CN1191590C - Copper alloy for electronic material - Google Patents

Copper alloy for electronic material Download PDF

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Publication number
CN1191590C
CN1191590C CNB01103064XA CN01103064A CN1191590C CN 1191590 C CN1191590 C CN 1191590C CN B01103064X A CNB01103064X A CN B01103064XA CN 01103064 A CN01103064 A CN 01103064A CN 1191590 C CN1191590 C CN 1191590C
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China
Prior art keywords
quality
copper alloy
intensity
conductivity
alloy
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Expired - Fee Related
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CNB01103064XA
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Chinese (zh)
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CN1310454A (en
Inventor
牧哲生
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JX Nippon Mining and Metals Corp
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Nippon Mining and Metals Co Ltd
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Publication of CN1310454A publication Critical patent/CN1310454A/en
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    • 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
    • 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
    • H01B1/026—Alloys based on copper

Abstract

The invention provides a copper alloy having good bendability as well as high strength and electric conductivity. This alloy has a composition containing, by mass, 1.5 to 3.5% Ni and 0.35 to 1.0% Si, furthermore containing 0.005 to 0.1% Fe and/or one or more kinds of Zr, Cr, Ti and Mo of 0.005 to 0.2% in total, in which, by a weight ratio, Ni/Si is also controlled to 3 to 7, and the balance Cu with inevitable impurities.

Description

Copper alloy for electronic material
Technical field
The invention relates to intensity, excellent conductivity, and then have the copper alloy for electronic material of excellent in vending workability and stamping-out processability.
Background technology
For the copper alloy for electronic material that is used for lead frame, terminal, connector etc., as the fundamental characteristics of goods, demanding intensity and high conductivity or thermal conductivity have both.And more require the miniaturization, highly integrated of electronic device in recent years, and therefore require raw-material thin plateization, in lead frame, terminal, connector, the increase of pin count etc., narrow and small spacingization develop.Further require the reliability in the complicated of device shape and the raising aggregate erection, therefore, except mechanical strength and excellent conductivity, also require excellent in vending workability for the material that uses.
In recent years, as copper alloy for electronic material, replace in the past phosphor bronze, brass etc. to be the solution strengthening type copper alloy of representative, from the viewpoint of high strength and high conductivity, the use amount of age-hardening type copper alloy increases.Age-hardening type copper alloy carries out Ageing Treatment by the supersaturated solid solution of solution treatment, and tiny precipitate is disperseed equably, in the intensity that improves alloy, reduce the solid solution element amount in the copper, thereby conductivity improves.Therefore, good as mechanical performances such as intensity, elasticity, and also the good material of conductivity, thermal conductivity uses.
In age-hardening type copper alloy, the Cu-Ni-Si series copper alloy is the representative copper alloy that has high strength and high conductivity simultaneously, as the electric mechanical material, has reached practicability.
The Cu-Ni-Si series copper alloy improves intensity and conductance by separate out tiny Ni-Si series intermetallic compound particle in the copper matrix.But, when the ratio of Ni that is added and Si is the composition of low concentration, though enough obtained conductivity, undercapacity.On the other hand, when high concentration is formed, obtain enough intensity, but the conductance reduction, and then have the improper situation that formabilities such as causing bendability easily reduces.In order to ensure intensity and processability, add other elements such as Sn sometimes, but conductance reduces greatly.
Bendability that it is generally acknowledged alloy is relevant with grain size, and grain size is more little, and bendability is good more.But, grain size is adjusted under the little situation, even create conditions, also form the duplex grain structure of mixing the non-recrystallization part easily, its result, generation is called the problem that bendability reduces.
Summary of the invention
The present invention finishes in order to solve the above problems, so purpose is to provide, and is in the alloy at the Cu-Ni-Si with enough intensity and conductance, the copper alloy for electronic material that bendability is also good.
In order to address the above problem, the inventor is that alloy has carried out research repeatedly about Cu-Ni-Si, discovery is in the alloy at Cu-Ni-Si, after carrying out the composition adjustment more than among interpolation Fe and/or Zr, Cr, Ti, the Mo any, contain Mg, Zn, Sn, Al, P, Mn, Ag or Be as required again, can provide only raw material as copper alloy for electronic material.
That is, the inventor is based on above-mentioned cognition and finishes, and therefore provides:
(1) copper alloy for electronic material of intensity, conductivity and has excellent bending properties, it is characterized in that, contain the Si of Ni, 0.35～1.0 quality % of 1.5～3.5 quality %, the Fe of 0.005～0.1 quality %, and being adjusted to Ni/Si=3～7 by weight, all the other are made of Cu and unavoidable impurities.
(2) copper alloy for electronic material of intensity, conductivity and has excellent bending properties, it is characterized in that, contain the Ni of 1.5～3.5 quality %, the Si of 0.35～1.0 quality %, and then count 0.005～0.2 quality % by total amount more than also containing among Zr, Cr, Ti, the Mo any, and being adjusted to Ni/Si=3～7 by weight, all the other are made of Cu and unavoidable impurities.
(3) copper alloy for electronic material of intensity, conductivity and has excellent bending properties, it is characterized in that, contain the Si of Ni, 0.35～1.0 quality % of 1.5～3.5 quality %, the Fe of 0.005～0.1 quality %, and then count 0.005～0.2 quality % by total amount more than also containing among Zr, Cr, Ti, the Mo any, and being adjusted to Ni/Si=3～7 by weight, all the other are made of Cu and unavoidable impurities.
(4) copper alloy for electronic material of intensity, conductivity and has excellent bending properties, it is characterized in that, contain the Si of Ni, 0.35～1.0 quality % of 1.5～3.5 quality %, the Fe of 0.005～0.1 quality %, and then as required, contain among Mg, Zn, Sn, Al, P, Mn, Ag or the Be more than one and count 0.005～0.24 quality % by total amount, and being adjusted to Ni/Si=3～7 by weight, all the other are made of Cu and unavoidable impurities.
(5) copper alloy for electronic material of intensity, conductivity and has excellent bending properties, it is characterized in that, contain the Ni of 1.5～3.5 quality %, the Si of 0.35～1.0 quality %, and count 0.005～0.2 quality % by total amount more than containing among Zr, Cr, Ti, the Mo any, and then as required, contain among Mg, Zn, Sn, Al, P, Mn, Ag or the Be more than one and count 0.005～0.24 quality % by total amount, and being adjusted to Ni/Si=3～7 by weight, all the other are made of Cu and unavoidable impurities.
(6) copper alloy for electronic material of intensity, conductivity and has excellent bending properties, it is characterized in that, contain the Si of Ni, 0.35～1.0 quality % of 1.5～3.5 quality %, the Fe of 0.005～0.1 quality %, and count 0.005～0.2 quality % by total amount more than containing among Zr, Cr, Ti, the Mo any, and then as required, contain among Mg, Zn, Sn, Al, P, Mn, Ag or the Be more than one and count 0.005～0.24 quality % by total amount, and being adjusted to Ni/Si=3～7 by weight, all the other are made of Cu and unavoidable impurities.
Embodiment
Below, illustrate that the compositing range of copper alloy is limited to aforesaid reason and effect thereof in the present invention.
(1) Ni and Si
Ni and Si are by carrying out Ageing Treatment, and Ni and Si form mutually with tiny Ni 2Si is the precipitation particles of master's intermetallic compound, the intensity of alloy is increased significantly, and conductance also maintains high level.But, Ni content less than 1.5% or Si content less than 0.35% o'clock, even add other composition, also can not get desired intensity.In addition, Ni content surpass 3.5% or Si content above 1.0% o'clock, though obtain enough intensity, but desired conductivity reduces, and the thick Ni-Si that does not help intensity to improve is that particle (crystal and precipitate) generates in parent phase, causes the reduction of bendability, etching and plating.Therefore, the content of Ni is defined as 1.5～3.5%, and the content of Si is defined as 0.35～1.0%.
It is because making the weight ratio of Ni in the alloy and Si approaching is the Ni of intermetallic compound that the weight ratio (representing with Ni/Si) of Si amount and Ni amount is defined as 3～7 reason 2The Ni of Si and the concentration ratio of Si can more improve the conductivity after the Ageing Treatment.At Ni/Si less than 3 o'clock, the relative Ni of Si concentration 2Si forms the surplus that becomes, and therefore except conductivity reduces, because the increase of the amount of the solid solution Si in the matrix when heat treatment, generates the Si oxide-film easily at material surface, becomes the reason of solderability and plating property deterioration.
Relative Ni 2The weight ratio that Si forms is Ni/Si=4, from above-mentioned reason, only can lower solid solution Si amount, therefore relative Ni 2Si forms, and the Ni amount can have some surplus a little.But, if Ni/Si surpasses 7, relative Ni 2Si forms, and superfluous NI quantitative change is many, thereby can not get desired conductance.Therefore, for the Si that obtains good electrical conductivity and the weight ratio of Ni are Ni/Si=3～7, preferably 4.5.
(2)Fe
Fe is used to improve fusing point, cooling stage after the solidifying and solidify of when casting carries out crystallization slightly and separates out, when the compound that is Ni, the Si of the principal component of alloy of the present invention carries out crystallization and separates out, tiny Fe particle becomes nuclear, and the effect that suppresses the alligatoring of Ni-Si particle is arranged.In addition, in the annealing process of following the crystallization of carrying out after cold rolling again, the Fe particle that is distributed in the matrix stops crystal boundary migration by the pinning effect, and the thick effect of the recrystal grain of inhibition is arranged, and therefore can access tiny and uniform recrystallized structure.
Therefore, tiny by making grain size, can improve the bendability of alloy.And then Fe improves the intensity and the stable on heating effect of alloy in addition.But, less than 0.005% o'clock, also can not get any effect at Fe content, if surpass 0.1%, plating property just reduces, and the Fe particle alligatoring in the matrix, bendability and the reduction of plating property, so the content of Fe is defined as 0.005～0.1%.
(3)Zr、Cr、Ti、Mo
Zr, Cr, Ti, Mo are the high-melting-point elements, and therefore the same with Fe have the effect that suppresses the alligatoring of Ni-Si particle and obtain tiny crystalline structure in the annealing of following crystallization again, thereby have the effect of improving bendability.Zr, Cr, Ti, Mo can compoundly add, but its content, less than 0.005% o'clock, in the above-mentioned desired effects that can not get on, if surpass 0.2%, when processability reduced, plating property also reduced by total amount.Therefore, Zr, Cr, Ti, Mo addition are defined as 0.005～0.2% by total amount.
(4) Mg, Zn, Sn, Al, P, Mn, Ag or Be
Mg, Zn, Sn, Al, P, Mn, Ag or Be have intensity and the stable on heating effect that improves the Cu-Ni-Si series copper alloy.In addition, in these metals, Zn improves the stable on heating effect of solder portion in addition, and Mg, Al and Mn also have the effect of improving hot rolling.Its reason is because the strong and sulphur of the compatibility of these elements and sulphur forms compound, thereby alleviates the segregation of sulphur to the ingot crystal boundary of the reason that becomes hot-rolled crackle.
The content of Mg, Zn, Sn, Al, P, Mn, Ag or Be if press total amount less than 0.005%, can not get above-mentioned effect, and on the other hand, if total content surpasses 2.0%, conductivity just reduces significantly.Therefore, their content is defined as 0.005～2.0% by total amount.
As mentioned above, relevant copper alloy of the present invention shows good intensity, electrical characteristic, and bendability is also good.
Embodiment
Below, according to embodiment the present invention is described.
The copper alloy that various one-tenth are grouped into shown in the melting table 1 in high frequency melting furnace is cast as the ingot of thickness 20mm.
Table 1
Alloy of the present invention and comparative example
Composition (weight %) Weight ratio Tensile strength N/mm 2 Conductance %IACS Grain size μ m 90 ° of bendings of bendability
Ni Si Fe Zr，Cr，Ti，Mo Accessory ingredient Ni/Si
Alloy of the present invention 1 2.50 0.55 0.05 - - 4.4 680 52 6 ○
2 2.83 0.82 0.007 - - 3.5 691 47 8 ○
3 3.20 0.57 0.08 - - 5.6 674 45 5 ○
4 2.75 0.41 0.04 - - 6.7 675 50 6 ○
5 1.63 0.35 - 0.02Zr - 4.7 618 55 7 ○
6 2.54 0.56 - 0.04Cr - 4.5 685 49 7 ○
7 2.07 0.41 - 0.03Zr 0.08Cr - 5.0 655 53 6 ○
8 3.86 0.58 0.03 0.01Ti - 6.8 688 41 5 ○
9 1.92 0.44 0.06 0.008Mo - 4.4 632 55 6 ○
10 2.83 0.80 0.007 0.02Cr - 3.5 698 44 6 ○
11 2.52 0.57 0.04 0.01Mo - 4.4 682 50 6 ○
12 2.33 0.69 0.08 - 0.12Mg 3.4 664 52 6 ○
13 2.35 0.64 0.06 - 0.11Zn 8.7 665 50 6 ○
14 2.37 0.68 0.04 - 0.24Sn 3.5 673 48 7 ○
15 2.80 0.89 0.009 - 0.008Be 3.1 695 48 8 ○
16 2.53 0.56 - 0.04Cr 0.13Mg 4.5 687 48 8 ○
17 3.21 0.58 - 0.03Zr 0.12Zn 5.5 676 44 6 ○
18 1.71 0.34 - 0.05Zr 0.21Sn 5.0 644 51 7 ○
19 1.85 0.46 0.05 0.07Cr 0.005P 0.03Al 4.0 640 56 6 ○
20 2.64 0.60 0.007 0.04Ti 0.03Ag 0.04Mn 4.4 688 52 7 ○
Compare alloy 1 1.22 0.25 0.08 - - 4.9 483 56 7 ○
2 4.14 0.53 0.07 - - 7.8 654 32 8 ○
3 3.48 1.17 0.06 - - 3.0 704 30 8 △
4 2.53 0.56 0.004 - - 4.5 656 51 Mix crystal grain ×
5 2.76 0.51 0.18 - - 5.4 670 49 9 ×
6 1.92 0.44 - 0.002Mo - 4.4 622 49 Mix crystal grain ×
7 2.86 0.88 - 0.23Cr - 3.2 680 47 1O △
8 2.64 0.60 - 0.18Zr 0.09Ti - 4.4 715 41 8 ×
9 2.61 0.58 0.08 - 0.78Al 1.43Sn 4.5 690 31 7 ○
10 1.64 0.79 0.07 - - 2.1 611 38 8 ○
11 3 22 0.37 0.04 - 1.52Zn 8.7 633 34 8 ○
Then, this ingot is hot-rolled down to thickness 8mm, after being used to remove the surfacing of surperficial oxide skin, utilizes the cold rolling plate that rolls into thick 1mm.After 750～850 ℃ temperature is carried out solution treatment, be cold-rolled to 0.4mm then.Then 400～600 ℃ scope, carry out 5 hours Ageing Treatment respectively in the temperature that obtains maximum intensity with each composition.After this, obtain higher intensity, utilize the cold rolling plate that rolls into thickness 0.25mm,, suitably carry out 30 seconds～1 hour heat treatment at last 400～500 ℃ of temperature.
Each alloy that obtains is like this carried out the evaluation of all characteristics.About intensity, in tension test aircraft measurements tensile strength.Conductivity is estimated according to conductance (%IACS).About the material after the final heat treatment,, measure grain size along axle perpendicular to the plate face according to the process of chopping of JISH0501.Utilize the W bend test, use the rectangle sample of wide 10mm, apply 5 tons of load loadings, carry out the bend test (bending axis is perpendicular to rolling direction) of parallel rolling direction with the identical bending radius of thickness of slab.
With light microscope multiplying power and bend surface after scanning electron microscopy (SEM) viewing test more than 50 times, with good (not having crackle and big rough surface) as zero, with big rough surface as △, with big rough surface and also take place crackle as *, be shown in Table 1.
Clearly illustrate that as table 1 alloy of the present invention has good intensity, conductivity, grain size all is tiny, and has good bendability.
On the other hand, relatively to form with alloy of the present invention be different to the part of alloy, but with alloy phase ratio of the present invention, the Ni of No.1, Si are low, so intensity is low.The Ni height of No.2, so conductance is low.The Si height of No.3, so conductance and bendability are inferior.No.4,6 Fe, Mo separately is low, so crystalline structure becomes non-recrystallization crystal grain and recrystal grain mixes the duplex grain structure that exists, and generates thick Ni-Si particle, and reduces bendability.
Therefore No.5,7 Fe, Cr height separately generate thick Fe or Cr particle, and reduce bendability in matrix.The Zr of No.8 and the total of Ti exceed scope of the present invention, owing to generate Zr, Ti particle, and reduce bendability.No.9 contains accessory ingredient with going beyond the scope, so conductance is inferior.In addition, though No.10,11 becomes component identical with the present invention, Ni/Si is than different, and the Ni/Si of No.10 is than low, so conductivity is inferior.The Ni/Si of No.11 is than big, so conductance is inferior.
As mentioned above, alloy of the present invention has good intensity and conductivity, and bendability is also good, is suitable as copper alloy for electronic material such as lead frame, terminal, connectors.

Claims (6)

1. the copper alloy for electronic material of intensity, conductivity and has excellent bending properties, it is characterized in that, contain the Si of Ni, 0.35～1.0 quality % of 1.5～3.5 quality %, the Fe of 0.005～0.1 quality %, and being adjusted to Ni/Si=3～7 by weight, all the other are made of Cu and unavoidable impurities.
2. the copper alloy for electronic material of intensity, conductivity and has excellent bending properties, it is characterized in that, contain the Ni of 1.5～3.5 quality %, the Si of 0.35～1.0 quality %, and then count 0.005～0.2 quality % by total amount more than also containing among Zr, Cr, Ti, the Mo any, and being adjusted to Ni/Si=3～7 by weight, all the other are made of Cu and unavoidable impurities.
3. the copper alloy for electronic material of intensity, conductivity and has excellent bending properties, it is characterized in that, contain the Si of Ni, 0.35～1.0 quality % of 1.5～3.5 quality %, the Fe of 0.005～0.1 quality %, and then count 0.005～0.2 quality % by total amount more than also containing among Zr, Cr, Ti, the Mo any, and being adjusted to Ni/Si=3～7 by weight, all the other are made of Cu and unavoidable impurities.
4. the copper alloy for electronic material of intensity, conductivity and has excellent bending properties, it is characterized in that, contain the Si of Ni, 0.35～1.0 quality % of 1.5～3.5 quality %, the Fe of 0.005～0.1 quality %, and then as required, contain among Mg, Zn, Sn, Al, P, Mn, Ag or the Be more than one and count 0.005～0.24 quality % by total amount, and being adjusted to Ni/Si=3～7 by weight, all the other are made of Cu and unavoidable impurities.
5. the copper alloy for electronic material of intensity, conductivity and has excellent bending properties, it is characterized in that, contain the Ni of 1.5～3.5 quality %, the Si of 0.35～1.0 quality %, and count 0.005～0.2 quality % by total amount more than containing among Zr, Cr, Ti, the Mo any, and then as required, contain among Mg, Zn, Sn, Al, P, Mn, Ag or the Be more than one and count 0.005～0.24 quality % by total amount, and being adjusted to Ni/Si=3～7 by weight, all the other are made of Cu and unavoidable impurities.
6. the copper alloy for electronic material of intensity, conductivity and has excellent bending properties, it is characterized in that, contain the Si of Ni, 0.35～1.0 quality % of 1.5～3.5 quality %, the Fe of 0.005～0.1 quality %, and count 0.005～0.2 quality % by total amount more than containing among Zr, Cr, Ti, the Mo any, and then as required, contain among Mg, Zn, Sn, Al, P, Mn, Ag or the Be more than one and count 0.005～0.24 quality % by total amount, and being adjusted to Ni/Si=3～7 by weight, all the other are made of Cu and unavoidable impurities.
CNB01103064XA 2000-01-27 2001-01-22 Copper alloy for electronic material Expired - Fee Related CN1191590C (en)

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JP2000018319A JP2001207229A (en) 2000-01-27 2000-01-27 Copper alloy for electronic material
JP18319/2000 2000-01-27

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CN1191590C true CN1191590C (en) 2005-03-02

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