CN102639732B - copper alloy plate - Google Patents
copper alloy plate Download PDFInfo
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- CN102639732B CN102639732B CN201080051566.7A CN201080051566A CN102639732B CN 102639732 B CN102639732 B CN 102639732B CN 201080051566 A CN201080051566 A CN 201080051566A CN 102639732 B CN102639732 B CN 102639732B
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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
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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
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- 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
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- 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
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- 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
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Abstract
It is an object of the invention to provide a kind of satisfaction the gloomy cupro-nickel silicon systems copper alloy plate of the section of characteristic is required as terminal, the intensity of connector and bendability etc..The copper alloy plate material for electric and electronic components of the present invention has excellent intensity and bendability, and the copper alloy plate includes copper alloy compositions, and the copper alloy compositions are included in terms of quality %：It is any one or two kinds of in 0.8 ~ 5% Ni or Co；0.2 ~ 1.5% Si；Surplus is Cu and inevitable impurity, wherein, the area occupation ratio control by the deviation angle being orientated relative to Cube less than 15 ° of crystal grain is less than 10%, and the area occupation ratio that the crystal grain with 15 ~ 30 ° of deviation angle will be orientated relative to Cube is controlled more than 15%.
Description
Technical field
The present invention relates to excellent copper alloy plate, more particularly to it is adapted to the connection members such as automobile terminal, connector and uses
The intensity on way and the copper alloy plate of excellent in bending workability.
Background technology
In recent years, the miniaturization of electronic instrument and light-weighted requirement are improved, the electric, miniaturization of electronic unit and light weight
Change is continued to develop.The low back of bonder terminal, thin space are developed, as a result, being made to these bonder terminals
Copper alloy plate requirement has higher intensity and more excellent bendability.Need high intensity and excellent bending adds
The copper alloy plate of work widely uses beryllium copper at present, but beryllium copper is very expensive, and metallic beryllium has stronger toxicity.Therefore,
The instead alloy of these materials, the usage amount of corson alloy (Cu-Ni-Si) is continuously increased.
Corson alloy is nickel silicide compounds (Ni2Si) the conjunction that the solid solution limit to copper changes with temperature
Gold, is the precipitation curing type alloy that solidification is handled by Precipitation, its heat resistance, conductance, intensity are good.
But, for the corson alloy, if improving the intensity of copper alloy plate, electric conductivity or bending
Processability is reduced.That is, in the corson alloy of high intensity, the problem of existing is, with good conductance and bending
Processability is extremely difficult.
For it is such the problem of, there is following technology：As the high strength copper alloy of excellent in bending workability, pass through control
The size of precipitate improves bendability in corson alloy (for example, referring to patent document 1).In addition, it is proposed that
Improve intensity, the technology of bendability by controlling the crystal particle diameter of corson alloy (for example, referring to patent document
2).But, for connector material, particularly will by the test film that is abreast cut out with plate width direction with rolling side
BW bending machinings are carried out to parallel sweep, but these materials do not reach the intensity of market demands, bendability,
It is required that the further raising of these characteristics.
On the other hand, in recent years, carried out improving the trial of bendability by charge-coupled knit of domination set.For example, depositing
Make the good method of bendability by controlling Cube orientations (with reference to patent document 3).In addition, also existing by improving
(200) diffracted intensity of X-ray improves the technology of bendability (for example, referring to patent document 4).But, according to this hair
The discovery of a person of good sense etc., improves (200) diffracted intensity of Cube orientations or X-ray really to improving bendability effectively, still
There are following problems：If improving these performances, processing solidification coefficient when material is deformed diminishes, tensile strength reduction.
Prior art literature
Patent document
Patent document 1:Japanese Unexamined Patent Publication 6-184680 publications
Patent document 2:Japanese Unexamined Patent Publication 2006-161148 publications
Patent document 3:Japanese Unexamined Patent Publication 2006-152392 publications
Patent document 4:Japanese Unexamined Patent Publication 2009-007666 publications
The content of the invention
Problems to be solved by the invention
The present inventor etc. is studied the mechanism in the bending machining of the gloomy cupro-nickel silicon systems copper alloy of section, results verification
The shear band that plate surface is produced during bending machining is the reason for cracking.In addition, it is thus identified that the shear band can be by making
Cube orientations are assembled and reduced, still, while, it was also found that the problem of there is tensile strength reduction.It is used as the original of the intensity decreases
Cause, it is believed that be due to：Processing solidification coefficient during due to deformation is small, therefore Cube orientations under low-intensity compared with deforming,
Intensity can not be fully improved, causes to be broken.
In view of the above problems, it is an object of the present invention to provide a kind of excellent in bending workability, and with excellent strong
Degree, is adapted to electric, electronic instrument lead frame, connector, terminal material etc., is particularly adapted to the connection of automobile mounted purposes etc.
Electric, the electronic instrument copper alloy plate of device and terminal material, relay, switch etc..
The method solved the problems, such as
The present inventor etc. has found, can pass through the crystal will have the deviation angle within 15 ~ 30 ° relative to Cube orientations
The area occupation ratio of orientation grain provide in particular range while realizing excellent bendability and high intensity.The present invention is to be based on
The discovery and complete.
That is, the present invention provides following scheme.
(1) a kind of copper alloy plate material for electric and electronic components, it has excellent intensity and bendability, the copper alloy
Sheet material includes copper alloy compositions, and the copper alloy compositions are included in terms of quality %：It is any one or two kinds of in 0.8 ~ 5% Ni or Co；
0.2 ~ 1.5% Si；Surplus be Cu and inevitable impurity, wherein, by the deviation angle being orientated relative to Cube be less than 15 °
Crystal grain area occupation ratio control less than 10%, and the face of the crystal grain with 15 ~ 30 ° of deviation angle will be orientated relative to Cube
Product rate control is more than 15%.
(2) copper alloy plate material for electric and electronic components described in above-mentioned (1), wherein, also containing 0.05 ~ 0.5% Cr.
(3) copper alloy plate material for electric and electronic components described in above-mentioned (1) or (2), wherein, also containing Zn, Sn, Mg, Ag,
More than one or both of Mn and Zr, its total amount is 0.01 ~ 1.0%.
(4) copper alloy plate material for electric and electronic components any one of above-mentioned (1) ~ (3), it is in solution processing
Afterwards, different friction (Iso frictions) cold-rolling treatment is implemented.
(5) a kind of manufacture method of copper alloy plate material for electric and electronic components, this method includes：Molten alloyed copper is carried out
The process of casting；The process for being heated or being homogenized heat treatment；Implement the process of different friction hot rolling treatment；Implement cold-rolling treatment
Process；Implement the process of intermediate annealing；Implement the process of solution processing；Implement different friction cold-rolling treatment process；And implement
The process of Ageing Treatment, the copper alloy metal liquation include copper alloy compositions, the copper alloy compositions in terms of quality %, comprising：
It is any one or two kinds of in 0.8 ~ 5% Ni or Co；0.2 ~ 1.5% Si；Surplus is Cu and inevitable impurity.
(6) manufacture method of the copper alloy plate material for electric and electronic components described in above-mentioned (5), wherein, the different friction is cold
Roll and carried out using the different up-down rollers of surface roughness.
The effect of invention
The copper alloy plate intensity of the present invention is high and with good bendability, and shows high conductivity.Separately
Outside, by adding other addition element, additionally it is possible to further improve the above-mentioned physical property of copper alloy plate.In addition it is possible to realize
The raising of processability and stress relaxation characteristics when resistance to thermally strippable, the raising of resistance to migration during welding, hot rolling.
Embodiment
High intensity following to the present invention and with good bendability, and the high electricity of the invention of conductance
The preferred metal structure of gas electronic component-use copper alloy plate is described in detail.Here, " Cu alloy material " refers to copper
Alloy raw material is processed into the material of given shape (for example, plate, bar, paper tinsel, rod, line etc.).Wherein, sheet material refers to specific thickness
Degree, dimensionally stable, the material in the surface direction with width, broadly including web.Here, in sheet material, " material surface "
Refer to " plate top layer ", " depth location of material " refers to " position in thickness of slab direction ".The thickness of sheet material is not particularly limited, but
It is, it is contemplated that effect of the invention is more notable and is adapted to practical application, more preferably preferably 8 ~ 800 μm, 50 ~ 70 μm.
In addition, the integrated rate (Ji Plot rates of atomic plane of the copper alloy plate of the present invention with milled sheet in given directions) rule
Its fixed characteristic, still, in the present invention, as long as with the above-mentioned characteristic as copper alloy plate, the shape of copper alloy plate
Shape is not limited to sheet material or web, and tubing can also be explained as sheet material and treated as sheet material.
(average grain diameter)
The average crystal particle diameter of the copper alloy plate of the present invention is preferably less than 50 μm.Average crystal particle diameter is in the above-mentioned upper limit
When value is following, in the case of Good Way (GW) bending machining, any bending machining of Bad Way (BW) bending machining, all
Shear band of the generation as Crack is difficult, therefore preferably.Here, Good Way refer to roll parallel direction, and Bad Way are
Refer to rolling vertical direction.In addition, crystal particle diameter is obtained by JIS H0501 (patterning method).
(regulation in EBSD measure)
For the set tissue of the copper alloy plate of the present invention, especially for while realizing intensity and bending machining
It is necessary to have following set tissue for property：According to the measurement result of SEM-EBSD methods (following), the deviation being orientated relative to Cube
Angle (misorientation) less than the area occupation ratio of 15 ° of crystal grain be less than 10%, and relative to the deviation angle that Cube is orientated for 15 ~
The area occupation ratio of 30 ° of crystal grain is more than 15%, and preferably 20% less than 50%.
In the case of copper alloy plate, primarily form and as follows be referred to as Cube orientations, Goss orientations, Brass
The set tissue of orientation, Copper orientations, S orientations etc., and there is the crystal face corresponding to above-mentioned set tissue.
The formation of these set tissues, also can be because of processing, the difference of heat treatment method in the case of the phase isomorphous system
And it is different.In the case of set tissue by rolling the materials such as the sheet material formed, represented with face and direction, face is represented with { ABC },
Direction is represented with ＜ DEF ＞.The method for expressing of crystal orientation in this specification uses and regard the rolling direction (RD) of material as X
Axle, plate width direction (TD) are as Y-axis, rolling normal direction (ND) as the rectangular coordinate system of Z axis, and each region in material is used
The indices of crystallographic plane (hkl) vertical with Z axis and the orientation index [uvw] parallel with X-axis, are represented in the form of (hkl) [uvw].Companion
With above-mentioned notation, each orientation is expressed as below.
As described above, the set tissue of common copper alloy plate is made up of considerable orientation factor, still, if these
The composition of crystal face changes, then the plastic behavior of the material such as sheet material changes, and the processability such as bending also changes.
The set of the gloomy cupro-nickel silicon systems high strength copper alloy sheet material of conventional section is organized in the feelings manufactured by usual way
Condition, as be described hereinafter described in embodiment, Cube orientations { 001 }<100>S orientations { 123 } in addition<634>And Brass orientations { 011 }<
211>As main body, the ratio of Cube orientations is reduced.Therefore, shear band is easily particularly produced in BW bending machinings, bent
Processability is deteriorated.On the other hand, it is curved to improve in the aggregation for improving crystal grain of the deviation angle less than 15 ° being orientated relative to Cube
In the case of song, the problem of intensity decreases are such can be produced.
On the other hand, copper alloy plate of the invention set tissue relative to Cube be orientated { 001 }<100>Deviation
The area occupation ratio for the crystal grain that angle is 15~30% is more than 15%, is intensity and the excellent set tissue of bendability.Need explanation
, in the present invention, as long as the area occupation ratio relative to the crystal grain that the Cube deviation angles being orientated are 15~30 ° is more than 15%
, it is allowed to other orientations exist as secondary orientation.
Copper alloy plate set tissue relative to Cube be orientated { 001 }<100>Deviation angle taken for 15~30 °
Determine and obtain by the following method to the concentration class of grain：The electron microscope tissue based on SEM is measured using EBSD, and
Orientation analysis is carried out based on obtained data, using crystal orientation distribution function (ODF).Here, to including more than 400 crystal grain
1200 μm of square Area of Sample, be scanned with 0.5 μm of step-length, and orientation is analyzed.It should be noted that due to
These distribution of orientations change on the thickness direction of material, it is therefore preferable that by a thickness direction to it is any some
Distribution of orientations is analyzed, and takes its average value to obtain.
The SEM-EBSD methods are Scanning Electron Microscopy-Electron Back Scattered
The abbreviation of Diffraction Pattern (ESEM-EBSD) method.That is, it is to scanning electron microscope
(SEM) each crystal grain irradiating electron beam shown on image, and the method for identifying by its diffracted electrons each crystal orientation.
On the deviation angle relative to ideal orientation by above-mentioned exponential representation, calculated centered on common axis of rotation
The anglec of rotation, is used as deviation angle.For example, being orientated (231) [6-43] relative to S, (121) [1-11] is by (201017) direction conduct
Rotary shaft, in 19.4 ° of relation of rotation, regard the angle as deviation angle.Common axis of rotation use can use minimum deviation
The rotary shaft of angle expression.The deviation angle is calculated to all measuring points, first is remained into after decimal point as significant figure
Word, with the area divided by whole aspect of measure that each crystal grain with the orientation being less than within 15 °, 15 ~ 30 ° is orientated relative to Cube
Product, is used as area occupation ratio.
When carrying out EBSD measure, in order to obtain the Kikuchi lines diffraction image of distinctness, after mechanical lapping, colloid two is used
The abrasive particle of silica is carried out to matrix surface after mirror ultrafinish, then is measured.
Here, being illustrated by the feature determined to comparing EBSD with X-ray diffraction measure.First, enumerated
Any is：It can only meet Bragg diffraction condition using what the method for X-ray diffraction was determined and can sufficiently be spread out
This five kinds of ND//(111), (200), (220), (311), (420) face of intensity is penetrated, the deviation angle phase being orientated relative to Cube
It can not be determined such as the crystal orientation that the high index table as ND//(511) face, ND//(951) face reaches when in 15 ~ 30 °.That is, lead to
Cross and determined using EBSD, the information of the orientation on them is obtained first, thus, specify that specific alloy structure and effect
Relation.Second point is：X-ray diffraction measure be crystal orientation included by ND//{ hkl } ± 0.5 ° of degree part, with
This is relative, make use of Kikuchi pattern because EBSD is determined, the especially extensive of particular crystal plane is not limited to therefore, it is possible to enlisted the services of
Alloy structure relevant information, as whole alloy material, can clearly using X-ray diffraction carry out regulation be difficult.
As described above, determining different with the content and property of the information that X-ray diffraction measure is obtained by EBSD.In addition, in this explanation
In book, unless otherwise specified, EBSD result is that the ND directions of copper alloy plate are carried out.
(alloy composition etc.)
Then, (the content % of record is with matter for the restriction reason constituted to the chemical composition in the copper alloy plate of the present invention
Amount % meters) illustrate.
·Ni、Co、Si
Ni content is 0.5 ~ 5.0%.Ni is together contained with following Si, is to be formed to separate out in Ageing Treatment
Ni2Si phases, so as to be favorably improved the element of copper alloy plate intensity.When Ni content is very few, above-mentioned Ni2Si phases are not enough, it is impossible to
Improve the tensile strength of copper alloy plate.On the other hand, if Ni content is excessive, conductance reduction, in addition, hot rolling workability becomes
Difference.Therefore, Ni content is 0.5 ~ 5.0%, preferably 1.5 ~ 4.0% scope.
Co content is 0.5 ~ 5.0%.Co and Si together contains, be in Ageing Treatment with Ni be identically formed analysis
The Co gone out2Si phases, so as to be favorably improved the element of copper alloy plate intensity.When Co content is very few, above-mentioned Co2Si phases are not enough,
The tensile strength of copper alloy plate can not be improved.On the other hand, if Co content is excessive, conductance reduction.In addition, hot rolling adds
Work is deteriorated.Therefore, Co content is 0.5 ~ 5.0%, preferably 0.8 ~ 3.0% scope.
Above-mentioned two kinds of Ni and Co can amount to and contain 0.5 ~ 5.0%.If containing both Ni and Co, carrying out Ageing Treatment
When, separate out Ni2Si and Co2Both Si, so as to improve aging strength.When the total amount of Ni and Co content is very few, it is impossible to improve
Tensile strength, if excessively, conductance, hot rolling workability reduction.Therefore, the total amount of Ni and Co content is 0.5 ~ 5.0%, excellent
Elect as 0.8 ~ 4.0% scope.Particularly in the case where needing high conductivity, Co addition is preferably set to be more than Ni addition
Amount.
Si together contains with above-mentioned Ni, Co, and the Ni separated out is formed in Ageing Treatment2Si or Co2Si phases, so as to contribute to
Improve the intensity of copper alloy plate.Si content in the case where being calculated as Ni/Si=4.2, Co/Si=4.2 with stoichiometric proportion,
The balance of conductance and intensity is best.Therefore, Si content is to make Ni/Si, Co/Si, (Ni+Co)/Si be 3.2 ~ 5.2, preferably
For the amount of 3.5 ~ 4.5 scope.
Deviateing the scope, in the case of excessively containing Si respectively, although the stretching that can improve copper alloy plate is strong
Degree, but Si solid solutions in the matrix of copper of excess electron excess fraction, the conductance reduction of copper alloy plate.In addition, what Si excessively contained
In the case of, castability, hot rolling during casting and it is cold rolling when rolling processability also reduce, easily produce casting crack and rolling split
Line.On the other hand, the scope, in the case that Si content is very few, Ni are being deviateed2Si and Co2Si precipitated phase is not enough, it is impossible to carry
The tensile strength of high plate.
Other elements
In addition to above-mentioned composition, copper alloy can also contain 0.01 ~ 0.5% Cr.Cr, which has, makes the crystal grain in alloy micro-
The effect of refinement, is favorably improved the intensity and bendability of copper alloy plate.If Cr contents are very few, the not no effect
Really, if Cr contents are excessive, crystal, aging strength reduction are formed during casting.It is preferred that content be 0.05 ~ 0.3%.
For the high strength copper alloy sheet material of the present invention, in addition to above-mentioned basic composition, as addition element, with
Quality % is counted, and can also contain the one or two or more kinds in following, i.e. Sn：0.05~1.0%、Zn：0.01~1.0%、Ag：0.01
~1.0%、Mn：0.01~1.0%、Zr：0.1~1.0%、Mg：0.01~1.0%.Wherein, containing in the case of more than two kinds, its total amount
For 0.01 ~ 1.0%.These elements are the further raising intensity of the main purpose with the copper alloy as the present invention and led
The element of the collective effect effect of any property in electric rate or bendability.Below, the work of the characteristic of each element is recorded
Meaning with effect and containing scope.
Sn is primarily used for improving the element of copper alloy plate intensity, in use, choosing in the purposes for paying attention to these characteristics
Contain to selecting property.If Sn content is very few, the effect that it improves intensity is insufficient.On the other hand, if containing Sn, deposit
The trend reduced in the conductance of copper alloy plate.Particularly if Sn is excessive, then the conductance for being difficult to make copper alloy plate is 20%
More than IACS.Therefore, in the case of containing Sn, the scope that the content for preferably making Sn is 0.01 ~ 1.0%.
By adding Zn, it is possible to increase resistance to thermally strippable and resistance to migration during welding.If Zn content is very few, its
Effect is insufficient.There is the trend of the conductance reduction of copper alloy plate when on the other hand, containing Zn, if Zn is excessive, be difficult to
The conductance for making copper alloy plate is more than 20%IACS.It is therefore preferable that the scope that the content for making Zn is 0.01 ~ 1.0%.
Ag is favorably improved the intensity of copper alloy plate.If Ag content is very few, its effect is insufficient.The opposing party
Face, when excessively containing Ag, its effect reaches saturation, therefore not preferred.Therefore, in the case of containing Ag, preferably make Ag's
Content is 0.01 ~ 1.0% scope.
Mn is mainly used for improving processability of the alloy in hot rolling.If Mn content is very few, its effect is insufficient.
On the other hand, if Mn is excessive, liquation mobility when copper alloy is cast is deteriorated, qualified casting reduction.Therefore, containing
In the case of Mn, the scope that the content for making Mn is 0.01 ~ 1.0%.
Zr mainly makes crystal grain miniaturization, so as to improve the intensity and bendability of copper alloy plate.If Zr content mistake
Few, then its effect is insufficient.On the other hand, if Zr is excessive, compound is formed, the processability drop of rolling of copper alloy plate etc.
It is low.Therefore, in the case of containing Zr, the scope that the content for making Zr is 0.01 ~ 1.0%.
Mg is used to improve stress relaxation characteristics.Therefore, in the case where needing stress relaxation characteristics, 0.01 ~ 1.0%
Scope optionally contains.It is insufficient as the effect of target if Mg is very few, when Mg is excessive, conductance can be caused to reduce
The drawbacks of, therefore it is not preferred.
(manufacture method etc.)
Then, the preferable production process (preferred embodiment) below to the copper alloy plate of the present invention is illustrated.
The corson alloy sheet material of the present invention is by casting, hot rolling, cold rolling 1, intermediate annealing, cold rolling 2, solution warm
Processing, cold rolling 3, aging strengthening model, pinch pass, each operation of process annealing are manufactured.The manufacture of the copper alloy plate of the present invention
Method in itself can be by manufacturing with the situation identical method of conventional corson alloy.For set tissue,
The manufacturing condition of restriction each operation is needed, especially for the copper alloy plate of the manufacture present invention, is preferably moved back in the middle of strict control
It is fiery and cold rolling 3 condition.
In the present embodiment, casting is that composition adjustment is cast into the copper alloy metal liquation after above-mentioned compositing range
Make.Then, ingot bar is carried out after the cutting of face, is heated or homogenized heat treatment at 800 ~ 1000 DEG C, then carry out hot rolling,
And water cooling is carried out to the plate after hot rolling.
After hot rolling, face cutting is carried out to surface, cold rolling 1 is then carried out.If the cold rolling 1 rolling rate is fully high, its
Afterwards until producing final products, Brass orientations and S orientations etc. also will not excessively develop, can fully improve relative to Cube
The deviation angle of orientation is 15 ~ 30 ° of area occupation ratio.Therefore, cold rolling 1 rolling rate is preferably more than 70%.
The Cu alloy material of the present invention is characterised by, between cold rolling 1 and solution heat treatment, at 300 ~ 800 DEG C
After the intermediate annealing for carrying out 5 seconds ~ 2 hours, application rolling rate is cold rolling the 2 of 3 ~ 80%.Intermediate annealing passes through with than solution
The low temperature of heat treatment temperature is heat-treated, and material perfect recrystallization is not made, so as to obtain there occurs partial, re-crystallization
Sub- annealed structure.In cold rolling 2, by the rolling of relatively low working modulus, microcosmic uneven answer can be imported in the material
Become.By the effect of above-mentioned two process, in the recrystallization set tissue after solution heat treatment, desired crystalline substance can be obtained
Body is orientated.The preferred scope of intermediate annealing is to be carried out 10 seconds ~ 1 minute at 400 ~ 700 DEG C, and particularly preferred scope is
Carried out 15 seconds ~ 45 seconds at 500 ~ 650 DEG C.The preferred scope of cold rolling 2 working modulus is 5 ~ 55%, further preferably
Scope be 7 ~ 45%.
In the past, the such heat treatment of above-mentioned intermediate annealing was in order that material recrystallized, and reduced intensity and carry out, thus
Reduce the load in the rolling of subsequent handling.In addition, the purpose of rolling is to reduce thickness of slab, if the energy of common roll mill
Power, then generally utilize more than 80% working modulus.Intermediate annealing and cold worked purpose and these common contents in the present invention
Difference, for making the crystal orientation after recrystallization that there is preferentially property.
In the present embodiment, solution processing is carried out 5 seconds ~ 300 seconds at 600 ~ 1000 DEG C.According to Ni's and Co
Concentration is different, and necessary temperature conditionss change, it is therefore desirable to appropriate temperature conditionss are selected according to Ni, Co concentration.If
Solution temperature is more than above-mentioned lower limit, then intensity can fully to be kept in ageing treatment process, if solution temperature is
Below above-mentioned higher limit, then material will not be softened to more than necessary degree, can suitably realize shape control, therefore preferably.Now,
It is preferred that the area occupation ratio for making the crystal grain that the deviation angle relative to Cube orientations is 15 ~ 30 ° is 15 ~ 50%.
After solution processing, cold rolling the 3 of progress 5 ~ 40%.When in progress, this is cold rolling, if implementing the cold of the working modulus
Roll, then gather tissue within the scope of the invention, therefore preferably.According to the discovery of the present inventor etc., if passing through cold roll
The different roller of roughness implements different friction rolling, then is carried out relative to crystal grain of the deviation angle less than 15 ° that Cube is orientated small
Orientation rotation, orientation can be made to concentrate on the deviation angle being orientated relative to Cube in 15 ~ 30 ° of orientation.It is believed that this
It is due to that in different friction rolling, its plastic constraint is different above and below for rolling stock, due to the plastic constraint not
Together, small detrusion can be imported.Here, it is preferred that the center line average roughness Ra of upper roller and lower roll difference is 0.05 ~ 3.0
μm, more preferably 2.4 ~ 2.8 μm.The roughness of roller is adjusted by using pouncing paper roller roughening.Cold rolling 3 have
Increase the effect of Precipitation amount, also contribute to intensity.
Ageing Treatment carries out the scope of 0.5 hour ~ 8 hours at 400 ~ 600 DEG C.It is different with Co concentration according to Ni, must
The temperature conditionss wanted change, therefore, it is necessary to select appropriate temperature conditionss according to Ni, Co concentration.The temperature of Ageing Treatment
When spending to be more than above-mentioned lower limit, Precipitation amount will not be reduced, and can fully keep intensity.In addition, the temperature of Ageing Treatment is
When below above-mentioned higher limit, precipitate will not coarsening, intensity can be kept.
It is preferred that the working modulus for making the pinch pass after solution processing is less than 0 ~ 20%.If working modulus is too high, Cube takes
Orientation rotation is carried out to grain to Brass, S and Copper orientation etc., set is organized in outside the scope of the present invention sometimes.
Whether the confirmation of the characteristic of copper alloy plate produced by the present invention can be by the tissue of copper alloy plate in prescribed limit
It is interior, the checking carried out analyzed using EBSD carry out.
Embodiment
Below, the present invention is further described based on embodiment, but the present invention is not limited to these embodiments.
Below, embodiments of the invention are illustrated.The copper alloy respectively constituted shown in table 1 below is cast, made
Copper alloy plate is made, and each characteristic such as its intensity, conductance, bendability is evaluated.
First, cast by DC (Direct Chill, direct cold shock) method, obtain thick 30mm, width 100mm, length
150mm ingot bar.Then, these ingot bars are heated to 900 DEG C, after the temperature is kept for 1 hour, are rolled into thickness 14mm, and
Rapid cooling.Then, two sides has been carried out to 1mm face cutting respectively, after deoxidation overlay film, it is 90 ~ 98% to implement rolling rate
Cold rolling 1.Then, the heat treatment of 1 hour is carried out at 600 ~ 700 DEG C, cold rolling 2 are implemented with 5 ~ 20% cold rolling rate.Then, 700
Solution processing is carried out under the conditions of ~ 950 DEG C various, is cooled down immediately with more than 15 DEG C/sec of cooling velocity.Then,
Implementation rolling rate is cold rolling the 3 of 5 ~ 40%.Now, using the roller that the difference of the surface roughness Ra of up-down rollers is 0.05 ~ 3.0 μm.Connect
, in non-reactive gas ambient, implement the Ageing Treatment of 2 hours at 400 ~ 600 DEG C, then carry out rolling rate be 20% with
Under finish rolling, make final thickness of slab it is regular be 0.15mm.After finish rolling, to being implemented at 400 DEG C at the process annealing of 30 seconds
Material after reason, carries out various evaluating characteristics.
For the copper alloy plate so manufactured, the sample cut out after each equal Use Limitation processing of example by copper alloy plate is implemented
Experiment and evaluation as follows.
It is less than 15 ° of crystalline substance to the tissue of copper alloy plate sample, relative to the deviation angle that Cube is orientated by the above method
The area occupation ratio and deviation angle of body orientation grain are that the area occupation ratio of the crystal orientation grain within 15 ~ 30 ° is determined.These results
It is as shown in the table.
It should be noted that device is determined as EBSD, the OIM5.0HIKARI for having used TSL companies to manufacture.
In addition, conductive to the area occupation ratio of (1) each crystal orientation grain of above-mentioned copper alloy plate sample, (2) tensile strength, (3)
Rate, (4) bendability are evaluated.
(1) for the area occupation ratio of crystal orientation grain, show that the deviation angle being orientated relative to Cube is less than 15 °
Area occupation ratio and the area occupation ratio that the deviation angle being orientated relative to Cube is 15 ~ 30 °.
(2) tensile strength is obtained using No. 5 test films described in JIS Z 2201 based on the standards of JIS Z 2241.Draw
The integral multiple that intensity is rounding to 5MPa is stretched, is indicated.
(3) conductance is obtained based on the standards of JIS H 0505.
(4) for bendability, by 5mm of bend test piece width w, curvature R=0 ~ 0.6 90 ° of bendings are carried out,
The ratio between the minimum profile curvature radius not cracked (R) and thickness of slab (t) are defined as R/t.
Embodiments of the invention are shown in the embodiment 1 ~ 31 of table 1.The set of embodiment 1 ~ 31 is organized in the model of the present invention
In enclosing, its intensity, excellent in bending workability.
Table 2 is illustrated that the comparative example relative to the present invention.The Ni or Co of comparative example 1,2,5 content ratio present invention provide that
Scope it is few, therefore tensile strength is significant lower.The Ni or Co of comparative example 3,4,6,7 content are excessive, therefore are produced during hot rolling
Crackle, so have ceased manufacture.
Table 3 is using the embodiment identical ingot bar with table 1, to the difference of the average roughness Ra of cold rolling 3 top and bottom rolls
The example studied the influence that set taeniae telarum comes.Embodiment 10-2,10-3,22-2,22-3,29-2,29-3's of table 3
Set is organized in the range of example of the present invention, its intensity and excellent in bending workability.On the other hand, comparative example 10-2,22-2,
29-2 Ra difference is small, therefore high relative to area occupation ratio of the deviation angle less than 15 ° that Cube is orientated, intensity decreases.In addition, than
The difference of Ra compared with example 10-3,22-3,29-3 is big, therefore the area occupation ratio within 15 ° ~ 30 ° of deviation angle being orientated relative to Cube
It is relatively low, bendability reduction.
In addition, the surface roughness Ra of roller is determined based on the standards of JIS B 0601.
[table 1]
| No. | Ni | Co | Si | Cr | It is other | The ※ 1 of area occupation ratio 1 | The ※ 2 of area occupation ratio 2 | Conductance | Tensile strength (MPa) | R/t | |
| Embodiment | 1 | 1.5 | 0.4 | Mg：0.1 | 5 | 18 | 44 | 740 | 0.33 | ||
| Embodiment | 2 | 2.3 | 0.5 | 7 | 15 | 42 | 850 | 0.67 | |||
| Embodiment | 3 | 2.3 | 0.5 | 0.3 | 8 | 20 | 41 | 870 | 0.67 | ||
| Embodiment | 4 | 2.3 | 0.5 | 0.1 | 6 | 19 | 42 | 865 | 0.67 | ||
| Embodiment | 5 | 2.3 | 0.5 | 0.1 | Mg：0.1.Sn：0.1.Zn：0.5 | 9 | 31 | 39 | 875 | 0.67 | |
| Embodiment | 6 | 2.3 | 0.5 | Mg：0.1.Sn：0.1 | 8 | 28 | 42 | 860 | 0.67 | ||
| Embodiment | 7 | 2.3 | 0.5 | Ag：0.1 | 6 | 22 | 43 | 855 | 0.67 | ||
| Embodiment | 8 | 2.3 | 0.5 | Mn：0.1 | 7 | 23 | 40 | 860 | 0.67 | ||
| Embodiment | 9 | 2.3 | 0.5 | Zr：0.1 | 7 | 22 | 40 | 860 | 0.67 | ||
| Embodiment | 10 | 3.8 | 0.9 | 0.1 | 7 | 23 | 38 | 900 | 1 | ||
| Embodiment | 11 | 3.8 | 0.9 | 0.1 | Mg：0.1.Sn：0.1.Zn：0.5 | 5 | 24 | 36 | 910 | 1 | |
| Embodiment | 12 | 3.8 | 0.9 | Sn：0.1 | 4 | 19 | 37 | 900 | 1 | ||
| Embodiment | 13 | 3.8 | 0.9 | 0.2 | 8 | 27 | 37 | 920 | 1 | ||
| Embodiment | 14 | 4.9 | 1.2 | Mg：0.1 | 8 | 17 | 33 | 935 | 1.5 | ||
| Embodiment | 15 | 4.9 | 1.2 | 8 | 25 | 34 | 930 | 1.5 | |||
| Embodiment | 16 | 4.9 | 1.2 | Mg：0.1.Sn：0.1.Zn：0.5 | 7 | 19 | 31 | 940 | 1.5 | ||
| Embodiment | 17 | 1.2 | 1.2 | 0.6 | Mg：0.1 | 6 | 17 | 50 | 870 | 0.67 | |
| Embodiment | 18 | 1.3 | 0.8 | 0.5 | Mg：0.1.Sn：0.1.Zn：0.5 | 8 | 16 | 51 | 860 | 0.67 | |
| Embodiment | 19 | 1.3 | 0.8 | 0.5 | Ag：0.1 | 8 | 22 | 52 | 860 | 0.67 | |
| Embodiment | 20 | 1.3 | 0.8 | 0.5 | Mn：0.1 | 6 | 24 | 49 | 865 | 0.67 | |
| Embodiment | 21 | 1.3 | 0.8 | 0.5 | Zr：0.1 | 9 | 25 | 49 | 865 | 0.67 | |
| Embodiment | 22 | 1.3 | 0.8 | 0.5 | 5 | 21 | 50 | 840 | 0.67 | ||
| Embodiment | 23 | 2.1 | 0.7 | 0.7 | 0.1 | 7 | 27 | 47 | 880 | 1 | |
| Embodiment | 24 | 2.4 | 1.2 | 0.9 | 8 | 40 | 42 | 900 | 1 | ||
| Embodiment | 25 | 0.8 | 2.6 | 0.8 | 7 | 19 | 41 | 880 | 1 | ||
| Embodiment | 26 | 0.6 | 2.8 | 0.8 | 8 | 26 | 62 | 890 | 1 | ||
| Embodiment | 27 | 0.8 | 0.2 | Mg：0.1 | 7 | 18 | 60 | 680 | 0 | ||
| Embodiment | 28 | 1.4 | 0.3 | Mg：0.1 | 4 | 20 | 55 | 780 | 0.5 | ||
| Embodiment | 29 | 2.3 | 0.5 | 8 | 16 | 55 | 860 | 0.67 | |||
| Embodiment | 30 | 3.1 | 0.7 | Mg：0.1.Sn：0.1.Zn：0.5 | 9 | 19 | 45 | 870 | 1 | ||
| Embodiment | 31 | 3.6 | 0.9 | Ag0.1 | 6 | 20 | 55 | 890 | 1 |
※2：Relative to the area occupation ratio that the deviation angle that Cube is orientated is less than 15 °
※3：Relative to the area occupation ratio that the deviation angle that Cube is orientated is 15~30 °
[table 2]
[table 3]
Then, for the copper alloy plate manufactured by conventional manufacturing condition, for the copper clearly with the present application
The difference of sheet alloy, makes copper alloy plate, and carried out the evaluation of characteristic project similar to the above under the conditions of it.Separately
Outside, the thickness of each sheet material unless otherwise specified, working modulus is adjusted in the way of thickness same as the previously described embodiments.It is following
The condition of example is all the usual manufacturing condition for considering the application when filing an application, using different in cold rolling after solution
Friction rolling.
The condition of (comparative example 101) ... Japanese Unexamined Patent Publication 2009-007666 publications
Using high-frequency melting furnace to being combined with the metallic element same with the invention described above example 1-1 and surplus by Cu and not
The alloy of evitable impurity composition is melted, and is cast the alloy with 0.1 ~ 100 DEG C/sec of cooling velocity, is obtained ingot bar.Will
After it is kept for 3 minutes to 10 hours at 900 ~ 1020 DEG C, carry out hot-working, then carry out water quenching, then carry out flush cut with
Except deoxidation rust deposite.Thereafter process is that the processing by implementing following processes A-3, B-3 has manufactured copper alloy c01.
Manufacturing process includes the solution heat treatment more than once or twice, here, with therein last solution
What is be heat-treated is front and rear by Activity Classification, using the process untill centre is solution as A-3 processes, will be middle solution later
Process is used as B-3 processes.
Process A-3：Implement the cold working that section slip is more than 20%, implement 5 minutes ~ 10 hours at 350 ~ 750 DEG C
Heat treatment, implement the cold working that section slip is 5 ~ 50%, implement 5 seconds ~ 30 minutes solution at 800 ~ 1000 DEG C
Heat treatment.
Process B -3：It is less than 50% cold working (being as good as friction) to implement section slip, and 5 are implemented at 400 ~ 700 DEG C
Minute ~ heat treatment of 10 hours, implement the cold working that section slip is less than 30%, implement 5 seconds ~ 10 at 200 ~ 550 DEG C
The quenched annealing of hour.
Obtained test body c01 is different on this point of different friction rolling the presence or absence of in manufacturing condition from above-described embodiment,
It is the result that tensile strength is unsatisfactory for requiring characteristic.
The condition of (comparative example 102) ... Japanese Unexamined Patent Publication 2006-283059 publications
The copper alloy of the invention described above example 1-1 composition is melted in an atmosphere, under charcoal cladding using electric furnace,
Judgement could be cast.Ingot bar after mill heat, finish rolling is into thickness 15mm.Then, cold rolling and hot place is implemented to the hot-finished material
Reason (cold rolling 1 → solution continuous annealing → cold rolling 2 (being as good as friction) → Ageing Treatment → annealing of cold rolling 3 → short time), manufacture
Copper alloy thin plate (c02) with given thickness.
Obtained test body c02 intermediate annealing and cold rolling 2, Yi Jiyou the presence or absence of in manufacturing condition with above-described embodiment 1
Difference in this 2 points of friction rolling is as good as, is the result for being unsatisfactory for bendability.
The condition of (comparative example 103) ... Japanese Unexamined Patent Publication 2006-152392 publications
The alloy with the invention described above example 1-1 compositions is carried out in air, under charcoal cladding in cryptol furnace
Melt, be cast as cast iron book mold, obtain thick 50mm, width 75mm, long 180mm ingot bar.Also, to the surface of ingot bar
Flush cut is carried out, thickness 15mm is then rolled at a temperature of 950 DEG C, is quenched from more than 750 DEG C of temperature in water.Connect
, after deoxidation rust deposite, progress is cold rolling, obtain the plate of given thickness.
Then, carried out at a temperature of after the solution processing of heating 20 seconds, after being quenched in water, led to using molten salt furnace
Later the pinch pass (being as good as friction) of half portion, is made the cold-reduced sheet of each thickness.Now, processing as follows, cold rolling to these
Rate (%) carries out various changes, and cold-reduced sheet (c03) is made.As shown below to the temperature (DEG C) of these cold-reduced sheets and time (hr)
Various changes are carried out, Ageing Treatment has been carried out.
Obtained test body c03 intermediate annealing and cold rolling 2, Yi Jiyou the presence or absence of in manufacturing condition with above-described embodiment 1
Difference in this 2 points of friction rolling is as good as, is the result for being unsatisfactory for bendability.
The condition of (comparative example 104) ... Japanese Unexamined Patent Publication 2008-223136 publications
Melting is carried out to the copper alloy shown in embodiment 1, and cast using vertical continuous casting machine.By what is obtained
Slab (thickness 180mm) cuts out thickness 50mm sample, is heated to after 950 DEG C and takes out, proceeds by hot rolling.Now, with
Rolling rate under 950 DEG C ~ 700 DEG C of temperature province is more than 60% and also rolled under the temperature province less than 700 DEG C
Mode set passage program list.The final passage temperature of hot rolling is between 600 DEG C ~ 400 DEG C.Total hot rolling rate of slab is about
90%.After hot rolling, the oxide layer on (flush cut) top layer is removed by mechanical lapping.
Then, progress is cold rolling, is provided to solution processing.By the thermocouples monitors solution for being installed on specimen surface
Change temperature change during processing, obtain the heating-up time from 100 DEG C to 700 DEG C in temperature-rise period.According to alloy composition 700 ~
It is adjusted to reach temperature in the range of 850 DEG C so that the average crystal particle diameter (twin boundary not being considered as into crystal boundary) after solution processing
For 10 ~ 60 μm, the retention time under 700 ~ 850 DEG C of temperature province is adjusted in the scopes of 10 seconds ~ 10 minutes.Then, it is right
Sheet material after above-mentioned solution processing implements middle cold rolling (being as good as friction) to roll rate, then implements Ageing Treatment.At timeliness
Reason temperature is 450 DEG C of material temperature, for aging time, and being adjusted to hardness under 450 DEG C of timeliness according to alloy composition is
The time of peak value.Constituted according to such alloy, optimal solution treatment conditions and aging time are held by preliminary experiment.
Then, pinch pass is carried out to roll rate.Then for carrying out the sample after pinch pass, further implement to load 400 DEG C of stove
In the process annealing of 5 minutes.Thus material to be tested c04 is obtained.It should be noted that as needed, carrying out plane in midway and cutting
Cut, make the thickness of slab of material to be tested neat, be 0.2mm.Main manufacturing condition is as described below.
[condition of Japanese Unexamined Patent Publication 2008-223136 embodiments 1]
Less than the hot rolling rate at 700 DEG C ~ 400 DEG C：56% (a time)
Solution before processing cold rolling rate：92%
Middle cold rolling cold rolling rate：20%
Pinch pass cold rolling rate：30%
Heating-up time from 100 DEG C to 700 DEG C：10 seconds
Obtained test body c04 intermediate annealing and cold rolling 2, Yi Jiyou the presence or absence of in manufacturing condition with above-described embodiment 1
It is as good as friction and rolls difference on this aspect, is the result for being unsatisfactory for bendability.
Claims (5)
1. a kind of copper alloy plate material for electric and electronic components, it has excellent intensity and bendability, the copper alloy plate
Comprising copper alloy composition, the copper alloy composition is included in terms of quality %：It is any one or two kinds of in 0.8 ~ 5% Ni or Co；0.2~
1.5% Si；Surplus is Cu and inevitable impurity, wherein, the deviation angle being orientated relative to Cube is less than 15 ° of crystalline substance
The area occupation ratio control of grain will be orientated the area occupation ratio of the crystal grain with 15 ~ 30 ° of deviation angle less than 10% relative to Cube
Control is more than 15%.
2. copper alloy plate material for electric and electronic components according to claim 1, wherein, also containing 0.05 ~ 0.5% Cr.
3. copper alloy plate material for electric and electronic components according to claim 1 or 2, wherein, also containing Zn, Sn, Mg, Ag,
More than one or both of Mn and Zr, its total amount is 0.01 ~ 1.0%.
4. a kind of connector, it is made up of the copper alloy plate material for electric and electronic components of any one of claim 1 ~ 3.
5. a kind of manufacture method of copper alloy plate material for electric and electronic components, it is the electricity of any one of manufacturing claims 1 ~ 3
The method of gas electronic component-use copper alloy plate, in the method, with following processes：
The process cast to the molten alloyed copper for the compositing range that composition adjustment is any one of claim 1 ~ 3；
Ingot bar is carried out after the cutting of face, is heated or homogenized heat treatment at 800 ~ 1000 DEG C, then carry out hot rolling, and to heat
The process that plate after rolling carries out water cooling；
After hot rolling, face cutting is carried out to surface, and carry out cold rolling 1 process that rolling rate is more than 70%；
Between cold rolling 1 and solution heat treatment, the intermediate annealing of 5 seconds ~ 2 hours is carried out at 300 ~ 800 DEG C, is then rolled
Cold rolling 2 process of rate 3 ~ 80% processed；
The process that the solution heat treatment of 5 seconds ~ 300 seconds is carried out at 600 ~ 1000 DEG C；
After solution heat treatment, the roller that upper roller and the center line average roughness Ra of lower roll difference are 0.05 ~ 3.0 μm is utilized
Different friction cold rolling is carried out, cold rolling 3 process of working modulus 5 ~ 40% is used as；
In the aging heat treatment process of 400 ~ 600 DEG C of progress 0.5 hour ~ 8 hours；And
It is processed the pinch pass that rate is 0 ~ 20%, the process for carrying out process annealing.
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| JP6226511B2 (en) * | 2012-02-14 | 2017-11-08 | Ｊｘ金属株式会社 | Copper alloy sheet with excellent heat dissipation and repeated bending workability |
| JP6111028B2 (en) * | 2012-03-26 | 2017-04-05 | Ｊｘ金属株式会社 | Corson alloy and manufacturing method thereof |
| JP6196757B2 (en) * | 2012-07-12 | 2017-09-13 | Ｊｘ金属株式会社 | Corson alloy and manufacturing method thereof |
| JP6639908B2 (en) * | 2013-09-06 | 2020-02-05 | 古河電気工業株式会社 | Copper alloy wire and method of manufacturing the same |
| KR102348993B1 (en) * | 2013-12-27 | 2022-01-10 | 후루카와 덴키 고교 가부시키가이샤 | Copper alloy sheet material, connector, and production method for copper alloy sheet material |
| KR102346254B1 (en) * | 2013-12-27 | 2022-01-03 | 후루카와 덴키 고교 가부시키가이샤 | Copper alloy sheet material, connector, and production method for copper alloy sheet material |
| CN105118570A (en) * | 2015-08-14 | 2015-12-02 | 太仓安托建筑材料有限公司 | Copper bar manufacturing process |
| CN105154714A (en) * | 2015-09-02 | 2015-12-16 | 太仓顺如成建筑材料有限公司 | Alloy copper bar |
| JP6246173B2 (en) | 2015-10-05 | 2017-12-13 | Ｊｘ金属株式会社 | Cu-Co-Ni-Si alloy for electronic parts |
| JP6166414B1 (en) * | 2016-03-30 | 2017-07-19 | 株式会社神戸製鋼所 | Copper or copper alloy strip for vapor chamber |
| JP6385382B2 (en) * | 2016-03-31 | 2018-09-05 | Ｊｘ金属株式会社 | Copper alloy sheet and method for producing copper alloy sheet |
| JP6302009B2 (en) * | 2016-07-12 | 2018-03-28 | 古河電気工業株式会社 | Rolled copper alloy, method for producing the same, and electric / electronic component |
| JP2017014624A (en) * | 2016-09-05 | 2017-01-19 | Ｊｘ金属株式会社 | Corson alloy and manufacturing method therefor |
| DE102017001846A1 (en) * | 2017-02-25 | 2018-08-30 | Wieland-Werke Ag | Sliding element made of a copper alloy |
| CN110573635B (en) | 2017-04-26 | 2021-08-03 | 古河电气工业株式会社 | Copper alloy sheet and method for producing same |
| CN107326214A (en) * | 2017-07-03 | 2017-11-07 | 广东省材料与加工研究所 | A kind of method that continuous casting rolling efficiently shapes corson alloy band |
| CN108149062B (en) * | 2018-02-10 | 2019-09-20 | 中南大学 | A kind of strong high conductive copper alloy of superelevation and preparation method thereof |
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| KR102403910B1 (en) * | 2021-11-29 | 2022-06-02 | 주식회사 풍산 | Method for manufacturing a copper alloy sheet material for automobiles or electric and electronic parts with excellent strength, electrical conductivity and bendability and copper alloy sheet material manufactured therefrom |
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