CN106978546B - A kind of complex intensifying copper alloy with high strength and high conductivity and preparation method thereof - Google Patents
A kind of complex intensifying copper alloy with high strength and high conductivity and preparation method thereof Download PDFInfo
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Abstract
The present invention is a kind of complex intensifying copper alloy with high strength and high conductivity and preparation method thereof, which is made of following: Cr, selected from least one of Ag, In element and selected from least one of La, Ce, Y element, and surplus is Cu and inevitable impurity element.Complex intensifying copper alloy with high strength and high conductivity each component content of the invention is respectively (being mass percent): Cr content is 0.26-1.0%；Ag, In one or two element total content are 0.05-0.4%；, two or three element total content a kind of selected from La or Ce or Y is 0.1-0.5%；Inevitable impurity element total amount is not higher than 0.5%；Surplus is Cu.By the optimizing components of complex intensifying copper alloy with high strength and high conductivity, available high-intensitive, highly conductive, highly resistance softening temperature copper alloy frame band or alloy wire.It can satisfy the use demand of the high-strength high conducting wire material such as integrated circuit frame material and contact line, alloy wire.
Description
Technical field
The present invention relates to copper alloy with high strength and high conductivity Material Field, specially a kind of complex intensifying copper alloy with high strength and high conductivity and its
Preparation method is suitable for blaster fuse frame material, high conductivity and strength alloy wire rod or band, connector material etc..
Background technique
With the fast development of modern industry, to the performance of copper alloy, higher requirements are also raised, in order to adapt to the modern times
The needs of industrial boom, English, beauty, Deng state have carried out largely copper alloy with high strength and high conductivity since the 1970s
Research-and-development activity, China had also obtained faster development in the field in recent years.For high-strength highly-conductive integrated circuit
Frame material, electric locomotive contact line, electrical engineering switch touching bridge, connector material etc., develop in succession Cu-Cr-Ag,
The copper alloy with high strength and high conductivity such as Cu-Cr-In, Cu-Cr-Zr.But develop at present above its intensity of various copper alloy with high strength and high conductivity,
Electric conductivity, anti-softening temperature have had reached certain limit, its further promoted encountered in comprehensive performance it is certain
Bottleneck.
Summary of the invention
Inventors be surprised to learn that being one or both of Ag, In element in Cu-Cr-X(X) etc. copper alloy with high strength and high conductivity
On the basis of, La, Y or Ce are added, new alloy can be generated, can further break through its performance boost bottleneck, improve the conjunction
The electric conductivity and tensile strength of gold.
The complex intensifying copper alloy with high strength and high conductivity is made of following four part: first part Cr, second part be selected from
At least one of Ag, In element, Part III are selected from least one of La, Ce, Y element, and Part IV is for Cu and not
Evitable impurity element.Each component content is (being mass percent): first part's content is 0.26%-1.0%；Second
Dividing total content is 0.05%-0.5%；Part III content is 0.1-0.5%；Surplus is Part IV.
Further, inevitable impurity content is lower than the 0.5% of Part IV gross mass in the Part IV.
Further, the second part is In, mass percentage content 0.15%-0.4%.
Further, the second part is Ag, mass percentage content 0.05%-0.1%.
Further, the second part be Ag and or In, Ag mass percentage content are as follows: 0.05%-0.1%, In mass
Degree are as follows: 0.2%-0.4%.
A kind of preparation method of complex intensifying copper alloy with high strength and high conductivity of the invention:
A. ingredient is carried out by the mass percent of the complex intensifying copper alloy with high strength and high conductivity, raw material is copper and rare earth member
Alloy, fine copper, fine silver, pure indium and the chromiumcopper of element；
B. in smelting furnace, the fine copper raw material for having weighed weight is added, is covered using borax, graphite powder, and heat temperature raising
Copper is melted to 1083~1250 DEG C；
C. by composition proportion requirement, weighed Cu-Cr intermediate alloy is added, and coverture is made to cover copper liquid surface；
D. until completely melted, the pure Ag or pure In for having weighed weight are added by component requirements, stands 5 until completely melted
~10min；
E. proportionately divide design requirement, add the Cu-RE intermediate alloy for having weighed weight (in Cu-La, Cu-Y or Cu-Ce
It is one or more), and coverture is made to cover copper liquid surface；
F. until completely melted, stirred evenly with graphite rod, and direct pouring is in the mould, alloy casting blank is made；
Bar is made through extrusion process for above-mentioned alloy casting blank or wire rod is made in drawn technique.
Further alloy casting blank is at 850 DEG C -980 DEG C, and after keeping the temperature 1-3h, the technique by extrusion ratio greater than 100% is carried out
Alloy bar material is made in hot extrusion.
Alloy bar material made from further can be that 90 ° -130 ° of mold carries out Equal Channel Angular Pressing by channel angle, squeeze
Press 5-12 passage that complex intensifying copper alloy with high strength and high conductivity bar is made.
Further complex intensifying copper alloy with high strength and high conductivity slab is by the hot extrusion technique of 200% or more compression ratio and isometrical
Angle, which squeezes, is made complex intensifying copper alloy with high strength and high conductivity bar.
The present invention enable high temperature intermetallics be crushed and Dispersed precipitate in the base；The complex intensifying high-strength highly-conductive
The tensile strength of copper alloy can reach 650MPa, and conductivity reaches as high as 92%, and anti-softening temperature reaches as high as 500 DEG C.
The present invention also has the advantage that the preparation of complex intensifying copper alloy with high strength and high conductivity can be in the Preparation equipment of former alloy
Upper progress.For the alloy of melting in air, as long as addition coverture, appropriate adjustment smelting technology (using Cu-RE intermediate alloy,
Control intermediate alloy addition time etc.) it can be realized.Therefore, complex intensifying copper alloy with high strength and high conductivity is prepared, input cost is low, work
Skill is simple；And manufactured complex intensifying copper alloy with high strength and high conductivity is superior to existing copper alloy performance.
Specific embodiment
Below with reference to preferred embodiment, the present invention will be further described.
Embodiment 1: raw material are fine copper, Cu-5%Cr intermediate alloy, pure Ag, Cu-5%Ce intermediate alloy, by Cu-
0.26Cr-0.05Ag-0.15Ce(mass percent Cr is 0.26%, Ag 0.05%, and Ce 0.15%, surplus Cu are closed below
Golden representation method is identical) component ratio carry out ingredient, melting is carried out in intermediate frequency furnace.A. fine copper is added in smelting furnace
Raw material is covered using borax, graphite powder, and being heated to 1150 DEG C melts copper；B. title is added after copper is completely melt
The Cu-5%Cr intermediate alloy taken, and coverture is made to cover copper liquid surface；C. it is estimated that and is matched according to temperature and feeding quantity
Material is completely melt the time, and subsequent step is identical；After Cu-5%Cr intermediate alloy to be added is completely melt, addition has weighed weight
Pure Ag, stand 10min after pure Ag is completely melt；D. the Cu-5%Ce intermediate alloy for having weighed weight is added, and makes coverture
Cover copper liquid surface；E. it after Cu-5%Ce is completely melt, is stirred evenly with graphite rod, then direct pouring is in cylindrical iron
In mould, φ 195mm complex intensifying copper alloy with high strength and high conductivity slab is made.Slab is heated to 850 DEG C, and crouches after keeping the temperature 1h through 500T
Formula extruder is squeezed into φ 15mm rod of metal alloy under the technique of extrusion ratio (λ=177)；The mould that rod of metal alloy is 90 ° by channel angle
Tool carries out Equal Channel Angular Pressing, squeezes 6 passages and φ 15mm complex intensifying copper alloy with high strength and high conductivity material is made；φ 15mm complex intensifying is high
Strong high-conductivity copper alloy material is drawn to φ 5mm copper wire through 5 passages；Solution treatment is quickly cooled down after 950 DEG C of heat preservation 1.5h；φ5mm
Rod of metal alloy is drawn to φ 2.0mm rod of metal alloy through 8 passages, and after 450 DEG C of heat preservation 0.5h timeliness, wire rod tensile strength reaches
389MPa, conductivity have reached 92.7%IACS, and anti-softening temperature is up to 450 DEG C, compared with Cu-0.26Cr-0.05Ag alloy, Cu-
0.26Cr -0.05Ag-0.015Ce complex intensifying copper alloy with high strength and high conductivity tensile strength, conductivity increase, and antioxygen
The property changed obtains certain promotion.
Embodiment 2: raw material are fine copper, in Cu-10%Cr intermediate alloy, pure In, Cu-10%La intermediate alloy, Cu-10%Y
Between alloy, by Cu-0.8Cr-0.15In-0.05La-0.05Y component ratio carry out ingredient, melted in intermediate frequency furnace
Refining.A. fine copper raw material is added in smelting furnace, is covered using borax, graphite powder, and being heated to 1250 DEG C melts copper；b.
Weighed Cu-10%Cr intermediate alloy is added after fusing, and coverture is made to cover copper liquid surface；C. after melting, stablize copper liquid
The pure In for having weighed weight is added at 1150 DEG C for temperature, stands 10min after fusing；D. the Cu-10% La for having weighed weight is added
With Cu-10% Y intermediate alloy, and coverture is made to cover copper liquid surface；E. it after melting, is stirred evenly with graphite rod, and directly
It casts in square graphite mould, φ 30mm complex intensifying copper alloy with high strength and high conductivity slab is made.Slab is at 920 DEG C, after keeping the temperature 2h
φ 18mm rod of metal alloy is squeezed into through 1500T horizontal extruder；φ 18mm rod of metal alloy is carried out by the mold that channel angle is 110 °
Equal Channel Angular Pressing squeezes 10 passages, and complex intensifying copper alloy with high strength and high conductivity material is made.Complex intensifying copper alloy with high strength and high conductivity material exists
It 920 DEG C, after keeping the temperature 2h, is hot-rolled down to by hot rolling technology with a thickness of 5mm；950 DEG C of heat preservation 1h solid solutions again；After plate is cold-rolled to 2mm,
Through 500 DEG C of heat preservation 1h ageing treatments, sheet alloy tensile strength is up to 600MPa, and conductivity has reached 80.5%, anti-softening temperature
Up to 475 DEG C.Compared with Cu-0.8Cr-0.15Zr alloy, the high-strength height of Cu-0.8Cr-0.15In-0.05La-0.05Y complex intensifying
Conductivity copper alloy tensile strength, conductivity get a promotion.
Embodiment 3: raw material are fine copper, Cu-10%Cr intermediate alloy, pure In, pure Ag, Cu-10%La intermediate alloy.It presses
The component ratio of Cu-0.7Cr-0.1Ag-0.3In-0.3La carries out ingredient, and melting is carried out in intermediate frequency furnace.A. in melting
Fine copper raw material is added in furnace, is covered using borax, graphite powder, charcoal, and being heated to 1250 DEG C melts copper；B. after melting
Weighed Cu-10%Cr intermediate alloy is added, and coverture is made to cover copper liquid surface；C. after melting, stablize copper liquid temperature and exist
1150 DEG C are added the pure In for having weighed weight, stand 10min until completely melted；D. the Cu-10% La for having weighed weight is added
With Cu-10% Y intermediate alloy, and coverture is made to cover copper liquid surface；E. it is stirred evenly after melting with graphite rod, and directly poured
Copper alloy slab is made in cylindrical swage in casting.Slab is squeezed into φ through 1500T horizontal extruder after heat preservation 1h at 850 DEG C
25mm rod of metal alloy；φ 25mm rod of metal alloy carries out isometrical extruding by the mold that channel angle is 90 °, squeezes 8 passages, obtains compound
Strengthen copper alloy with high strength and high conductivity material；φ 25mm complex intensifying copper alloy with high strength and high conductivity material is drawn to φ 10mm alloy through drawing process
Copper bar；Solution treatment is quickly cooled down after 950 DEG C of heat preservation 1h；φ 10mm alloyed copper bar is drawn to φ 4.5mm through drawing process and closes
Golden bar, after 450 DEG C of heat preservation 2h timeliness, wire rod tensile strength reaches 576MPa, and conductivity has reached 80.6%IACS, anti-softening
Temperature is up to 500 DEG C, Cu-0.7Cr-0.1Ag-0.3In -0.3La complex intensifying copper alloy with high strength and high conductivity bar tensile strength, conduction
Rate increases.The content of Ag can also reduce to 0.05% in alloy proportion in the present embodiment.
Embodiment 4: raw material are fine copper, Cu-10%Cr intermediate alloy, pure In, Cu-10%La intermediate alloy.By Cu-
The component ratio of 1.0Cr-0.4In-0.5La carries out ingredient, and melting is carried out in intermediate frequency furnace.A. it is added in smelting furnace pure
Copper raw material is covered using borax, graphite powder, charcoal, and being heated to 1250 DEG C melts copper；B. it is added and weighs after melting
Cu-10%Cr intermediate alloy, and coverture is made to cover copper liquid surface；C. stablize copper liquid temperature after melting at 1150 DEG C and add
The pure In for entering to have weighed weight, stands 10min after fusing；D. the Cu-10% La intermediate alloy for having weighed weight is added, and makes to cover
Lid agent covers copper liquid surface；After e fusing, stirred evenly with graphite rod, and direct pouring is made high-strength in cylindrical swage
High-conductivity copper alloy slab.Slab is squeezed into φ 25mm rod of metal alloy through 1500T horizontal extruder after heat preservation 1h at 850 DEG C；φ25mm
Rod of metal alloy carries out isometrical extruding by the mold that channel angle is 120 °, squeezes 10 passages, obtains complex intensifying high-strength high-conductivity copper
Alloy material；φ 25mm complex intensifying copper alloy with high strength and high conductivity material is drawn to φ 7mm copper bar through drawing process；In 950 DEG C of heat preservation 2h
After be quickly cooled down solution treatment；φ 7mm rod of metal alloy is drawn to φ 4mm rod of metal alloy through drawing process, in 500 DEG C of heat preservation 1.5h timeliness
Afterwards, wire rod tensile strength reaches 650MPa, and conductivity has reached 65.8%IACS, and anti-softening temperature is up to 500 DEG C, with respective alloy
It compares, Cu-1.0Cr-0.4In -0.5La complex intensifying copper alloy with high strength and high conductivity bar tensile strength, conductivity are improved.
Embodiment 5: raw material are fine copper, Cu-5%Cr intermediate alloy, pure In, pure Ag, Cu-10%La intermediate alloy, Cu-5%
Ce intermediate alloy, Cu-5%Y intermediate alloy.By the ingredient ratio of Cu-0.5Cr-0.1Ag-0.2In -0.05La-0.15Ce-0.05Y
Example carries out ingredient, and melting is carried out in intermediate frequency furnace.A. fine copper raw material is added in smelting furnace, is covered using borax, graphite powder
Lid, and being heated to 1150 DEG C melts copper；B. weighed Cu-5%Cr intermediate alloy is added after melting, and makes coverture
Cover copper liquid surface；C. after to be melted, the pure In for having weighed weight is added, stands 10min after to be melted；D. it is added and weighs
Cu-10% La, Cu-5%Ce the and Cu-5% Y intermediate alloy of weight, and coverture is made to cover copper liquid surface；E. after to be melted,
It is stirred evenly with graphite rod, and copper alloy slab is made in cylindrical swage in direct pouring.Slab is at 850 DEG C, after keeping the temperature 1h
φ 30mm rod of metal alloy is squeezed into through 1500T horizontal extruder；φ 30mm rod of metal alloy is carried out by the mold that channel angle is 110 °
Isometrical extruding squeezes 9 passages, obtains complex intensifying copper alloy with high strength and high conductivity material；φ 30mm high property copper alloy material is through drawer
Skill is drawn to φ 12mm copper wire；Solution treatment is quickly cooled down after 950 DEG C of heat preservation 1h；φ 12mm rod of metal alloy is through drawing process drawing
To φ 3.5mm rod of metal alloy, after 450 DEG C of heat preservation 0.75h timeliness, wire rod tensile strength reaches 468MPa, and conductivity reaches
84.6%IACS, anti-softening temperature reach 500 DEG C, compared with Cu-0.5Cr-0.1Ag-0.2In alloy, Cu-0.5Cr-0.1Ag-
0.2In-0.05La-0.15Ce-0.05Y complex intensifying copper alloy with high strength and high conductivity bar tensile strength, conductivity are promoted.
Fine copper must be used in above-described embodiment, it is inevitable in manufactured complex intensifying copper alloy with high strength and high conductivity to guarantee
Impurity is lower than 0.5%.
With the development of modern industrial technology, rare earth element is in traditional fields such as petroleum, chemical industry, metallurgy with extensive.It is special
It is not that in recent years, with the rapid development of the field of functional materials such as luminescent material, permanent-magnet material, hydrogen storage material, rare-earth usage is anxious
Play increases.But rare earth all becomes product as Coexisting Elements together in exploitation, extractive process.And current each rare earth element
With uneven, as the elements such as La, Y, Ce are less with ground field.And with the rapid growth of rare earth material demand, it is dilute
The contradictions such as soil resource wastes, utilization rate is low become increasingly conspicuous.Therefore, become the weight of current research how to efficiently use rare earth resources
It wants and the key of China's Rare-earth Industry sustainable development.And the present invention, on the basis of former alloy, rare earth is added to a certain amount of
When, rare earth La, Ce, Y can be contour with Cu, In, Ag meeting reaction in-situ generation In3Ce, In3La, InY2, AgY, Ag2Ce, Ag2La
Melting point metals compound deforms in conjunction with large scales such as large extrusion ratio, isometrical extruding, keeps alloy structure broken, high-melting-point chemical combination
The second phase that object forms Dispersed precipitate is present in alloy substrate, and it is compound to form a kind of generated in-situ second-phase dispersion reinforcing
Material.By techniques such as rolling or drawing, solid solution, timeliness, the copper alloy with high strength and high conductivity material of different model specification can be prepared.This
Invention uses for elements such as La, Y, Ce and provides effective way.
It is described above simply to illustrate that of the invention, it is understood that the present invention is not limited to the above embodiments, meets
The various variants of inventive concept are within the scope of the present invention.
Claims (8)
1. a kind of complex intensifying copper alloy with high strength and high conductivity, which is characterized in that be made of following four part: first part Cr, the
Two parts be Ag and or In, Part III include at least one of La, Ce, Y element, Part IV is Cu and inevitably
Impurity；It is 0.26%-0.5% that each component mass percent, which is respectively as follows: first part's content,；The second part content is
0.05%-0.4%；The Part III content is 0.1%-0.3%；Surplus is Part IV；It is prepared using following steps:
1) ingredient is carried out by the mass percent of the complex intensifying copper alloy with high strength and high conductivity, raw material is the conjunction of copper and rare earth element
Gold, fine copper, fine silver, pure indium and chromiumcopper；
2) in smelting furnace, the fine copper raw material in ingredient is added, is covered using borax, graphite powder, and it is heated to 1083~
1250 DEG C melt copper；
3) chromiumcopper in ingredient is added, and coverture is made to cover copper liquid surface；
4) after the chromiumcopper is completely melt, the fine silver in ingredient or pure indium or fine silver, pure indium mixture is added, it is to be added
Ingredient be completely melt after stand 5~10min；
5) alloy of copper and rare earth element in ingredient is added, and coverture is made to cover copper liquid surface；
6) it after ingredient to be added is completely melt, is stirred evenly with graphite rod, then casts in the mould, alloy casting blank is made.
2. complex intensifying copper alloy with high strength and high conductivity according to claim 1, which is characterized in that can not in the Part IV
The impurity content avoided is lower than the 0.5% of Part IV gross mass.
3. complex intensifying copper alloy with high strength and high conductivity according to claim 2, which is characterized in that the second part is In,
Mass percentage content is 0.15%-0.4%.
4. complex intensifying copper alloy with high strength and high conductivity according to claim 2, which is characterized in that the second part is Ag,
Mass percentage content is 0.05%-0.1%.
5. complex intensifying copper alloy with high strength and high conductivity according to claim 2, which is characterized in that the second part be Ag and
In, Ag mass percentage content are as follows: 0.05%-0.1%, In mass percentage content are as follows: 0.2%-0.3%.
6. complex intensifying copper alloy with high strength and high conductivity according to claim 1, which is characterized in that the alloy casting blank is 850
DEG C -980 DEG C, after keeping the temperature 1-3h, the technique by extrusion ratio greater than 100% carries out hot extrusion, and alloy bar material is made.
7. complex intensifying copper alloy with high strength and high conductivity according to claim 6, which is characterized in that the alloy bar material is by logical
The mold that road angle is 90 ° -130 ° carries out Equal Channel Angular Pressing, squeezes 5-12 passage and complex intensifying copper alloy with high strength and high conductivity stick is made
Material.
8. complex intensifying copper alloy with high strength and high conductivity according to claim 6, which is characterized in that the pressure of the hot extrusion technique
Ratio contract 200% or more.
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Effective date of registration: 20210926 Address after: 331400 third floor, electronic science and technology park complex building, Xingguo County Economic Development Zone, Ganzhou City, Jiangxi Province Patentee after: Jiangxi permanent magnet Maglev Technology Co.,Ltd. Address before: 341000 No. 156, Hakka Road, Ganzhou, Jiangxi Patentee before: Jiangxi science and Technology Industry Co., Ltd |
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