CN104204248A - Corson alloy and method for manufacturing same - Google Patents
Corson alloy and method for manufacturing same Download PDFInfo
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- CN104204248A CN104204248A CN201280069731.0A CN201280069731A CN104204248A CN 104204248 A CN104204248 A CN 104204248A CN 201280069731 A CN201280069731 A CN 201280069731A CN 104204248 A CN104204248 A CN 104204248A
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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
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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
- H01B1/026—Alloys based on copper
Abstract
Provided are a Corson alloy in which the occurrence of sagging is significantly reduced, and a method for manufacturing the Corson alloy. A Corson alloy containing 0.8 to 4.5% by mass of one or more of Ni and Co and 0.2 to 1.0% by mass of Si with the balance made up by copper and unavoidable impurities. The Corson alloy has a Young's modulus (bending flexure coefficient) in the 90-degree direction (where the degree represents the angle with respect to the rolling direction on the rolling plane of the copper foil; the same applies below) of 100 to 120 GPa, and the Young's modulus (bending flexure coefficient) in the 45-degree direction is no greater than 140 GPa.
Description
Technical field
The present invention relates to be suitable as the lead frame material of the semiconductor devicess such as the power spring materials such as junctor, terminal, rly., switch, transistor, unicircuit (IC), possess gloomy (Corson) alloy of section and the manufacture method thereof of outstanding intensity, fatigue characteristic, bendability, proof stress relaxation property, electroconductibility etc.
Background technology
In recent years, miniaturization electric, electronic unit is developed, to requiring good intensity, electric conductivity and bendability for the copper alloy of these parts.Respond this requirement, substitute the solution strengthening such as phosphor bronze, brass type copper alloy in the past, there is the increase in demand of the precipitation strength type copper alloy such as Corson alloy of high strength and electric conductivity.Corson alloy is the alloy of having separated out the intermetallic compounds such as Ni-Si, Co-Si, Ni-Co-Si in Cu matrix, has high strength, high conductivity, good bendability concurrently.
For example, junctor is made up of female terminal and male terminal, and by making, two terminals are chimeric obtains electrical connection.At electric contact place, female terminal keeps male terminal by its spring force, to obtain the contact force of expectation.
If the intensity of female terminal material is low,, in the time inserting male terminal, produce tension set (regression (へ り)) at female terminal.If generation regression, the contact force at place of electric contact portion reduces, and resistance increases.Therefore,, in order to suppress the generation of regression, yield strength, Cu alloy material (such as patent documentation 1 etc.) that elastic limit value is high have been developed.
In addition, in patent documentation 2, motion has elastic displacement in order to make junctor compared with large and be the Corson alloy below 105GPa by the sag coefficient adjustment of rolling direction.But the regression characteristic of this material particularly can not say fully in the situation that spring is applied to deflection repeatedly, and also existence causes the significantly reduced problem of spring contact power.
Prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2004-131829 communique;
Patent documentation 2:WO2011/068134 communique.
Summary of the invention
The problem that invention will solve
In order to improve the regression characteristic of Cu alloy material, effectively improve yield strength, elastic limit value equal strength characteristic.But, because processibility is followed high strength and the reasons such as deterioration, only carry out regression improvement with high strength and have the limit.
Therefore, in the present invention, to provide by also utilizing scheme beyond high strength to suppress significantly Corson alloy that regression occurs and manufacture method thereof as problem.
For the scheme of dealing with problems
The spring portion of junctor is reduced to socle girder, with the principle that illustrates that regression occurs.As shown in Figure 1, if the position that the inboardend of the leaf spring fixing from one end is started to length L applies deflection d, obtain the contact force P representing with following formula 1, on the inboardend surface of leaf spring, the maximum stress S representing with following formula 2 occur:
P=dEwt
3/ 4L
3(formula 1)
S=3tEd/2L
2(formula 2)
Be Young's modulus at this E, w is that plate is wide, and t is thickness of slab.
If S exceedes the yield strength for the copper alloy of the material of leaf spring, leaf spring tension set, produces regression at leaf spring.According to formula 2, the Young's modulus of material is lower, and the deflection that starts to occur regression is larger,, can think more difficult generation regression that is.
Conventionally, the length direction of the spring portion of junctor etc. is designed in rolling plane and rolling direction orthogonal (the 90 degree directions of Fig. 2).Thereby, can say, importantly, become the Young's modulus of direction of an angle of 90 degrees degree low with rolling direction.
On the other hand, the deflection that the spring portion of junctor etc. is applied is not only for once, is mostly that plug by terminal etc. applies thousands of above deflections.Particularly, in rly. etc., number of flexings is significantly more.
The inventor has found: for apply the regression deflection repeatedly in the direction that becomes an angle of 90 degrees degree with rolling direction for, be not only the Young's modulus that becomes the direction of an angle of 90 degrees degree with rolling direction, become the Young's modulus of the direction of miter angle degree also to bring considerable influence with rolling direction.
The present invention who completes based on above discovery is a kind of Corson alloy in a side, contain more than one 0.8～4.5 quality % among Ni and Co, contain Si0.2～1.0 quality %, remainder is made up of copper and inevitable impurity, 90 degree directions (degree for the rolling plane of Copper Foil in rolling direction angulation, same below) Young's modulus (sag coefficient) be 100～120GPa, 45 degree directions Young's moduluss (sag coefficient) be below 140GPa.
In an embodiment of Corson alloy involved in the present invention, contain more than one 0.8～4.5 quality % among Ni and Co, contain Si0.2～1.0 quality %, remainder is made up of copper and inevitable impurity, the Young's modulus (sag coefficient) of 90 degree directions is 106～120GPa, and the Young's modulus (sag coefficient) of 45 degree directions is 106～140GPa.
In an other embodiment of Corson alloy involved in the present invention, by total, contain more than one 0.005～3.0 quality % among Sn, Zn, Mg, Fe, Ti, Zr, Cr, Al, P, Mn and Ag.
The present invention is a kind of manufacture method of Corson alloy in an other side, wherein, make ingot casting, described ingot casting contains more than one 0.8～4.5 quality % among Ni and Co, contain Si0.2～1.0 quality %, remainder is made up of copper and inevitable impurity, after described ingot casting is hot-rolled down to thickness 5～20mm at 800～1000 DEG C, carry out the cold rolling of degree of finish 30～99%, the average heating speed that makes 400～500 DEG C is 1～50 DEG C/sec and keeps 5～600 seconds under the temperature band of 500～700 DEG C, thereby implement the preannealing of softening degree 0.25～0.75, carry out the cold rolling of degree of finish 7～50%, then, carry out at 700～900 DEG C the solutionizing processing of 5～300 seconds, and the ageing treatment of 2～20 hours at 350～550 DEG C,
Described softening degree is represented by the S in following formula:
S＝(σ
0-σ)/(σ
0-σ
900)
At this, σ
0for the tensile strength before preannealing, σ and σ
900tensile strength after annealing after being respectively preannealing and at 900 DEG C.
In an embodiment of the manufacture method of Corson alloy involved in the present invention, by total, described ingot casting contains more than one 0.005～3.0 quality % among Sn, Zn, Mg, Fe, Ti, Zr, Cr, Al, P, Mn and Ag.
The present invention is in another other side, for possessing the copper stretching product (Shen Copper product of Corson alloy of the present invention).
The present invention is in another other side, for possessing the electronic equipment part of Corson alloy of the present invention.
The effect of invention
According to the present invention, a kind of Corson alloy and manufacture method thereof can be provided, this kind of Corson alloy be as along in rolling plane during with the electronic unit such as the junctor of the orthogonal direction design spring of rolling direction, follows the regression of spring work to produce and suppressed significantly.
Brief description of the drawings
Fig. 1 is the explanatory view that the principle of regression occurs;
Fig. 2 illustrates respectively rolling direction in the rolling plane of rolled copper foil of Corson alloy, becomes the direction of 45 degree with rolling direction, becomes the figure of the direction of 90 degree with rolling direction;
Fig. 3 is annealing temperature while making alloy involved in the present invention annealing with all temps and the graph of a relation of tensile strength;
Fig. 4 is the explanatory view of the related flexure test of embodiment.
Embodiment
(addition of Ni, Co and Si)
Ni, Co and Si separate out as intermetallic compounds such as Ni-Si, Co-Si, Ni-Co-Si by carrying out suitable ageing treatment.By the effect of this precipitate, the intensity of copper alloy improves, and by separating out, Ni, the Co and the Si that are solid-solubilized in Cu matrix reduce, thereby electric conductivity improves.But, if the total amount of Ni and Co is less than 0.8 quality % or Si is less than 0.2 quality %, can not get desired intensity, on the contrary, if the total amount of Ni and Co exceedes 4.5 quality % or Si exceedes 1.0 quality %, electric conductivity reduces.Therefore, in Corson alloy involved in the present invention, making more than one the addition among Ni and Co is 0.8～4.5 quality %, and the addition that makes Si is 0.2～1.0 quality %.And the addition of more than one among Ni and Co is preferably 1.0～4.0 quality %, the addition of Si is preferably 0.25～0.90 quality %.
(other add element)
Sn, Zn, Mg, Fe, Ti, Zr, Cr, Al, P, Mn, Ag rise helpful to intensity.And the raising of the heat-resisting separability of Zn to Sn coating produces effect, the raising of Mg counter stress relaxation properties produces effect, and Zr, Cr, Mn produce effect to the raising of high temperature process.If the total amount of Sn, Zn, Mg, Fe, Ti, Zr, Cr, Al, P, Mn, Ag is less than 0.005 quality %, can not get above-mentioned effect, if exceed 3.0 quality % electric conductivity significantly reduce.Therefore, in Corson alloy involved in the present invention, be preferably by total and contain these elements 0.005～3.0 quality %, be more preferably and contain 0.01～2.5 quality %.
(Young's modulus)
By control the Young's modulus of 90 degree directions compared with lowland, the regression of the spring designing along rolling orthogonal directions diminishes.The Young's modulus of 90 degree directions of common Corson alloy is 125～130GPa left and right.By this Young's modulus is adjusted into below 120GPa, regression significantly diminishes compared with common Corson alloy.On the other hand, if Young's modulus step-down, as from above-mentioned formula 1, the contact force of electric contact reduces.If the Young's modulus of 90 degree directions is less than 100GPa, cannot ignores and follow the contact resistance that contact force reduces to increase.Therefore, the Young's modulus of 90 degree directions is adjusted into 100～120GPa.From contact force aspect, more than the Young's modulus of 90 degree directions is preferably 106GPa.Preferred Young's modulus scope is 110～115GPa.
On the other hand, the Young's modulus of 90 degree directions being adjusted in the Corson alloy of 100～120GPa, the Young's moduluss of 45 degree directions exceed 140GPa, more than sometimes also reaching 150GPa.Rise by the Young's modulus that suppresses this 45 degree direction, the Young's modulus of 45 degree directions is adjusted into below 140GPa, more preferably, for being adjusted into below 130GPa, being not only the regression while applying a deflection, the regression while applying deflection repeatedly also improves.
In addition, the Young's modulus of 90 degree directions being adjusted in the Corson alloy of 100～120GPa, adjust in any case its manufacture method, the situation that the Young's modulus of 45 degree directions is less than 106GPa is all few, the situation that is less than 110GPa is also less, and the situation that is less than 120GPa is also less.In other words, the Young's modulus of 90 degree directions is being adjusted into 100～120GPa, the Young's modulus of 45 degree directions is adjusted in the Corson alloy of the present invention below 140GPa, more than the Young's modulus of 45 degree directions typically is 106GPa, be more typically more than 110GPa, more typically more than 120GPa.In addition, Young's modulus value of the present invention is the value as the sag coefficient determination of socle girder.
(manufacture method)
In the general manufacturing processed of Corson alloy, first utilize smelting furnace that the raw materials such as electrolytic copper, Ni, Co, Si are melted, to obtain the liquation (molten Soup) of desired constituents.Then, this liquation is cast into ingot casting (ingot).Afterwards, be finally processed as and there is bar, the paper tinsel of expecting thickness and characteristic according to the order of hot rolling, cold rolling, solutionizing processing, ageing treatment.After thermal treatment, in order to remove the surface film oxide generating when the timeliness, can also carry out surperficial pickling, grinding etc.In addition, for high strength, can also be between solutionizing processing and timeliness or carry out cold rolling after timeliness.
In the present invention, in order to obtain above-mentioned Young's modulus, before solutionizing is processed, heat-treat cold rolling (below also referred to as the saddening) of (below also referred to as preannealing) and lower degree of finish.
In preannealing, by material is kept to 5～600 seconds under the temperature band of 500～700 DEG C, in the rolling structure of the cold rolling formation by after hot rolling, partly generate recrystallize grain.There is optimum value in the ratio of the recrystallize grain in rolling structure, the too much or very few Young's modulus that all can not get expectation.The recrystallize grain of optimum proportion obtains by the softening degree S of following definitions is adjusted into 0.25～0.75.
In Fig. 3, exemplify annealing temperature while making the anneal of material before the related preannealing of alloy of the present invention with all temps and the relation of tensile strength.The test portion that thermopair is installed is inserted to the tube furnace of 950 DEG C, in the time that the test portion temperature of utilizing thermocouple measurement both reaches fixed temperature, test portion is taken out from stove and carry out coolingly, measured tensile strength.Between 500～700 DEG C, recrystallize carries out, and tensile strength sharply reduces.The slow reduction of the tensile strength of high temperature side is the result of the growth of recrystallize grain.
Softening degree S with in following formula definition preannealing:
S＝(σ
0-σ)／(σ
0-σ
900)
At this, σ
0for the tensile strength before preannealing, σ and σ
900it is respectively the tensile strength after annealing after preannealing and at 900 DEG C.If because make stably perfect recrystallization of alloy involved in the present invention annealing at 900 DEG C, thereby adopt the temperature of 900 DEG C as the reference temperature for understanding the tensile strength after recrystallize.
If S is less than 0.25 or exceed 0.75, the Young's moduluss of 90 degree directions exceed 120GPa.
For S is adjusted into 0.25～0.75, preferably material is kept 5～600 seconds under the temperature band of 500～700 DEG C.If material temperature exceedes 700 DEG C, if or the hold-time exceed 600 seconds, be difficult to S to be adjusted into below 0.75.If the hold-time is less than 5 seconds, be difficult to S to be adjusted into more than 0.25.Be less than 500 DEG C if material arrives temperature, the material hold-time at 500～700 DEG C is 0, thereby to be less than the situation of 5 seconds same with this hold-time, is difficult to S to be adjusted into more than 0.25.
In addition, the adjustment towards 0.25～0.75 of S can be carried out in the following order:
(1) the tension test intensity (σ of the material before mensuration preannealing
0).
(2) at 900 DEG C, make the anneal of material before preannealing.Particularly, the test portion that thermopair is installed is inserted to the tube furnace of 950 DEG C, in the time that the test portion temperature of utilizing thermocouple measurement reaches 900 DEG C, test portion is taken out from stove and carry out water-cooled.
(3) ask the tensile strength (σ of the material after above-mentioned 900 DEG C of annealing
900).
(4) for example,, at σ
0for 800MPa, σ
900in situation for 300MPa, be respectively 675MPa and 425MPa with softening degree 0.25 and 0.75 suitable tensile strength.
(5) determine annealing conditions taking the tension test intensity after annealing as the mode of 425～675MPa.
Except the control of S, also control the material heat-up rate in preannealing.In order to obtain the Young's modulus of expectation, the average intensification temperature from 400 DEG C to 500 DEG C need to be adjusted into the scope of 1～50 DEG C/sec, be more preferably the scope of 1.5～40 DEG C/sec, be more preferably the scope of 2～20 DEG C/sec.
Above-mentioned average heating speed is lower than 1 DEG C/sec or exceed 50 DEG C/sec, and the Young's modulus of 45 degree directions all exceedes 140GPa.And, if above-mentioned average heating speed lower than 1 DEG C/sec, 90 degree directions Young's moduluss be sometimes less than 100GPa, if exceed 50 DEG C/sec 90 degree directions Young's moduluss sometimes exceed 120GPa.
As the annealing way of industrial use in the manufacture of copper stretching product, exist bar walk and the continuous annealing of heating and by coiled material (coil) the insertion stove that bar is wound around and these two kinds, the batch annealing stove heating in stove.Generally speaking, the heat-up rate of 400～500 DEG C of the bar in continuous annealing is for being greater than 50 DEG C/sec, and the heat-up rate of 400～500 DEG C of the bar in batch annealing is for being less than 1 DEG C/sec.For example, by give the countermeasures such as gradient to the temperature distribution in stove in continuous annealing, can realize the heat-up rate of 1～50 DEG C/sec.
In addition, " in the time that the test portion temperature of utilizing thermocouple measurement reaches 900 DEG C; test portion is taken out from stove and carry out water-cooled " in above-mentioned operation (2) particularly, for example, by test portion being suspended in stove to line, in tank below being located at, carry out water-cooled thereby cut off line and it is fallen at the time point that arrives 900 DEG C, or tank is medium carries out from taking out rapidly and be immersed in stove by handwork at once after test portion temperature arrives 900 DEG C.
After above-mentioned preannealing, before solutionizing is processed, carry out the saddening of degree of finish 7～50%.Define degree of finish R (%) with following formula:
R=(t
0-t)/t
0× 100 (t
0: the thickness of slab before rolling, t: the thickness of slab after rolling)
If degree of finish departs from this scope, the Young's modulus of 90 degree directions exceedes 120GPa.
If the manufacture method of alloy involved in the present invention is listed according to process sequence, as follows:
(1) casting of ingot casting
(2) hot rolling (800～1000 DEG C of temperature, until thickness 5～20mm left and right)
(3) cold rolling (degree of finish 30～99%)
(4) preannealing (softening degree: S=0.25～0.75, the average heating speed of 400～500 DEG C: 1～50 DEG C of second)
(5) saddening (degree of finish 7～50%)
(6) solutionizing processing (at 700～900 DEG C 5～300 seconds)
(7) cold rolling (degree of finish 1～60%)
(8) ageing treatment (at 350～550 DEG C 2～20 hours)
(9) cold rolling (degree of finish 1～50%)
(10) except strain (the askew り that gets) annealing (at 300～700 DEG C 5 seconds～10 hours).
At this, can under the condition of general Corson alloy, carry out hot rolling (2), complete until water-cooled is carried out in the rolling of set thickness afterwards immediately material temperature being remained under more than 350 DEG C states but be preferably.Thus, the formation of the thick precipitate (high strength to goods does not help) in cooling after hot rolling is inhibited.
The degree of finish of cold rolling (3) is preferably 30～99%.In order partly to generate recrystallize grain in preannealing (4), need in cold rolling (3), import strain, utilize more than 30% degree of finish to obtain effective strain.On the other hand, if degree of finish exceedes 99%, sometimes produce crack, the Materials Fracture in rolling at the edge of rolling stock etc.
Cold rolling (7) and (9) are the operations of carrying out alternatively for high strength, and intensity increases along with the increase of rolling degree of finish, but on the contrary, bendability reduces.With cold rolling (7) and (9) have or not and point other degree of finish irrelevant, can obtain the effect of the present invention that suppresses regression by the control of Young's modulus.Cold rolling (7) and (9) can carry out also can not carrying out.But, the situation that cold rolling (7) and (9) point other degree of finish exceedes above-mentioned higher limit is not preferred from the viewpoint of bendability, and point other degree of finish is not preferred lower than the situation of above-mentioned lower value from the viewpoint of the effect of high strength.
Except strain annealing (10) is to carry out alternatively in recoveries such as the elastic limit values of this cold rolling middle reduction in order to make in the situation that carrying out cold rolling (9).With except strain annealing (10) have or not irrelevantly, can obtain the effect of the present invention that suppresses regression by the control of Young's modulus.Except strain annealing (10) can be carried out also can not carrying out.
In addition,, about operation (6) and (8), select generally creating conditions of Corson alloy.
Corson alloy of the present invention can be processed as various copper stretching product, for example plate, bar and paper tinsel, and also Corson alloy of the present invention can be used in lead frame, junctor, pin, terminal, rly., switch, the electronic equipment parts such as foil for secondary cell.
Embodiment
Below embodiments of the invention and comparative example are together illustrated, but these embodiment provide in order to understand better the present invention and advantage thereof, be not intended to limit invention.
(embodiment 1)
To contain Ni:2.6 quality %, Si:0.58 quality %, Sn:0.5 quality % and Zn:0.4 quality %, the alloy that remainder is made up of copper and inevitable impurity, as experiment material, has been inquired into the relation of preannealing and saddening condition and Young's modulus and the impact that Young's modulus causes the regression characteristic of goods.
Utilize high frequency smelting furnace in argon atmospher, to use the plumbago crucible of internal diameter 60mm, degree of depth 200mm to melt 2.5kg electrolytic copper.Add alloying element obtaining above-mentioned alloying constituent, melt temperature being adjusted into after 1300 DEG C, be cast into mold made of iron, manufactured the ingot casting of thickness 30mm, width 60mm, length 120mm.This ingot casting is carried out to hot rolling, and after heating 3 hours at 950 DEG C, rolling in the situation that material temperature being remained more than 350 DEG C is until thickness 10mm has carried out water-cooled afterwards immediately.With shredder (grinder) grinding and removed the oxide skin on hot-rolled sheet surface.Thickness after grinding is 9mm.Afterwards, implement rolling and thermal treatment according to following process sequence, made the goods test portion of thickness of slab 0.15mm:
(1) cold rolling: according to the rolling degree of finish of saddening, to be cold rolled to set thickness.
(2) preannealing: test portion is inserted and is adjusted into both electric furnaces of fixed temperature, after keeping given time, by test portion be placed in atmosphere, carry out cooling.During this time, measure test portion temperature with the thermopair that is welded in test portion, ask and arrive temperature, the average heating speed of 400～500 DEG C and the hold-time of 500～700 DEG C.
(3) saddening: carry out according to various rolling degree of finish cold rolling, until thickness is 0.18mm.
(4) solutionizing processing: test portion is inserted to the electric furnace that is adjusted into 800 DEG C, after keeping 10 seconds, test portion is put into tank and carry out cooling.
(5) ageing treatment: use electric furnace to heat in Ar atmosphere 5 hours at 450 DEG C.
(6) cold rolling: from 0.18mm to 0.15mm, to have carried out cold rolling with degree of finish 17%.
(7) except strain annealing: test portion is inserted to the electric furnace that is adjusted into 400 DEG C, after keeping 10 seconds, by test portion be placed in atmosphere, carry out cooling.
About the test portion after preannealing and goods test portion (being just except strain annealing is complete in this case), carry out following evaluation:
(the softening degree evaluation in preannealing)
About the test portion before preannealing and after preannealing, use tensile testing machine to measure abreast tensile strength according to JIS Z 2241 with rolling direction, will divide other value as σ
0and σ.In addition, at 900 DEG C, make annealing test portion according to aforementioned order (insert the stove of 950 DEG C, carry out cooling) in the time that test portion arrives 900 DEG C, with the rolling direction same tensile strength of having measured abreast, ask σ
900.According to σ
0, σ, σ
900, ask softening degree S by following formula:
S＝(σ
0-σ)/(σ
0-σ
900)
(tension tests of goods)
Use tensile testing machine to measure abreast 0.2% yield strength according to JIS Z2241 and rolling direction.
(Young's modulus mensuration)
Measure Young's modulus according to Japanese copper stretching association (JACBA) technological standard " the socle girder sag coefficient determination method of copper and copper alloy lath ".
Become the direction of an angle of 90 degrees degree with rolling direction and become the direction of miter angle degree along the length direction of the test portion shown in Fig. 2, chosen respectively rectangular (short Books) shape test portion of thickness of slab t, width w (=10mm), length 100mm.One end of this test portion is fixed, to apply the load of P (=0.15N) apart from the position of inboardend L (=100t), is utilized following formula to ask Young's modulus E according to deflection d now:
E＝4P(L/t)
3/(wd)
(flexure test)
Become the direction of an angle of 90 degrees degree along the length direction of the test portion shown in Fig. 2 with rolling direction, chosen the elongate in shape test portion of width 5mm.
Then, as shown in Figure 4, one end of this test portion is fixed, the position butt apart from this inboardend distance L is processed as top to the drift of the edge of a knife, after test portion is applied to deflection d, make drift return to starting position to unload.The translational speed that makes drift is 1mm/ minute.
First apply a deflection and measure contact force P (acting on the load of drift), after unloading, ask regression δ.In addition, apply 5000 deflections, ask the regression δ after unloading.
Evaluation result is shown in to table 1.At this, flexure test is carried out under the condition of t (thickness of slab)=0.15mm, w (plate is wide)=5mm, L (spring length)=10mm, d (deflection)=3mm.In addition, with the resolving power determination regression δ of 0.01mm, in the situation that regression δ not detected, be labeled as < 0.01mm.
[table 1]
Example 1～16 has all been carried out preannealing and saddening under condition given to this invention, and the Young's modulus of 90 degree directions and 45 degree directions meets regulation of the present invention, regression all do not detected after a deflection and after 5000 times.In addition, exist contact force to follow the reduction of Young's modulus of 90 degree directions and the tendency that reduces, the Young's modulus lower (for 105GPa, 102GPa) of 90 degree directions although the contact force of example 6,16 and the contact force of other examples compared with lower, but in all examples, successfully maintain the contact force that exceedes 1.2N.
The contact force (P) obtaining by flexure test is not only subject to the impact of the alloy characteristics such as Young's modulus (E), yield strength, and as aforementioned formula 1[P=dEwt
3/ 4L
3] shown in, be also subject to test material shape (t, w), flexing conditions (L, impact d).For the contact force of expecting according to test material shape and flexing conditions, the level of the above-mentioned contact force obtaining by example can be described as fully.
Comparative example 1 does not carry out preannealing and saddening, is equivalent to general Corson alloy.Because the Young's modulus of 90 degree directions exceedes 120GPa, therefore produce regression in a deflection, this regression increases a little under 5000 deflections.
Although comparative example 2 has carried out preannealing and saddening, arrival temperature when preannealing exceedes 700 DEG C, and softening degree exceedes 0.75.Because softening degree is excessive, therefore the Young's modulus of 90 degree directions has exceeded 120GPa.Its result produces regression in a deflection, and this regression increases a little under 5000 deflections.
Although comparative example 3 has carried out preannealing and saddening, discontented 5 seconds of hold-time when preannealing, softening degree is lower than 0.3.Because softening degree is too small, therefore the Young's modulus of 90 degree directions has exceeded 120GPa.Its result produces regression in a deflection, and this regression increases a little under 5000 deflections.
In comparative example 4 and 5, although carried out preannealing and saddening, it is too small and excessive that degree of finish when saddening is respectively, therefore the Young's modulus of 90 degree directions has exceeded 120GPa.Its result produces regression in a deflection, and this regression increases a little under 5000 deflections.
In comparative example 6, because the softening degree of preannealing and the degree of finish of saddening are appropriate condition, therefore the Young's moduluss of 90 degree directions are in the scope of 100～120GPa.But, due to discontented 1 DEG C/sec of the heat-up rate of 400～500 DEG C in preannealing, therefore the Young's modulus of 45 degree directions has exceeded 140GPa., although regression do not detected in a deflection, under 5000 deflections, there is regression in its result.
Comparative example 7 is same with comparative example 6, although the heat-up rate in preannealing is too small, but because this heat-up rate is slow especially, therefore not only the Young's modulus of 45 degree directions exceedes 140GPa, under 5000 deflections, there is regression, and 90 degree directions Young's modulus be less than 100GPa, contact force is less than 1N, is reduced to 2/3 left and right of example.If contact force is reduced to this level, be processed as junctor so that the used time, produce the problem such as contact resistance abnormal ascending of contact.
Comparative example 8 is because the softening degree of preannealing and the degree of finish of saddening are appropriate condition, therefore the Young's moduluss of 90 degree directions are in the scope of 100～120GPa.But, because the heat-up rate of 400～500 DEG C in preannealing exceedes 50 DEG C/sec, therefore the Young's modulus of 45 degree directions has exceeded 140GPa., although regression do not detected in a deflection, under 5000 deflections, there is regression in its result.
Comparative example 9 is same with comparative example 8, although the heat-up rate in preannealing is excessive, because this heat-up rate is large especially, therefore not only the Young's modulus of 45 degree directions exceedes 140GPa, and the Young's modulus of 90 degree directions exceedes 120GPa.Its result has produced regression in a deflection, and this regression significantly increases under 5000 deflections.
Although comparative example 10 has carried out preannealing and saddening, hold-time when preannealing exceedes 600 seconds, and softening degree is excessive, and heat-up rate is too small in addition.The Young's modulus of 90 degree directions exceedes 120GPa, in a deflection, produces regression, and this regression increases a little under 5000 deflections.
(embodiment 2)
Confirm that can obtain the regression shown in embodiment 1 by heterogeneity and the Corson alloy of creating conditions improves effect.
By method similarly to Example 1 cast, hot rolling and surfacing, obtained the plate of the thickness 9mm of the composition with table 2.According to following process sequence, this plate is implemented to rolling and thermal treatment, has made the goods test portion of the thickness of slab shown in table 2:
(1) cold rolling
(2) preannealing: utilize method similarly to Example 1 to implement.
(3) saddening
(4) solutionizing processing: test portion is inserted and is adjusted into both electric furnaces of fixed temperature, after keeping 10 seconds, test portion is put into tank and carry out cooling.This temperature is selected in following scope, that is, the mean diameter of recrystallize grain is the scope of 5～25 μ m.
(5) cold rolling (rolling 1)
(6) ageing treatment: use electric furnace both heating in Ar atmosphere 5 hours under fixed temperature.The mode of the tensile strength maximum of this temperature after with timeliness is selected.
(7) cold rolling (rolling 2)
(8) except strain annealing: test portion is inserted and is adjusted into both electric furnaces of fixed temperature, after keeping 10 seconds, by test portion be placed in atmosphere, carry out cooling.
About the test portion after preannealing and goods test portion, carry out evaluation similarly to Example 1.In addition, in flexure test, establish w=5mm, to the each group of alloys of aftermentioned, easily to find that the mode of effect of the present invention set L and d.
Evaluation result is shown in to table 2 and 3.In the case of not being rolled 1, rolling 2, except any in strain annealing, in the hurdle of point other degree of finish or temperature, be labeled as " nothing ".
[table 2]
[table 3]
(alloy A)
Alloy A only contains Ni and Si as alloying constituent, and remainder is made up of copper and inevitable impurity.In addition, rolling 1, rolling 2, all carry out except any in strain annealing.
In example A-1, because Young's modulus meets regulation, therefore regression all do not detected after a deflection and after 5000 times.
In Comparative examples A-1, the Young's modulus that exceedes 0.75,90 degree direction due to the softening degree in preannealing exceedes 120GPa, therefore there is regression in a deflection.
In Comparative examples A-2, because the heat-up rate of preannealing is discontented with 1 DEG C/sec, the Young's moduluss of 45 degree directions exceed 140GPa, therefore there is regression under 5000 deflections.
In Comparative examples A-3, because total concn and the Si concentration of Ni and Co are too small, therefore the yield strength of goods reduces, in a deflection, there is regression.
Observe contact force, in example A-1, Comparative examples A-1 and Comparative examples A-2, because the Young's modulus of 90 degree directions is more than 100GPa, therefore obtained according to the contact force of the level of test material shape and flexing conditions expectation.On the other hand, although exceed in Comparative examples A-3 that 100GPa yield strength is significantly lower in the Young's modulus of 90 degree directions, with respect to example A-1, Comparative examples A-1 and Comparative examples A-2, only obtained the contact force of 2/3 left and right.
(alloy B)
Alloy B contains 1.6%Ni, 0.36%Si, 0.5%Sn and 0.4%Zn (% is quality %, below same) as alloying constituent, remainder by copper and inevitably impurity form.In addition, be rolled 2 and except strain annealing.
In example B-1, because Young's modulus meets regulation, therefore regression all do not detected after a deflection and after 5000 times.
In comparative example B-1, owing to not carrying out preannealing and saddening, the Young's modulus of 90 degree directions exceedes 120GPa, therefore there is regression in a deflection.
In comparative example B-2, because the heat-up rate of preannealing exceedes 50 DEG C/sec, the Young's modulus of 45 degree directions exceedes 140GPa, therefore there is regression under 5000 deflections.
In addition, because 90 Young's moduluss of spending directions of example B-1, comparative example B-1 and comparative example B-2 are all more than 100GPa, therefore obtained according to the contact force of the level of test material shape and flexing conditions expectation.
(alloy C)
Alloy C contains 3.8%Ni, 0.81%Si, 0.1%Mg and 0.2%Mn as alloying constituent, and remainder is made up of copper and inevitable impurity.In addition, be rolled 2 and except strain annealing.
In example C-1, because Young's modulus meets regulation, therefore regression all do not detected after a deflection and after 5000 times.
In comparative example C-1, the Young's modulus that exceedes 0.75,90 degree direction due to the softening degree in preannealing exceedes 120GPa, therefore there is regression in a deflection.
In comparative example C-2, because the Young's modulus of discontented 0.25, the 90 degree direction of the softening degree in preannealing exceedes 120GPa, therefore there is regression in a deflection.
In comparative example C-3, because the heat-up rate of preannealing is discontented with 1 DEG C/sec, the Young's moduluss of 45 degree directions exceed 140GPa, therefore there is regression under 5000 deflections.
In addition, because 90 Young's moduluss of spending directions of example C-1, comparative example C-1, comparative example C-2, comparative example C-3 are all more than 100GPa, therefore obtained according to the contact force of the level of test material shape and flexing conditions expectation.
(alloy D)
Alloy D contains 2.3%Ni, 0.46%Si and 0.2%Mg as alloying constituent, and remainder is made up of copper and inevitable impurity.In addition, be rolled 1.
In example D-1, because Young's modulus meets regulation, therefore regression all do not detected after a deflection and after 5000 times.
In Comparative Example D-1, the Young's modulus that exceedes 50%, 90 degree direction due to the degree of finish of saddening exceedes 120GPa, therefore there is regression in a deflection.
In Comparative Example D-2, because the heat-up rate of preannealing exceedes 50 DEG C/sec, the Young's modulus of 45 degree directions exceedes 140GPa, therefore there is regression under 5000 deflections.
In addition, because 90 Young's moduluss of spending directions of example D-1, Comparative Example D-1, Comparative Example D-2 are all more than 100GPa, therefore obtained according to the contact force of the level of test material shape and flexing conditions expectation.
(alloy E)
Alloy E contains 2.0%Ni, 0.69%Si, 1.1%Co and 0.1%Cr as alloying constituent, and remainder is made up of copper and inevitable impurity.In addition, be rolled 2 and except strain annealing.
In example E-1, because Young's modulus meets regulation, therefore regression all do not detected after a deflection and after 5000 times.
In Comparative Example E-1, the Young's modulus of spending direction due to the degree of finish discontented 7%, 90 of saddening exceedes 120GPa, therefore there is regression in a deflection.
In addition, because 90 Young's moduluss of spending directions of example E-1, Comparative Example E-1 are all more than 100GPa, therefore obtained according to the contact force of the level of test material shape and flexing conditions expectation.
In Comparative Example E-2, the heat-up rate of preannealing is very little.Therefore, the Young's modulus of 45 degree directions exceedes 140GPa, under 5000 deflections, regression has occurred.And the Young's modulus of 90 degree directions is less than 100GPa, contact force is reduced to below the half of example E-1 and Comparative Example E-1.
(alloy F)
Alloy F contains 2.4%Ni, 0.71%Si, 0.2%Sn, 0.5%Ag, 0.2%Cr and 0.01%P as alloying constituent, and remainder is made up of copper and inevitable impurity.In addition, be rolled 2.
In example F-1, because Young's modulus meets regulation, therefore regression all do not detected after a deflection and after 5000 times.
In Comparative Example F-1, because the heat-up rate of preannealing is very large, therefore the Young's modulus of 45 degree directions exceedes 140GPa, the Young's modulus of 90 degree directions has exceeded 120GPa simultaneously.Its result produces regression in a deflection, and this regression increases under 5000 deflections.
In addition, because 90 Young's moduluss of spending directions of example F-1, Comparative Example F-1 are all more than 100GPa, therefore obtained according to the contact force of the level of test material shape and flexing conditions expectation.
(alloy G)
Alloy G contains 1.9%Co, 0.44%Si, 0.02%Cr, 0.02%Zr as alloying constituent, and remainder is made up of copper and inevitable impurity.In addition, be rolled 2 and except strain annealing.
In example G-1, G-2, because Young's modulus meets regulation, therefore regression all do not detected after a deflection and after 5000 times.
In comparative example G-1, the Young's modulus that exceedes 0.75,90 degree direction due to the softening degree in preannealing exceedes 120GPa, therefore there is regression in a deflection.
In comparative example G-2, because the heat-up rate of preannealing is very large, therefore the Young's modulus of 45 degree directions exceedes 140GPa, the Young's modulus of 90 degree directions has exceeded 120GPa simultaneously.Its result produces regression in a deflection, and this regression increases under 5000 deflections.
Due in foregoing invention example G-1, example G-2, comparative example G-1, comparative example G-2, Young's modulus is more than 100GPa, therefore obtained according to the contact force of the level of test material shape and flexing conditions expectation.At this, although that Young's modulus is less than for 100GPa is above compared with the contact force of example G-2 of 106GPa and the contact force of other embodiment is slightly low, but be no problem level aspect practical.
In comparative example G-3, the heat-up rate of preannealing is very little.Therefore, the Young's modulus of 45 degree directions exceedes 140GPa, under 5000 deflections, regression has occurred.And the Young's modulus of 90 degree directions is less than 100GPa, contact force is reduced to the half left and right of example G-1, example G-2, comparative example G-1, comparative example G-2.
Claims (7)
1. a Corson alloy, contain more than one 0.8～4.5 quality % among Ni and Co, contain Si0.2～1.0 quality %, remainder is made up of copper and inevitable impurity, 90 degree directions (degree for the rolling plane of Copper Foil in rolling direction angulation, same below) Young's modulus (sag coefficient) be 100～120GPa, 45 degree directions Young's moduluss (sag coefficient) be below 140GPa.
2. Corson alloy according to claim 1, wherein, contain more than one 0.8～4.5 quality % among Ni and Co, contain Si0.2～1.0 quality %, remainder is made up of copper and inevitable impurity, the Young's modulus (sag coefficient) of 90 degree directions is 106～120GPa, and the Young's modulus (sag coefficient) of 45 degree directions is 106～140GPa.
3. Corson alloy according to claim 1 and 2, wherein, by total, contains more than one 0.005～3.0 quality % among Sn, Zn, Mg, Fe, Ti, Zr, Cr, Al, P, Mn and Ag.
4. the manufacture method of a Corson alloy, wherein, make ingot casting, described ingot casting contains more than one 0.8～4.5 quality % among Ni and Co, contain Si0.2～1.0 quality %, remainder is made up of copper and inevitable impurity, after described ingot casting is hot-rolled down to thickness 5～20mm at 800～1000 DEG C, carry out the cold rolling of degree of finish 30～99%, the average heating speed that makes 400～500 DEG C is 1～50 DEG C/sec and keeps 5～600 seconds under the temperature band of 500～700 DEG C, thereby implement the preannealing of softening degree 0.25～0.75, carry out the cold rolling of degree of finish 7～50%, then, carry out at 700～900 DEG C the solutionizing processing of 5～300 seconds, and the ageing treatment of 2～20 hours at 350～550 DEG C,
Described softening degree is represented by the S in following formula:
S＝(σ
0-σ)/(σ
0-σ
900)
At this, σ
0for the tensile strength before preannealing, σ and σ
900tensile strength after annealing after being respectively preannealing and at 900 DEG C.
5. the manufacture method of Corson alloy according to claim 4, wherein, by total, described ingot casting contains more than one 0.005～3.0 quality % among Sn, Zn, Mg, Fe, Ti, Zr, Cr, Al, P, Mn and Ag.
6. copper stretching product, possess the Corson alloy described in any one in claim 1～3.
7. an electronic equipment part, possesses the Corson alloy described in any one in claim 1～3.
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| JP2012029490A JP5039862B1 (en) | 2011-07-15 | 2012-02-14 | Corson alloy and manufacturing method thereof |
| JP2012-029490 | 2012-02-14 | ||
| PCT/JP2012/075263 WO2013121620A1 (en) | 2012-02-14 | 2012-09-28 | Corson alloy and method for manufacturing same |
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| WO2011068134A1 (en) * | 2009-12-02 | 2011-06-09 | 古河電気工業株式会社 | Copper alloy sheet material having low young's modulus and method for producing same |
| JP2011216463A (en) * | 2010-03-15 | 2011-10-27 | Jx Nippon Mining & Metals Corp | Rolled copper foil, and negative electrode collector, negative electrode plate and secondary battery using the same |
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| JP4255330B2 (en) * | 2003-07-31 | 2009-04-15 | 日鉱金属株式会社 | Cu-Ni-Si alloy member with excellent fatigue characteristics |
| JP4143662B2 (en) * | 2006-09-25 | 2008-09-03 | 日鉱金属株式会社 | Cu-Ni-Si alloy |
| EP2610359A4 (en) * | 2010-08-27 | 2017-08-02 | Furukawa Electric Co., Ltd. | Copper alloy sheet and method for producing same |
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| JP2006283060A (en) * | 2005-03-31 | 2006-10-19 | Dowa Mining Co Ltd | Copper alloy material and its manufacturing method |
| CN102245787A (en) * | 2008-12-12 | 2011-11-16 | Jx日矿日石金属株式会社 | Ni-Si-Co copper alloy and manufacturing method therefor |
| WO2011068134A1 (en) * | 2009-12-02 | 2011-06-09 | 古河電気工業株式会社 | Copper alloy sheet material having low young's modulus and method for producing same |
| JP2011216463A (en) * | 2010-03-15 | 2011-10-27 | Jx Nippon Mining & Metals Corp | Rolled copper foil, and negative electrode collector, negative electrode plate and secondary battery using the same |
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| CN110205570A (en) * | 2019-04-15 | 2019-09-06 | 深圳万佳互动科技有限公司 | A kind of heat treatment method of electrical and electronic parts copper alloy |
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| CN104204248B (en) | 2016-08-24 |
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