CN101512026B - Cu-ni-si alloy - Google Patents
Cu-ni-si alloy Download PDFInfo
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- CN101512026B CN101512026B CN2007800326042A CN200780032604A CN101512026B CN 101512026 B CN101512026 B CN 101512026B CN 2007800326042 A CN2007800326042 A CN 2007800326042A CN 200780032604 A CN200780032604 A CN 200780032604A CN 101512026 B CN101512026 B CN 101512026B
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Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
- H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
- H01L23/495—Lead-frames or other flat leads
- H01L23/49579—Lead-frames or other flat leads characterised by the materials of the lead frames or layers thereon
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/04—Alloys based on copper with zinc as the next major constituent
-
- 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
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/18—Hardening; Quenching with or without subsequent tempering
- C21D1/25—Hardening, combined with annealing between 300 degrees Celsius and 600 degrees Celsius, i.e. heat refining ("Vergüten")
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
Abstract
A Cu-Ni-Si alloy for electronic material that with the addition of other alloy elements minimized, simultaneously exhibits enhanced electric conductivity, strength, flexure and stress relaxation performance. There is provided a Cu-Ni-Si alloy comprising 1.2 to 3.5 mass% Ni, Si in a concentration (mass%) of 1/6 to 1/4 of the Ni concentration (mass%) and the balance Cu and impurities whose total amount is 0.05 mass% or less, the Cu-Ni-Si alloy having its configuration of crystal grains and width of nonprecipitation zone regulated so as to fall within appropriate ranges through controlling of solution treatment conditions, aging treatment conditions and degree of roll working. Thus, there can be provided a copper alloy strip of 55 to 62% IACS electric conductivity and 550 to 700 MPa tensile strength, being free from cracking at 180 DEG contact bending and exhibiting a stress relaxation ratio, as measured upon heating at 150 DEG C for 1000 hr, of 30% or below.
Description
Technical field
The present invention relates to a kind ofly be applicable to that the Cu-Ni-Si of various electronic units such as lead frame, junctor, plug, terminal, rly., switch is an alloy.The invention still further relates to the manufacture method of this alloy.In addition, the invention still further relates to the electronic unit that utilizes this alloy.
Background technology
As middle copper alloy for electronic material that uses such as electronic units, require to satisfy simultaneously high strength and high conductivity (or thermal conductivity) as essential characteristic.In addition, also require to have plating characteristic (あ つ I characteristic), solder wettabilities such as bendability, proof stress relaxation property, thermotolerance, heat-resisting spalling, etching and processing, stamping-out, erosion resistance etc.
Under such background, in recent years as copper alloy for electronic material, replace in the past be the solution strengthening type copper alloy of representative with phosphor bronze, brass etc., increase at the consumption of the timeliness curing copper alloy that is better than solution strengthening type copper alloy aspect intensity, specific conductivity, the stress relaxation characteristics.For timeliness curing copper alloy, carry out ageing treatment by supersaturated solid solution, thereby make fine precipitate homodisperse the process solution treatment, alloy strength increases, and the solid solution element amount in the copper reduces simultaneously, and electroconductibility improves.
In timeliness curing copper alloy, Cu-Ni-Si is that alloy is the copper alloy with high electrical conductivity and intensity, in the industry cycle is one of alloy of developing just actively at present.In this Albatra metal-, owing to separate out fine Ni-Si series intermetallic compound particle in the copper matrix, so intensity and specific conductivity raising.
For example, the spy to open and disclose the Cu-Ni-Si that has high strength and bendability concurrently in the 2002-266042 communique (patent documentation 1) be alloy.And the ageing treatment front and back that disclose in the manufacturing processed of this copper alloy should make cold rolling working modulus sum below 40%; Should select to make the particle diameter of recrystallization grain in solution treatment is the heating condition of 5～15 μ m; Ageing treatment should be carried out under 440～500 ℃ 30～300 minutes.
The concrete disclosed copper alloy of the document does not crack under the W bending, and tensile strength is 520MPa when specific conductivity is up to 53%IACS, and specific conductivity is 46%IACS (with reference to the table 2 of embodiment) when tensile strength is up to 710MPa.
The spy opens to have put down in writing in the 2001-207229 communique (patent documentation 2) and attempts developing not only have intensity, electroconductibility, and the Cu-Ni-Si that also has excellent in vending workability is the example of alloy.According to document record, the weight ratio by making Ni in the alloy and Si is near intermetallic compound Ni
2The concentration of Si promptly, is Ni/Si=3～7 by the weight ratio that makes Ni and Si, can obtain good electrical conductivity.Also to have put down in writing to Cu-Ni-Si be to carry out the composition adjustment more than adding among Fe and/or Zr, Cr, Ti, the Mo any one in the alloy to the document in addition, make it contain Mg, Zn, Sn, Al, P, Mn, Ag or Be more as required, thereby a kind of starting material that are suitable as copper alloy for electronic material can be provided.
Concrete disclosed copper alloy does not crack under 90 ° of bendings (not being 180 ° of bendings) in the document, and tensile strength is 640MPa when specific conductivity is up to 56%IACS, and specific conductivity is 44%IACS (with reference to the table 1 of embodiment) when tensile strength is up to 698MPa.In addition, among the embodiment of the document before ageing treatment and the cold rolling working modulus of carrying out afterwards reach 60% and 37.5% respectively (adding up to 97.5%).
The spy opens clear 61-194158 communique (patent documentation 3) and discloses the above specific conductivity of a kind of 60%IACS of having, high strength, and rigidity intensity and repeated flex excellence, and the Cu-Ni-Si with high heat resistance is an alloy.Put down in writing according to the document, as adding element, contain Mn:0.02～1.0wt%, Zn:0.1～5.0wt%, Mg:0.001～0.01wt%, and should further contain 0.001～0.01wt%, be selected from one or more the metal among Cr, Ti, the Zr.
Tensile strength 51.0kgf/mm is disclosed among the embodiment of the document
2(500MPa), the data of specific conductivity 67.0%IACS, and tensile strength 62.0kgf/mm
2(593MPa), (with reference to table 2) such as data of specific conductivity 64.0%IACS.
This Cu-Ni-Si is that alloy is cold-rolled to 0.25mm from finishing hot rolled 10mm, does not carry out full annealed midway.Infer that it is 97.5% that rolling working modulus at this moment significantly increases, bendability extremely worsens.In addition, in cold rolling process and after cold rolling, carry out 450 ℃ annealing, and be in the situation of alloy, do not carry out recrystallization though under this temperature, carry out evolution reaction at Cu-Ni-Si.
It is alloy that Te Kaiping 11-222641 communique (patent documentation 4) discloses a kind of Cu-Ni-Si that has excellent mechanical characteristics, conductivity, stress relaxation characteristics and bendability concurrently, it has added Sn, the Mg of specified quantitative or has further added Zn, limited S, O content, and made grain size number surpass 1 μ m and below 25 μ m.And, put down in writing in the document, for grain size number being adjusted to above-mentioned scope, should handle carrying out recrystallization after the cold working, under 700～920 ℃.
Disclose among the embodiment of the document that can to carry out the fit Cu-Ni-Si of crooked (the bent げ of adherence) of 180 degree under tensile strength is the condition of 610～710Mpa be alloy.The specific conductivity of this alloy is 31～42%IACS, and the stress relaxation rate when carrying out heating in 1000 hours for 150 ℃ is 14～22%.
It is alloy that No. 3520034 communique of patent (patent documentation 5) discloses a kind of Cu-Ni-Si, it has following feature: Mg, the Sn, Zn, the S that contain specified quantitative, the crystallization particle diameter is above 0.001mm and below 0.025mm, and the major diameter of the crystal grain on the cross section that will be parallel with final plastic working direction is made as a, to be made as b with the major diameter of crystal grain on the rectangular cross section of final plastic working direction, the ratio (a/b) of a and b is more than 0.8 below 1.5; This Cu-Ni-Si is that alloy has excellent bendability and stress relaxation characteristics.
Disclosing tensile strength among the embodiment of the document is that 685～710MPa, specific conductivity are 32～40%IACS, and can carry out the crooked Cu-Ni-Si of 180 degree applyings is alloy.
In addition, as recently being the research of alloy characteristic improvement about Cu-Ni-Si, non-patent literature 1 and 2 etc. has been reported and has been conceived to not have the technology that band (PFZ) improves intensity and bendability of separating out.Do not have to separate out to be with and be meant that the crystal boundary response type during by timeliness is separated out (discontinuous separating out) and is formed near crystal boundary belt-like zone, that do not have fine precipitate to exist.Owing to do not have a fine precipitate that helps intensity,, cause the decline of tensile strength and bendability in case therefore apply external force then this nothing is separated out band and can viscous deformation be taken place preferentially.
According to non-patent literature 1, it is effective that the interpolation of P, Sn and two sections timeliness are separated out band to the inhibition nothing.About the latter, put down in writing by before the common timeliness of 450 ℃ * 16h, increasing by the preliminary aging of 250 ℃ * 48h, be largely increased thereby destroy stretching and intensity.Specifically, the Cu-Ni-Si that discloses tensile strength 770～900MPa, specific conductivity 34～36%IACS is an alloy.
According to non-patent literature 2 records, along with the increase of aging time, the width of PFZ also increases.
[patent documentation 1] TOHKEMY 2002-266042 communique
[patent documentation 2] TOHKEMY 2001-207229 communique
[patent documentation 3] Japanese kokai publication sho 61-194158 communique
[patent documentation 4] Japanese kokai publication hei 11-222641 communique
No. 3520034 communique of [patent documentation 5] Japanese Patent
[non-patent literature 1] crosses limit thousand and seeks, and the palace waist wins, western small island literary composition, bright in front of the door one: " improvement of the mechanical characteristics of Cu-4.0 quality %Ni-0.95 quality %Si-0.02 quality %P alloy ", copper and copper alloy, copper association is stretched by Japan, 2006, the 45th volume, No. 1, P16-22
I is bright for [non-patent literature 2] her rattan, and Suzuki person of outstanding talent is bright, ▲ と う
Celebrating is flat, the good discipline in Yamamoto, and she stretches English by rattan, " Ni, Si amount and aging condition are the influence of the bendability of sheet alloy to Cu-Ni-Si ", and copper and copper alloy, copper association is stretched by Japan, and 2006, the 45th volume, No. 1, P71-75
Summary of the invention
As mentioned above, be that the characteristic of alloy is improved and to have been developed the whole bag of tricks about Cu-Ni-Si, but all be up to now to seek the method that characteristic is improved by adding other alloying element.But, consider recirculation problem in recent years, thereby require to reduce the interpolation element in the alloy gradually.
In addition, along with the development to highly integrated, miniaturization and slimming of electronic unit in recent years, Cu-Ni-Si is that the specific conductivity of alloy need improve.This is because owing to the sectional area minimizing at energising position, and cause the temperature rising of the parts that caused by joule heating to increase.
ΔT＝J
2·L
2/(2·E·H·S
2)
Wherein, Δ T is that temperature rises, and J is an electric current, and E is a specific conductivity, and H is a thermal conductivity, and L and S are respectively the length and the sectional areas of conducting parts.H and E are linear, so temperature rises and square being inversely proportional to of specific conductivity.
On the other hand, if the sectional area of parts reduces, then its elastic force in purposes such as junctor will reduce, thereby the characteristics relevant with elastic force such as tensile strength, proof stress slackness also come into one's own.Therefore, be difficult to allow specific conductivity not improve and tensile strength and the decline of proof stress slackness.Same, along with the miniaturization of parts, it is complicated that the processing of parts becomes, and therefore also is difficult to allow bendability to descend.
Therefore, problem of the present invention provides does not a kind ofly add other alloying element as far as possible, and has the Cu-ni-si-based alloy for electronic material of improved specific conductivity, intensity, bendability and stress relaxation characteristics concurrently.
In addition, another problem of the present invention provides the manufacture method that this Cu-Ni-Si is an alloy.
In addition, another problem of the present invention to provide and use this Cu-Ni-Si be the copper alloy calendered goods (Shen Copper product of alloy) and electronic unit.
The inventor etc. further investigate for solving above-mentioned problem, found that, at the Cu-Ni-Si that suppresses impurity as far as possible is in the manufacturing processed of alloy, by to the heat-up rate of ageing treatment, material be up to Da Wendu and aging time is given special conditions, and further suitably regulate rolling working modulus before and after solution treatment condition and the ageing treatment, thereby the Cu-Ni-Si that can obtain to have concurrently excellent specific conductivity, tensile strength, proof stress relaxation property and bendability is an alloy.
The Cu-Ni-Si that one aspect of the invention is that finishes based on above-mentioned discovery is an alloy, it is characterized in that, the Ni, concentration (quality %) that contains 1.2～3.5 quality % is 1/6～1/4 Si of Ni concentration (quality %), rest part is that impurity below the 0.05 quality % is formed by Cu and total amount, and has following characteristic concurrently:
(A) specific conductivity: 55～62%IACS
(B) tensile strength: 550～700MPa
(C) bendability: do not crack under 180 degree applyings are crooked
(D) proof stress slackness: the stress relaxation rate of heating in the time of 1000 hours is below 30% under 150 ℃.
In addition, if in above-mentioned alloy, add Zn then specific conductivity can have reduction slightly, but the effect of heat-resisting spalling of improving Sn coating (Sn あ つ I) is very big, and therefore especially when the heat-resisting spalling of the good Sn coating of needs, can add with 0.5 quality % in above-mentioned alloy be the Zn of the upper limit.
Therefore, another aspect of the present invention is that Cu-Ni-Si is an alloy, it is characterized in that, the Ni, concentration (quality %) that contains 1.2～3.5 quality % is 1/6～1/4 the following Zn of Si, 0.5 quality % of Ni concentration (quality %), rest part is that impurity below the 0.05 quality % is formed by Cu and total amount, and has following characteristic concurrently:
(A) specific conductivity: 55～62%IACS
(B) tensile strength: 550～700MPa
(C) bendability: do not crack under 180 degree applyings are crooked
(D) proof stress slackness: the stress relaxation rate of heating in the time of 1000 hours is below 30% under 150 ℃
(E) heat-resisting spalling: after the heat-resisting spalling test of Sn coating, do not find plating exfoliation.
In addition, in an embodiment of copper alloy of the present invention, in the metallographic in the cross section parallel, will be made as a with the median size of the orthogonal direction of rolling direction of crystal grain with rolling surface, when the median size of direction that will be parallel with rolling direction is made as b,
a＝1～15μm，b/a＝1.05～1.67
And the width average that the nothing in the metallographic is separated out band is 10～100nm.
In addition, also aspect of the present invention is for using the copper alloy calendered goods of above-mentioned copper alloy.
In addition, another aspect of the present invention for the lead frame that uses above-mentioned copper alloy, junctor, plug, terminal, rly., switch, secondary cell with electronic units such as foils.
In addition, another aspect of the present invention is that above-mentioned Cu-Ni-Si is the manufacture method of alloy, and this method comprises carries out solution treatment, cold rolling, ageing treatment, cold rolling operation successively, wherein, carries out each operation under the following conditions:
(solution treatment) adjusts to the average crystallite particle diameter scope of 1～15 μ m.
(ageing treatment) makes the top temperature of the material in the thermal treatment is below 550 ℃, and material was kept in 450～550 ℃ temperature range 5～15 hours.In addition, in temperature-rise period, make the average heating speed of the material in each temperature ranges of 200～250 ℃, 250～300 ℃ and 300～350 ℃ be 50 ℃/below the h.
(cold rolling) makes before the timeliness that the rolling working modulus in cold rolling adds up to 5～40% after the rolling working modulus in cold rolling and timeliness.
According to the present invention, a kind of alloying element that does not add except that Ni and Si can be provided, perhaps do not add the alloying element except that Ni, Si and Zn, and to have the Cu-Ni-Si that the electronic material of improved specific conductivity, intensity, bendability and stress relaxation characteristics uses concurrently be alloy.
Description of drawings
[Fig. 1] is the explanatory view of stress relaxation test method.
[Fig. 2] is the hygrogram ((a) and (b) be example, (c) be conventional example) of ageing treatment.
Embodiment
Alloy composition
In copper alloy of the present invention, Si concentration (quality %) is 1/6～1/4 scope of Ni concentration (quality %).This is because if Si exceeds this scope, then can't obtain good specific conductivity (for example more than the 55%IACS).The scope of Si is preferably 1/5.5～1/4.2 of Ni.The scope of Si more preferably Ni 1/5.2～1/4.5.
In addition, Ni is 1.2～3.5 quality %.If being lower than 1.2 quality %, Ni can't obtain good tensile (for example more than the 550MPa)., Ni can't obtain excellent in vending workability (for example cracking under the 180 degree applying bendings) if surpassing 3.5 quality %.The concentration of Ni is preferably 1.4～2.5 quality %, and the scope of Ni is 1.5～2.0 quality % more preferably.
It is that the mode of adding various alloying elements in the alloy is carried out the improvement of alloy characteristic that prior art mainly adopts to Cu-Ni-Si, and will get rid of other alloying element (being also referred to as impurity in the present invention) according to purpose of the present invention as far as possible.And also known, contain in the situation of other alloying element having a mind to, have the tendency that can not get sufficient specific conductivity, the Cu-Ni-Si that also is difficult to obtain to have concurrently intensity, specific conductivity, bendability and stress relaxation characteristics is an alloy.Thereby total impurities of the present invention is controlled at below the 0.05 quality %, below the preferred 0.02 quality %, more preferably below the 0.01 quality %.Therefore, preferred implementation of the present invention is, is the alloying element that does not exist except unavoidable impurities in the alloy except that Ni and Si at Cu-Ni-Si.
But because Zn is smaller to the influence of specific conductivity, it is big that the heat-resisting spalling of Sn coating is improved effect, therefore especially when the heat-resisting spalling of the good Sn coating of needs, also can add Zn.Per 0.1 quality %Zn causes specific conductivity to reduce about 0.5%IACS.But,, when Zn less than 0.05 quality %, the heat-resisting spalling of Sn coating is not almost improved effect if Zn surpasses 0.5 quality % then is difficult to obtain sufficient specific conductivity (for example more than the 55%IACS).Therefore, the concentration of Zn is preferably 0.05～0.5 quality %, and the concentration of Zn is 0.1～0.3 quality % more preferably.
Metallographic
In the metallographic in the cross section parallel with rolling surface, will be made as a with the median size of the rolling direction orthogonal directions of crystal grain, when the median size of direction that will be parallel with rolling direction is made as b,
a＝1～15μm，b/a＝1.05～1.67。
If a less than 1 μ m then can't obtain good stress relaxation rate (for example surpass 30%).In addition, the Ni that separates out during timeliness
2The Si deficiency can't obtain good tensile.On the other hand, if a surpasses 15 μ m, then can't obtain excellent in vending workability (for example cracking under the 180 degree applying bendings).Preferred a=2～10 μ m, when paying attention to bendability, more preferably a=2～5 μ m, when paying attention to intensity and proof stress relaxation property, more preferably a=5～10 μ m.
If b/a less than 1.05 then can't obtain good tensile (for example being lower than 550MPa).On the other hand, if b/a surpasses 1.67 then can't obtain good bendability (for example 180 degree are fitted and cracked under crooked).Preferred b/a=1.10～1.40, more preferably b/a=1.20～1.30.
In addition, in the metallographic in the cross section parallel with rolling surface, the width average that the nothing in the metallographic is separated out band is 10～100nm.Do not increase if there is the width of separating out band, then can't obtain sufficient bendability, proof stress slackness and tensile strength.Do not surpass 100nm if there is the width of separating out band, then can't obtain good bendability (for example cracking under the 180 degree applying bendings), can't obtain good stress relaxation rate (for example surpassing 30%) yet.It is the smaller the better not have the width of separating out band, if but it is suppressed to not enough 10nm, also can't obtain good specific conductivity (for example more than the 55%IACS) even then carry out the distinctive ageing treatment of the present invention of aftermentioned explanation.Therefore, for balance well and improve specific conductivity, bendability and proof stress slackness, do not have the width average of separating out band and be preferably 20～90nm, do not have the width average 30～80nm more preferably that separates out band.
In addition, also separate out by adjusting above-mentioned metallographic, have nm size Ni-Si series intermetallic compound particle diameter, the fine particle that helps to improve intensity with high frequency.
Alloy characteristic
In the embodiment of copper alloy of the present invention, have following characteristic concurrently:
(A) specific conductivity: 55～62%IACS
(B) tensile strength: 550～700MPa
(C) bendability: do not crack under 180 degree applyings are crooked
(D) proof stress slackness: the stress relaxation rate of heating in the time of 1000 hours is (being 15～30% in the example) below 30% under 150 ℃
In the preferred implementation of copper alloy of the present invention, have following characteristic concurrently:
(A) specific conductivity: 56～60%IACS
(B) tensile strength: 600～660MPa
(C) bendability: do not crack under 180 degree applyings are crooked
(D) proof stress slackness: the stress relaxation rate of heating in the time of 1000 hours is (being 15～25% in the example) below 25% under 150 ℃
In another preferred implementation of copper alloy of the present invention, have following characteristic concurrently:
(A) specific conductivity: 60～62%IACS
(B) tensile strength: 600～610MPa
(C) bendability: do not crack under 180 degree applyings are crooked
(D) proof stress slackness: the stress relaxation rate of heating in the time of 1000 hours is (being 20～25% in the example) below 25% under 150 ℃
In copper alloy of the present invention, added in another preferred implementation of Zn, can realize following characteristic simultaneously:
(A) specific conductivity: 55～62%IACS
(B) tensile strength: 550～700MPa
(C) bendability: do not crack under 180 degree applyings are crooked
(D) proof stress slackness: the stress relaxation rate of heating in the time of 1000 hours is (being 15～30% in the example) below 30% under 150 ℃
(E) heat-resisting spalling: after the heat-resisting spalling test of Sn coating, do not find plating exfoliation
In copper alloy of the present invention, added in the preferred implementation of Zn, can realize following characteristic simultaneously:
(A) specific conductivity: 56～60%IACS
(B) tensile strength: 600～660MPa
(C) bendability: do not crack under 180 degree applyings are crooked
(D) proof stress slackness: the stress relaxation rate of heating in the time of 1000 hours is (being 15～25% in the example) below 25% under 150 ℃
(E) heat-resisting spalling: after the heat-resisting spalling test of Sn coating, do not find plating exfoliation
In copper alloy of the present invention, added in another preferred implementation of Zn, can realize following characteristic simultaneously:
(A) specific conductivity: 56～60%IACS
(B) tensile strength: 640～660MPa
(C) bendability: do not crack under 180 degree applyings are crooked
(D) proof stress slackness: the stress relaxation rate of heating in the time of 1000 hours is (being 15～20% in the example) below 20% under 150 ℃
(E) heat-resisting spalling: after the heat-resisting spalling test of Sn coating, do not find plating exfoliation
In addition, to put the method for the Sn plating exfoliation of evaluation test sheet below above-mentioned " the heat-resisting spalling test of Sn coating " is meant and adopts.
The Sn coating of the Cu of plating thickness 0.3 μ m plating bottom and thickness 1 μ m on test film, and 300 ℃ down heating 20 seconds handle as soft heat.
Then, carry out 90 ° of bendings and crooked (the bent げ of recovery of bending radius 0.5mm along Good Way (GW, bending axis is the direction of vertical with rolling direction (craspedodrome))
) (once carry out 90 ° of bendings back and forth), then perimembranous surface Continuous pressing device for stereo-pattern (plating masking tape in crooked; Base material: polyester; Bounding force: 3.49N/cm (peeling off for 180 °); Example: Sumitomo 3M makes #851A) again it is torn.
Whether observe crooked interior perimembranous surface with opticmicroscope (20 times of multiplying powers), estimating has plating exfoliation.
Known to the inventor, have same composition with copper alloy of the present invention, and the example that can balance reaches characteristic (being specific conductivity, intensity, bendability and stress relaxation characteristics) level of the present invention, that be equal to mutually with copper alloy of the present invention does not well exist also so far.
Manufacture method
Cu-Ni-Si is that the conventional manufacturing process of alloy is, at first uses the atmosphere calciner, under the charcoal lining, raw materials such as electrolytic copper, Ni, Si is fused, and this fused solution is cast as ingot casting.Afterwards, carry out hot rolling, and carry out cold rolling and thermal treatment repeatedly, make bar and paper tinsel (for example thickness of 0.08～0.64mm) with target thickness and characteristic.Thermal treatment comprises solution treatment and ageing treatment.In the solution treatment, heat under about 700～about 1000 ℃ high temperature, the thick Ni-Si based compound solid solution in Cu mother metal (female ground) that produces when making casting etc. makes Cu mother metal recrystallization simultaneously.Sometimes also in hot rolling, carry out solution treatment simultaneously.In the ageing treatment, more than about 350～about 550 ℃ temperature range internal heating 1h, the Ni of solid solution in the solution treatment and the compound of Si are separated out as minuteness particle.Intensity and specific conductivity rise under this ageing treatment.In order to obtain higher intensity, carry out cold rolling sometimes before timeliness and/or after the timeliness.And,, after cold rolling, carry out stress relief annealing (askew getting burnt Blunt) (low-temperature annealing) sometimes when after timeliness, carrying out when cold rolling.
In ageing treatment, if Heating temperature is certain changed heat-up time, then specific conductivity is dull in time rises.On the other hand, tensile strength reaches maximum value within a certain period of time usually, reduces in time afterwards.When making temperature variation even the time is certain, specific conductivity also can rise and dull the rising with temperature, and tensile strength descends after demonstrating maximum value.Tensile strength is reached the timeliness of carrying out under the peaked condition is called the peak timeliness, and with tensile strength in time or the timeliness of carrying out in the zone that descends with temperature be called overaging.
In order to improve Cu-Ni-Si is that the specific conductivity of alloy can be carried out overaging.That is,, just can obtain good specific conductivity (for example about 60%IACS) with comparalive ease as long as select suitable aging time and temperature.But not only tensile strength decline (for example dropping to about 500MPa), and proof stress relaxation property and bendability also can deteriorations.Afterwards, if carry out the cold rolling of high working modulus then tensile strength returns to about 600MPa, but can be because of machining deformation cause the remarkable deterioration of bendability, and the proof stress relaxation property also can't improve.Disclosed existing high conductivity Cu-Ni-Si such as patent documentation 3 are that alloy substantially all is a technology of having used this overaging.
The inventor has carried out research repeatedly for balance improves specific conductivity, intensity, bendability and proof stress relaxation property well, found that, by being in the manufacturing processed of alloy at the Cu-Ni-Si that suppresses impurity as far as possible, to the heat-up rate of ageing treatment, material be up to Da Wendu and aging time is given specific conditions, and further suitably regulate rolling working modulus before and after solution treatment condition and the ageing treatment, thereby the Cu-Ni-Si that can obtain having concurrently excellent specific conductivity, tensile strength, proof stress relaxation property and bendability is an alloy.
Therefore, in the manufacturing of copper alloy of the present invention, need carry out the operation after the solution treatment, the flow process of promptly cold rolling (intermediate rolling), ageing treatment, cold rolling (finally rolling) series of features.The particularly important is and carry out distinctive ageing treatment.
(ageing treatment)
As aging condition, the time under the temperature that Da Wendu, material be maintained at 450～550 ℃ of being up to of heat-up rate, material and the heat-up rate of material have been stipulated.
(1) heat-up rate: if slowly raise material temperature, then intragranular generates the fine nuclear of separating out in temperature-rise period, and crystal boundary response type is afterwards separated out promptly not to be had the growth of separating out band and be suppressed.Therefore, even carry out long timeliness in order to obtain high conductivity, nothing is separated out band and also can not grown into such degree, therefore the decline that also can not produce mechanical characteristics (intensity, bending, stress relaxation etc.).That is, in the prior art, suppress not have and separate out band, then can't obtain high conductivity if shorten aging time in order to improve mechanical characteristics.In addition, if prolong aging time, then can't obtain growing not having and separate out the good mechanical properties of band in order to improve specific conductivity.We can say the present invention and deposit and be significant aspect such opposite characteristic.In addition, the above-mentioned mechanism for the present invention infers does not limit the present invention.
Specifically, need make in each temperature ranges of 200～250 ℃, 250～300 ℃ and 300～350 ℃ the material average heating speed 50 ℃/below the h.In addition, from the viewpoint of production efficiency, average heating speed be preferably 10 ℃/more than the h.Typical this average heating speed is 20～40 ℃/h.
Wherein, though pass through the thermal pretreatment of 250 ℃ * 48h of increase non-patent literature 1 record, the nothing that can obtain is to a certain degree separated out the inhibition effect of band, can cause production efficiency significantly to reduce because of increasing thermal pretreatment.The control method of heat-up rate of the present invention reduces production efficiency hardly, is at industrial extremely effective means.
(2) material be up to Da Wendu: below 550 ℃.If surpass 550 ℃, then control heat-up rate in any case and all can cause not having the width increase (for example surpassing 100nm) of separating out band.Be preferably below 530 ℃, more preferably below 500 ℃.On the other hand, if be up to 450 ℃ of Da Wendu less thaies then can't obtain good specific conductivity, therefore be up to Da Wendu and be preferably more than 450 ℃, more preferably more than 480 ℃.
Retention time under (three) 450～550 ℃: 5～15 hours.Underheating did not then have the narrowed width (for example not enough 10nm) of separating out band in 5 hours, even and control heat-up rate also can't obtain sufficient specific conductivity.If surpass 15 hours, then can cause not having the width of separating out band increases (for example surpassing 100nm).If also consider production efficiency then more preferably 6～10 hours time.
(solution treatment)
In the solution treatment, the average crystallite particle diameter is adjusted in the scope of 1～15 μ m.Average crystallite particle diameter after the solution treatment is equal to a in the product stage of afore mentioned rules in fact, if so average crystallite particle diameter less than 1 μ m here, also less than 1 μ m of a that is obtained by the metallographic of product then, a also surpasses 15 μ m if the average crystallite particle diameter here surpasses 15 μ m.The average crystallite particle diameter is 2～10 μ m more preferably, the a=2 that obtains～10 μ m.
The Heating temperature and the heating condition itself of the solution treatment of carrying out in order to obtain above-mentioned crystallization particle diameter are known technologies, so long as those skilled in the art just can suitably set, for example, by material is kept 5～600 seconds appropriate time under 700～800 ℃ proper temperature, carry out air cooling or water cooling afterwards fast, can obtain above-mentioned crystallization particle diameter.
(cold rolling)
Make the working modulus and the final rolling working modulus of intermediate rolling add up to 5～40%.If add up to working modulus less than 5%, the b/a less than of being obtained by the metallographic of product 1.05 then is if add up to working modulus to surpass 40% then b/a surpasses 1.67.Add up to working modulus more preferably 10～25%, can obtain b/a=1.10～1.40.In addition, even an intermediate rolling and a final side's in rolling rolling working modulus is zero also no problem.
Working modulus R through type R (%)=(t
0-t)/t
0* 100 (t
0: the thickness before rolling, t: the thickness after rolling) define." the total R of working modulus
Sum(%) ", the thickness in intermediate rolling is made as from t
0To t
1, be made as from t in rolling final
1To t
2The time, by R
Sum(%)=(t
0-t
1)/t
0* 100+ (t
1-t
2)/t
1* 100 and try to achieve.
(stress relief annealing)
Final cold rolling after, can carry out to improve spring threshold value etc. is the purpose stress relief annealing.Stress relief annealing can be carried out (for example 300 ℃ * 30 minutes) at low temperatures for a long time, and also at high temperature the short period of time is carried out (for example 500 ℃ * 30 seconds).If temperature is too high or overlong time, then the decline of tensile strength can increase.It is 10～50MPa that selected condition optimization makes the slippage of tensile strength.
In addition, even copper alloy of the present invention is carried out surface treatments such as zinc-plated and gold-plated, also can keep effect of the present invention.
Therefore, a preferred implementation of the manufacture method of copper alloy of the present invention comprises the operation of carrying out in the following order:
The operation of-fusion casting ingot casting, the Ni, concentration (quality %) that this ingot casting contains 1.2～3.5 quality % be for 1/6～1/4 Si of Ni concentration (quality %) and as the Zn below the 0.5 quality % of optional member, and rest part is that impurity below the 0.05 quality % is formed by Cu and total amount;
-hot-rolled process;
-cold rolling process;
-the average crystallite particle diameter is adjusted to solution treatment operation in 1～15 mu m range;
-the cold rolling process that carries out with working modulus 0～40%;
-to make the top temperature of material in the thermal treatment be below 550 ℃, material was kept in 450～550 ℃ temperature range 5～15 hours, and the average heating speed that makes material in temperature-rise period in each temperature range of 200～250 ℃, 250～300 ℃ and 300～350 ℃ is 50 ℃/a ageing treatment process below the h;
-the cold rolling process (adding up to 5～40%) that carries out with working modulus 0～40% with the cold rolling working modulus of carrying out before the ageing treatment;
-optional stress relief annealing operation.
In addition, so long as those skilled in the art can both understand and can carry out operations such as grinding suitable, that be used to remove surface scale, grinding, shot-peening pickling at the intermittence of above-mentioned each operation.
Cu-Ni-Si of the present invention is that alloy can be processed into each Albatra metal-calendered goods, for example plate, bar, pipe, rod and line, in addition, Cu-Ni-Si class copper alloy of the present invention is particularly preferred for the lead frame material of electroconductibility spring materials such as junctor, terminal, rly., switch and semiconductor instruments such as transistor or unicircuit.
Below, in order to understand the present invention better and advantage has been enumerated embodiment, but the present invention is not subjected to these qualification.
Embodiment
Use high frequency furnace, fusion 2kg electrolytic copper in the plumbago crucible of internal diameter 60mm, degree of depth 200mm.Behind charcoal sheet covering fused solution surface, add Ni, the Si of specified amount and add Zn as required, the fused solution temperature is adjusted to 1200 ℃.Then, fused solution is cast in the mould, makes the ingot casting of width 60mm, thickness 30mm.The element of obtaining beyond Ni in the ingot casting, Si and the Zn by the full element semi-quantitative analysis of glow discharge-mass analysis is the concentration of impurity, and the result is for adding up to about 0.01 quality %.The higher unit of concentration ratio have Fe (0.005 quality %), S (0.001 quality %), C (0.001 quality %).
With ingot casting 950 ℃ down heating be hot-rolled down to thickness 8mm after 3 hours, with the shredder grinding, remove surperficial oxide skin.Then, process-thermal treatment according to the order of cold rolling, solution treatment, cold rolling (intermediate rolling), ageing treatment, cold rolling (finally rolling), stress relief annealing.Thickness of slab when adjusting each working modulus in rolling and thermal treatment, to finish final rolling thickness of slab be 0.25mm thereby make.After the solution treatment, after the ageing treatment and after the stress relief annealing,, carry out pickling and carry out mechanical polishing with 10 quality % sulfuric acid-1 quality % superoxols successively with the #1200 emery paper in order to remove the surface film oxide that produces in the thermal treatment.
In the solution treatment, insert test portion in the electric furnace be adjusted to specified temperature with the specified time after, from electric furnace, directly take out and carry out air cooling.
In the ageing treatment, use electric furnace under all temps condition, test portion to be heated.In the ageing treatment, make the test portion patch thermocouple and measure the test portion variation of temperature.
In the stress relief annealing, after in the electric furnace of 300 ℃ of test portion insertions 30 minutes, from electric furnace taking-up carrying out air cooling.In addition, final when rolling when not carrying out, do not carry out this stress relief annealing yet.
The test portion that obtains is carried out following evaluation.
(1) grain shape
For the test portion of (is final rolling back for the test portion that does not carry out stress relief annealing) after the test portion of finishing solution treatment and the stress relief annealing (below be called product), observe the tissue in the cross section parallel with rolling surface.After adopting mechanical polishing and electropolishing that rolling surface is ground to form minute surface, make by etching crystal boundary to occur, and take and organize photo.For etching solution, use the aqueous solution that has mixed ammoniacal liquor and aquae hydrogenii dioxidi; For the shooting of organizing photo, be fit to use opticmicroscope or scanning electronic microscope.On the other hand, when the crystallization particle diameter little and when being difficult to distinguish crystal boundary by etching, minute surface test portion behind the use electropolishing is by electron backscattered style method (EBSP, Electron Backscattering Pattern) method is taken bearing images (orientation マ Star プ picture), with this image grain shape is measured.
Organize in the photo above-mentioned, with the vertical direction of rolling direction on draw 3 straight lines arbitrarily, obtain the number of the crystal grain that is cut off by straight line.Then, with collinear length divided by the value of this crystal grain number as a.Equally, with direction that rolling direction parallels on draw 3 straight lines arbitrarily, obtain the number of the crystal grain that is cut off by straight line, with collinear length divided by the value of this crystal grain number as b.
In finishing the test portion of solution treatment, obtain the value of (a+b)/2, with it as the average crystallite particle diameter; And obtain the value of b/a in the product.
(2) there is not the width of separating out band
For the cross section parallel, near the crystal boundary of transmission type microscope, obtain and do not have the width average (mean values at any 30 places) of separating out band with about 100,000 times multiplying power observation product with rolling surface.
(3) specific conductivity
For product, be standard with JIS H 0505, measure specific conductivity with four-terminal method.
(4) tensile strength
For product, applying pressure mechanism is made JIS 13 B test films, so that draw direction is parallel with rolling direction.Carry out the tension test of this test film according to JIS-Z 2241, obtain tensile strength.
(5) bendability
From product, extract the rectangle test portion of width 10mm, with JIS Z 2248 is standard, along Good Way (GW, bending axis are and the vertical direction of rolling direction) and BadWay (BW, bending axis is the direction parallel with rolling direction), carry out 180 degree applying pliability tests.For the test portion after the bending, observe the crackle that whether has from bend surface and cross section, be evaluated as zero when not observing crackle, be evaluated as when finding crackle *.Need to prove that the be full of cracks that the degree of depth is surpassed 10 μ m is considered as crackle.
(6) stress relaxation rate
From product, extract the rectangle test film of width 10mm, length 100mm, make the length direction of test film parallel with rolling direction.Shown in Fig. 1-A, be point of application with the position of l=25mm, test film is applied the amount of deflection of yo, and 80% suitable stress (σ o) of load and 0.2% yield strength (rolling direction is measured based on JIS-Z2241).Obtain yo according to following formula.
yo＝(2/3)·1
2·σo/(E·t)
Wherein, E is a young's modulus, and t is the thickness of test portion.Heating was removed load after 1000 hours under 150 ℃, measured set deformation volume (height y) shown in Fig. 1-B, and the value of calculating y/yo * 100 is as stress relaxation rate (%).
(7) the heat-resisting spalling test of Sn coating
Carry out alkaline degreasing and with behind 10% sulfuric acid washing, carry out plating at the bottom of the Cu of thickness 0.3 μ m again, carry out the plating Sn of thickness 1 μ m then, handle, 300 ℃ of heating 20 seconds down as soft heat.The plating condition is as described below.
(plating at the bottom of the Cu)
Plating bath is formed: copper sulfate 200g/L, sulfuric acid 60g/L
Plating bath temperature: 25 ℃
Current density: 5A/dm
2
(plating Sn)
Plating bath is formed: tin protoxide 41g/L, sulfocarbolic acid 268g/L, tensio-active agent 5g/L
Plating bath temperature: 50 ℃
Current density: 9A/dm
2
Extract the rectangle test film of width 10mm the test portion after soft heat, under 150 ℃ temperature, heated 1000 hours in the atmosphere.Then, along Good Way (GW, bending axis for and the vertical direction of rolling direction) carry out 90 ℃ of bendings of bending radius 0.5mm and crookedly recover (once carrying out 90 ° of bendings back and forth), and further in crooked the surperficial Continuous pressing device for stereo-pattern of perimembranous (Sumitomo 3M makes #851A) again it is torn.Whether then, observe crooked interior perimembranous surface with opticmicroscope (20 times of multiplying powers), estimating has plating exfoliation.Be not evaluated as zero when finding plating exfoliation fully.When coating peels off in the form of sheets, be evaluated as *.When coating is that local point-like is evaluated as △ when peeling off.When being used for purposes such as junctor, even be that the level of △ is also no problem in practicality.
Test example 1
Illustrate and create conditions the metallographic of product and the influence of characteristic.The composition that makes test portion is a Cu-1.60 quality %Ni-0.35 quality %Si alloy, changes solution treatment condition, ageing treatment condition and rolling condition, is processed into product.
(representational example and conventional example)
Fig. 2 is the hygrogram of representational ageing treatment, and dotted line is represented the temperature of the environment that test portion contacts, and solid line is represented the test portion temperature.
(a) in, with material insert temperature adjust in 200 ℃ the electric furnace keep 1 hour after, with 5 hours furnace temperature is warming up to 350 ℃ from 200 ℃.Then, with 1 hour with furnace temperature rise to 500 ℃ and keep 8 hours after, take out from electric furnace and to carry out air cooling.
(b) in, with material insert temperature adjust in 200 ℃ the electric furnace keep 1 hour after, with 3 hours furnace temperature is warming up to 250 ℃ from 200 ℃, be warming up to 300 ℃ with 2 hours then, be warming up to 350 ℃ with 1 hour again.Then, with 1 hour with furnace temperature rise to 490 ℃ and keep 10 hours after, take out from electric furnace and to carry out air cooling.
(c) in, material is inserted temperature adjust in 500 ℃ the electric furnace, carry out air cooling through taking out from electric furnace after 9 hours.This is equivalent to heat treatment process of the prior art.
About each aging characteristic curve of Fig. 2, obtain 200 → 250 ℃, 250 → 300 ℃ and 300 → 350 ℃ average heating speed, material be up to hold-times in Da Wendu, 450～550 ℃ of temperature ranges.In addition, under solution treatment condition of the present invention and rolling condition, be processed into product, and evaluation of tissue and characteristic.Its result is shown in the No.1-3 of table 1.(a) of Fig. 2 be the No.1,2,3 of (c) difference correspondence table 1 (b).
The No.1 that makes under condition of the present invention, 2 satisfies the metallographic and the characteristic of the product of the present invention regulation.
Greater than the scope of the invention, condition in addition is identical with No.1 as the heat-up rate of the No.3 of conventional example.Do not separate out band above 100nm owing to having, so tensile strength crack under 180 degree applyings are crooked, and stress relaxation rate surpasses 30% below 550MPa.
No.4 also is a conventional example, for the tensile strength that makes No.3 more than 550MPa, improved rolling working modulus.Surpass 100nm because not only working modulus height, and nothing is separated out band, therefore the crooked test portion down of 180 degree applyings produces the obvious crackle of fracture level, and stress relaxation rate has surpassed 30%.
No.5 is that Cu-Ni-Si common in the prior art is an alloy.Carry out the peak timeliness, and to carry out with tensile strength be preferential characteristic manufacturing.Bendability and proof stress slackness are good, but the not enough 50%IACS of specific conductivity.
(heat-up rate under the timeliness)
Data during for the heat-up rate in the No.1 change timeliness are as shown in table 2.The result shows, because heat-up rate is slow, does not have the width of separating out band and reduces.Do not reduce if there is the width of separating out band, then tensile strength, bendability, proof stress slackness improve.Among the comparative example No.9,10, since heat-up rate in any one temperature range all above 50 ℃/h, therefore do not have the width of separating out band surpass 100nm, tensile strength be lower than 550MPa, 180 degree fit crack under crooked and stress relaxation rate above 30%.
(hold-time that is up to Da Wendu and 450～550 ℃ in the timeliness)
For No.2 change in the timeliness be up to hold-time of Da Wendu and 450～550 ℃ the time data as shown in table 3.
If 450～550 ℃ hold-time prolongs, though then specific conductivity raises, nothing is separated out band and is broadened.In 5 hours comparative example No.11 of aging time less than, not have to separate out and be with not enough 10nm, specific conductivity is less than 55%IACS.In aging time surpasses 15 hours comparative example No.14, do not have the width of separating out band surpass 100nm, tensile strength be lower than 550MPa, 180 degree fit crooked crack down and stress relaxation rate above 30%.
Raise if be up to Da Wendu, though then specific conductivity raises, nothing is separated out band and is broadened.In aging time surpasses 550 ℃ comparative example No.16, do not have the width of separating out band surpass 100nm, tensile strength be lower than 550MPa, 180 fit crooked crack down and stress relaxation rate above 30%.
(rolling working modulus)
The rolling working modulus of data when changing to(for) No.1 are as shown in table 4.Along with working modulus increases, the b/a that is obtained by the metallographic of product increases, and tensile strength increases.B/a less than 1.05 among the No.17 of intermediate rolling working modulus and final rolling working modulus total less than 5%, and the not enough 550MPa of tensile strength.Intermediate rolling working modulus and final rolling working modulus add up to surpass among 40% the No.23 b/a greater than 1.67, tensile strength surpasses 700MPa and 180 degree and fits and crack under crooked.
(finish solution treatment after crystallization particle diameter)
The crystallization particle diameter finish after the solution treatment of data when changing to(for) No.2 are as shown in table 5.Increase along with finishing solution treatment post crystallization particle diameter, a that is obtained by the metallographic of product increases, and stress relaxation rate reduces.Finish among the No.24 of the crystallization particle diameter less than 1 μ m after the solution treatment a less than 1 μ m, stress relaxation rate and surpass 30% and cause tensile strength to be lower than 550MPa because of solid solution is not enough.Finish crystallization particle diameter after the solution treatment and surpass that a surpasses 15 μ m among the No.29 of 15 μ m, and 180 degree are fitted and cracked under crooked.
Test example 2
Illustrate that alloying constituent is to the metallographic of product and the influence of characteristic.Under create conditions identical, be that alloy is processed into product with the Cu-Ni-Si of various compositions with foregoing invention example No.1.In addition, after carrying out solution treatment under 750 ℃ * 60 seconds the condition, though, for the crystallization particle diameter of whole test portions, still fallen into preferable range of the present invention because of heterogeneity has changed the crystal grain footpath a little.
(influence of Ni concentration/Si concentration ratio)
With the Ni concentration fixed at 1.60 quality % and the data when changing Si concentration as shown in table 6.No.1 is identical with the test portion of table 1 with No.5.Wherein, No.5 is the existing alloy of the not enough 55%IACS of specific conductivity, and it creates conditions different with other test portion.
If Ni concentration/Si concentration ratio exceeds 4～6 scope, the not enough 55%IACS of specific conductivity then.In addition, if Ni concentration/Si concentration ratio reduces, then tensile strength raises, and this is because the increase of Si concentration causes Ni
2The amount of separating out of Si increases.
The heat-resisting spalling evaluation result of the Sn coating of alloy of the present invention is △ (point-like is peeled off).On the other hand, No.5,34 evaluation result be *.This is because solid solution Si reduces heat-resisting spalling.That is to say, because Ni among the No.5
2The amount of separating out of Si reduces, and has added superfluous Si with respect to Ni among the No.34, thereby solid solution Si increases.
(influence of Ni)
Data when changing Ni concentration when keeping Ni concentration/Si concentration ratio within the scope of the present invention are as shown in table 7.Ni concentration is lower than among the No.35 of 1.2 quality %, the not enough 550MPa of tensile strength.Ni concentration surpasses among the No.41 of 3.5 quality %, and tensile strength surpasses 700MPa, and cracks under the 180 degree applying bendings.
(influence of Zn)
As the influence of adding Zn, the data when adding the Zn of various concentration in No.1 are as shown in table 8.By adding the Zn more than the 0.05 quality %, make that the heat-resisting spalling evaluation result of Sn coating is zero (nothing is peeled off).On the other hand, along with the increase specific conductivity of Zn descends, but can obtain the specific conductivity more than the 55%IACS in the scope below Zn is 0.5 quality %.
(influence of impurity)
As impurity, the data that the impurity of No.43 is increased are as shown in table 9.Suppose the sneaking into of copper product of plating Sn and add Sn, and when fusion hypothesis residual deoxidant element and add Mg, thereby change the total amount of impurity.Impurity surpasses in the test portion of 0.05 quality %, the not enough 55%IACS of specific conductivity.
[table 1]
[table 2]
[table 3]
[table 4]
[table 5]
[table 6]
[table 7]
[table 8]
[table 9]
Claims (5)
1.Cu-Ni-Si be alloy, it is characterized in that: Ni, the concentration that contains 1.2～3.5 quality % is 1/6～1/4 Si of Ni concentration, and rest part is that impurity below the 0.05 quality % is formed by Cu and total amount, and described concentration is in quality %; And have following characteristic concurrently:
(A) specific conductivity: 55～62%IACS
(B) tensile strength: 550～700MPa
(C) bendability: do not crack under 180 degree applyings are crooked
(D) proof stress slackness: the stress relaxation rate of heating in the time of 1000 hours is below 30% under 150 ℃;
In the metallographic in the cross section parallel with rolling surface, will be made as a with the median size of the orthogonal direction of rolling direction of crystal grain, when the median size of direction that will be parallel with rolling direction is made as b,
a＝1～15μm，b/a＝1.05～1.67，
And the width average that the nothing in the metallographic is separated out band is 10～100nm.
2.Cu-Ni-Si be alloy, it is characterized in that: Ni, the concentration that contains 1.2～3.5 quality % is the following Zn of 1/6～1/4 Si, 0.5 quality % of Ni concentration, rest part is that impurity below the 0.05 quality % is formed by Cu and total amount, and described concentration is in quality %; And have following characteristic concurrently:
(A) specific conductivity: 55～62%IACS
(B) tensile strength: 550～700MPa
(C) bendability: do not crack under 180 degree applyings are crooked
(D) proof stress slackness: the stress relaxation rate of heating in the time of 1000 hours is below 30% under 150 ℃
(E) heat-resisting spalling: after the heat-resisting spalling test of Sn coating, do not find plating exfoliation;
In the metallographic in the cross section parallel with rolling surface, will be made as a with the median size of the orthogonal direction of rolling direction of crystal grain, when the median size of direction that will be parallel with rolling direction is made as b,
a＝1～15μm，b/a＝1.05～1.67，
And the width average that the nothing in the metallographic is separated out band is 10～100nm.
3. copper alloy calendered goods, it is alloy that this copper alloy calendered goods uses claim 1 or 2 described Cu-Ni-Si.
4. electronic unit, it is alloy that this electronic unit uses claim 1 or 2 described Cu-Ni-Si.
5. claim 1 or 2 described Cu-Ni-Si are the manufacture method of alloy, and this method comprises carries out solution treatment, cold rolling, ageing treatment, cold rolling operation successively, wherein, carries out each operation under the following conditions:
Solution treatment: the scope of the average crystallite particle diameter being adjusted to 1～15 μ m;
Ageing treatment: the top temperature that makes the material in the thermal treatment is below 550 ℃, material was kept in 450～550 ℃ temperature range 5～15 hours, in addition, in temperature-rise period, make the average heating speed of the material in each temperature ranges of 200～250 ℃, 250～300 ℃ and 300～350 ℃ be 50 ℃/below the h;
Cold rolling: as to make before the timeliness that the rolling working modulus in cold rolling adds up to 5～40% after the rolling working modulus in cold rolling and timeliness.
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|---|---|---|---|
| JP259294/2006 | 2006-09-25 | ||
| JP2006259294A JP4143662B2 (en) | 2006-09-25 | 2006-09-25 | Cu-Ni-Si alloy |
| PCT/JP2007/068420 WO2008038593A1 (en) | 2006-09-25 | 2007-09-21 | Cu-Ni-Si ALLOY |
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| CN101512026B true CN101512026B (en) | 2011-03-09 |
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| US (1) | US20100000637A1 (en) |
| JP (1) | JP4143662B2 (en) |
| KR (1) | KR101056973B1 (en) |
| CN (1) | CN101512026B (en) |
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| JP2010255042A (en) * | 2009-04-24 | 2010-11-11 | Hitachi Cable Ltd | Copper alloy and method for producing copper alloy |
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| KR101703679B1 (en) * | 2010-07-07 | 2017-02-07 | 미츠비시 신도 가부시키가이샤 | Cu-ni-si copper alloy plate with excellent deep-draw characteristics and production method thereof |
| WO2012026611A1 (en) * | 2010-08-27 | 2012-03-01 | 古河電気工業株式会社 | Copper alloy sheet and method for producing same |
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| CN102021359B (en) * | 2010-11-03 | 2013-01-02 | 西安理工大学 | Cu-Ni-Si alloy with high Ni and Si content and preparation method thereof |
| JP5192536B2 (en) * | 2010-12-10 | 2013-05-08 | 三菱伸銅株式会社 | Cu-Ni-Si based copper alloy sheet excellent in deep drawing workability and fatigue resistance and method for producing the same |
| JP5180283B2 (en) * | 2010-12-24 | 2013-04-10 | 三菱伸銅株式会社 | Cu-Ni-Si based copper alloy sheet having excellent fatigue resistance and spring characteristics after bending, and method for producing the same |
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| US10923248B2 (en) * | 2013-06-07 | 2021-02-16 | Vdm Metals International Gmbh | Method for producing a metal film |
| JP6301618B2 (en) * | 2013-09-17 | 2018-03-28 | 古河電気工業株式会社 | Copper alloy material and method for producing the same |
| CN107119247B (en) * | 2017-06-08 | 2018-10-30 | 西安交通大学 | It is a kind of improve in high tonnage melting CuNiSiCr alloy property stability heat treatment method |
| CN112813368B (en) * | 2020-12-25 | 2022-05-13 | 大连交通大学 | High-performance Cu-Ni-Si alloy plate strip and production process thereof |
| CN113249666A (en) * | 2021-05-14 | 2021-08-13 | 太原晋西春雷铜业有限公司 | Preparation method for reducing heat shrinkage rate of Cu-Ni-Si alloy |
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| CN115613043A (en) * | 2022-11-11 | 2023-01-17 | 安徽鑫科铜业有限公司 | Copper-nickel-silicon alloy strip surface treatment solution and copper-nickel-silicon alloy strip surface treatment method |
| CN115627380B (en) * | 2022-11-11 | 2023-07-25 | 安徽鑫科铜业有限公司 | Low-concentration copper-nickel-silicon alloy material and preparation method thereof |
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| KR20090016485A (en) | 2009-02-13 |
| CN101512026A (en) | 2009-08-19 |
| TWI355426B (en) | 2012-01-01 |
| WO2008038593A1 (en) | 2008-04-03 |
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| KR101056973B1 (en) | 2011-08-16 |
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