CN104342581B - Cu Co Si series copper alloy strips and its manufacture method - Google Patents
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Abstract
[problem] present invention, which is provided, maintains electrical conductivity, intensity and the Cu Co Si series copper alloy strips and its manufacture method of excellent in workability and the high current electronic unit and heat transmission electronic unit that have used the copper alloy plate.[solution] Cu Co Si series copper alloy strips, it contains Co：0.5 ~ 3.0 mass %, Si：0.1 ~ 1.0 mass %, Co/Si mass ratio：3.0 ~ 5.0, remainder is made up of copper and inevitable impurity, and Lankford value r is more than 0.9（Wherein, when sample r values along obtained from carrying out tension test relative to rolling parallel direction for 0 degree, 45 degree, 90 degree of direction being denoted as into r0, r45, r90 respectively, r=（R0+2 × r45+r90）/4）.
Description
Technical field
The present invention relates to Cu-Co-Si series copper alloy strips and the energization that can be suitable for manufacturing the electronic units such as electronic material
With or heat transmission electronic unit, more particularly, to as the terminal carried in motor electronic instrument, automobile etc., connector, after
The raw material of the electronic units such as electrical equipment, switch, socket, bus, lead frame, heat sink and the Cu-Co-Si series copper alloys used
Bar and the electronic unit for having used the copper alloy bar.Wherein, it is related to and is suitable for making in electric automobile, hybrid vehicle etc.
High current is used with high currents such as connector or terminals with the purposes or smart mobile phone or tablet personal computer of electronic unit
The Cu-Co-Si series copper alloy strips of the purposes of heat transmission electronic unit such as liquid crystal frame and used the ministry of electronics industry of the copper alloy bar
Part.
Background technology
It is used as being used for for the terminal of electronic instrument, connector, switch, socket, relay, bus, lead frame, heat sink etc.
The material of conductive or heat conduction, widely uses intensity and the excellent copper alloy bar of electrical conductivity.Herein, electric conductivity and thermal conductivity exist than
Example relation.However, in recent years, for the connector of electronic instrument, high currentization is promoted, it is believed that need to have well
Bendability, more than 55%IACS electrical conductivity, more than 550MPa yield strength.In addition, in order to ensure tin-welding, to connection
The good plating of device material requirements, solder wettability.
On the other hand, for example the thermal component for being referred to as liquid crystal frame is used in smart mobile phone, the liquid crystal of tablet personal computer.I.e.
Make for the copper alloy bar of this radiating purposes, high thermal conductivity coefficientization is promoted, it is believed that needed with good bending
Property, high intensity.Therefore, for even for the copper alloy bar of radiating purposes, it is believed that be also required to the conductance with more than 55%IACS
Rate, more than 550MPa yield strength.
However, it is difficult to realize more than 60%IACS electrical conductivity by Ni-Si series copper alloys, Co-Si series copper alloys are opened
Hair is promoted.Co in copper alloy comprising Co-Si2Si solid solution capacity is few, therefore compared with Ni-Si series copper alloys, Neng Gouti
High conductivity.
As the Co-Si series copper alloys, disclose a kind of size by making field trash and reduce thick analysis for less than 2 μm
The copper alloy of plating excellent adhesion obtained from going out thing（Patent document 1）.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2008-056977 publications.
The content of the invention
Problems to be solved by the invention
However, the electrical conductivity of Co-Si series copper alloys, excellent strength, but be not suitable for drawing, the convex shaping of drum（Zhang り go out）It
The processing of class, processing when easily crack, shape defect.Therefore there is following unfavorable condition：Co-Si series copper alloys are fitted
It is difficult to fabrication design when connector, heat sink for electronic instrument etc., or (lead using electrical conductivity when being difficult to
Hot coefficient) not enough other alloys and necessary function can not be obtained.
That is, the present invention is carried out to solve above-mentioned problem, and its object is to provide maintenance electrical conductivity, intensity and add
The excellent Cu-Co-Si series copper alloy strips of work and its manufacture method.And then, it is an object of the present invention to provide the copper alloy bar
Manufacture method and be suitable for high current purposes or radiate purposes electronic unit.
The means used to solve the problem
The Cu-Co-Si series copper alloy strips of the present invention contain Co：0.5 ~ 3.0 mass %, Si：0.1 ~ 1.0 mass %, Co/Si's
Mass ratio：3.0 ~ 5.0, remainder is made up of copper and inevitable impurity, and Lankford value r is more than 0.9（Wherein, will
Sample r values along obtained from carrying out tension test relative to rolling parallel direction for 0 degree, 45 degree, 90 degree of direction are denoted as respectively
When r0, r45, r90, r=（R0+2 × r45+r90）/4）.
For the Cu-Co-Si series copper alloy strips of the present invention, it is preferred that will be 0 relative to rolling parallel direction
Degree, 45 degree, 90 degree of elongation is when being denoted as E1, E45, E90 respectively, E1, E45, E90 are more than 5%.
With（Yield strength/tensile strength）The yield ratio of expression is preferably less than 0.95.Wherein, it is strong using MPa as surrender
Degree obtains yield ratio with the unit of tensile strength.
Preferably comprise total 0.001 ~ 2.5 mass % selected from Ni, Cr, Mg, Mn, Ag, P, Sn, Zn, As, Sb, Be, B, Ti,
More than a kind in Zr, Al and Fe.
The manufacture method of the Cu-Co-Si series copper alloy strips of the present invention is the manufacturer of foregoing Cu-Co-Si series copper alloy strips
Method, wherein, it is more than 10% first cold rolling, solution treatment, Ageing Treatment that hot rolling, the first annealing, degree of finish are carried out successively, and
By foregoing first annealing and foregoing first it is cold rolling repeat more than 2 times, it is foregoing first annealing be set to annealing before and after stretching it is strong
Degree reduces by 10 ~ 40% condition.
Another of the present invention is the high current electronic unit for having used above-mentioned Cu-Co-Si series copper alloy strips sideways.
Another of the present invention is the heat transmission electronic unit for having used above-mentioned Cu-Co-Si series copper alloy strips sideways.
In accordance with the invention it is possible to provide maintenance electrical conductivity, intensity and the Cu-Co-Si series copper alloy strips of excellent in workability and
Its manufacture method and the electronic unit for being suitable for high current purposes or the purposes that radiates.The copper alloy bar can be suitable as terminal,
The raw material of the electronic units such as connector, switch, socket, relay, bus, lead frame, particularly as circulation high current
The raw material of the raw material of electronic unit or the electronic unit of the big heat of bulk storage are useful.
Embodiment
Hereinafter, illustrated for the Cu-Co-Si series copper alloy strips of embodiments of the present invention.It should be noted that
In the present invention, % represents quality % in case of no particular description.
First, the restriction reason for the composition of copper alloy bar is illustrated.
＜ Co and Si ＞
Co and Si is by carrying out Ageing Treatment, and Co and Si formation are with fine Co2The analysis of intermetallic compound based on Si
Go out particle, dramatically increase the intensity of alloy.In addition, along with the Co by Ageing Treatment2Si precipitation, electric conductivity is improved.
Wherein, when Co concentration is less than 0.5%, or Si concentration is less than 0.1（The 1/5 of Co%）During %, the phase is also cannot get even if other compositions are added
The intensity of prestige.In addition, when Co concentration is more than 3.0%, or Si concentration is more than 1.0（The 1/3 of Co%）During %, although result in fully
Intensity, but electric conductivity step-down, and then generation does not contribute to improve the thick Co-Si systems particle of intensity in parent phase（Crystallization
Thing and precipitate）, the reduction of bendability, etching and plating can be caused.Therefore, Co content is set to 0.5 ~
3.0 mass %.It is preferred that Co content is set into 1.0 ~ 2.0 mass %.Similarly, Si content is set to 0.1 ~ 1.0 mass %.It is excellent
Si content is set to 0.2 ~ 0.7 mass % by choosing.
When Co/Si mass ratio is set into 3.0 ~ 5.0, the intensity after precipitation-hardening and electrical conductivity can be improved in the lump.Co/
, will not be with Co when Si mass ratio is less than 3.02The concentration for the Si that Si form is separated out becomes many, electrical conductivity reduction.Co/Si matter
, will not be with Co when amount is than more than 52The concentration for the Co that Si form is separated out becomes many, electrical conductivity reduction.
And then, preferably comprise total 0.001 ~ 2.5 mass % selected from Ni, Cr, Mg, Mn, Ag, P, Sn, Zn, As, Sb, Be,
More than a kind in B, Ti, Zr, Al and Fe.These elements are favorably improved intensity by solution strengthening, precipitation strength etc..
When the total amount of these elements is less than 0.001 mass %, the effect above can not be obtained sometimes.In addition, the total amount of these elements surpasses
When crossing 2.5 mass %, electrical conductivity is reduced or ruptured because of hot rolling sometimes.
The thickness of the Cu-Co-Si series copper alloy strips of the present invention is not particularly limited, for example, can be set to 0.03 ~ 0.6mm.
＜ Lankford value r ＞
Then, the regulation for the feature as copper alloy bar is illustrated.Known to the present inventor etc.：By with specific
Condition manufactures Cu-Co-Si series copper alloy strips, results in the alloy that Lankford value r reaches more than 0.9.It is believed that this is
Since by repeating to anneal and rolling with following conditions, the grain shape in rolling direction and thickness of slab direction, the importing of deformation
Mode can become uniform, and the reduction in thickness of slab direction during deformation can be inhibited.
Herein, r represents plastic deformation value easily along the which direction deformation in thickness of slab direction and plate width direction, and r is bigger
Then deep drawability is more excellent.
For in theory, r is obtained by following formula.
r=ln（Wo/W）/ln（to/t）
Wherein, Wo, W be deformation before, deformation after plate it is wide, to, t be deformation before, deformation after thickness of slab.Wherein, r is because taking out
The position of test film and change, therefore in the present invention,
Pass through formula 1：r=（R0+2 × r45+r90）/ 4 and obtain r.
（Wherein, by sample along be 0 degree relative to rolling parallel direction, 45 degree, the progress tension test of 90 degree of direction obtains
To r values be designated as r0, r45, r90 respectively）.
Also, as the condition of manufacture Cu-Co-Si series copper alloy strips, carry out hot rolling, the first annealing successively to ingot casting, add
Work degree is more than 10% first cold rolling, solution treatment, Ageing Treatment, and by the first annealing and first it is cold rolling repeat 2 times with
On, during the condition for the tensile strength reduction 20 ~ 40% the first annealing being set to before and after annealing, the alloy bar of r >=0.9 can be obtained.
It should be noted that final cold rolling can be carried out between solution treatment and Ageing Treatment.
It is believed that by cold rolling with the annealing of above-mentioned condition progress first and first, as described above, rolling direction and thickness of slab
The grain shape of direction and plate width direction, deformation lead-in mode become uniform, and the reduction in thickness of slab direction during deformation is inhibited.
When first annealing and the first cold rolling number of repetition are less than 2 times, it is impossible to obtain the effect above, r is less than 0.9.
In first anneals, when the reduction of the tensile strength before and after annealing is less than 10%, it is impossible to obtain the effect above, r is not enough
0.9.On the other hand, when the reducing by more than 40% of tensile strength before and after annealing, crystallization particle diameter becomes too much, and r is less than 0.9.First
The tensile strength that annealing is preferably set to before and after annealing reduces by 15 ~ 30% condition.
When first cold rolling degree of finish is less than 10%, it is impossible to obtain the effect above, r is less than 0.9.It should be noted that first
The upper limit of cold rolling degree of finish is, for example, 97%.When degree of finish is more than 97%, the 2nd cold rolling degree of finish is less than 10%.First is cold rolling
Degree of finish be preferably 15 ~ 50%.
It can be carried out between hot rolling and the first annealing cold rolling（It is initial cold rolling）, its degree of finish can be 0 ~ 98%.
Other conditions can be equal with the manufacturing conditions of common Cu-Co-Si series copper alloy strips.
When E1, E45, E90 are more than 5%, it is positively more than 0.9 that can make r, and the processability of copper alloy bar is improved, because
And it is preferred that.
With（Yield strength/tensile strength）When the yield ratio of expression is less than 0.95, uniform elongation region is resulted in
（One Specifications stretches び Collar domains, the increased region of deformation with the increase puted forth effort）Load region become big, result in good shaping
Shape, thus preferably.
Embodiment
Using cathode copper as raw material, the copper alloy of composition shown in table 1, table 2 is founded using air calciner, ingot casting is cast.It is right
The ingot casting carries out appropriate face and cut, so that 10mm thickness is made with 850 ~ 1000 DEG C of progress hot rollings.Thereafter, according to table 1, table 2
Shown condition carries out initial cold rolling（Aliquot does not carry out initial cold rolling）.
Then, first annealing and first cold rolling are repeated 2 times or 3 times according to condition shown in table 1, table 2 respectively.Enter
And, with the solution treatment of 850 ~ 1000 DEG C of progress 5 ~ 100 seconds, then degree of being processed is 0 ~ 20% final cold rolling, and then is carried out
Ageing Treatment（Carried out 5 hours in the case where intensity reaches the temperature of maximum）, the sample that manufacture thickness is 0.2mm.
For each sample, following evaluate is carried out.
＜ tensile strengths（TS）＞
Using cupping machine, according to JIS-Z2241, the tensile strength in the direction parallel with rolling direction is determined（TS）.
The yield strengths of ＜ 0.2%（YS）＞
Using cupping machine, according to JIS-Z2241,0.2% yield strength in the direction parallel with rolling direction is determined
（YS）.By 0.2% yield strength（YS）It is denoted as yield strength.
＜ elongation at breaks ＞
Using cupping machine, according to JIS-Z2241, along relative to the side that rolling parallel direction is 0 degree, 45 degree, 90 degree
To stretching, length L is obtained with the gauge length L0 difference before testing in the form of % between punctuate when test film is broken.Will be relative
E1, E45, E90 are denoted as respectively for 0 degree, 45 degree, 90 degree of elongation at break in rolling parallel direction.
＜ r values ＞
It it is respectively 0 degree, 45 degree, 90 degree along relative to rolling parallel direction according to JIS-Z2241 using cupping machine
Direction stretching.Determine that plate of elongation when be 5% (elongation at break is 2.5% when be less than 5%) be wide and length, examination will be stretched
Plate before and after testing is wide to be denoted as W respectively0, W, the length before and after tension test is denoted as L respectively0, L, pass through r values=ln（Wo/W）/ln
（WL/W0Lo）To calculate r values.
For 0 degree, 45 degree, 90 degree of r values will be denoted as r0, r45, r90 respectively relative to rolling parallel direction, by r=（r0
+ 2 × r45+r90）/ 4 calculate.
＜ yield ratios ＞
Obtained by the ratio between above-mentioned YS/TS.
＜ electrical conductivity（%IACS）＞
The electrical conductivity of sample as obtained by being determined quadripolar mesh procedure（%IACS）.
＜ drawing process ＞
By the Erichsen test method based on JIS-Z2247, the signature untill producing cracking into sample is entered into depth is
More than 3mm sample is designated as drawing process zero（Well）, give as security the sample into depth less than 3mm be designated as drawing process ×（No
It is good）.
Acquired results are shown in table 1.It should be noted that in each embodiment, TS is that more than 550MPa, electrical conductivity are
More than 55%IACS.
[table 1]
[table 2]
Can be clear and definite by table 1, table 2, by the first annealing and degree of finish for more than 10% first it is cold rolling repeat 2 times with
On, and the first annealing is set to the tensile strength before and after annealing reduce 20 ~ 40% condition and the situation of each embodiment that manufactures
Under, r is more than 0.9, and drawing process is improved.
On the other hand, by the tensile strength before and after the annealing of the first annealing reduce by more than 40% in the way of the comparison that manufactures
In the case of example 1 ~ 4, r is less than 0.9, and drawing process is poor.
In the case of by the first annealing and the first cold rolling comparative example 5 being only repeated 1 times, r is also less than 0.9, drawing process
Difference.
In the case of not carrying out the first annealing and the first cold rolling comparative example 6, r is also poor less than 0.9, drawing process.
In the case of comparative example 7 of the first cold rolling degree of finish less than 10%, r is also poor less than 0.9, drawing process.
Claims (7)
1.Cu-Co-Si series copper alloy strips, it contains Co：0.5 ~ 3.0 mass %, Si：0.1 ~ 1.0 mass %, Co/Si mass ratio：
3.0 ~ 5.0, remainder is made up of copper and inevitable impurity,
Lankford value r is more than 0.9, wherein, by sample along relative to the direction that rolling parallel direction is 0 degree, 45 degree, 90 degree
When r values obtained from carrying out tension test are denoted as r0, r45, r90 respectively, r=（R0+2 × r45+r90）/4.
2. Cu-Co-Si series copper alloy strips according to claim 1, wherein, will be 0 degree relative to rolling parallel direction, 45
When degree, 90 degree of elongation are denoted as E1, E45, E90 respectively, E1, E45, E90 are more than 5%.
3. Cu-Co-Si series copper alloy strips according to claim 1 or 2, wherein, represented with yield strength/tensile strength
Yield ratio is less than 0.95.
4. Cu-Co-Si series copper alloy strips according to claim 1 or 2, wherein, contain total 0.001 ~ 2.5 mass %'s
More than a kind in Ni, Cr, Mg, Mn, Ag, P, Sn, Zn, As, Sb, Be, B, Ti, Zr, Al and Fe.
The manufacture method of 5.Cu-Co-Si series copper alloy strips, it is the Cu-Co-Si systems copper any one of claim 1 ~ 4
The manufacture method of alloy bar, wherein,
It is more than 10% first cold rolling, solution treatment, Ageing Treatment to carry out hot rolling, the first annealing, degree of finish successively, and by institute
State the first annealing and it is described first it is cold rolling repeat more than 2 times,
The tensile strength that first annealing is set to before and after annealing reduces by 10 ~ 40% condition.
6. high current electronic unit, it uses the Cu-Co-Si series copper alloy strips any one of claim 1 ~ 4.
7. heat transmission electronic unit, it uses the Cu-Co-Si series copper alloy strips any one of claim 1 ~ 4.
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| JP2013158462A JP5437519B1 (en) | 2013-07-31 | 2013-07-31 | Cu-Co-Si-based copper alloy strip and method for producing the same |
| JP2013-158462 | 2013-07-31 |
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| CN104912626B (en) * | 2015-05-20 | 2017-09-29 | 黄钦生 | A kind of automobile ultralow emission device |
| JP2017089003A (en) * | 2015-11-03 | 2017-05-25 | 株式会社神戸製鋼所 | Copper alloy sheet for heat radiation component |
| WO2018144891A1 (en) * | 2017-02-04 | 2018-08-09 | Materion Corporation | A process for producing copper-nickel-tin alloys |
| CN108118186A (en) * | 2018-02-06 | 2018-06-05 | 重庆熵臻科技有限公司 | A kind of transformer durable copper alloy type Materials And Manufacturing Processes of environment-friendly type high-melting-point |
| JP6879971B2 (en) * | 2018-03-30 | 2021-06-02 | Ｊｘ金属株式会社 | Manufacturing method of copper alloy material, electronic parts, electronic equipment and copper alloy material |
| JP6816056B2 (en) * | 2018-03-30 | 2021-01-20 | Ｊｘ金属株式会社 | Manufacturing method of copper alloy material, electronic parts, electronic equipment and copper alloy material |
| JP6928597B2 (en) * | 2018-12-13 | 2021-09-01 | 古河電気工業株式会社 | Copper alloy plate material and its manufacturing method, drawn products, electrical and electronic parts parts, electromagnetic wave shielding materials and heat dissipation parts |
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| CN102844452A (en) * | 2010-04-14 | 2012-12-26 | Jx日矿日石金属株式会社 | Cu-si-co alloy for electronic materials, and method for producing same |
| CN103052728A (en) * | 2010-08-24 | 2013-04-17 | Jx日矿日石金属株式会社 | Copper-cobalt-silicon alloy for electrode material |
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| JP4708497B1 (en) | 2010-06-03 | 2011-06-22 | Ｊｘ日鉱日石金属株式会社 | Cu-Co-Si alloy plate and method for producing the same |
| JP2013104082A (en) * | 2011-11-11 | 2013-05-30 | Jx Nippon Mining & Metals Corp | Cu-Co-Si-BASED ALLOY AND METHOD FOR PRODUCING THE SAME |
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| CN102844452A (en) * | 2010-04-14 | 2012-12-26 | Jx日矿日石金属株式会社 | Cu-si-co alloy for electronic materials, and method for producing same |
| CN103052728A (en) * | 2010-08-24 | 2013-04-17 | Jx日矿日石金属株式会社 | Copper-cobalt-silicon alloy for electrode material |
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| TWI550107B (en) | 2016-09-21 |
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| JP2015028201A (en) | 2015-02-12 |
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| JP5437519B1 (en) | 2014-03-12 |
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