherent interface.
Embodiment 5：
Using pure Cu, pure Ag, Cu-20%Cr intermediate alloy, Cu-10%Zr intermediate alloys and Cu-10%Si intermediate alloys as original
Material, heating up to melt and cast using vacuum melting furnace obtains Cu-3%Ag-0.8%Cr-0.5%Zr-0.3%Si casting rods, and casting rod is existed
Room temperature, which carries out multi pass drawing, makes its sectional shrinkage reach 95%.Sample is placed in 250 DEG C of 128 h of annealing afterwards, by gained sample
Product carry out drawing again, and this stage sectional shrinkage is 50%, and finally sample is placed in liquid nitrogen and is incubated after 100 h with 8 DEG C/min
Heating recovers room temperature, gained alloy is included a large amount of fine and closely woven Ag nanofibers and Cr, Zr, Si nano-particle.Nanofiber is put down
The equal nm of diameter 40, length are more than 1500 nm, and fiber is smaller than 2000 nm, and the interface of fiber and Copper substrate is half coherence
Interface, at interval of 9 Cu's on Cu/Ag interfaces（111）There is a misfit dislocation in atomic plane.Cr, Zr, Si nano-particle are put down
Equal diameter 15nm, is smaller than 90 nm.Cr, Zr, Si nano-particle Dispersed precipitate in copper intra-die and fiber interface, Cr,
The boundary of Zr, Si nano-particle and Cu matrixes is semicoherent interface, and the boundary with X fibers is semicoherent interface.
The alloy obtained to above-described embodiment is shown in using the content results of X and Y solid solution atoms in power spectrum test Copper substrate
Table 1, the alloy obtained to above-described embodiment measure fiber and base using ESEM and transmission electron microscope Momentum profiles technology
Nano particle accounts for the ratio of overall nano particle on the boundary of body, the results are shown in Table 1.
Copper substrate X and Y are dissolved the content of atom, and nanometer on the boundary of fiber and matrix in the embodiment alloy of table 1
Grain proportion
The alloy obtained to above-described embodiment is using standard tensile experimental test intensity and four-point method test room temperature conductance
Rate, and 2h test intensity rates of descent of being annealed at 400 degree.The performance obtained is shown in Table 2.
The 2-in-1 golden main performance contrast of table
* comparative alloy CuCrZrZnCoTiLa data come from patent CN1417357A.
Claims (9)
- A kind of 1. method for preparing copper alloy, it is characterised in that：The copper alloy composition meets this form：CuXY, wherein X are selected from At least one of Ag, Nb and Ta, Y are selected from least one of Cr, Zr and Si；In copper alloy, the total content of X element is more than 0.01 and not higher than 20%, the total content of Y element is more than 0.01 and not higher than 2%, also, Cr content range is 0.01 ~ 1.5%, Zr content range 0.01 ~ 0.5%, Si content range 0.01 ~ 0.3%；Methods described is：By simple substance and/or middle conjunction Golden raw material loads vacuum melting furnace according to the alloying component proportioning of design, and heating, which is melted and pours to cast from, obtains ingot casting in mould, right Ingot casting carries out multi pass drawing and is deformed into long bar or line at room temperature, sample in cross section shrinkage factor is reached more than 80%, right afterwards Long bar or line are annealed, and the temperature of annealing is chosen at the fiber for forming X element and nodularization fracture does not occur and can make Y element The scope of nanometer precipitated phase is formed, the time of annealing is chosen at the fiber for forming X element and nodularization fracture does not occur and makes to be more than 50% Y element forms the scope of nanometer precipitated phase, carries out drawing again to gained alloy afterwards, this stage sample cross-sectional constriction Rate carries out liquid nitrogen frozen processing to gained alloy afterwards within 50%, makes to remain in the X in Copper substrate or Y solid solution atoms continue Separate out, be slowly warming up to room temperature afterwards so as to obtain copper alloy.
- 2. the method as described in claim 1, it is characterised in that：The total content of X element is 3% ~ 12% in copper alloy.
- 3. the method as described in claim 1, it is characterised in that：The total content of Y element is 0.1% ~ 1.5% in copper alloy.
- 4. method as claimed in claim 2, it is characterised in that：The total content of Y element is 0.1% ~ 1.5% in copper alloy.
- 5. the method as described in claim 1, it is characterised in that described copper alloy is one of following：Cu-12%Ag-0.3%Cr- 0.1%Zr-0.05%Si、Cu-0.1%Ag-0.1%Cr-0.1%Zr、Cu-12%Nb-1%Cr-0.4%Zr-0.1%Si、Cu-6%Ag-6% Ta-0.1%Cr、Cu-3%Ag-0.8%Cr-0.5%Zr-0.3%Si。
- 6. the method as described in one of claim 1 ~ 5, it is characterised in that：Liquid nitrogen frozen processing time is 1 ~ 100 hour.
- 7. the method as described in one of claim 1 ~ 5, it is characterised in that：After carrying out liquid nitrogen frozen processing to alloy, with 2 ~ 10 DEG C/min speed is warming up to room temperature.
- 8. method as claimed in claim 6, it is characterised in that：After carrying out liquid nitrogen frozen processing to alloy, with 2 ~ 10 DEG C/min Speed be warming up to room temperature.
- 9. the method as described in one of claim 1 ~ 5, it is characterised in that obtained copper alloy includes following characteristics：At ambient temperature, X element exists in the form of pure phase and two kinds of atom of solid solution in the copper alloy, wherein to be dissolved atom The X element content of form is less than 0.5%；Y element is deposited in the form of pure phase and solid solution atom or CuY compounds and solid solution atom Wherein the content of the Y element in the form of being dissolved atom is less than 0.1%；The copper alloy exists in the form of long bar or line, wherein, the fiber shape that the X element of pure phase is arranged with less parallel Formula is inside the copper alloy, and fiber is axially with Copper alloy bar or bobbin to almost parallel, and the diameter of fiber is less than 100 nm, grows Degree is more than 1000 nm, and fiber is smaller than 1000 nm, and the boundary of fiber and Cu matrixes is semicoherent interface, is distributed on interface There is the misfit dislocation of periodic arrangement；The Y element of pure phase or compound form is in granular form inside copper alloy, and more than 30% particle in the copper alloy It is distributed in X fibers and on the boundary of Cu matrixes, the diameter of particle is less than 30 nm, is smaller than 200 nm, particle and Cu matrixes And the boundary of particle and X fibers is semicoherent interface or incoherent interface.
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