CN101646792A - Cu-Ni-Si-based alloy for electronic material - Google Patents
Cu-Ni-Si-based alloy for electronic material Download PDFInfo
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- CN101646792A CN101646792A CN200880010189A CN200880010189A CN101646792A CN 101646792 A CN101646792 A CN 101646792A CN 200880010189 A CN200880010189 A CN 200880010189A CN 200880010189 A CN200880010189 A CN 200880010189A CN 101646792 A CN101646792 A CN 101646792A
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- 239000012776 electronic material Substances 0.000 title claims abstract description 14
- 229910045601 alloy Inorganic materials 0.000 title abstract description 33
- 239000000956 alloy Substances 0.000 title abstract description 33
- 229910017876 Cu—Ni—Si Inorganic materials 0.000 title abstract description 24
- 150000001875 compounds Chemical class 0.000 claims abstract description 44
- 229910000881 Cu alloy Inorganic materials 0.000 claims abstract description 34
- 229910019819 Cr—Si Inorganic materials 0.000 claims abstract description 30
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 24
- 239000010949 copper Substances 0.000 claims abstract description 17
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 15
- 239000012535 impurity Substances 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 6
- 239000006185 dispersion Substances 0.000 claims abstract 3
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- 229910052785 arsenic Inorganic materials 0.000 claims description 3
- 229910052790 beryllium Inorganic materials 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 7
- UREBDLICKHMUKA-CXSFZGCWSA-N dexamethasone Chemical compound C1CC2=CC(=O)C=C[C@]2(C)[C@]2(F)[C@@H]1[C@@H]1C[C@@H](C)[C@@](C(=O)CO)(O)[C@@]1(C)C[C@@H]2O UREBDLICKHMUKA-CXSFZGCWSA-N 0.000 abstract description 6
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000011651 chromium Substances 0.000 description 46
- 238000001816 cooling Methods 0.000 description 21
- 239000000243 solution Substances 0.000 description 14
- 239000006104 solid solution Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- 229910018098 Ni-Si Inorganic materials 0.000 description 11
- 229910018529 Ni—Si Inorganic materials 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 230000032683 aging Effects 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 239000012071 phase Substances 0.000 description 7
- 238000005097 cold rolling Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000007669 thermal treatment Methods 0.000 description 6
- 238000005452 bending Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000012467 final product Substances 0.000 description 5
- 229910000765 intermetallic Inorganic materials 0.000 description 5
- 229910021332 silicide Inorganic materials 0.000 description 5
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 5
- 230000035882 stress Effects 0.000 description 5
- 206010020880 Hypertrophy Diseases 0.000 description 4
- 238000005266 casting Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000004881 precipitation hardening Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 229910019974 CrSi Inorganic materials 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000000864 Auger spectrum Methods 0.000 description 2
- 229910000952 Be alloy Inorganic materials 0.000 description 2
- 229910000905 alloy phase Inorganic materials 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005098 hot rolling Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- 239000011856 silicon-based particle Substances 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910008458 Si—Cr Inorganic materials 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910021357 chromium silicide Inorganic materials 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009661 fatigue test Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000002650 habitual effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- -1 it contains Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005058 metal casting Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- 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
- C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
-
- 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
-
- 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
- C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
- H01B1/026—Alloys based on copper
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/02—Single bars, rods, wires, or strips
Landscapes
- 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)
- Lead Frames For Integrated Circuits (AREA)
- Non-Insulated Conductors (AREA)
Abstract
本发明的课题在于，提供一种通过在Cu－Ni－Si系合金中使添加Cr的效果更良好地发挥，而使特性飞跃性提高，即高强度、高导电性的科森系合金。该电子材料用铜合金含有Ni：1.0～4.5质量％、Si：0.50～1.2质量％、Cr：0.0030～0.3质量％(其中，Ni与Si的质量比为3≤Ni/Si≤5.5)，且剩余部分包含Cu及不可避免的杂质，其中，关于分散在材料中的大小为0.1μm以上～5μm以下的Cr－Si化合物而言，其分散粒子中的Cr与Si的原子浓度比为1～5，其分散密度为1×106个/mm2以下。An object of the present invention is to provide a Corson-based alloy having high strength and high conductivity by making the effect of adding Cr more favorable to Cu—Ni—Si-based alloys, thereby dramatically improving properties. The copper alloy for electronic materials contains Ni: 1.0 to 4.5% by mass, Si: 0.50 to 1.2% by mass, and Cr: 0.0030 to 0.3% by mass (wherein the mass ratio of Ni to Si is 3≤Ni/Si≤5.5), and The remainder contains Cu and unavoidable impurities, wherein, for a Cr-Si compound dispersed in the material with a size of 0.1 μm or more to 5 μm or less, the atomic concentration ratio of Cr and Si in the dispersed particles is 1 to 5 , and its dispersion density is below 1×10 6 /mm 2 .
Description
Technical field
The invention relates to a kind of precipitation hardening type copper alloy, is alloy about a kind of Cu-Ni-Si-Cr that is suitable for various electronic equipments parts especially.
Background technology
For the copper alloy for electronic material that is used for various electronic equipments parts such as lead frame, junctor, pin, terminal, rly., switch, as its fundamental characteristics, requirement can realize high strength and high conductivity (or thermal conductivity) simultaneously.In recent years, the highly integrated and miniaturization of electronic unit, thin-walled property fast development, correspondingly, to the also more raising of calling hierarchy of employed copper alloy in the electronic equipments parts.
With regard to the viewpoint of high strength and high conductivity, in recent years, as copper alloy for electronic material, the usage quantity of precipitation hardening type copper alloy increases, and is the solution strengthening type copper alloy of representative with phosphor bronze, brass etc. with its replacement in the past.In the precipitation hardening type copper alloy,, fine precipitate is disperseed equably, thereby improve the intensity of alloy, reduce the solid solution element amount in the copper simultaneously, to improve electroconductibility by the supersaturated solid solution through solution treatment is carried out ageing treatment.Therefore, can obtain mechanical properties excellences such as intensity, elasticity, and electroconductibility, the good material of thermal conductivity.
In the precipitation hardening type copper alloy, the Cu-Ni-Si series copper alloy that to be commonly referred to as section gloomy (Corson) be alloy is the typical copper alloy that has higher electroconductibility, intensity, stress relaxation properties and bendability concurrently, is one of alloy of the at present positive active development of industry.In this copper alloy, can precipitate into the raising that realizes intensity and electric conductivity in the copper matrix by making fine Ni-Si series intermetallic compound particle.
The precipitate of Ni-Si series intermetallic compound particle generally is made of stoichiometric composition, for example, has put down in writing in the patent documentation 1: the mass ratio by making Ni in the alloy and Si is near the Ni as intermetallic compound
2The quality ratio of components of Si-(nucleidic mass of nucleidic mass * 2:Si of Ni * 1) promptly, is made as Ni/Si=3～7 by the weight concentration ratio with Ni and Si, thereby obtains good electrical conductivity.
Yet, as putting down in writing in the patent documentation 1, by the approaching Ni of the mass ratio that makes Ni and Si as intermetallic compound
2The quality ratio of components of Si (nucleidic mass of nucleidic mass * 2:Si of Ni * 1) though can realize the improvement of characteristic, is found in the reality to cause electric conductivity decline to a certain degree because of excessive Si.
Therefore, it is generally acknowledged can add Cr etc. can and Si form the element of compound, make its with excessive Si chemical combination with the raising electric conductivity.Cr is one of its element, and can form the Cu-Ni-Si that contains Cr is alloy.
As being added with the Cu-Ni-Si of Cr as alloying element is alloy, can enumerate the example of record in patent documentation 2, the patent documentation 3.
In the patent documentation 2, put down in writing a kind of heat treating method of Corson alloy, it is characterized in that, to contain Ni:1.5～4.0 weight %, Si:0.35～1.0 weight %, when arbitrarily being selected from least a kind of metal 0.05～1.0 weight % among Zr, Cr, the Sn, remainder and heating (or cooling) by the Corson alloy that Cu and unavoidable impurities constitute, in 400～800 ℃ temperature province, above-mentioned Corson alloy is heated (or cooling) so that the stretching thermal deformation of above-mentioned Corson alloy is 1 * 10
-4Below.According to this method, the ingot bar in the time of can preventing thermal treatment breaks.
Put down in writing a kind of high-tensile strength copper alloy of excellent in bending workability in the patent documentation 3, it is characterized in that, contain Ni:2～5 weight %, Si:0.5～1.5 weight %, Zn:0.1～2 weight %, Mn:0.01～0.1 weight %, Cr:0.001～0.1 weight %, Al:0.001～0.15 weight %, Co:0.05～2 weight %, and will be limited in below the 15ppm as the content of the S of impurity component, remainder is made of Cu and unavoidable impurities.According to this invention, Cr strengthens the crystal boundary of ingot bar, improves the element of hot workability.In addition, if the content of Cr surpasses 0.1 weight %, then molten metal meeting oxidation, thus cause the castibility variation.Put down in writing in addition: this copper alloy is in kryptol furnace, coats charcoal and carry out the fusion casting in atmosphere.
In addition, with regard to the viewpoint of the compound of Cr and Si, can enumerate patent documentation 4.In the patent documentation 4, at containing Cr:0.1～0.25 weight %, Si:0.005～0.1 weight %, Zn:0.1～0.5 weight %, Sn:0.05～0.5 weight %, the weight ratio of Cr and Si is 3～25, and remainder is made of Cu and unavoidable impurities, and in the copper parent phase, with 1 * 10
3～5 * 10
5Individual/mm
2Individual number density exist have 0.05 μ m～the CrSi compound of 10 μ m sizes and the size of Cr compound (beyond the CrSi compound) be made as the following etching and processing of 10 μ m and the electronic equipments copper alloy of punch process excellence, put down in writing the hot processing temperature and the timeliness thermal treatment temp of ingot bar.According to this method, can use etching and processing and compacting stampability suitably.
[patent documentation 1] TOHKEMY 2001-207229 communique
No. 2862942 communique of [patent documentation 2] Japanese Patent
No. 3049137 communique of [patent documentation 3] Japanese Patent
[patent documentation 4] TOHKEMY 2005-113180 communique
Summary of the invention
The Cu-Ni-Si that promptly contains Cr for alloy system of the present invention is an alloy, meets in recent years the requirement to the tremendous raising of the material behavior of the Highgrade integration fast of electronic unit and miniaturization, thin-walled property too.
Yet, do not add Cr in the patent documentation 1, can find in the reality because of excessive N i, Si cause electric conductivity decline to a certain degree, thereby can't reach the tremendous raising of characteristic.In patent documentation 2 and the patent documentation 3, though at Cu-Ni-Si is to be added with Cr in the alloy, but the purpose of adding Cr in the patent documentation 2 is in order to the realization solution strengthening, and the purpose of patent documentation 3 is in order to improve hot workability, to find with key of the present invention to be not the relevant record of Cr-Si compound.Therefore, can't easily expect the solution of the problem that institute of the present invention desire solves by these patent documentations.
In the patent documentation 4, put down in writing by the individual number density and the size of control CrSi compound and improved etching and processing and punch process, but owing to do not add Ni, only consider that the condition of Cr-Si compound formation gets final product so need not consider the formation of Ni-Si compound, thereby can't easily expect the solution of the problem that institute of the present invention desire solves.
Therefore, problem of the present invention is, provides a kind of by being that the effect of adding Cr is brought into play more well at Cu-Ni-Si, thereby makes the tremendous raising of characteristic, and promptly the section of high strength, high conductivity is gloomy is alloy.
The inventor has carried out wholwe-hearted research for solving above-mentioned problem, found that following invention.At Cu-Ni-Si is in the alloy, setting Si with respect to Ni is excessive composition, positively separate out to realize high strength except making, make excessive Si and the Cr reacting generating compound that is added on the other hand to realize high conductionization with Ni addition corresponding N i silicide.And crucial part of the present invention is that the growth of control Cr-Si compound should become not enough with Ni bonded Si with the chemical combination hypertrophy of avoiding Cr and Si.Particularly, the inventor is conceived to the composition and size, individual number density of Cr-Si compound, finds can bring into play its effect better by the temperature and the speed of cooling of control heat treatment step.
That is, the present invention is as follows:
(1) a kind of copper alloy for electronic material, it contains, and Ni:1.0～4.5 quality %, Si:0.50～1.2 quality %, Cr:0.003～0.3 quality % (wherein, the weight ratio of Ni and Si is 3≤Ni/Si≤5.5), and remainder comprises Cu and unavoidable impurities, wherein, about the size that is dispersed in the material is the Cr-Si compound of 0.1 μ m～5 μ m, and the Cr in its dispersed particle is 1～5 with the atomic percent of Si ratio, its minute bulk density be 1 * 10
6Individual/mm
2Below.
(2) the described copper alloy for electronic material of claim 1 wherein, is the Cr-Si compound of 0.1 μ m～5 μ m about size, its minute bulk density be higher than 1 * 10
4Individual/mm
2
(3) as (1) or (2) described copper alloy for electronic material, wherein, further contain 0.05～2.0 quality % be selected among Sn and the Zn more than a kind or 2 kinds.
(4) as any described copper alloy for electronic material in (1)～(3), wherein, further contain 0.001～2.0 quality % be selected among Mg, Mn, Ag, P, As, Sb, Be, B, Ti, Zr, Al, Co and the Fe more than a kind or 2 kinds.
(5) any described copper alloy in its use (1)～(4) a kind of copper product (Shen Copper product of stretching).
(6) a kind of electronic equipments parts, any described copper alloy in its use (1)～(4).
According to the present invention, can bring into play the additive effect of alloying elements cr better, so can obtain electronic material that intensity and electric conductivity be significantly improved with the gloomy series copper alloy of section.
Embodiment
The addition of Ni and Si
Ni and Si form Ni silicide (Ni as intermetallic compound by implementing suitable thermal treatment
2Si etc.), do not make the electric conductivity variation to realize high strength.Preferred as mentioned above 3≤Ni/Si≤5.5 of the mass ratio of Si and Ni, more preferably 3.5≤Ni/Si≤5.0 near the metering composition.
Yet, even if Ni/Si has the ratio of above-mentioned scope, but if the Si addition is less than 0.5 quality %, then still can't obtain desirable strength, and if surpass 1.2 quality %, though then can realize high strength, electric conductivity can significantly reduce, further can generate liquid phase and cause hot workability to descend in segregation portion, thus not good.Therefore, be made as Si:0.5～1.2 quality % and get final product, be preferably 0.5～0.8 quality %.The Ni addition is set according to the Si addition and is got final product to satisfy above-mentioned preferred ratio, in order to average out with the Si addition, to be made as Ni:2.5～4.5 quality % and to get final product, and is preferably Ni:3.2～4.2 quality %, more preferably Ni:3.5～4.0 quality %.
The addition of Cr
At common Cu-Ni-Si is in the alloy, if Ni-Si concentration is risen, then the sum of precipitation particles can increase, and therefore can realize that intensity improves by precipitation strength.On the other hand, along with the rising of adding concentration, the solid solution capacity that is helpless to separate out also can increase, so electric conductivity can reduce, though the peak strength separated out of timeliness can rise as a result, the peak strength of electric conductivity can descend.Yet, if to above-mentioned Cu-Ni-Si is the Cr that adds 0.003～0.3 quality % in the alloy, the Cr that is preferably 0.01～0.1 quality %, then in final response, with the Cu-Ni-Si with identical Ni-Si concentration is the alloy phase ratio, electric conductivity is risen, further can improve hot workability and improve yield rate.
At Cu-Ni-Si is the composition of the particle of separating out when being added with Cr in the alloy, though will be that the precipitation particles of the bcc structure of principal constituent is separated out separately easily with Cr, also separates out easily with the compound of Si.Cr is by implementing suitable thermal treatment, can be in the copper parent phase be chromium silicide (Cr easily with the compound of Cr and Si
3Si etc.) separate out,, can make not as Ni so form in the step of alloy characteristic in combination solution treatment, cold rolling, ageing treatment
2Si etc. and the solid solution Si composition of separating out are separated out with the form of Cr-Si compound.Therefore, the reduction of the electric conductivity that causes because of solid solution Si can be suppressed, thereby the raising of electric conductivity can be realized without detriment to intensity.
At this moment, if the Si concentration in the Cr particle is low, then Si can residue in the parent phase, thereby electric conductivity can reduce, on the other hand, if the Si concentration height in the Cr particle then can reduce in order to the Si concentration of separating out the Ni-Si particle, thereby intensity can reduce.Further, when the Si concentration among the Cr was high, thick Cr-Si compound can increase, and meeting variation such as bending, fatigue strength.Further, even if the speed of cooling after the solid solution of slowing down or excessively prolongs the timeliness heat treatment time, the Cr-Si compound still can thickization and the Si concentration that forms the Ni-Si compound is reduced, thereby cause helping the Ni-Si compound deficiency strengthened.Its reason is that Si among the Cu and the velocity of diffusion of Cr are faster than Ni, so easy thickization of Cr-Si compound, thereby the speed of separating out of Cr-Si compound becomes faster than the speed of separating out of Ni-Si compound.
Therefore, if the speed of cooling of control after the solid solution, compare more high temperature, the condition of longer time, the then composition of may command Cr-Si compound, size and density with the aging condition of maximum strength to avoid becoming.Therefore, Cr concentration is made as 0.003 quality %～0.3 quality %, the atomic percent ratio of the Cr in the Cr-Si compound and Si is made as 1～5.
In addition, owing to can preferentially separate out to crystal boundary in the process of cooling of Cr when fusion is cast, so can strengthen crystal boundary, breaking when making hot-work is difficult for producing, thereby can suppress decrease in yield.That is, when fusion is cast, separate out solid solution again in solution treatment etc., and when follow-up timeliness is separated out, generate silicide to the Cr of crystal boundary.In the Si amount that common Cu-Ni-Si is in the alloy to be added, be helpless to Si solid solution still that timeliness separates out in parent phase and suppress the raising of electric conductivity, but by adding silicide forming element Cr, silicide is further separated out, thereby with Cu-Ni-Si in the past be the alloy phase ratio, can reduce solid solution Si amount, thereby electric conductivity is improved.
The size of Cr-Si compound, branch bulk density
The size of Cr-Si compound can impact bendability and fatigue strength etc., and the branch bulk density that surpasses the Cr-Si compound of 5 μ m or 0.1～5 μ m when the size of Cr-Si compound surpasses 1 * 10
6Individual/mm
2The time, bendability or fatigue strength can show variation.Further, individual number density can influence the excessive or not enough of Si concentration in the parent phase, so can't obtain required strength characteristics under the state that is dispersed with macroparticle in a large number.Therefore, divide bulk density on be limited to 1 * 10
6Individual/mm
2Below get final product, be preferably 5 * 10
5Individual/mm
2Below, more preferably 1 * 10
5Individual/mm
2Below.In addition, 1 * 10
4Individual/mm
2During following situation, by add that Cr realizes to improve effect little, so preferably surpass 1 * 10
4Individual/mm
2
Sn and Zn
Cu-Ni-Si of the present invention is in the alloy, with the total amount of 0.05～2.0 quality % add be selected among Sn and the Zn more than a kind or 2 kinds, can improve stress relaxation properties etc. thus, and can significantly not damage intensity, electric conductivity.If its addition is less than 0.05 quality %, then effect can be not enough, if surpass 2.0 quality %, then can damage the electric conductivity of manufacturings such as castibility, hot workability, goods, therefore preferred 0.05～2.0 quality % that adds.
Other adds element
By adding Mg, Mn, Ag, P, As, Sb, Be, B, Ti, Zr, Al, Co and the Fe of specified quantitative, can present various effects, and by supplying mutually, not only can improve intensity, electric conductivity, also can improve manufacturing, for example improvement of the hot workability that realizes of bendability, plating or the miniaturization by the ingot bar tissue etc., therefore, Cu-Ni-Si of the present invention is in the alloy, can according to desired characteristic suitably add total amount be in these elements below the 2.0 quality % more than a kind or 2 kinds.For this addition, if the total amount of these elements is less than 0.001 quality %, then can't obtain required effect, and if surpass 2.0 quality %, then the variation of the reduction of electric conductivity or manufacturing can become apparent, therefore total amount preferably is made as 0.001～2.0 quality %, more preferably is made as 0.01～1.0 quality %.
And, can be not that the characteristic of alloy causes in the dysgenic scope to Cu-Ni-Si of the present invention, also can add in this specification sheets the element of concrete record.
Then manufacture method of the present invention is described.Cu-Ni-Si of the present invention is an alloy, except that the condition of the solution treatment of controlling Ni-Si compound, Cr-Si compound, ageing treatment, can be that the habitual manufacture method of alloy is made by Cu-Ni-Si, those skilled in the art should be according to forming and the suitableeest method for making of desired characteristic selection, so need not specify, below will be to describing in order to illustrative general manufacture method.
At first, use the air melting stove,, obtain the molten metal of required composition the fusing of raw materials such as electrolytic copper, Ni, Si, Cr.Then, this molten metal casting is become ingot casting.Carry out hot rolling then, and carry out cold rolling and thermal treatment repeatedly, to be finish-machined to bar or paper tinsel with desired thickness and characteristic.Thermal treatment exists solution treatment and ageing treatment.In the solution treatment, heat, make Ni-Si based compound or the solid solution of Cr-Si based compound in the Cu parent phase, make Cu parent phase recrystallization simultaneously with 700～1000 ℃ high temperature.Solution treatment is also undertaken by hot rolling sometimes.
In this solution treatment, speed of cooling and Heating temperature are all important.Speed of cooling after control was not heated in the past so tank is set to carry out water-cooled in outlet one side (exit side) of process furnace, perhaps adopts the air cooling under the atmospheric environment atmosphere.At this moment, speed of cooling is easily because of the setting change of Heating temperature, speed of cooling in the past below 1 ℃/second～range changing more than 10 ℃/second.Therefore, be difficult to carry out control as the characteristic of the alloy system of example of the present invention.
Speed of cooling is preferably 1 ℃/second～10 ℃/second scope.In the ageing treatment, in 350～550 ℃ temperature range, carry out the heating more than the 1h, be typically the heating of carrying out 3～24h, the Ni of solid solution in the solution treatment and the compound of Si and the compound of Cr and Si are separated out with the form of minuteness particle.By this ageing treatment, intensity and electric conductivity can improve.For obtaining higher intensity, carry out cold rolling sometimes before timeliness and/or after the timeliness.In addition, when after timeliness, carrying out after cold rolling, carrying out stress relief annealing (low temperature annealing, low-temperature annealing) sometimes when cold rolling.
Cu-Ni-Si series copper alloy of the present invention in one embodiment, can make 0.2% yield-point is more than the 780MPa and electric conductivity is more than the 45%IACS, further can make 0.2% yield-point is more than the 860MPa and electric conductivity is more than the 43%IACS, and further can make 0.2% yield-point is more than the 890MPa and electric conductivity is more than the 40%IACS.
Cu-Ni-Si of the present invention is that alloy can be processed into the various copper product of stretching, for example plate, bar, pipe, rod and line, further, the Cu-Ni-Si series copper alloy of the present invention lead frame, junctor, pin, terminal, rly., switch, secondary cell that can be used for requiring simultaneously high strength and high conductivity (or thermal conductivity) is with electronic equipments parts such as foils.
[embodiment]
Below concrete example of the present invention is described, but these embodiment provide in order further to understand the present invention and advantage thereof, and are not intended to be used for limit invention.
Used copper alloy in the embodiments of the invention has the composition that suitably is added with Sn, Zn, Mg, Mn, Co and Ag in the copper alloy of the some variations of content that make Ni, Si and Cr as shown in table 1.In addition, in the comparative example used copper alloy to be respectively the Cu-Ni-Si with extraneous parameter of the present invention be alloy.
Utilize high frequency melting furnace, the copper alloy that the various one-tenth of record are grouped in the his-and-hers watches 1 under 1300 ℃ temperature carries out melting, is cast as the ingot casting that thickness is 30mm.Then, after heating under 1000 ℃ the temperature, being hot-rolled down to thickness of slab is 10mm, cools off fast again with this ingot casting.For removing the scale (scale) on surface, implementing surfacing to thickness is 8mm, subsequently by the cold rolling plate of making thickness 0.2mm.Then, in Ar compression ring border, implement solution treatment,, after under 800～900 ℃ temperature, keeping 120 seconds, change speed of cooling and be cooled to room temperature according to the addition of Ni and Cr.Speed of cooling is controlled by the gas flow that changes the sample winding-up after heating, and instrumentation is cooled to time till 400 ℃ as speed of cooling from the temperature that is up to of sample.The speed of furnace cooling during blowing gas is not 5 ℃/s, and further, as the example that delays speed of cooling, the speed of cooling when one side control is added thermal output and simultaneously lowers the temperature is made as 1 ℃/s.Then, be cold-rolled to 0.1mm, last, according to addition, under 400～550 ℃ temperature, in inert gas environment, respectively implement 1～12 hour ageing treatment, produce sample.
Each alloy that obtains is in this way carried out the evaluating characteristics of intensity and electric conductivity.For intensity, roll tension test on the parallel direction to measure 0.2% yield-point (YS; And electric conductivity (EC MPa); %IACS) then measure and obtain by the volume specific resistance that utilizes Wheatstone bridge.
W font mould is used in the evaluation of bendability, at the ratio of sample thickness of slab and bending radius is to carry out 90 ° of bending machining under 1 the condition.In the evaluation,, will not observe fissured situation and be judged as practical upward no problem, and mark zero with observation by light microscope bending machining portion surface, will observe fissured situation to be labeled as *.Fatigue test is according to JIS Z 2273, applies repeated stress, and the number of occurrence of obtaining till fracture is 10
7Inferior stress (MPa).
The observation of Cr-Si compound is after the plate face to material carries out electropolishing, observes by FE-AES, in many places be with size particle more than the 0.1 μ m as object, utilize Ar
+Carry out sputter to remove the element (C, O) that in fact is adsorbed in its top layer, measure the auger spectrum (Augerspectrum) of each particle then, when detected element is carried out the weight concentration conversion by the sensitivity coefficient method as the semidefinite value, be object with the particle that detects Cr and Si." composition " of Cr-Si compound, " size ", " branch bulk density " are defined as FE-AES and observe down mean number in the average composition that the size that is drawn is the Cr-Si particle of 0.1～5 μ m, minimum circular diameter, each field of view is analyzed in many places.
The results are shown in table 1 and table 2.
In the example 1～25, by suitable speed of cooling, the branch bulk density of Cr-Si compound is 1 * 10
6Below, and Cr/Si is 1～5 scope, so obtain good characteristic.
On the other hand, in the comparative example 1～3, because speed of cooling is slow, thus Cr-Si compound hypertrophy, thus full intensity can't be obtained, and bendability is also poor.
In the comparative example 4,5 because speed of cooling is fast, so the Cr-Si compound do not grow, excessive Si solid solution in alloy, intensity and electric conductivity variation.In the comparative example 6,7, because the aging temp height, so Cr-Si compound hypertrophy, thus full intensity can't be obtained, and bendability is also poor.In the comparative example 8,9, because the excessive concentration of Cr, so Cr-Si compound hypertrophy, thus full intensity can't be obtained, and bendability is also poor.
Claims (6)
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| JP094441/2007 | 2007-03-30 | ||
| JP2007094441 | 2007-03-30 | ||
| PCT/JP2008/056138 WO2008123433A1 (en) | 2007-03-30 | 2008-03-28 | Cu-ni-si-based alloy for electronic material |
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| CN101646792B CN101646792B (en) | 2012-02-22 |
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| US (1) | US20100086435A1 (en) |
| EP (1) | EP2154257B1 (en) |
| JP (1) | JP4418028B2 (en) |
| KR (1) | KR101211984B1 (en) |
| CN (1) | CN101646792B (en) |
| TW (1) | TWI395824B (en) |
| WO (1) | WO2008123433A1 (en) |
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- 2008-03-28 EP EP08739256.9A patent/EP2154257B1/en active Active
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Also Published As
| Publication number | Publication date |
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| EP2154257A1 (en) | 2010-02-17 |
| WO2008123433A1 (en) | 2008-10-16 |
| EP2154257A4 (en) | 2012-01-11 |
| CN101646792B (en) | 2012-02-22 |
| US20100086435A1 (en) | 2010-04-08 |
| EP2154257B1 (en) | 2016-10-05 |
| KR101211984B1 (en) | 2012-12-13 |
| TWI395824B (en) | 2013-05-11 |
| TW200902732A (en) | 2009-01-16 |
| JPWO2008123433A1 (en) | 2010-07-15 |
| KR20090123017A (en) | 2009-12-01 |
| JP4418028B2 (en) | 2010-02-17 |
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