CN106978546A - 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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- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
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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, and the alloy is made up of following：Cr, selected from least one of Ag, In element and selected from least one of La, Ce, Y element, surplus is Cu and inevitable impurity element.The present invention complex intensifying copper alloy with high strength and high conductivity each component content be respectively（It is mass percent）：Cr contents are 0.26 1.0%；Ag, In one or two element total content are 0.05 0.4%；It is 0.1 0.5% selected from La or Ce or Y one kind, two or three of element total content；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, the copper alloy framework band or alloy wire of high intensity, highly conductive, high anti-softening temperature can be obtained.The use demand of the high-strength high wire material such as integrated circuit frame material and contact line, alloy wire can be met.
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, it is adaptable to blaster fuse frame material, high conductivity and strength alloy wire rod or band, connector material etc..
Background technology
With the fast development of modern industry, the performance to copper alloy it is also proposed higher requirement, in order to adapt to the modern times
The need for industrial boom, English, U.S., Deng states have been carried out largely since 1970s to copper alloy with high strength and high conductivity
Research-and-development activity, in recent years China also obtained faster development in the field.For high-strength highly-conductive integrated circuit
Frame material, electric locomotive contact line, electrical engineering switch touch 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 any of the above copper alloy with high strength and high conductivity its intensity,
Electric conductivity, anti-softening temperature have reached certain limit, its further lifted encountered in combination property it is certain
Bottleneck.
The content of the invention
Inventors be surprised to learn that in Cu-Cr-X（X is one or both of Ag, In element）Deng copper alloy with high strength and high conductivity
On the basis of, La, Y or Ce are added, new alloy can be generated, its performance boost bottleneck can be further broken through, improve the conjunction
The electric conductivity and tensile strength of gold.
The complex intensifying copper alloy with high strength and high conductivity is made up of following four part：Part I is Cr, Part II be selected from
At least one of Ag, In element, Part III are that Part IV is for Cu and not selected from least one of La, Ce, Y element
Evitable impurity element.Each component content is（It is mass percent）：Part I content is 0.26%-1.0%；Second
It is 0.05%-0.5% to divide total content；Part III content is 0.1-0.5%；Surplus is Part IV.
Further, inevitable impurity content is less than the 0.5% of Part IV gross mass in the Part IV.
Further, the Part II is In, and mass percentage content is 0.15%-0.4%.
Further, the Part II is Ag, and mass percentage content is 0.05%-0.1%.
Further, the Part II be Ag and or In, Ag mass percentage content be：0.05%-0.1%, In mass
Degree is： 0.2%-0.4%.
A kind of preparation method of complex intensifying copper alloy with high strength and high conductivity of the present invention：
A. dispensing 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 element
Alloy, fine copper, fine silver, pure indium and chromiumcopper；
B. in smelting furnace, the fine copper raw material for having weighed weight is added, covers using borax, graphite powder, and is heated to
1083~1250 DEG C melt copper；
C. by composition proportion requirement, the Cu-Cr intermediate alloys weighed are added, and coverture is covered copper liquid surface；
D. until completely melted, added by component requirements and weighed the pure Ag or pure In of weight, stand 5 until completely melted~
10min；
E. by composition design requirement, the Cu-RE intermediate alloys for having weighed weight are added（One in Cu-La, Cu-Y or Cu-Ce
Plant or a variety of）, and coverture is covered copper liquid surface；
F. until completely melted, stirred with graphite rod, and direct pouring is in the mould, and 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 blanks are at 850 DEG C -980 DEG C, after insulation 1-3h, and the technique for being more than 100% by extrusion ratio is carried out
Hot extrusion, is made alloy bar material.
Alloy bar material made from further can be that 90 ° -130 ° of mould carries out Equal Channel Angular Pressing by passage angle, squeeze
Press 5-12 passages 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 strand is by the hot extrusion technique of compression ratio more than 200% and isometrical
Complex intensifying copper alloy with high strength and high conductivity bar is made in angle extruding.
The present invention enable high temperature intermetallics crush and Dispersed precipitate in the base；The complex intensifying high-strength highly-conductive
The tensile strength of copper alloy can reach 650MPa, and conductance reaches as high as 92%, and anti-softening temperature reaches as high as 500 DEG C.
The present invention also has the advantage that：Complex intensifying copper alloy with high strength and high conductivity prepare can former alloy Preparation equipment
It is upper to carry out.For the alloy of melting in air, as long as addition coverture, suitably adjusts smelting technology（Using Cu-RE intermediate alloy,
Control intermediate alloy addition time etc.）It can be achieved.Therefore, complex intensifying copper alloy with high strength and high conductivity is prepared, input cost is low, work
Skill is simple；And the complex intensifying copper alloy with high strength and high conductivity being made is superior to existing copper alloy performance.
Embodiment
With reference to preferred embodiment, the present invention will be further described.
Embodiment 1：Raw material are fine copper, Cu-5%Cr intermediate alloys, pure Ag, Cu-5%Ce intermediate alloy, by Cu-
0.26Cr-0.05Ag-0.15Ce（Mass percent Cr is that 0.26%, Ag is that 0.05%, Ce is 0.15%, and surplus is Cu, is closed below
Golden method for expressing is identical）Component ratio carry out dispensing, 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 alloys taken, and coverture is covered copper liquid surface；C. it is estimated that and is matched somebody with somebody according to temperature and feeding quantity
Material is completely melt the time, and subsequent step is identical；After Cu-5%Cr intermediate alloys to be added are completely melt, addition has weighed weight
Pure Ag, stand 10min after pure Ag is completely melt；D. the Cu-5%Ce intermediate alloys for having weighed weight are added, and make coverture
Cover copper liquid surface；E. after Cu-5%Ce is completely melt, stirred with graphite rod, then direct pouring is in cylindrical iron
In mould, φ 195mm complex intensifying copper alloy with high strength and high conductivity strands are made.Heating strand is incubated after 1h sleeping through 500T to 850 DEG C
Formula extruder is in extrusion ratio（λ=177）Technique under be squeezed into φ 15mm rod of metal alloy；Rod of metal alloy passes through the mould that passage angle is 90 °
Tool carries out Equal Channel Angular Pressing, and φ 15mm complex intensifying copper alloy with high strength and high conductivity materials are made in 6 passages of extruding；φ 15mm complex intensifyings are high
Strong high-conductivity copper alloy material is drawn to φ 5mm copper cash through 5 passages；Solution treatment is quickly cooled down after being incubated 1.5h at 950 DEG C；φ5mm
Rod of metal alloy is drawn to φ 2.0mm rod of metal alloy through 8 passages, and after 450 DEG C are incubated 0.5h timeliness, wire rod tensile strength reaches
389MPa, conductance has reached 92.7%IACS, and anti-softening temperature is up to 450 DEG C, compared with Cu-0.26Cr-0.05Ag alloys, Cu-
0.26Cr -0.05Ag-0.015Ce complex intensifying copper alloy with high strength and high conductivity tensile strength, conductance increase, and antioxygen
The property changed obtains certain lifting.
Embodiment 2：Raw material is in fine copper, Cu-10%Cr intermediate alloys, 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 dispensing, 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.
The Cu-10%Cr intermediate alloys weighed are added after fusing, and coverture is covered copper liquid surface；C. after melting, stabilized copper liquid
Temperature adds the pure In for having weighed weight at 1150 DEG C, and 10min is stood after fusing；D. the Cu-10% La for having weighed weight are added
With Cu-10% Y intermediate alloys, and coverture is set to cover copper liquid surface；E. after melting, stirred with graphite rod, and directly
Cast in square graphite mould, φ 30mm complex intensifying copper alloy with high strength and high conductivity strands are made.Strand is at 920 DEG C, after insulation 2h
φ 18mm rod of metal alloy is squeezed into through 1500T horizontal extruders；φ 18mm rod of metal alloy is carried out by the mould that passage angle is 110 °
Equal Channel Angular Pressing, extrudes 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
920 DEG C, it is incubated after 2h, thickness is hot-rolled down to for 5mm by hot rolling technology；950 DEG C of insulation 1h solid solutions again；Sheet material is cold-rolled to after 2mm,
Through 500 DEG C of insulation 1h Ageing Treatments, sheet alloy tensile strength is up to 600MPa, and conductance has reached 80.5%, anti-softening temperature
Up to 475 DEG C.Compared with Cu-0.8Cr-0.15Zr alloys, the high-strength height of Cu-0.8Cr-0.15In-0.05La-0.05Y complex intensifyings
Conductivity copper alloy tensile strength, conductance get a promotion.
Embodiment 3：Raw material are fine copper, Cu-10%Cr intermediate alloys, pure In, pure Ag, Cu-10%La intermediate alloy.Press
Cu-0.7Cr-0.1Ag-0.3In-0.3La component ratio carries out dispensing, and melting is carried out in intermediate frequency furnace.A. in melting
Fine copper raw material is added in stove, is covered using borax, graphite powder, charcoal, and being heated to 1250 DEG C melts copper；B. after melting
The Cu-10%Cr intermediate alloys weighed are added, and coverture is covered copper liquid surface；C. after melting, stable copper liquid temperature exists
1150 DEG C add the pure In for having weighed weight, and 10min is stood until completely melted；D. the Cu-10% La for having weighed weight are added
With Cu-10% Y intermediate alloys, and coverture is set to cover copper liquid surface；E. stirred, and directly poured with graphite rod after melting
Copper alloy strand is made in cylindrical swage in casting.Strand is squeezed into φ after insulation 1h at 850 DEG C through 1500T horizontal extruders
25mm rod of metal alloy；φ 25mm rod of metal alloy carries out isometrical extruding by the mould that passage angle is 90 °, extrudes 8 passages, is combined
Strengthen copper alloy with high strength and high conductivity material；φ 25mm complex intensifying copper alloy with high strength and high conductivity materials are drawn to φ 10mm alloys through drawing process
Copper bar；Solution treatment is quickly cooled down after being incubated 1h at 950 DEG C；φ 10mm alloyed coppers bars are drawn to φ 4.5mm through drawing process and closed
Golden bar, after 450 DEG C are incubated 2h timeliness, wire rod tensile strength reaches 576MPa, and conductance 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 bars tensile strength, conduction
Rate increases.Ag content can also reduce to 0.05% in alloy proportion in the present embodiment.
Embodiment 4：Raw material are fine copper, Cu-10%Cr intermediate alloys, pure In, Cu-10%La intermediate alloy.By Cu-
1.0Cr-0.4In-0.5La component ratio carries out dispensing, and melting is carried out in intermediate frequency furnace.A. 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. add and weigh after melting
Cu-10%Cr intermediate alloys, and coverture is covered copper liquid surface；C. stable copper liquid temperature is at 1150 DEG C after melting and adds
Enter to have weighed the pure In of weight, 10min is stood after fusing；D. the Cu-10% La intermediate alloys for having weighed weight are added, and make to cover
Lid agent covers copper liquid surface；After e fusings, stirred with graphite rod, and direct pouring is in cylindrical swage, is made high-strength
High-conductivity copper alloy strand.Strand is squeezed into φ 25mm rod of metal alloy after insulation 1h at 850 DEG C through 1500T horizontal extruders；φ25mm
Rod of metal alloy carries out isometrical extruding by the mould that passage angle is 120 °, extrudes 10 passages, obtains complex intensifying high-strength high-conductivity copper
Alloy material；φ 25mm complex intensifying copper alloy with high strength and high conductivity materials are drawn to φ 7mm copper bars through drawing process；2h is incubated at 950 DEG C
Quick cooling solution treatment afterwards；φ 7mm rod of metal alloy is drawn to φ 4mm rod of metal alloy through drawing process, and 1.5h timeliness is incubated at 500 DEG C
Afterwards, wire rod tensile strength reaches 650MPa, and conductance has reached 65.8%IACS, and anti-softening temperature is up to 500 DEG C, with respective alloy
Compare, Cu-1.0Cr-0.4In -0.5La complex intensifying copper alloy with high strength and high conductivity bars tensile strength, conductance are improved.
Embodiment 5：Raw material are fine copper, Cu-5%Cr intermediate alloys, pure In, pure Ag, Cu-10%La intermediate alloy, Cu-5%
Ce intermediate alloys, Cu-5%Y intermediate alloys.By Cu-0.5Cr-0.1Ag-0.2In -0.05La-0.15Ce-0.05Y composition ratio
Example carries out dispensing, 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. the Cu-5%Cr intermediate alloys weighed are added after melting, and make coverture
Cover copper liquid surface；C. after to be melted, add the pure In for having weighed weight, it is to be melted after stand 10min；D. add and weigh
Cu-10% La, Cu-5%Ce and Cu-5% Y intermediate alloys of weight, and coverture is covered copper liquid surface；E. after to be melted,
Stirred with graphite rod, and direct pouring is in cylindrical swage, and copper alloy strand is made.Strand is at 850 DEG C, after insulation 1h
φ 30mm rod of metal alloy is squeezed into through 1500T horizontal extruders；φ 30mm rod of metal alloy is carried out by the mould that passage angle is 110 °
Isometrical extruding, extrudes 9 passages, obtains complex intensifying copper alloy with high strength and high conductivity material；φ 30mm high property copper alloy materials are through drawer
Skill is drawn to φ 12mm copper cash；Solution treatment is quickly cooled down after being incubated 1h at 950 DEG C；φ 12mm rod of metal alloy is through drawing process drawing
To φ 3.5mm rod of metal alloy, after 450 DEG C are incubated 0.75h timeliness, wire rod tensile strength reaches 468MPa, and conductance reaches
84.6%IACS, anti-softening temperature reaches 500 DEG C, compared with Cu-0.5Cr-0.1Ag-0.2In alloys, Cu-0.5Cr-0.1Ag-
0.2In-0.05La-0.15Ce-0.05Y complex intensifying copper alloy with high strength and high conductivity bars tensile strength, conductance have been lifted.
Fine copper must be used in above-described embodiment, it is inevitable in the complex intensifying copper alloy with high strength and high conductivity being made to ensure
Impurity is less than 0.5%.
With the development of modern industrial technology, rare earth element is in traditional fields such as oil, chemical industry, metallurgy with extensive.It is special
It is not that in recent years, with developing rapidly for the field of functional materials such as luminescent material, permanent-magnet material, hydrogen storage material, rare-earth usage is anxious
Play is increased.But rare earth is as Coexisting Elements, all turn into product 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
Soil resource is wasted, the low contradiction of utilization rate.Therefore, how the weight of current research is efficiently turned into using rare earth resources
Will, it is also the key of China's Rare-earth Industry sustainable development.And it is of the 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, is deformed in conjunction with vast scales such as large extrusion ratio, isometrical extruding, crushes alloy structure, high-melting-point chemical combination
The second of thing formation Dispersed precipitate is mutually present in alloy substrate, forms a kind of generated in-situ second-phase dispersion reinforcing compound
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
Invent to use for elements such as La, Y, Ce and provide effective way.
It is described above simply to illustrate that of the invention, it is understood that the invention is not limited in above example, meet
The various variants of inventive concept are within protection scope of the present invention.
Claims (9)
1. a kind of complex intensifying copper alloy with high strength and high conductivity, it is characterised in that be made up of following four part：Part I is Cr, the
Two parts be Ag and or In, Part III includes at least one of La, Ce, Y element, and Part IV is Cu and inevitably
Impurity；Each component mass percent is respectively：The Part I content is 0.26%-1.0%；The Part II content is
0.05%-0.4%；The Part III content is 0.1%-0.5%；Surplus is Part IV.
2. complex intensifying copper alloy with high strength and high conductivity according to claim 1, it is characterised in that can not in the Part IV
The impurity content avoided is less than the 0.5% of Part IV gross mass.
3. complex intensifying copper alloy with high strength and high conductivity according to claim 2, it is characterised in that the Part II 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, it is characterised in that the Part II 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, it is characterised in that the Part II is Ag
With or In, Ag mass percentage content be：0.05%-0.1%, In mass percentage content is： 0.2%-0.3%.
6. the preparation method of complex intensifying copper alloy with high strength and high conductivity according to any one of claim 1 to 5, its feature exists
In comprising the following steps：
1）Dispensing 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 added in dispensing is covered using borax, graphite powder, and it is heated to 1083~
1250 DEG C melt copper；
3）The chromiumcopper added in dispensing, and coverture is covered copper liquid surface；
4）After the chromiumcopper is completely melt, the fine silver or pure indium or fine silver, pure indium mixture added in dispensing is to be added
Dispensing be completely melt after stand 5~10min；
5）The copper and the alloy of rare earth element added in dispensing, and coverture is covered copper liquid surface；
6）After dispensing to be added is completely melt, stirred with graphite rod, then cast in the mould, alloy casting blank is made.
7. the preparation method of complex intensifying copper alloy with high strength and high conductivity according to claim 6, it is characterised in that the alloy
Strand is at 850 DEG C -980 DEG C, after insulation 1-3h, and the technique for being more than 100% by extrusion ratio carries out hot extrusion, and alloy bar material is made.
8. the preparation method of complex intensifying copper alloy with high strength and high conductivity according to claim 7, it is characterised in that the alloy
Bar can be that 90 ° -130 ° of mould carries out Equal Channel Angular Pressing by passage angle, and it is high-strength that complex intensifying is made in extruding 5-12 passages
High-conductivity copper alloy bar.
9. the preparation method of complex intensifying copper alloy with high strength and high conductivity according to claim 7, it is characterised in that the hot extrusion
The compression ratio of technique is pressed more than 200%.
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| CN112708799A (en) * | 2020-12-21 | 2021-04-27 | 江西理工大学 | High-strength conductive softening-resistant copper alloy and preparation method thereof |
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