CN105925923A - Preparation method of high-strength and high-conductivity copper alloy serving as contact line material of high-speed rail with speed per hour of above 400 km - Google Patents

Abstract

The invention discloses a preparation method of a high-strength and high-conductivity copper alloy serving as a contact line material of a high-speed rail with speed per hour of above 400 km. Components of the alloy alloy accord with a form of CuXY, wherein X is at least one of Ag, Nb and Ta; and Y is at least one of Cr, Zr and Si. The method comprises the following steps: a simple substance and/or raw materials of an intermediate alloy are fed in a vacuum smelting furnace according to a designed alloy component ratio for heating, melting and casting in a mold to obtain an ingot; the ingot is drawn by multiple times at room temperature to deform as a bar or a line; the section shrinkage of a sample reaches above 80%; then, the bar or the line is annealed; the alloy is drawn again; in the phase, the section shrinkage of the sample is within 50%; then, the liquid nitrogen freeze treatment is performed for the obtained alloy, so that remained X or Y solid soluble atoms in a copper matrix are continuously separated out; and then, the copper alloy is obtained through slowly heating to reach the room temperature.

Description

Preparation method as the copper alloy with high strength and high conductivity of more than 400 kilometers high-speed railway contact wire materials of speed per hour

Technical field

The present invention relates to the preparation method of a kind of Cu alloy, especially as the preparation method of the copper alloy contacting wire material of high-speed railway particularly more than 400 kilometers high-speed railways of speed per hour.

Background technology

Obtaining substantive rapid development from 2009 Nian Qi China high-speed electric railways (hereinafter referred to as high ferro), Beijing-Tianjin line, Jing-Hu Railway and Beijing-Guangzhou Railway are the most open-minded, and high ferro stable operation speed is 300 kilometers/hour.The development of high-speed electric railway produces the huge market demand and harsh performance requirement to its critical component contact line.Require that the material being used as contact line is provided simultaneously with following characteristic: high intensity, low line density, good electric conductivity, good rub, good corrosion resistance etc., especially intensity and electrical conductivity are most crucial indexs.

The conductor material that the line of high ferro contact at present uses mainly has Cu-Mg, and the serial Cu alloy such as Cu-Sn, Cu-Ag, Cu-Sn-Ag, Cu-Ag-Zr, Cu-Cr-Zr, wherein Cu-Cr-Zr shows the most excellent intensity and electrical conductivity combination property.Patent CN200410060463.3 and CN200510124589.7 disclose the technology of preparing of two kinds of alloys of Cu-(0.02 ~ 0.4) %Zr-(0.04 ~ 0.16) %Ag and Cu-(0.2 ~ 0.72) %Cr-(0.07 ~ 0.15) %Ag.By melting, casting, thermal deformation, solid solution, cold deformation, timeliness and again the technique such as cold deformation prepare finished product.Patent CN03135758.X disclose employing rapid solidification flour, pressed compact, sinter, extrude acquisition Cu-(0.01 ~ 2.5) %Cr-(0.01 ~ 2.0) %Zr-(0.01 ~ 2.0) % (Y, La, Sm) alloy bar material or the preparation method of sheet material, it is possible to obtain good conduction, heat conduction and softening resistant performance.Patent CN200610017523.2 discloses Cu-(0.05 ~ 0.40) %Cr-(0.05 ~ 0.2) %Zr-< 0.20% (Ce+Y) alloying component and technology of preparing thereof, obtains high-strength highly-conductive combination property and preferable heat resistance and wearability by melting, forging, solid solution, deformation, timeliness.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 obtain higher intensity and electrical conductivity by processes such as melting, hot rolling, solid solution, cold rolling, timeliness, finish to gauges.

United States Patent (USP) US6679955 discloses and obtains the supersaturated solid solution technology of preparing through Cu-(3 ~ 20) %Ag-(0.5 ~ 1.5) %Cr-(0.05 ~ 0.5) the %Zr alloy of thermomechanical treatment precipitation-hardening by rapid solidification.US7172665 discloses the technology of preparing of Cu-(2 ~ 6) %Ag-(0.5 ~ 0.9) %Cr alloy, the process such as technique includes uniformly post-processing, thermal deformation and solution treatment, and can add (0.05 ~ 0.2) %Zr again.US6881281 provides a kind of high-strength highly-conductive Cu-(0.05 ~ 1.0) %Cr-(0.05 ~ 0.25) %Zr alloy with excellent tired and middle temperature characteristics, ensures superperformance by the strict solution treatment parameter that controls with the concentration of regulation S.

Sustainable development along with high-speed electric railway, especially country 13 planning clearly proposes to build up speed per hour high speed rail system more than 400 kilometers at the year two thousand twenty, matched contact wire material performance also must be improved to intensity>680 MPa, electrical conductivity>78%IACS and 400 DEG C annealing the 2h intensity rate of descent<levels of 10%.The harshest performance standard makes Cu-Mg, Cu-Sn, the Cu-Ag used at present, Cu-Sn-Ag, Cu-Ag-Zr, Cu-Cr-Zr alloy all cannot meet the minimum requirements to contact wire material performance of the speed per hour high speed rail system more than 400 kilometers.Novel high-performance alloy must be developed to adapt to the lasting speed-raising development of high ferro.

Summary of the invention

It is an object of the invention to provide the preparation method of a kind of copper alloy with high strength and high conductivity, this copper alloy can meet the requirement to contact wire material of the speed per hour high speed rail system more than 400 kilometers.

The technical scheme used the present invention for achieving the above object below illustrates.

The invention provides a kind of method preparing copper alloy, this copper alloy composition meets this form: CuXY, wherein at least one in Ag, Nb and Ta of X, at least one in Cr, Zr and Si of Y；In copper alloy, the total content of X element be more than 0.01 and not higher than 20%, the total content of Y element be more than 0.01 and not higher than 2%, and, the content range of Cr is 0.01 ~ 1.5%, and the content range of Zr is 0.01 ~ 0.5%, and the content range of Si is 0.01 ~ 0.3%；nullDescribed method is: according to the alloying component proportioning of design, simple substance and/or intermediate alloy raw material are loaded vacuum melting furnace，Heat up to melt and water and cast from acquisition ingot casting in mould，Ingot casting is at room temperature carried out multi pass drawing and is deformed into long bar or line，Sample in cross section shrinkage factor is made to reach more than 80%，Afterwards long bar or line are annealed，The temperature of annealing is chosen at the fiber making X element form and nodularization fracture does not occur and Y element can be made to form the scope of nanometer precipitated phase，The time of annealing is chosen at the fiber making X element form and nodularization fracture does not occur and makes the Y element more than 50% form the scope of nanometer precipitated phase，Afterwards gained alloy is carried out again drawing，This stage sample sectional shrinkage is within 50%，Afterwards gained alloy is carried out liquid nitrogen frozen process，X or the Y solid solution atom remaining in Copper substrate is made to continue to separate out，The most slowly it is warmed up to room temperature thus obtains copper alloy.

Further, in copper alloy, the total content of X element is preferably 3% ~ 12%.

Further, in copper alloy, the total content of Y element is preferably 0.1% ~ 1.5%.

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, the liquid nitrogen frozen process time is preferably 1 ~ 100 hour.

Further, after alloy is carried out liquid nitrogen frozen process, preferably with the ramp of 2 ~ 10 DEG C/min to room temperature.

In the present invention, preparing raw material can be simple substance and/or intermediate alloy, and 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, in this copper alloy, X element exists with pure phase and two kinds of forms of solid solution atom, is wherein less than 0.5% with the X element content of the form of solid solution atom；Y element is presented in pure phase and solid solution atom or CuY compound and solid solution atom, wherein with the content of the Y element of the form of solid solution atom less than 0.1%；

This copper alloy is presented in long bar or line, wherein, the X element of pure phase is embedded in inside copper alloy with the fibers form that less parallel arranges, fiber axially with Copper alloy bar or bobbin to almost parallel, and the diameter of fiber is more than 1000 nm less than 100 nm, length, fiber spacing is less than 1000 nm, fiber is semicoherent interface with the boundary of Cu matrix, and the misfit dislocation of periodic arrangement is distributed on interface；It will be understood by those skilled in the art that, absolute " arranged in parallel " that X fiber is unlikely to be in mathematical meaning in copper alloy, fiber is axially and Copper alloy bar or bobbin are absolute " axially in parallel " in mathematical meaning to being also impossible to, and more tallies with the actual situation so being used herein as " approximation " and " substantially "；

In this copper alloy, the Y element of pure phase or compound form is embedded in inside copper alloy in granular form, and more than 30% distribution of particles on the boundary of X fiber and Cu matrix, the diameter of particle is less than 30 nm, being smaller than 200 nm, particle is semicoherent interface or incoherent interface with the boundary of Cu matrix and particle and X fiber.

This Albatra metal intensity disclosed by the invention reaches 690 more than MPa, electrical conductivity reach more than 79%IACS and 400 DEG C of annealing 2h intensity rates of descent < 10%, reached the requirement to contacting wire material of the high speed rail system of speed per hour more than 400 kilometers.

Compared with prior art, the method have the advantages that

1, the present invention utilizes liquid nitrogen cryogenics to process, and significantly reduces the alloying element solid solubility at Copper substrate, improves precipitation trend, promotes that remaining solid solution atom continues to separate out, and further purifying copper matrix improves electrical conductivity.

2, the copper alloy that the present invention prepares has the structure of uniqueness, the high density nanofiber utilizing X element to be formed effectively hinders dislocation motion to produce huge nanofiber strengthening effect, promote alloy bulk strength level so that copper alloy intensity can reach 690 more than MPa；

3, utilize fiber the most axially in parallel with alloy bar or line, reduce the electron waves scattering at boundary, it is ensured that alloy electrical conductivity is maintained at higher level, reaches more than 79%IACS；

4, utilize nano particle to be pinned on the boundary of fiber and Copper substrate, stop nanofiber nodularization trend in annealing process, ensure that alloy has the highest anti-softening temperature so that its 400 DEG C annealing 2h intensity rates of descent < 10%.

Accompanying drawing explanation

The scanning electron microscope (SEM) photograph of the copper alloy that Fig. 1 is obtained by embodiment 4；

In the alloy that Fig. 2 is obtained by embodiment 1, Ag fiber and the transmission electron microscope photo of Cu matrix semicoherent interface, interface exists the misfit dislocation of periodic arrangement.

The stereoscan photograph of Nb nanofiber in the alloy that Fig. 3 is obtained by embodiment 2；

The transmission electron microscope photo of Cr nano particle in the alloy that Fig. 4 is obtained by embodiment 3.

Detailed description of the invention

With specific embodiment, technical scheme is described further below, but protection scope of the present invention is not limited to this:

Embodiment 1:

With pure Cu, pure Ag, pure Cr, pure Zr and pure Si as raw material, use vacuum melting furnace intensification fusing acquisition Cu-12%Ag-0.3%Cr-0.1%Zr-0.05%Si casting rod of casting, casting rod is carried out multi pass drawing in room temperature and makes its sectional shrinkage reach 80%.Gained sample is placed in 300 DEG C of annealing 24h, drawing is continued afterwards in room temperature, this stage sectional shrinkage is 50%, is finally placed in liquid nitrogen by sample and is incubated after 24 h with 10 DEG C/min rate recovery room temperature, makes gained alloy comprise the finest and closely woven Ag nanofiber and Cr, Zr, Si nano particle.Nanofiber average diameter 50 nm, length is more than 2000 nm, and fiber spacing is less than 1000 nm, and the interface of fiber and Copper substrate is semicoherent interface, and on interface, a misfit dislocation occurs in (111) atomic plane at interval of 9 Cu.Average diameter 30 nm of Cr, Zr, Si nano particle, is smaller than 200 nm, and Cr, Zr, Si nano particle is semicoherent interface with the boundary of Cu matrix, is incoherent interface with the boundary of X fiber.

Embodiment 2:

With pure Cu, Cu-20%Nb intermediate alloy, Cu-5%Cr intermediate alloy, pure Zr and pure Si as raw material, use vacuum melting furnace intensification fusing acquisition Cu-12%Nb-1%Cr-0.2%Zr-0.1%Si casting rod of casting, casting rod is carried out multi pass drawing in room temperature and makes its sectional shrinkage reach 85%.Afterwards sample is placed in 320 DEG C of annealing 16 h, gained sample is carried out again drawing, this stage sectional shrinkage is 30%, finally being placed in liquid nitrogen by sample after being incubated 100 h heats up with 5 DEG C/min recovers room temperature, makes gained alloy comprise the finest and closely woven Nb nanofiber and Cr, Zr, Si nano particle.Nanofiber average diameter 100 nm, length is more than 1000 nm, and fiber spacing is less than 8000 nm, and the interface of fiber and Copper substrate is semicoherent interface, and on interface, a misfit dislocation occurs in (111) atomic plane at interval of 13 Cu.Average diameter 25nm of Cr, Zr, Si nano particle, is smaller than 150 nm, and Cr, Zr, Si nano particle is semicoherent interface with the boundary of Cu matrix, is incoherent interface with the boundary of X fiber.

Embodiment 3:

With pure Cu, pure Ag, Cu-15%Ta intermediate alloy, Cu-3%Cr intermediate alloy as raw material, use vacuum melting furnace intensification fusing acquisition Cu-6%Ag-6%Ta-0.1%Cr casting rod of casting, casting rod is carried out multi pass drawing in room temperature and makes its sectional shrinkage reach 85%.Afterwards sample is placed in 400 DEG C of annealing 8h, gained sample is carried out again drawing, this stage sectional shrinkage is 40%, heats up with 2 DEG C/min and recovers room temperature, make gained alloy comprise the finest and closely woven Ag and Ta nanofiber and Cr nano particle after sample is finally placed in liquid nitrogen insulation 1h.Nanofiber average diameter 100 nm, length is more than 1000 nm, fiber spacing is less than 1000 nm, and the interface of fiber and Copper substrate is semicoherent interface, on Cu/Ag interface, there is a misfit dislocation in (111) atomic plane at interval of 9 Cu, and on Cu/Ta interface, a misfit dislocation occurs in (111) atomic plane at interval of 10 Cu.Average diameter 20 nm of Cr nano particle, is smaller than 100 nm.Cr nano particle Dispersed precipitate is semicoherent interface at copper intra-die and fiber interface, Cr nano particle with the boundary of Cu matrix, is incoherent interface with the boundary of X fiber.

Embodiment 4:

With pure Cu, pure Ag, Cu-50%Nb intermediate alloy, Cu-10%Cr intermediate alloy, Cu-15%Zr intermediate alloy and Cu-5%Si intermediate alloy as raw material, use vacuum melting furnace intensification fusing acquisition Cu-12%Ag-12%Nb-1.3%Cr-0.4%Zr-0.3%Si casting rod of casting, casting rod is carried out multi pass drawing in room temperature and makes its sectional shrinkage reach 95%.Afterwards sample is placed in 300 DEG C of annealing 8h, gained sample is carried out again drawing, this stage sectional shrinkage is 30%, heat up with 10 DEG C/min after finally sample is placed in liquid nitrogen insulation 200h and recover room temperature, make gained alloy comprise the finest and closely woven Ag and Nb nanofiber and Cr, Zr, Si nano particle.Nanofiber average diameter 100 nm, length is more than 3000 nm, fiber spacing is less than 800 nm, and the interface of fiber and Copper substrate is semicoherent interface, on Cu/Ag interface, there is a misfit dislocation in (111) atomic plane at interval of 9 Cu, and on Cu/Nb interface, a misfit dislocation occurs in (111) atomic plane at interval of 13 Cu.Average diameter 25nm of Cr, Zr, Si nano particle, is smaller than 130 nm.Cr, Zr, Si nano particle Dispersed precipitate is semicoherent interface at copper intra-die and fiber interface, Cr, Zr, Si nano particle with the boundary of Cu matrix, is incoherent interface with the boundary of X fiber.

Embodiment 5:

With pure Cu, pure Ag, Cu-20%Cr intermediate alloy, Cu-10%Zr intermediate alloy and Cu-10%Si intermediate alloy as raw material, use vacuum melting furnace intensification fusing acquisition Cu-3%Ag-0.8%Cr-0.5%Zr-0.3%Si casting rod of casting, casting rod is carried out multi pass drawing in room temperature and makes its sectional shrinkage reach 95%.Afterwards sample is placed in 250 DEG C of annealing 128 h, gained sample is carried out again drawing, this stage sectional shrinkage is 50%, finally being placed in liquid nitrogen by sample after being incubated 100 h heats up with 8 DEG C/min recovers room temperature, makes gained alloy comprise the finest and closely woven Ag nanofiber and Cr, Zr, Si nano particle.Nanofiber average diameter 40 nm, length is more than 1500 nm, and fiber spacing is less than 2000 nm, and the interface of fiber and Copper substrate is semicoherent interface, and on Cu/Ag interface, a misfit dislocation occurs in (111) atomic plane at interval of 9 Cu.Average diameter 15nm of Cr, Zr, Si nano particle, is smaller than 90 nm.Cr, Zr, Si nano particle Dispersed precipitate is semicoherent interface at copper intra-die and fiber interface, Cr, Zr, Si nano particle with the boundary of Cu matrix, is semicoherent interface with the boundary of X fiber.

The alloy being obtained above-described embodiment uses the content results of X and Y solid solution atom in power spectrum copper test matrix to be shown in Table 1, the alloy being obtained above-described embodiment uses ESEM and transmission electron microscope Momentum profiles commercial measurement fiber to account for the ratio of overall nano particle with nano particle on the boundary of matrix, the results are shown in Table 1.

Nano particle proportion on Copper substrate X and the content of Y solid solution atom in table 1 embodiment alloy, and the boundary of fiber and matrix

The alloy being obtained above-described embodiment uses standard tensile experimental test intensity and four-point method test room-temperature conductivity, and tests intensity rate of descent at 400 degree of annealing 2h.The performance obtained is shown in Table 2.

Table 2-in-1 gold main performance contrast

* comparative alloy CuCrZrZnCoTiLa data come from patent CN1417357A.

Claims (9)

1. the method preparing copper alloy, it is characterised in that: this copper alloy composition meets this form: CuXY, wherein at least one in Ag, Nb and Ta of X, at least one in Cr, Zr and Si of Y；In copper alloy, the total content of X element be more than 0.01 and not higher than 20%, the total content of Y element be more than 0.01 and not higher than 2%, and, the content range of Cr is 0.01 ~ 1.5%, and the content range of Zr is 0.01 ~ 0.5%, and the content range of Si is 0.01 ~ 0.3%；nullDescribed method is: according to the alloying component proportioning of design, simple substance and/or intermediate alloy raw material are loaded vacuum melting furnace，Heat up to melt and water and cast from acquisition ingot casting in mould，Ingot casting is at room temperature carried out multi pass drawing and is deformed into long bar or line，Sample in cross section shrinkage factor is made to reach more than 80%，Afterwards long bar or line are annealed，The temperature of annealing is chosen at the fiber making X element form and nodularization fracture does not occur and Y element can be made to form the scope of nanometer precipitated phase，The time of annealing is chosen at the fiber making X element form and nodularization fracture does not occur and makes the Y element more than 50% form the scope of nanometer precipitated phase，Afterwards gained alloy is carried out again drawing，This stage sample sectional shrinkage is within 50%，Afterwards gained alloy is carried out liquid nitrogen frozen process，X or the Y solid solution atom remaining in Copper substrate is made to continue to separate out，The most slowly it is warmed up to room temperature thus obtains copper alloy.

2. the method for claim 1, it is characterised in that: in copper alloy, the total content of X element is 3% ~ 12%.

3. the method for claim 1, it is characterised in that: in copper alloy, the total content of Y element is 0.1% ~ 1.5%.

4. method as claimed in claim 2, it is characterised in that: in copper alloy, the total content of Y element is 0.1% ~ 1.5%.

5. the method for 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-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.

6. the method as described in one of claim 1 ~ 5, it is characterised in that: the liquid nitrogen frozen process time is 1 ~ 100 hour.

7. the method as described in one of claim 1 ~ 5, it is characterised in that: after alloy is carried out liquid nitrogen frozen process, with the ramp of 2 ~ 10 DEG C/min to room temperature.

8. method as claimed in claim 6, it is characterised in that: after alloy is carried out liquid nitrogen frozen process, with the ramp of 2 ~ 10 DEG C/min 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, in this copper alloy, X element exists with pure phase and two kinds of forms of solid solution atom, is wherein less than 0.5% with the X element content of the form of solid solution atom；Y element is presented in pure phase and solid solution atom or CuY compound and solid solution atom, wherein with the content of the Y element of the form of solid solution atom less than 0.1%；

This copper alloy is presented in long bar or line, wherein, the X element of pure phase is embedded in inside copper alloy with the fibers form that less parallel arranges, fiber axially with Copper alloy bar or bobbin to almost parallel, and the diameter of fiber is more than 1000 nm less than 100 nm, length, fiber spacing is less than 1000 nm, fiber is semicoherent interface with the boundary of Cu matrix, and the misfit dislocation of periodic arrangement is distributed on interface；

In this copper alloy, the Y element of pure phase or compound form is embedded in inside copper alloy in granular form, and more than 30% distribution of particles on the boundary of X fiber and Cu matrix, the diameter of particle is less than 30 nm, being smaller than 200 nm, particle is semicoherent interface or incoherent interface with the boundary of Cu matrix and particle and X fiber.