CN101693960A - Copper alloy, copper alloy plate, and process for producing the same - Google Patents

Abstract

A copper alloy with an excellent stress relaxation resistance including Ni: 0.1 through 3.0 mass%, Sn: 0.01 through 3.0 mass%,P: 0.01 through 0.3 mass% and remainder copper and inevitable impurities, and the Ni content in extracted residues separated and left on a filter having filter mesh size of 0.1 [mu]m by using an extracted residues method accounting for 40 mass% or less of the Ni content in the copper alloy, wherein the extracted residues method requires that 10 g of the copper alloy is immersed in 300 ml of a methanol solution which contains 10 mass% of ammonium acetate, and using the copper alloy as the anode and platinum as the cathode, constant-current electrolysis is performed at the current density of 10 mA/cm 2 , and the solution in which the copper alloy is thus dissolved is subjected to suction filtration using a membrane filter of polycarbonate whose filter mesh size is 0.1 [mu]m, thereby separating and extracting undissolved residues on said filter, and the Ni content in the extracted residues is identified through analysis by ICP after dissolving said undissolved residues separated and left on said filter into a solution prepared by mixing aqua regia and water at the ratio of 1 : 1.

Description

Copper alloy, copper alloy plate and manufacture method thereof

The application is an application number: 200680015290.0, and the applying date: 2006.06.08, denomination of invention: the dividing an application of the application of " copper alloy, copper alloy plate and manufacture method thereof ".

Technical field

The present invention relates to bendability, punching and proof stress relaxation property excellence, be particularly suitable for copper alloy, the copper alloy utmost point and the manufacture method thereof of automobile with terminal/junctor.

Background technology

In recent years to the connect elements of automobile, require under the such hot environment of engine room and can guarantee that the performance of reliability is in low cost with terminal/junctor etc.One of most important characteristic is the characteristic of keeping of point of contact inlay resultant force in the reliability under this hot environment, is exactly so-called proof stress relaxation property.Promptly, during the normal displacement of spring shape element that gives constituting by copper alloy, for example by under the such situation of the tab (tab) of the chimeric male terminal of point of contact that is the spring shape of female terminal, if these connect elements are maintained under the such hot environment of engine room, then can lose this point of contact inlay resultant force as time passes, but so-called proof stress slackness is exactly the resistant property to it.

As the copper alloy of proof stress relaxation property excellence, be that alloy, Cu-Ti are that alloy, Cu-Be are alloy etc. always by the extensively cognitive Cu-Ni-Si that has.Because they all contain strong oxidizing property element (Si, Ti, Be etc.),, then can't avoid expensive from productive aspect so can not fuse with the spacious greatly extensive calciner of the peristome in atmosphere.

With respect to this, adding the fewer Cu-Ni-Sn-P of amount of element is alloy, can carry out so-called shaft furnace (shaft furnace) ingot casting, because of its high productivity can be realized significantly cost degradation.At this Cu-Ni-Sn-P is in the alloy, and the raising countermeasure of proof stress relaxation property etc. also propose to have multiple all the time.And according to manufacture method with add stress relaxation characteristics that amount of element given play to have reached Cu-Be be the alloy peer-level, be alloy system very likely.

For example, in following patent documentation 1, the manufacture method of a kind of junctor of proof stress relaxation property excellence with copper base alloy disclosed.This manufacture method is to be alloy at Cu-Ni-Sn-P, make that homogeneous disperses the Ni-P intermetallic compound imperceptibly in its matrix, when being improved, the conductivity degree improves proof stress relaxation property etc., according to same document, in order to obtain desired characteristics, need control hot rolled cooling beginning, final temperature, its speed of cooling closely, also have 5～720 minutes the heat treated temperature and time of in the cold rolling process way, implementing thereafter.

In addition, in following patent documentation 2,3,, disclose and reduced P content as far as possible and become the solid solution type copper alloy of separating out that has suppressed the Ni-P compound as the Cu-Ni-Sn-P alloy and the manufacture method thereof of proof stress relaxation property excellence.The advantage of bringing in view of the above is, do not need the heat treatment technics of height, just can make by the thermal treatment of utmost point short period of time.

Patent documentation 1: No. 2844120 communique of patent

Patent documentation 2: the spy opens flat 11-293367 communique

Patent documentation 3: the spy opens the 2002-294368 communique

In the specification JASO-C400 of Corporation's automotive engineering meeting, about the proof stress relaxation property, the stress relaxation rate after 150 ℃ * 1000hr keeps is defined as below 15%.The testing apparatus that shows the proof stress relaxation property in Fig. 1 (a) and (b).Use this testing apparatus, an end that cuts into the test film of slat is fixed on the rigid body testing table 2, lift to cantilevered the other end and make it crooked (crooked big or small d), after its temperature and time maintenance with regulation, removal load at room temperature, with the size (permanent strain) of the bending after the removal load as δ and try to achieve.Stress relaxation rate is by (RS)=(δ/d) * 100 expression.

There is anisotropy in the stress relaxation rate of copper alloy plate, and the length direction of test film is relative with the rolling direction of copper alloy plate, which direction can cause different values towards actually.In general, with respect to rolling direction, its stress relaxation rate of a side of parallel direction is littler than right angle orientation.But, in aforementioned JASO specification,, therefore, no matter be among either party of parallel direction or right angle orientation with respect to rolling direction always, as long as reach the stress relaxation rate below 15% not for the regulation of this direction.But in recent years, copper alloy plate is on respect to the rectangular direction of its rolling direction, and expectation has high proof stress relaxation property.

The cross-section structure that shows representational box-shaped junctor (female terminal 3) among Fig. 2.In Fig. 2, the 4 upper cantilever supports of last side stand (holder) portion have compressing piece 5, if male terminal 6 is inserted into, then recoverable deformations take place compressing piece 5, by the fixing male terminal 6 of its reactive force.Also have, in Fig. 2, the 7th, wire connecting portion, the 8th, fixedly use tongue.Wherein, extrusion processing copper alloy plate and when making female terminal 3, cutting mode be make female terminal 3 length direction (length direction of compressing piece 5) towards right angle orientation with respect to rolling direction.Why requiring extra high proof stress relaxation property in compressing piece 5, is at compressing piece 5 bending (recoverable deformation) in the longitudinal direction.Therefore, copper alloy plate is just required, on right angle orientation, have high proof stress relaxation property with respect to its rolling direction.

With respect to this, in described patent documentation 2,3 disclosed solid solution type copper alloys,, on right angle orientation, do not reach as yet though the high proof stress relaxation property of stress relaxation rate below 15% reached substantially in the parallel direction with respect to rolling direction.

Therefore,,, just require on right angle orientation,, also have the high proof stress relaxation property of stress relaxation rate below 15% compared with parallel direction with respect to rolling direction with respect to rolling direction about this solid solution type copper alloy from the user side.

In addition, the generation of Ni-P intermetallic compound can be extremely low, by easy thickization of the thermal treatment in the copper alloy manufacturing process, given play to present automotive engineering require the level other stress relaxation characteristics in, also can produce such as the deterioration of the bendability of the correctness that guarantees terminal shape and make the drawback of the punching press burr extension etc. of abrasion terminal stamping-out metal pattern.

Here, if watch the cross-section structure of representational box-shaped junctor (female terminal 3), as shown in Figure 2, the 4 upper cantilever supports of upside cradle portion have compressing piece 5, if male terminal 6 is inserted into, then recoverable deformations take place compressing piece 5, by the fixing male terminal 6 of its reactive force.Also have, in Fig. 2, the 7th, wire barrel (wire barrel), the 8th, fixedly use tongue.During by the such junctor of the former material plate of copper alloy manufacturing, adopt bending machining more and cut and dash processing.In order to make the junctor of miniature precision, all need excellent bendability with respect to the parallel direction of rolling direction and the both sides of right angle orientation.In addition, dash in the processing if big burr take place cutting, then burr are clipped in the bending machining position and hinder accurate bending machining, if burr occur in wire barrel portion, then can produce the cut-out of wiring when bending machining, the generation of burr also can be quickened the abrasion of stamping-out metal pattern in addition.Therefore, this copper alloy plate is just required excellent bendability and punching.

With respect to this, the bendability and the punching of the solid solution type copper alloy of existing C u-Ni-Sn system still do not claim fully.

Summary of the invention

Some the objective of the invention is in view of this, is alloy for Cu-Ni-Sn-P, on the right angle orientation with respect to rolling direction, reaches the high proof stress relaxation property of stress relaxation rate below 15%.

In addition, the present invention also aims to, obtain a kind of electrical connecting element copper alloy plate in the solid solution type copper alloy of Cu-Ni-Sn system, it has excellent bendability on respect to the right angle orientation of rolling direction and vertical direction, have the punching of excellence simultaneously.

In order to reach this purpose, the main idea of the copper alloy of proof stress relaxation property excellence of the present invention is, contain Ni:0.1～3.0%, Sn:0.01～3.0%, P:0.01～0.3% in quality %, surplus is copper and unavoidable impurities, according to following extraction residue method, making the following Ni amount in the extraction residue of institute's extraction separation on the strainer of mesh size 0.1 μ m, is below 40% with respect to the ratio of the Ni content in the described copper alloy.

At this, described extraction residue method is to be the described copper alloy of dipping 10g among the methanol solution 300ml of 10 quality % in ammonium acetate concentration, this copper alloy as anode, is used platinum as negative electrode, at 10mA/cm ²Current density under carry out the constant current electrolysis, and to utilize mesh size be the membrane filter of polycarbonate (polycarbonate) system of 0.1 μ m, to making the described solution of this copper alloy dissolved carry out suction filtration, separation and Extraction solute residue not on this strainer.

In addition, the described Ni amount in the described extraction residue is to utilize with 1 to 1 ratio after in addition blended solution dissolves the not solute residue on the aforementioned strainer with chloroazotic acid and water, tries to achieve by the ICP analysis of emission spectrography again.

In addition, for the main idea of the manufacture method of the copper alloy plate of the proof stress relaxation property excellence of the present invention of reaching described purpose is, be to make the method for described main idea to the copper alloy plate of aftermentioned optimal way, when obtaining copper alloy plate through the casting of copper alloy, hot rolling, cold rolling, final annealing, it is in 1200 seconds that the interpolation of the alloying element from the copper alloy calciner finishes to casting the required time that begins, in addition, after the process furnace of ingot casting takes out ingot casting to hot rolling terminated required time be below 1200 seconds.

In addition, electrical connecting element copper alloy plate of the present invention, it consists of and contains Ni:0.4～1.6%, Sn:0.4～1.6%, P:0.027～0.15%, Fe:0.0005～0.15%, the ratio Ni/P of Ni content and P content is lower than 15, surplus is made of copper and unavoidable impurities in fact, and in the copper alloy parent phase, has a tissue that has disperseed precipitate, described precipitate diameter is below the 60nm, can be observed 20 of precipitates more than the diameter 5nm, below the 60nm in the visual field of 500nm * 500nm.

The composition of described copper alloy plate, can contain any more than a kind that Zn:1% is following, Mn:0.1% following, Si:0.1% is following, Mg:0.3 is following as required, or Cr, Co, Ag, In, Be, Al, Ti, V, Zr, Mo, Hf, Ta, B count below 0.1% with total amount.

According to the present invention, in the copper alloy of Cu-Ni-Sn-P system, can reach the high proof stress relaxation property of stress relaxation rate below 15% in right angle orientation with respect to rolling direction.In addition, the curved characteristic excellence, electric conductivity (more than about 30%IACS) and intensity (yield-point that about 480MPa is above) are also excellent or the like, can access the copper alloy that has excellent characteristic as terminal connector usefulness.

Present inventors, in the described existing solid solution type copper alloy that separating out of Ni-P compound suppressed, with regard to the high proof stress relaxation property of stress relaxation rate below 15%, can reach substantially in parallel direction, but study in the reason that right angle orientation still can't be reached with respect to rolling direction.

It found that if oxide compound, crystallisate, the precipitate of the thick Ni more than the certain size suppressed, then the high proof stress relaxation property of stress relaxation rate below 15% can be reached on respect to the right angle orientation of rolling direction.

That is, oxide compound, crystallisate, the precipitate of the thick Ni that this what is called certain size is above are equivalent in the described main idea of the present invention, are extracted the Ni amount in the isolating extraction residue on the strainer of mesh size 0.1 μ m.If will extract the Ni amount in the residue, main idea of the present invention as described, with with respect to the proportional meter of the Ni content in the described copper alloy and be suppressed at below 40%, then the high proof stress relaxation property of stress relaxation rate below 15% can be reached on the right angle orientation with respect to rolling direction.In addition, can also make curved characteristic, electric conductivity and intensity also excellent simultaneously.

In addition, if the Ni compound (Ni resultant) to the oxide compound that surpasses the thick Ni more than the certain size of 0.1 μ m, crystallisate, precipitate etc. is suppressed like this, on the other hand, then be related to the amount that to guarantee the following fine Ni compound of 0.1 μ m (cluster that comprises the following fine Ni of millimicro level) etc. and the solid solution capacity of Ni.Also have the cluster of so-called Ni (cluster), the group that says at the atom on the atomic structure level, before the generation crystallization.

Patent documentation 1 is in the alloy substrate during the fine dispersion of homogeneous Ni-P intermetallic compound at Cu-Ni-Sn-P so only as described above, proof stress relaxation property can not be improved, but fine Ni compound amount that described 0.1 μ m is following and the solid solution capacity of Ni need be guaranteed with respect to the rolling direction right angle orientation.Just fine Ni compound amount below these 0.1 μ m and the solid solution capacity of Ni can not directly be measured.

With respect to this, in the present invention,, can guarantee fine Ni compound amount that these 0.1 μ m are following and the solid solution capacity of Ni indirectly by suppressing the described thick Ni compound that surpasses 0.1 μ m.

In the present invention,, guarantee fine Ni compound amount that 0.1 μ m is following and the solid solution capacity of Ni simultaneously in order to suppress the described thick Ni compound that surpasses 0.1 μ m, just need create conditions different with ordinary method.Promptly, the main idea of the manufacture method of copper alloy plate of the present invention as described, when obtaining copper alloy plate through the casting of copper alloy, hot rolling, cold rolling, final annealing, need finish from the interpolation of the alloying element the copper alloy calciner to the short period of timeization of casting beginning, also have after the process furnace of ingot casting takes out ingot casting to hot rolling terminated short period of timeization.

In the manufacturing process of general this copper alloy plate, these required times are long-timeization easily, therefore, the oxide compound, the crystallisate that produce when the major part of the Ni content that is added is brought into fusion/casting, and from being soaked to the thick precipitate that hot rolling finishes to be produced of ingot casting, fine Ni compound amount that the Ni content that should corresponding be added and the 0.1 μ m that generates are following and the solid solution capacity accident of Ni have tailed off.

Usually, in general manufacturing process, being by hot rolling, and then obtaining soleplate (finished product) repeatedly by cold rolling and annealed, mainly is to control fine Ni compound amount below the 0.1 μ m and the solid solution capacity of Ni by cold rolling condition, annealing conditions.At this moment, alloying elements such as Ni suitably make the solid solution capacity of Ni etc. and the amount of the separating out stabilization of fine resultant to the diffusion of dispersive intermetallic compound, and intention is carried out the control of characteristic of the machinery of intensity rank etc. thus.

But, in the manufacturing process of these general this copper alloy plates, as described in the operation of leading portion, 0.1 the absolute magnitude of fine Ni compound amount that μ m is following and the solid solution capacity of Ni tails off, therefore, even by hot rolling later cold rolling condition, annealing conditions aforementioned fine resultant is separated out in a large number, the absolute magnitude of fine Ni compound amount that 0.1 μ m is following and the solid solution capacity of Ni is still just not enough, thereby is difficult to make intensity and proof stress relaxation property to improve.

In addition, described thick oxide compound, crystallisate and precipitate (Ni compound) for a long time, the fine resultant of separating out in cold rolling, annealing operation is captured by this thick resultant, self-existent fine resultant further tails off in the matrix.Therefore in aforesaid general manufacture method, the addition of Ni can not obtain the proof stress relaxation property of full intensity and excellence at high proportion the time.

With respect to this, among the present invention,, can guarantee fine Ni compound amount that necessary (useful) 0.1 μ m is following and the solid solution capacity of Ni by suppressing the described thick Ni compound that surpasses 0.1 μ m.Consequently, the high proof stress relaxation property of stress relaxation rate below 15% can be reached on the right angle orientation with respect to rolling direction.In addition, can also make curved characteristic, electric conductivity and intensity also excellent simultaneously.

In addition,, in the solid solution type copper alloy of Cu-Ni-Sn system, can access on and have excellent bendability, have the electrical connecting element copper alloy plate of excellent punching simultaneously with respect to the right angle of rolling direction and vertical direction according to the present invention.

Description of drawings

Fig. 1 is the sectional view of the proof stress relaxation test of explanation copper alloy plate.

Fig. 2 is the front view (a) and the sectional view (b) of the structure of expression box-shaped junctor (female terminal).

Nomenclature

1 test film

3 female terminals

Embodiment

Embodiment 1

(copper alloy becomes to be grouped into)

At first, be grouped into following about the one-tenth of copper alloy of the present invention and describe.In the present invention, it is alloy that the composition of copper alloy consists of Cu-Ni-Sn-P, and as prerequisite, as described above, it is to carry out the shaft furnace ingot casting, and can realize that significantly the Cu-Ni-Sn-P of cost degradation is an alloy because of its high productivity.

Then, desired with the connect elements of terminal/junctor etc. in order to make as automobile, in high proof stress relaxation property excellence with respect to the right angle orientation of rolling direction, also make simultaneously curved characteristic, electric conductivity and excellent strength, copper alloy contains Ni:0.1～3.0%, Sn:0.01～3.0%, P:0.01～0.3% basically respectively, and surplus is made of copper and unavoidable impurities.Also have, the % of the content of each element represents it all is the meaning of quality %.Below about the alloying element of copper alloy, add reason and suppress reason describing with regard to it.

(Ni)

Ni and P form fine precipitate, are to improve intensity and the required element of proof stress relaxation property.When it contains when being lower than 0.1%, even according to the manufacture method of the present invention of the best, the absolute magnitude of fine Ni compound amount that 0.1 μ m is following and the solid solution capacity of Ni is still not enough.Therefore, in order to bring into play the effect of Ni effectively, need contain more than 0.1%.

But, if make it to contain superfluously above 3.0%, thickization of compound of the oxide compound of Ni, crystallisate, precipitate etc. then, perhaps thick Ni compound increases, and the Ni amount in the described extraction residue can not be below 40% with respect to the ratio of the Ni content in the copper alloy.Consequently, the solid solution capacity of fine Ni compound amount below the 0.1 μ m and Ni reduces.In addition, because the Ni compound of these thickization becomes the destructive starting point, thus not only intensity and the reduction of proof stress relaxation property, and bendability also reduces.Therefore, the content of Ni is 0.1～3.0% scope.Be preferably 0.3～2.0% scope.

(Sn)

Sn solid solution and intensity is improved in copper alloy.In addition, the Sn precipitate can suppress because of softening that the recrystallize in the annealing causes.But, in copper alloy of the present invention, be that precipitate generates in order to make Sn energetically, need the annealing under the higher temperature, but when Sn content was lower than 0.1%, it is softening that the recrystallize in then can not suppressing to anneal causes, thereby intensity reduces.Therefore, Sn content is lower than at 0.1% o'clock, and the final cold rolling draft after the needs increase annealing waits and carries out high strength.In this case, can follow a little reduction of electric conductivity and proof stress relaxation property.But when Sn content was lower than 0.01%, Sn was very few, even increase the final cold rolling draft after the annealing, intensity is still just low excessively, and these balance of properties do not reach the level of expectation.On the other hand, if surpass 3.0%, then electric conductivity reduces, and can not reach 30%ISCA.Therefore, the content of Sn is 0.01～3.0% scope, is preferably 0.1～2.0% scope, more preferably 0.3～2.0% scope.

(P)

P and Ni form fine precipitate, are to improve intensity and the required element of proof stress relaxation property.Be lower than 0.01% and contain sometimes, because the fine precipitate particle deficiency of P system, so need contain more than 0.01%.But, contain sometimes if make it surplus above 0.3%, thickization of Ni-P intermetallic compound precipitation particles, not only intensity and proof stress relaxation property reduce, and hot workability also reduces.Therefore, the content of P is 0.01～3.0% scope.Be preferably 0.02～0.2% scope.

(Fe、Zn、Mn、Si、Mg)

Fe, Zn, Mn, Si, Mg sneak into from the dissolving raw material of chip (scrap) etc. easily.Though these yuan have containing and produce effect separately, and electric conductivity is reduced.In addition, if it is many to contain quantitative change, then be difficult to use the shaft furnace ingot casting.Therefore, during electric conductivity more than obtaining 30%IACS, be respectively that Fe:0.5% is following, Zn:1% is following, Mn:0.1% is following, Si:0.1% is following, below the Mg:0.3%.In other words, allow in the present invention to contain below the higher limit at these.

The same recrystallization temperature that can improve copper alloy of Fe with Sn.But, reduce if surpass 0.5% electric conductivity, thereby can not reach 30%IACS.Be preferably below 0.3%.

Zn prevents tinned peeling off.But, surpass 1% o'clock electric conductivity and reduce, can not reach 30%IACS.Be preferably below 0.05% during in addition, with the shaft furnace ingot casting.

And, if,, also have to prevent the zinc-plated effect of peeling off even then contain below 0.05% as the temperature province (about 150～180 ℃) of automobile with the terminal use.

Mn, Si are effective as reductor.But if surpass 0.1%, then electric conductivity reduces and can not reach 30%IACS.In addition, with the shaft furnace ingot casting time, also distinguish below the preferred Mn:0.001%, below the Si:0.002%.

Mg has the effect that the proof stress relaxation property is improved.But if surpass 0.3%, then electric conductivity reduces and can not reach 30%IACS.With the shaft furnace ingot casting time, preferred below 0.001% in addition.

(Ca、Zr、Ag、Cr、Cd、Be、Ti、Co、Au、Pt)

Copper alloy of the present invention also allows to contain Ca, Zr, Ag, Cr, Cd, Be, Ti, Co, these elements of Au, Pt add up to below 1.0%.These elements have the effect of thickization that prevents crystal grain, but the total of these elements surpasses at 1.0% o'clock, and electric conductivity reduces, and can not reach 30%IACS.Be difficult to use the shaft furnace ingot casting in addition.

In addition, Hf, Th, Li, Na, K, Sr, Pd, W, S, C, Nb, Al, V, Y, Mo, Pb, In, Ga, Ge, As, Sb, Bi, Te, B, norium are impurity, and the total of these elements is controlled at below 0.1%.

(extracting the residue regulation)

In the present invention, as described above, suppress to surpass oxide compound, crystallisate, the precipitate (Ni compound) of thick Ni of the certain size of 0.1 μ m, thereby on right angle orientation, reach stress relaxation rate high proof stress relaxation property below 15% with respect to rolling direction.

The thick Ni compound amount that this certain size is above is defined as the Ni amount that is extracted in the isolating extraction residue in the present invention on the strainer of mesh size 0.1 μ m.And the Ni amount (thick Ni compound) in this extraction residue is decided to be below 40% with respect to the proportional divider of the Ni content in the described copper alloy.

So,, then produce the inhibition effect of these thick Ni compounds, and guarantee the fine Ni compound amount below the 0.1 μ m and the effect of Ni solid solution capacity if suppress decide the above thick Ni compound amount of certain size.Consequently, stress relaxation rate high proof stress relaxation property below 15% is reached on respect to the right angle orientation of rolling direction.In addition, also can make curved characteristic, electric conductivity and intensity also excellent simultaneously.

Ni amount in the described extraction residue surpasses at 40% o'clock with respect to the ratio of the Ni content in the described copper alloy, and described thick compound amount increases.In addition, correspondingly, fine Ni compound amount that 0.1 μ m is following and the solid solution capacity deficiency of Ni.Therefore, reduce with respect to proof stress relaxation property on the right angle orientation of rolling direction and intensity.Meanwhile, because described thick compound becomes the destructive starting point, so bendability also reduces.

(extracting the residue method)

The extraction residue method of stipulating among the present invention is measured the condition determination that reproducibility is arranged and stipulate to specialize in order to make.That is, in the methanol solution 300ml of ammonium acetate concentration 10 quality %, the described copper alloy of dipping 10g as anode, uses with platinum this copper alloy, on the other hand at 10mA/cm as negative electrode ²Current density under carry out the constant current electrolysis.Thus, the membrane filter of the polycarbonate system by mesh size 0.1 μ m carries out suction filtration to making the described solution of this copper alloy dissolved, and separation and Extraction goes out not solute residue on this strainer.Also have, the mesh size of this strainer 0.1 μ m is the minimum mesh size of real middle filtrator.

In the described solution that makes copper alloy fusion, the Ni of solid solution in advance dissolving in the copper matrix, and the thick Ni compound and the following fine Ni compound of 0.1 μ m that surpass 0.1 μ m do not dissolve, but disperse.Therefore, the not solute residue of separated extraction has only the thick Ni compound that surpasses 0.1 μ m on the strainer of described mesh size 0.1 μ m.On the other hand, the following fine Ni compound of the Ni of solid solution in advance and 0.1 μ m then sees through described strainer with solution.

(extracting the Ni amount in the residue)

In addition, Ni in the residue of described separated extraction amount is to utilize with 1 to 1 ratio after in addition blended solution is dissolved the not solute residue on the described strainer with chloroazotic acid and water, tries to achieve by the ICP analysis of emission spectrography again.

(copper alloy manufacture method)

Next, carry out following explanation with regard to the manufacture method of copper alloy of the present invention.Its operation of copper alloy of the present invention itself can be made according to conventional methods.That is, adjusted the molten alloyed copper that becomes to be grouped into and passed through casting, ingot casting building up by welding, soaking, hot rolling, then obtained final (finished product) plate with annealing by cold rolling repeatedly.Then, the control of the characteristic of the machinery of intensity rank etc. also is to realize by the separating out of controlling below the 0.1 μ m of fine resultant, and the separating out of controlling below the 0.1 μ m of fine resultant mainly is to utilize cold rolling condition, annealing conditions.

But, as the manufacture method that is used to make copper alloy plate the best of the present invention be, when obtaining copper alloy plate through the casting of copper alloy, hot rolling, cold rolling, final annealing, make the interpolation of the alloying element from the copper alloy calciner finish to the required time of casting beginning be in 1200 seconds, in addition, by the process furnace of ingot casting take out after the ingot casting to hot rolling terminated required time be below 1200 seconds.

Among the present invention, in order to suppress the described thick Ni compound that surpasses 0.1 μ m, guarantee fine Ni compound amount that 0.1 μ m is following and the solid solution capacity of Ni simultaneously, need so interpolation of the alloying element from the copper alloy calciner to finish, also have after the process furnace of ingot casting takes out ingot casting to hot rolling terminated short period of timeization to the short period of timeization of casting beginning.

In the manufacturing process of general this copper alloy plate, these required times are long-timeization easily.Therefore, in the oxide compound that produces when the major part of the Ni content that is added is brought into fusion/casting, the crystallisate, and from being soaked to the thick precipitate that hot rolling finishes to be produced of ingot casting, fine Ni compound amount that the Ni content that should corresponding be added and the 0.1 μ m that generates are following and the solid solution capacity of Ni tail off.

Therefore, even by back segment is main cold rolling condition, annealing conditions, and make the solid solution capacity of fine Ni compound amount below the 0.1 μ m and Ni controlled, but in the operation of described leading portion, the absolute magnitude of fine Ni compound amount that 0.1 μ m is following and the solid solution capacity of Ni tails off.In addition, described thick Ni compound amount for a long time, the fine resultant of separating out in cold rolling, the annealing operation is by should thick resultant capture, self-existent fine growing amount further reduces in matrix.Therefore, according to aforesaid general manufacture method, under the many degree of the addition of Ni, can not obtain full intensity and excellent proof stress relaxation property.

Therefore, in the present invention, on higher level, suppress thick Ni compound in the described manufacturing process.That is, particularly for the inhibition of thick Ni compound, (1) alloying element from calciner add finish very important to the time management of hot rolling terminated to ingot casting is taken out in the time management of casting beginning and (2) by process furnace after.

At first, fusion/casting can be carried out according to the usual method of continuous casting, semicontinuous casting etc. originally.But, the alloying element from calciner in described (1) adds and finishes to the time management of casting beginning, element in calciner adds and finishes 1200 seconds afterwards in, preferably cast with interior at 1000 seconds, the expectation of cooling/setting rate is more than 0.1 ℃/second, is preferably more than 0.2 ℃/second.

Thus, can suppress to contain the generation of the oxide compound of Ni and crystallisate and growth, thickization, and they are disperseed imperceptibly.From the viewpoint of the generation of the oxide compound that suppresses to contain Ni, carry out vacuum melting/cast or fusion/casting of carrying out under the low atmosphere of oxygen partial pressure more preferred.

Always, for fusion positively contains the mother alloy of the Cu-P that adds element etc., and make solid solution the interpolation element be dispersed in equably in the liquation, and because the analysis again after needing raw material to append, institute is down to beginning to cast needs about 1500 seconds or the above time.But, if to casting spended time like this, then contain the generation/thickization promotion of the oxide compound of Ni as can be known, and the yield rate of adding element reduced.

For fear of such generation/thickization that contains the Ni oxide compound, copper alloy of the present invention adds the alloying element in the calciner required time that finishes to the casting beginning as described and shortens in 1200 seconds during fabrication, preferably shortens in 1100 seconds.Like this to the shortening of time of casting, the composition after the prediction raw material appends on the basis of melting real result that can be by is in the past analyzed the needed time again and is waited and reach thereby shorten.

Secondly, to the time management of hot rolling terminated, behind process furnace heating ingot casting, the ingot casting that is removed from stove to hot rolling begins and can produce waiting time after described (2) take out ingot casting by process furnace.But, for thickization of making Ni compound of the present invention obtained the copper alloy that suppresses, recommendation is carried out from described fusion to the time of casting beginning and the control of cooling/setting rate, and will be controlled at below 1200 seconds, preferably be controlled at below 1100 seconds from the moment to required (total process) time of hot rolling terminated that process furnace takes out ingot casting.

In the past, be taken out to the problem that the hot rolling terminated time manages from process furnace and do not obtain research such, because the prolongation of the hot rolling time that brings from the carrying of process furnace thermotropism rolling line with along with the maximization that rises to the slab of target with productivity, generally can spend and surpass 1500 seconds time.But, spended time if so, the thick precipitate that then has Ni system is as can be known therebetween separated out, and can serve as to examine to separate out Ni and P with the crystallisate and the oxide compound of generation in the fusion/casting also in addition.If these thick precipitation particles increase, then described Ni level of residue increases also superfluously, so intensity and the reduction of proof stress relaxation property.

For fear of the effect of the minimizing of such solid solution Ni and thickization of Ni compound etc., copper alloy of the present invention will be taken out to the hot rolling terminated from process furnace energetically as described and add up to the required time management in 1200 seconds during fabrication.Such time management can avoid using elongated big parison of hot rolling time by promptly carrying ingot casting from process furnace thermotropism rolling line, reaches but initiatively use small-sized base to wait.

In hot rolling, to follow ordinary method and get final product, hot rolled approaching side temperature is about 600～1000 ℃, final temperature is about 600～850 ℃.Carry out water-cooled after the hot rolling or put cold.

Carry out cold rolling with anneal become production board thick copper alloy thereafter.Annealing and cold rollingly also can carry out repeatedly according to final (finished product) thickness of slab.Cold roughing is to select working modulus in the mode that obtains the working modulus about 30～80% in final finish rolling.Intermediary recrystallization annealing can suit in the way of cold roughing to be mingled with.

Final annealing for the copper alloy plate after the cold roughing can be continuous annealing, also can be batch annealing.Just,, must in continuous annealing (short period of time), improve the maintenance temperature, keep temperature and in batch annealing (for a long time), reduce in order to increase the amount of separating out of fine Ni-P intermetallic compound.This point, as the target of treatment temp (body temperature) and hold-time, the preferred time is 500～800 ℃ * 10～60 seconds in the continuous annealing, the preferred time is 300～600 ℃ * 2～20 seconds in the batch annealing (for a long time).Also have, preferably carry out chilling behind this final annealing with the speed of cooling more than 10 ℃/second.

Removal strain annealing or stabilizing annealing after the final cold finish rolling preferably carry out with 250～450 ℃ * 20～40 seconds body temperature.In view of the above, the strain that is imported by final finish rolling is removed, and material can not soften, and the reduction of intensity is few.

Embodiment 2

Below, describe for the copper alloy plate of the mode 2 of enforcement of the present invention.At first, the composition with regard to the copper alloy of embodiments of the present invention 2 describes.

Ni is solid-solubilized in the copper alloy and strengthens the proof stress relaxation property, is the element that intensity is improved.But in 0.4% this effect not then when following, if surpass 1.6%, then easily with the P precipitating metal that adds simultaneously between compound, thereby solid solution Ni reduces, the reduction of proof stress relaxation property.Therefore, content is 0.4～1.6%.0.7～0.9% scope more preferably.

Sn is solid solution in copper alloy, is the element that utilizes work hardening to bring intensity to improve.In this external alloy system also is to help stable on heating element.In copper alloy plate of the present invention,, need at high temperature carry out final annealing in order to make bendability and punching raising, but when Sn content is lower than 0.4%, and hot reduction advances because of recrystallize is softening in final annealing, so can not improve the temperature of final annealing fully.On the other hand, if surpass 1.6%, then electric conductivity reduces, and can not reach 30%ISCA in the copper alloy plate final finished.Therefore, Sn content is that the scope of 0.4～1.6% scope .0.6～1.3% is more preferred.Also have,, can fully obtain the advantage that the proof stress relaxation property improves needed solid solution Ni in addition by at high temperature carrying out final annealing.

P manifests the Ni-P precipitate in the manufacturing process way, be the element that the thermotolerance when making final annealing improves.Thus, the final annealing under the high temperature be can carry out, thereby bendability and punching improved.But when being lower than 0.027%, the P and the easy chemical combination that becomes than the relative Ni of Duoing of its addition, and form strong Ni-P intermetallic compound, on the other hand, surpass 0.15% if P is added, then the Ni-P intermetallic compound amount of separating out further increases, and the solid solution again of Ni-P intermetallic compound can not take place in final annealing which kind of situation, bendability and punching reduction, and can not fully obtain to be used to improve the solid solution Ni of proof stress relaxation property.Therefore, P content is 0.027～0.15%.More preferably 0.05～0.08%.

In addition, make the Ni/P ratio be lower than 15 reason be for make following both and deposit, promptly, decomposition, the solid solution again of the Ni-P precipitate when being used under high final annealing temperature, carrying out Ni the recrystallize that thermotolerance improves and final annealing causes that brings of solid solution and dislocation fixed Ni-P precipitate is softening again.The Ni/P ratio is 15 when above, and thermotolerance improves insufficient and have to carry out final annealing under lower temperature, and bendability and punching can't improve, and can not get sufficient proof stress relaxation property.

Fe is the element that suppresses thickization of recrystallize grain in final annealing.By in copper alloy, adding more than 0.0005%, can be in final annealing copper alloy be heated to high temperature and makes and add the abundant solid solution of element, suppress thickization of recrystallize grain simultaneously.But, reduce if surpass 0.15% electric conductivity, can not reach about 30%IACS.

Copper alloy of the present invention also has Zn, Mn, Si, Mg as submember, also can add other.

In order to prevent tinned peeling off, Zn can add below 1%.Yet,, add below 0.05% promptly abundant if be in the temperature province of using as the automobile terminal (about 150～180 ℃).During in addition, with the shaft furnace ingot casting preferably below 0.05%.

Mn, Si can add below 0.01% respectively as reductor.But, respectively preferably below 0.001%, below 0.002%.

Mg has the effect that the proof stress relaxation property is improved.Can add below 0.3%.But it is with the shaft furnace ingot casting time, preferred below 0.001%.

Cr, Co, Ag, In, Be, Al, Ti, V, Zr, Mo, Hf, Ta, B etc. have the effect of the coarsening of preventing, can add below 0.1% in total amount.

Pt is preferably limited to below 0.001% as impurity.

Secondly, the tissue with regard to copper alloy plate of the present invention describes.

Copper alloy plate of the present invention has the tissue that is dispersed with the precipitate of Ni-P intermetallic compound in the copper alloy parent phase.Diameter surpasses the particle of 60nm among the precipitate, and (R: bending radius, t: thickness of slab) become the reason that crackle takes place in the little bending machining, bendability reduces if it exists then at R/t.Also have, during precipitate particle separable spherical, the external circular diameter (major diameter) of this precipitate particle diameter as said precipitate among the present invention.

On the other hand, precipitate become cut towards the time the starting point of crackle, side's punching excellence that it distributes with high-density.Diameter is lower than the so fine precipitate of 5nm, in shear stress field, cause the work hardening characteristic of locality alternately with dislocation, though help to cut the transmission of dashing/advance, but if the above fine dispersion of precipitate of diameter 5nm, then be to cut the fracture of dashing where in order to pass to it, with further raising stampability, thereby help to reduce burr.Therefore, for the particle below the diameter 60nm that bendability is reduced, above in the visual field of 500nm * 500nm, on average the existing more than 20, more preferably more than 30 of preferred 5nm.

Next, the manufacture method with regard to copper alloy plate of the present invention describes.

Copper alloy plate of the present invention, can make by the following method: to copper alloy casting ingot homogenize handle after, carry out hot rolling and cold roughing, then the copper alloy plate after the cold roughing is carried out final continuous annealing, advance cold rolling again and the stabilization fire of bringing down a fever.

Because copper alloy of the present invention is not the precipitation type copper alloy, so in the processing that homogenizes, hot rolling and cold roughing, the condition aspect there is no need to carry out tight especially management.For example homogenize to handle and carried out 800～1000 ℃ * 0.5～4 hour, hot rolling is carried out with 800～950 ℃, carries out water-cooled after the hot rolling or puts cold.Cold roughing is to select working modulus in the mode that obtains the working modulus about 30～80% in final finish rolling.Intermediary recrystallization annealing can suit in the way of cold roughing to be mingled with.

On the other hand, can be to need to carry out tight management in the continuous annealing at final annealing for the copper alloy plate after the cold roughing, set suitable maintenance temperature and hold-time.

One of significant feature of alloy system in the present invention stipulates is that in surpassing under 650 ℃ the annealing of tens of seconds hold-time, precipitated phase shifts.If keep temperature low, it is many then to observe thick precipitate as described above.On thermodynamics, keep temperature, then general further thickization of aggegation of precipitate as if further improving.Yet from 600 to 650 ℃ of interval precipitated phases shift in this alloy system, that is, near the temperature 600 to 650 ℃ is the border, and in the thick precipitate decomposition/solid solution again that low-temperature region takes place, the cenotype that fine Ni-P compound is separated out manifests.This precipitate helps bendability to improve and the punching press burr reduce.

When keeping temperature low, observe the precipitate particle that diameter surpasses 60nm easily, in addition in the few compositing area of the content of Ni and P, the particle deficiency that diameter 60nm is following.On the other hand, even surpass 650 ℃ annealing temperature, if the hold-time is short, the then dispersion of thick precipitate/solid solution is still insufficient again, and fine precipitate will be difficult to manifest, and diameter is residual above the precipitate of 60nm.If opposite long, then thickization of recrystallize grain has the possibility of causing the bendability reduction.

Under the situation that copper alloy of the present invention is formed, remain on by body temperature and to surpass 650 ℃ temperature, hold-time is to anneal between 15～30 seconds high temperature, short time, can access the tissue that in copper alloy parent phase appropriateness is dispersed with the precipitate of Ni-P intermetallic compound.Chilling is preferably carried out with the speed of cooling more than 10 ℃/second in the annealing back.

Also have, by carry out final annealing under the condition between described such high temperature, short time, the precipitate solid solution again of the Ni-P intermetallic compound of separating out in the temperature-rise period can obtain the advantage that the proof stress relaxation property improves required solid solution Ni in addition fully.

Stabilizing annealing after the final finish rolling preferably carried out with 250～450 ℃ * 20～40 seconds.Thus, the strain that is imported by final finish rolling is removed, and material can not soften, and the reduction of intensity seldom.

Embodiment

Embodiment 1

Embodiments of the invention below are described.The different Cu-Ni-Sn-P of state that makes the Ni compound in the tissue is the various copper alloy thin plate of alloy, the characteristic of valence, electric conductivity, proof stress relaxation property etc.

Specifically, the copper alloy of each chemical ingredients shown in the table 1 being formed with coreless induction furnace in addition after the melting, carries out ingot casting with the semicontinuous casting method respectively, obtains the ingot casting of thick 70mm * wide 200mm * long 500mm.Each ingot casting unification is rolled by following condition and manufactures copper alloy thin plate.After the surface of each ingot casting carried out building up by welding and heating, carry out hot rolling and become the plate of thick 16mm, from the chilling water of the temperature more than 650 ℃.

[table 1]

*-below the expression detection boundary.

* other elements A group: the total content of Ca, Zr, Ag, Cr, Cd, Be, Ti, Co, Au, Pt.

* other element B group: the total content of Hf, Tb, Li, Na, K, Sr, Pd, W, S, C, Nb, Al, V, Y, Mo, Pb, In, Ga, Ge, As, Sb, Bi, Te, B, rare earth alloys.

This plate except that behind the descaling, is carried out cold rolling → continuous annealing → cold rolling → strain and removes annealing, manufacture copper alloy thin plate.That is, the plate after the once cold rolling (slightly cold rolling, middle extension is cold rolling) is carried out building up by welding, after carrying out final annealing, draft is carried out pinch pass as 50% in the continuous annealing that kept 20 seconds under 660 ℃ the body temperature.But, the example 16 of having only table 2 and comparative example 19 its Sn content are less to being lower than 0.1%, thereby softening (recrystallize in the annealing) that can not suppress to anneal and cause, because intensity reduces, so the draft of pinch pass is improved higher 80%, improves to realize intensity., carry out body temperature 400 ℃ * 20 second cryogenic strain remove annealing, obtain the copper alloy thin plate of thick 0.25mm thereafter.

At this moment, as shown in table 2, cooled and solidified speed, process furnace when alloying element from calciner being added finish required time (record and narrate in the table 2 and be the required time to the casting beginning) to the casting beginning, casting take out temperature, hot rolling final temperature, be fetched into hot rolling terminated required time (record and narrate the table 2 for to hot rolling terminated required time) from process furnace, and various changes take place, with the state of the Ni compound in the control copper alloy thin plate tissue.

Extract 10g from each copper alloy thin plate that so obtains and extract the test film that residue is measured usefulness, according to preceding method, Ni contained in the extraction residue for the sieve mesh extraction separation that passes through mesh 0.1 μ m measures, and tries to achieve by aforesaid ICP analysis of emission spectrography.Then, try to achieve the pairing ratio of Ni content (%) of described copper alloy.These results are presented in the table 2.

[table 2]

In addition, downcut test portion, carry out tension test, electric conductivity measuring, stress relaxation rate mensuration, pliability test from each copper alloy plate that obtains with each example.These results are also shown in the table 2.

(tension test)

Extract test film from described copper alloy thin plate, make the test film length direction, so be made into JIS5 tension test sheet by mechanical workout with respect to the rolling direction of the sheet material direction that meets at right angles.Then, utilize 5882 type Instron (Instron) companies to make the energy trier,, measure the characteristic of machinery under the condition of GL=50mm at trial speed 10.0mm/min.Also have, yield-point is the tensile strength that is equivalent to permanent extension rate 0.2%.

(electric conductivity measuring)

Extract test film from described copper alloy thin plate, measure electric conductivity.The electric conductivity of copper alloy plate test, be to process the test film of the short slat of wide 10mm * long 300mm by Milling (milling), non-ferrous metal material electric conductivity measuring method according to the JIS-H0505 defined, utilize doube bridge formula (dubble bridge) opposing determinator to measure the electricity opposing, and calculate electric conductivity according to the average cross-section method.

(stress relaxation characteristics)

Measure the stress relaxation rate of described copper alloy thin plate, estimate the proof stress relaxation property of this direction with respect to the right angle orientation of rolling direction.Specifically, extract test film, adopt cantilevered fashion shown in Figure 1 to measure from described copper alloy thin plate.Downcut the short slat test film 1 (length direction is a right angle orientation with respect to the rolling direction of sheet material) of wide 10mm, the one end is fixed on the rigid body testing table 2, the part of the long L of span of test film 1 is applied the d (=10mm) amount of scratching of size.At this moment, determined L so that be equivalent to 80% surface stress of material yield point by the mode of material load.It is kept taking out after 30 hours in 180 ℃ drying oven (oven), measure the permanent strain δ when having removed the amount of scratching d, according to RS=(the computed stress relaxation rate (RS) of δ/d) * 100.Also have, 180 ℃ * 30 hours maintenance then almost was equivalent to keep 150 ℃ * 1000 hours if calculate with Larsen-Miller parameter (Larson-Miller parameter).

(evaluation test of bendability)

The pliability test of copper alloy plate test portion is followed Japan and is stretched copper association technological standard and carry out.Sheet material is cut into wide 10mm, long 30mm, carry out Good Way (bending axis and rolling direction meet at right angles) bending with the bending radius of 0.5mm, with having or not of 50 times opticmicroscope visual observation bend crackles.Flawlessly be evaluated as zero, crack be evaluated as *.

As indicated in table 2, the example 101～116th of the copper alloy (alloy numbering 1～13) in forming as the present invention of table 1, manufactured in following preferred condition: promptly, alloying element from calciner added the required time that finishes to the casting beginning in 1200 seconds, casting be that the cooled and solidified speed on ground is more than 0.5 ℃/second, be taken out to required time that hot rolling begins in 1200 seconds from process furnace.In addition, process furnace takes out temperature, the hot rolling final temperature is all appropriate.

Therefore, the example 101～116 of table 2, making according to the Ni in the extraction residue of described extraction method extraction separation amount is below 80% with respect to the ratio of alloy Ni content, and control surpasses the Ni compound of the thick Ni oxide compound, crystallisate, precipitate etc. of 0.1 μ m in this way.Therefore, be estimated to be the amount that to guarantee the following fine Ni compound of 0.1 μ m (cluster that contains the following fine Ni of millimicro level) etc. and the solid solution capacity of Ni.

Consequently, example 101～116 of the present invention can be reached the high proof stress relaxation property of stress relaxation rate below 15% on the right angle orientation with respect to rolling direction.In addition, curved characteristic excellence, intensity are also excellent or the like, use as terminal/junctor to have excellent characteristic.

But, in the comparison among the example 101～106 of table 2, alloying element in the calciner adds the long example 102,106 of required time that finishes to the casting beginning, be taken out to the long example 103,104 of required time that hot rolling begins from process furnace, they are compared with relatively shorter example 101,105, and the proof stress relaxation property is lower.

In addition, among the example 101～106 of table 2, also have the example 109～115 (alloy of table 1 be numbered 6～12) of other amount of element above described preferred upper limit, its electric conductivity is compared also low with example 101～108.

Example 109～113, the alloy of its Fe, Zn, Mn, Si, Mg such as table 1 numbering 6～10 high respectively exceeds the described preferred upper limit.

The total of the element of example 114 its Ca, Zr, Ag, Cr, Cd, Be, Ti, Co, Au, Pt, the alloy numbering 11 as table 1 exceeds the described preferred upper limit 1.0 quality %.

The total of example 115 its Hf, Th, Li, Na, K, Sr, Pd, W, S, C, Nb, Al, V, Y, Mo, Pb, In, Ga, Ge, As, Sb, Bi, Te, B, norium, alloy numbering 12 as table 1 exceeds the described preferred upper limit 0.1 quality %.

On the other hand, example 116 is as the alloy 13 of table 1, and Sn content is low to moderate and is lower than 0.1%, though the draft that makes pinch pass as described above than higher realizing that intensity improves because softening of causing of annealing, to compare its intensity still lower with other examples.

With respect to this, the comparative example 123～126 of table 2, though be the in-house copper alloy of the present invention (alloy numbering 1) of table 1, each disengaging preferable range of creating conditions.

It adds comparative example 123,124 to finish to the required time of casting beginning from the alloying element calciner and surpasses 1200 seconds and long.In addition, comparative example 125,126 its be taken out to that required time that hot rolling begins surpasses 1200 seconds and long from process furnace.

Therefore, the comparative example 123～126 of table 2, it surpasses 40% by the Ni in the extraction residue of described extraction residue method extraction separation amount with respect to the ratio of alloy Ni content, and the Ni compound that surpasses the thick Ni oxide compound, crystallisate, precipitate etc. of 0.1 μ m too much and not is suppressed.Therefore, be estimated as the amount that to guarantee fine Ni compound that 0.1 μ m is following etc. and the solid solution capacity of Ni.

Consequently, comparative example 123～126, its proof stress relaxation property with respect to the right angle orientation of rolling direction is lower than example significantly.

The present invention of the alloy numbering 14～19 of comparative example 117～122 employing tables 1 of table 2 forms outer copper alloy.Therefore, be in the preferable range although create conditions, the Ni amount in the residue extracted with respect to each of the ratio of alloy Ni content, proof stress relaxation property, curved characteristic, electric conductivity, intensity all significantly than example difference.

The content of its Ni of copper alloy of comparative example 117 is low as to break away from lower limit (the alloy numbering 14 of table 1).Therefore, intensity and proof stress relaxation property are low.

The content height of its Ni of copper alloy of comparative example 118 must break away from the upper limit (the alloy numbering 15 of table 1).Therefore, intensity, proof stress relaxation property, bendability are low.

The content of its Sn of copper alloy of comparative example 119 is low as to break away from lower limit (the alloy numbering 16 of table 1).Therefore, comparative example 119 makes the draft of pinch pass improve with realization intensity than higher as described above, but because softening of annealing and cause still causes the low excessively result of intensity.

The content height of its Sn of copper alloy of comparative example 120 must break away from the upper limit (the alloy numbering 17 of table 1).Therefore electric conductivity is low.

The content of its P of copper alloy of comparative example 121 is low as to break away from lower limit (the alloy numbering 18 of table 1).Therefore intensity and proof stress relaxation property are low.

The content height of its P of copper alloy of comparative example 122 must break away from the upper limit (the alloy numbering 19 of table 1).Therefore, intensity, proof stress relaxation property, bendability are low.

According to above result, carry on the basis that is illustrated in high strength, high conductivityization, be used to make with respect to the becoming to be grouped into, organize of the copper alloy plate of the present invention of the proof stress relaxation property of the right angle orientation of rolling direction and excellent in bending workability, also be useful on the meaning of preferably creating conditions that obtains tissue

Embodiment 2

Next, the embodiment of copper alloy plate of the mode 2 of enforcement of the present invention is described.

In cryptol furnace (kryptol furnace),, obtain having the thick ingot casting (No.201～209) of 45mm of the composition shown in the table 3 with copper alloy fusion under the wooden carbon covering in atmosphere.Then, after the evenly heating of carrying out 3 hours evenly heating processing with 965 ℃ or carried out 30 minutes with 850 ℃ is handled, carry out hot rolling and to become 15mm thick, in quench more than 830 ℃ (water-cooled), the 1mm building up by welding is respectively carried out and to become 13mm thick in the two sides, carry out cold roughing afterwards and become the thickness shown in the table 3.

Then, carry out final continuous annealing, carry out batch-wise centre and final annealing to be mingled with cold rolling mode for No.209 for No.201～208, in addition, carry out pinch pass after, carry out low-temperature annealing (stabilizing annealing).The condition of each operation is documented in the table 3.Also have, the final finished thickness of slab is 0.25mm.

[table 3]

Each confession examination material for the final finished state that obtains, measure characteristic (tensile strength, yield-point, unit elongation), elastic force threshold value, proof stress relaxation property, bendability and the punching of its electric conductivity, hardness, machinery by following main points, this external application transmission electron microscope (TEM) is observed the distribution of precipitate.Its result is presented in the table 4.

[table 4]

* print: the position of specialized range of the present invention or fiery characteristic difference

Electric conductivity: electric conductivity measuring is undertaken by the four-terminal method that has used doube bridge according to the non-ferrous metal material electric conductivity measuring method of JIS-H0505 defined.

Hardness: the mensuration of hardness increases the weight of 100g (0.9807N) in test and measures Vickers' hardness down according to the small hardness test method of JIS-Z2251 defined.

The characteristic of machinery: make length direction become parallel direction (LD) and vertical direction (TD), make JIS5 tension test sheet by mechanical workout in this way, implement tension test and measure according to JIS-Z3341 with respect to the rolling direction of sheet material.Yield-point is the tensile strength that is equivalent to permanent extension rate 0.2%.

Elastic force threshold value: use AKASHI system elastic force threshold value trier (MODEL:APT) to try to achieve by the test of moment formula.The test direction of material becomes parallel direction (LD) and vertical direction (TD) for the rolling direction with respect to sheet material.

Proof stress relaxation property: adopt cantilevered fashion shown in Figure 1 to measure stress relaxation rate.Make length direction become parallel direction (LD) and vertical direction (TD) with respect to the rolling direction of sheet material, so cut the short slat test film 1 of wide 10mm down, the one end is fixed on the rigid body testing table 2, the part of the long L of span of test film 1 is applied the d (=10mm) amount of scratching of size.At this moment, determined L so that be equivalent to 80% surface stress of material yield point by the mode of material load.It is kept taking out after 30 hours in 180 ℃ drying oven, measure the permanent strain δ when having removed the amount of scratching d, according to RS=(the computed stress relaxation rate (RS) of δ/d) * 100.Also have, 180 ℃ * 30 hours maintenance then almost was equivalent to keep 150 ℃ * 1000 hours if calculate with Larsen-Miller parameter (Larson-Miller parameter).

Bendability: make length direction become parallel direction (LD) and vertical direction (TD) with respect to the rolling direction of sheet material, so cut wide 10mm down, the confession examination material of long 35mm, so that the vertical mode of curve and length direction, adopt the Type B bending jig of CESM0002 metallic substance W pliability test defined that it is clamped, use the system universal testing machine RH-30 of Shimadzu Seisakusho Ltd., under the loading of 1t, make R/t=2 (R: bending radius, t: thickness of slab) carry out 90 ° of W bending machining, estimate bend afterwards flawless is arranged, flawlessly be evaluated as zero, crack be evaluated as *.

Punching: the circular punching test of copper association criterion JCBAT310 (shearing test method of copper and copper alloy thin plate bar) is stretched by implementation basis Japan, measures and shears the burr height.Specifically, will be coated with the confession examination material of the unipresPA-5 of Nippon Mitsubishi Oil lubricating oil by pre-brush, by drift TCA

The punch die footpath

Punching press and be washed into circle.The gap of this punching press (clearance) is (side is the thickness of slab of (interval of punch die cutting edge and drift periphery)/confession examination material at interval) * 100 (%))=8%, velocity of shear is 50mm/min.For the burr that take place around the circular port that is washed into, circumference is measured 4 places for per 90 °, adopts mean value as the burr height.

The observation of the distribution of precipitate: will make the tem observation film for the examination material with electrolytic membrane method (Twin Jet method).Use the system TEM H-800 (acceleration voltage 200kV) of Hitachi, it is taken, on copy paper, be amplified to 1.5 times and transfer printings again with 40000 times and 100000 shooting bit rate.Take on the copy paper at these 60000 times, statistics is equivalent to the number that diameter in the foursquare visual field of 1000nm * 1000nm surpasses the precipitate of 60nm, and on 150000 times of shooting copy papers, the number of adding up the precipitate of diameter 5nm～60nm in the foursquare visual field that is equivalent to 500nm * 500nm.It is carried out a plurality of visuals field observe, calculate mean value.Also have, viewed described precipitate particle all is spherical in the visual field.

As shown in table 4, diameter surpasses No.201～207 that the precipitate of 60nm is not observed, and its LD, TD direction bendability are all excellent.In addition, in the visual field of 500nm * 500nm, observe more than the 5nm, below the 60nm 20 of precipitates with No.201～204 and No.208, average burr height is little, and the burr height of No.201～204 is especially little.In addition, its stress relaxation rate of No.201～204 on LD, TD direction also below 15%.

With respect to this, its Ni addition of No.205～207 is few, is difficult to take place though surpass the thick precipitate of 60nm, but because the final annealing temperature is low, so not translating near 650 ℃ is the fine cenotype of separating out that the boundary takes place, fine Ni-P compound does not reach the number of separating out of regulation yet.Because make the following fine precipitate deficiency of 60nm of the property sheared raising, so the burr height surpasses 10 μ m, punching is poor.Because it is few to add the Ni amount, seized the solid solution Ni in the matrix in addition in the precipitate, so the Ni solid solution capacity does not reach the amount that can keep stress relaxation characteristics, stress relaxation rate uprises (particularly in the TD direction).

No.208 is not because the final annealing temperature reaches 600 ℃ and be higher than 650 ℃, and the thick precipitate of 60nm decomposes fully, solid solution and some is residual again so surpass, and bendability is poor.Though not translating into fully near 650 ℃ is the fine cenotype of separating out that the boundary takes place, because the Ni addition is many, so a part of fine precipitate takes place, the burr height is depressed.In addition, because Ni-P precipitate total amount is many, Ni is the solid solution capacity deficiency again, does not fully obtain the stress relaxation rate height of TD direction so the proof stress relaxation property improves needed solid solution Ni amount.

No.209 is owing to the batch annealing that is lower than 650 ℃ becomes the precipitate aggegation at the above state of 60nm.Name recrystallize complete though carry out the batch annealing of secondary, do not reach branch deagglomeration precipitate so that the temperature that fine precipitate manifests, so bendability reduces, the burr height also uprises simultaneously.

Utilize possibility on the industry

As described above, according to the present invention, can provide a kind of proof stress relaxation property height of the right angle orientation with respect to rolling direction, and the Cu-Ni-Sn-P that has had both high strength, high conductivity, excellent bendability is alloy. Consequently, particularly as the Connection Element usefulness of automobile with terminal/connector, the purposes that can suitably have the proof stress relaxation property to require in the right angle orientation with respect to rolling direction.

Claims (4)

1. an Albatra metal-, it is characterized in that, contain Ni:0.4～1.6%, Sn:0.4～1.6%, P:0.027～0.15%, Fe:0.0005～0.15% in quality %, the ratio Ni/P of Ni content and P content is lower than 15, surplus comprises Cu and impurity in fact, and having the tissue that in the copper alloy parent phase, is dispersed with precipitate, the diameter of described precipitate is below the 60nm, observes diameter more than 20 and be the precipitate more than the 5nm, below the 60nm in the visual field of 500nm * 500nm.

2. copper alloy according to claim 1 is characterized in that, any more than a kind during described copper alloy also contains below the Zn:1%, below the Mn:0.1%, below the Si:0.1%, below the Mg:0.3% in quality %.

3. copper alloy according to claim 1 and 2 is characterized in that described copper alloy also contains Cr, Co, Ag, In, Be, Al, Ti, V, Zr, Mo, Hf, Ta, B, and these elements are below 0.1% in quality % total amount.

4. an electrical connecting element copper alloy plate is characterized in that, has used each described copper alloy in the claim 1～3.

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