CN103781925A - Cu-Ni-Si alloy and method for manufacturing same - Google Patents

Cu-Ni-Si alloy and method for manufacturing same Download PDF

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CN103781925A
CN103781925A CN201280042580.XA CN201280042580A CN103781925A CN 103781925 A CN103781925 A CN 103781925A CN 201280042580 A CN201280042580 A CN 201280042580A CN 103781925 A CN103781925 A CN 103781925A
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orientation
quality
copper
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rolling
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长野真之
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JX Nippon Mining and Metals Corp
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JX Nippon Mining and Metals Corp
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H01B1/026—Alloys based on copper

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Abstract

Provided is a Cu-Ni-Si alloy and a method for manufacturing the Cu-Ni-Si alloy, the Cu-Ni-Si alloy being provided with exceptional strength and bendability, and being suitable as an electro-conductive spring material for a connector, terminal, relay, switch or other component. The Cu-Ni-Si alloy contains 1.0 to 4.5 wt% of Ni, 0.2 to 1.0 wt% of Si, and copper and inevitable impurities constituting the balance. Electron back-scatter diffraction (EBSD) measuring is performed. When the crystal orientation is analyzed the area of cube orientation {001} <100>; constitutes 5% or more, the area of brass orientation {110} <112>; constitutes 20% or less, and the area of copper orientation {112} <111>; constitutes 20% or less. The work-hardening coefficient is 0.2 or less.

Description

Cu-Ni-Si is associated gold and manufacture method thereof
Technical field
The present invention relates to suitable copper alloy and manufacture method thereof electroconductibility spring material, that there is excellent intensity, bendability as junctor, terminal, rly., switch etc.
Background technology
In recent years, follow the miniaturization of electronic machine, the miniaturization development of electrical and electronic parts.And, for the copper alloy for these parts, require good intensity, electric conductivity.
In vehicle mounted terminal, follow miniaturization, used copper alloy is also required to good intensity, electric conductivity.And then, the many otch processing of bending inner face being implemented to be called as local stamping-out (notching) processing before pressurization bending machining of vehicle mounted female terminal.This is the processing that the form accuracy for improving after pressurization bending machining carries out.Follow product miniaturization, have the tendency that local stamping-out processing is deepened in order further to improve the form accuracy of terminal.Therefore,, for the copper alloy for vehicle mounted female terminal, except good intensity, electric conductivity, also require good bendability.And then, in relay terminal, follow miniaturization, in order to obtain desired intensity, material is implemented to closely sealed bending, thereby also require good bendability for material.
Corresponding to these requirements, use has the precipitation strength type copper alloys such as the Corson alloy of high intensity and electric conductivity and replaces the solution strengthening such as phosphor bronze or brass type copper alloy in the past, and this demand constantly increases.In Corson alloy, Cu-Ni-Si is associated gold and has high strength and higher electric conductivity concurrently, and its strengthening mechanism is that the intermetallic compound particles by separate out Ni-Si system in Cu matrix improves intensity and electric conductivity.
Conventionally, intensity and bendability are contrary character, even be associated gold for Cu-Ni-Si, also wish maintaining the high-intensity bendability that simultaneously improves.
Be associated the improvement method of golden bendability as Cu-Ni-Si, just like the method for crystallization control orientation described in patent documentation 1～3.In patent documentation 1 by make the area ratio of { 001 } < 100 > of the measurement result that EBSD analyzes be 50% with on improve bendability; In patent documentation 2, improve bendability by make the area ratio of { 001 } < 100 > of the measurement result that EBSP analyzes be more than 50% and do not have stratiform border; In patent documentation 3, by making, the area ratio of { 110 } < 112 > of the measurement result that EBSD analyzes is below 20%, the area ratio of { 121 } < 111 > is below 20%, the area ratio of { 001 } < 100 > is 5～60% to improve bendability.
In addition, in patent documentation 4 by make work hardening exponent be 0.05 with on improve bending forming.
Prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2006-283059 communique
Patent documentation 2: TOHKEMY 2006-152392 communique
Patent documentation 3: TOHKEMY 2011-017072 communique
Patent documentation 4: TOHKEMY 2002-266042 communique.
Summary of the invention
The technical problem that invention will solve
The inventor etc. have carried out proof test to the effect of aforementioned existing invention.Result is known, for the technology of patent documentation 3, although with bending radius 0.15mm(bending radius/thickness of slab=1) W bending can confirm certain effect of improving when bendability is evaluated, but with bending radius 0.075mm(bending radius/thickness of slab=0.5) while carrying out W pliability test, break, the improvement of bendability is insufficient.Therefore, problem of the present invention is to provide suitable Cu-Ni-Si electroconductibility spring material, that have excellent intensity, bendability as junctor, terminal, rly., switch etc. to be associated gold and manufacture method thereof.
For the means of technical solution problem
In prior art, improve Cu-Ni-Si and be associated golden bendability by controlling the crystalline orientation of copper alloy, but find by crystallization control orientation not only but also controlled working hardenability value (n value) can obtain excellent bendability.
The present invention who completes take above-mentioned opinion as background, in one aspect, be that Cu-Ni-Si is associated gold, the Si of the Ni that it contains 1.0～4.5 quality % and 0.2～1.0 quality %, and remainder is made up of copper and inevitable impurity, carrying out EBSD(Electron Back-Scatter Diffraction: Electron Back-Scattered Diffraction) when measuring and analyzing crystalline orientation, the area occupation ratio of Cube orientation { 001 } < 100 > is more than 5%, the area occupation ratio of Brass orientation { 110 } < 112 > is below 20%, the area occupation ratio of Copper orientation { 112 } < 111 > is below 20%, work hardening exponent is below 0.2.
Cu-Ni-Si of the present invention be associated gold contain in one embodiment with total amount count among Sn, Zn, Mg, Fe, Ti, Zr, Cr, Al, P, Mn, Co, Cr and the Ag of 0.005～2.5 quality % more than a kind.
In addition, the present invention is associated golden manufacture method for Cu-Ni-Si of the present invention in another aspect, wherein, the ingot casting that the Si of the Ni that making contains 1.0～4.5 quality % and 0.2～1.0 quality % and remainder are made up of copper and inevitable impurity, by after described slab hot-rolling, carries out cold rolling, carry out after the thermal treatment of softening degree 0.25～0.75, carry out the cold rolling of degree of finish 7～50%, then carry out solution treatment, then carry out ageing treatment and rate of straining 1 × 10 with random order -4(1/ second) following cold rolling.
Cu-Ni-Si of the present invention is associated in an embodiment of golden manufacture method, described ingot casting contain with total amount count among Sn, Zn, Mg, Fe, Ti, Zr, Cr, Al, P, Mn, Co, Cr and the Ag of 0.005～2.5 quality % more than a kind.
The present invention again on the other hand in for stretching brass work, it possesses above-mentioned copper alloy.
The present invention is being electronic instrument part on the other hand again, and it possesses above-mentioned copper alloy.
Invention effect
According to the present invention, the Cu-Ni-Si that the suitable electroconductibility spring material as junctor, terminal, rly., switch etc. can be provided and have excellent intensity, a bendability is associated gold and manufacture method thereof.
Accompanying drawing explanation
[Fig. 1] illustrates at various temperatures the figure of the relation of annealing temperature when Cu-Ni-Si of the present invention is associated gold and is annealed and tensile strength.
Embodiment
(Ni and Si concentration)
Ni and Si by carrying out ageing treatment with Ni 2the form of the intermetallic compounds such as Si is separated out.This compound can make intensity improve, and reduces Ni and the Si of solid solution in Cu matrix by separating out, thereby electric conductivity improves.But if Ni concentration less than 1.0 quality % or Si concentration less than 0.2 quality % cannot obtain desired intensity, otherwise if Ni concentration exceedes 4.5 quality % or Si concentration exceedes 1.0 quality %, hot workability variation.Therefore, Cu-Ni-Si of the present invention is associated in gold, is 1.0～4.5 quality % by the control of Ni concentration, is 0.2～1.0 quality % by the control of Si concentration.Ni concentration is preferably 1.3～4.0 quality %, and Si concentration is preferably 0.3～0.9 quality %.
(other adds element)
Being added with of Sn, Zn, Mg, Fe, Ti, Zr, Cr, Al, P, Mn, Co, Cr and Ag helps intensity raising.And then Zn has the effect of the heat-resisting separability that improves plating Sn, Mg has the effect that improves stress relaxation properties, and Zr, Cr, Mn have the effect that improves hot workability.If the concentration of Sn, Zn, Mg, Fe, Ti, Zr, Cr, Al, P, Mn, Co, Cr and Ag is in total amount less than 0.005 quality %, can not get above-mentioned effect, if otherwise exceed 2.5 quality %, electric conductivity significantly reduces and cannot be used as electrical and electronic parts material.Therefore, Cu-Ni-Si of the present invention is associated in gold, preferably contains these elements of counting 0.005～2.5 quality % with total amount, more preferably contains 0.1～2.0 quality %.
(crystalline orientation)
For copper alloy, Cube orientation is many, Brass orientation and Copper are orientated in few situation, and inhomogenous distortion is suppressed, and bendability improves.Here, Cube orientation is to instigate (0 0 1) facing to rolling surface normal direction (ND), makes (1 0 0) state facing to rolling direction (RD), and represents with the index of { 001 } < 100 >.Brass orientation is to instigate (1 1 0) facing to ND, makes (1 1 2) state facing to RD, and represents with the index of { 110 } < 112 >.Copper orientation is to instigate (1 1 2) facing to ND, makes (1 1 1) state facing to RD, and represents with the index of { 112 } < 111 >.
It is more than 5% by the area occupation ratio control of Cube orientation that Cu-Ni-Si of the present invention is associated gold.If the sharply variation of 5% bendability of area occupation ratio less than of Cube orientation.Although from the viewpoint of bendability, the higher limit of the area occupation ratio of Cube orientation is also unrestricted, is associated in golden situation at Cu-Ni-Si of the present invention, no matter makes manufacture method how change, the area occupation ratio of Cube orientation also can not exceed 80%.
It is below 20% that Cu-Ni-Si of the present invention is associated the golden area occupation ratio that Copper is orientated and Brass is orientated is controlled respectively.If in the area occupation ratio of the area occupation ratio of Copper orientation or Brass orientation, any one exceedes 20%, sharply variation of bendability.Although from the viewpoint of bendability, the lower value of the area occupation ratio of Copper orientation and Brass orientation is also unrestricted, but be associated in golden situation at Cu-Ni-Si of the present invention, no matter make manufacture method how change, any one of the area occupation ratio of the area occupation ratio of Copper orientation or Brass orientation also can sufficient 1%.
(work hardening coefficient)
If make Plastic Deformation deformation, stress is piled up, and work hardening occurs, and the tensile strength of metal rises.Work hardening coefficient (following table is shown n value) refers to the finger target value as this work hardening.N value is larger represents that this metal is larger by the rising of the tensile strength due to work hardening.
For electronic unit, the bending machining of must pressurizeing such as be junctor by forming materials.If pressurize bending machining, material meeting work hardening, its tensile strength can rise.
Conventionally, the tensile strength of material and bendability are the relations of mutual choice (trade off), and the higher bendability of tensile strength is poorer.
Therefore, the rising of the tensile strength due to the work hardening causing because of the pressurization bending machining of material if suppress is difficult to break in the time of pressurization bending machining.In other words, n value is more little more can obtain good bendability.
Cu-Ni-Si of the present invention is associated gold n value is controlled at below 0.2.N value is preferably below 0.1, less than 0.05 more preferably.If n value exceedes 0.2, sharply variation of bendability.Although from the viewpoint of bendability, the lower value of n value is also unrestricted, is associated in golden situation at Cu-Ni-Si of the present invention, no matter makes manufacture method how change, n value also can sufficient 0.01.
(manufacture method)
As manufacture method of the present invention, first use the raw materials such as calciner fusion electrolysis copper, Ni, Si, obtain the liquation of required composition.Then, this liquation is cast as to ingot casting.Then, take hot rolling, first cold rolling, thermal treatment, second cold rolling, solution treatment, ageing treatment, the 3rd cold rolling order precision work as have desired thickness and characteristic article or paper tinsel.After thermal treatment, solution treatment and ageing treatment, the surface film oxide generating while heating in order to remove, also can carry out surperficial pickling or grinding etc.Can also change ageing treatment and the 3rd cold rolling order.In addition, in order to realize high strength, also can between solution treatment and timeliness, carry out cold rolling.And then, for the reduction that makes the 3rd elastic limit value due to cold rolling recovers, can carry out stress relief annealing after cold rolling the 3rd.
In the present invention, in order to obtain aforementioned crystalline orientation, before solution treatment, heat-treat the second cold rolling of (following, be called preannealing) and lower degree of finish.Under the condition that preannealing is 0.25～0.75 at softening degree S, carry out.
Fig. 1 illustrates Cu-Ni-Si of the present invention is associated to the annealing temperature of gold while annealing at various temperatures and the relation of tensile strength.The sample that thermopair is installed is dropped into and is heated in the stove of specified temperature, in the time reaching specified temperature with the specimen temperature of thermocouple measurement, sample is taken out from stove and carry out water-cooled, measure tensile strength.Arriving temperature at sample is between 500～700 ℃, to carry out recrystallize, and tensile strength sharply reduces.The mild reduction of the tensile strength of high temperature side is by due to the growth of recrystal grain.
With the softening degree S in following formula definition preannealing,
S＝（σ 0-σ）/（σ 0-σ 900）。
Here σ, 0for the tensile strength before preannealing, σ and σ 900tensile strength after annealing after being respectively preannealing and at 900 ℃.Anneal if Cu-Ni-Si of the present invention is associated to gold at 900 ℃, stably perfect recrystallization, thereby adopt the temperature of 900 ℃ to be used as knowing the reference temperature of the tensile strength after recrystallize.
If S less than 0.25, the area occupation ratio of Copper orientation increases and exceedes 20%, produces with it the reduction of the area occupation ratio of Cube orientation together.
If S exceedes 0.75, the area occupation ratio of Brass orientation increases and exceedes 20%, also produces with it the reduction of the area occupation ratio of Cube orientation together.
Temperature, time and the speed of cooling of preannealing are not particularly limited, and importantly S are adjusted to above-mentioned scope.Conventionally, use when continuous annealing furnace, at 400～700 ℃ of furnace temperature, carry out with the scope of 5 seconds～10 minutes, while using intermittently annealing furnace, at 350～600 ℃ of furnace temperature, carry out with the scope of 30 minutes～20 hours.
Should illustrate, softening degree S is adjusted to 0.25～0.75 can be undertaken by following steps.
(1) the tension test intensity (σ to the material before preannealing 0) measure.
(2) material before preannealing is annealed at 900 ℃.Particularly, the material that thermopair is installed is inserted in the tube furnace of 950 ℃, in the time reaching 900 ℃ with the specimen temperature of thermocouple measurement, sample is taken out from stove, carry out water-cooled.
(3) obtain the tensile strength (σ of the material after above-mentioned 900 ℃ of annealing 900).
(4) for example, σ 0for 800MPa, σ 900during for 300MPa, be respectively 675MPa and 425MPa with softening degree 0.25 and 0.75 suitable tensile strength.
(5) mode take the tensile strength after annealing as 425～675MPa is determined annealing conditions.
Should illustrate, " in the time reaching 900 ℃ with the specimen temperature of thermocouple measurement; sample is taken out from stove; carry out water-cooled " in above-mentioned operation (2) specifically undertaken by following manner, for example, in stove, sample is hung in advance in wire, cut off wire in the moment that reaches 900 ℃, fall into and set in advance in the tank of below, carry out thus water-cooled; Or after specimen temperature has just reached 900 ℃ by manual operations from taking out rapidly in stove and to be dipped in tank medium.
After above-mentioned annealing, before solution treatment, make degree of finish R be 7～50% second cold rolling.Degree of finish R(%) use
R＝（t 0-t）/t 0×100
(t 0: the thickness of slab before rolling, t: the thickness of slab after rolling)
Define.
If degree of finish R departs from this scope, the area occupation ratio of Cube orientation becomes less than 5%.
And then, be below 0.2 for n value is controlled, be 1 × 10 by the 3rd cold rolling rate of straining control -4below (1/ second).Rate of straining of the present invention by specifically for roll speed/roller contact arc length, for rate of straining is reduced, effectively makes roll speed slack-off, increases the passage number of times of rolling, makes roller contact arc length elongated etc.Although from the lower value of the viewpoint rate of straining of n value unrestricted, if carry out lower than 1 × 10 -5the rolling of (1/ second), its rolling time is elongated, not preferred in industrialness.The rate of straining of common industrial rolling is 2 × 10 -4～5 × 10 -4(1/ second) left and right.
If list the manufacture method of alloy of the present invention according to operation order, as described below.
(1) casting of ingot casting
(2) hot rolling (800～1000 ℃ of temperature, thickness are until 5～20mm left and right)
(3) cold rolling (degree of finish 30～99%)
(4) preannealing (softening degree S=0.25～0.75)
(5) saddening system (degree of finish 7～50%)
(6) solution treatment (at 700～900 ℃ 5～300 seconds)
(7) cold rolling (degree of finish 1～60%, rate of straining 1 × 10 -4(1/ second) is following)
(8) ageing treatment (at 350～550 ℃ 2～20 hours)
(9) cold rolling (degree of finish 1～50%, rate of straining 1 × 10 -4(1/ second) is following)
(10) stress relief annealing (at 300～700 ℃ 5 seconds～10 hours)
Here, the degree of finish of cold rolling (3) is preferably made as 30～99%.In order partly to generate recrystal grain in preannealing (4), need in cold rolling (3), to import in advance strain, under the degree of finish more than 30%, can obtain effective strain.On the other hand, if degree of finish exceedes 99%, have at edge of rolling stock etc. break, the situation of Materials Fracture in rolling.
Optionally carry out in order to realize high strength and control n value cold rolling (7) and (9), and intensity increases along with the increase of rolling degree of finish, and but then, bendability can reduce.No matter the degree of finish of cold rolling (7) and (9) how, all can obtain effect of the present invention.Wherein, from the viewpoint of bendability, preferably degree of finish does not separately exceed above-mentioned higher limit in cold rolling (7) and (9), from the viewpoint of high strength effect, preferably degree of finish separately lower than above-mentioned lower value.In addition, in order to control n value, need to carry out in cold rolling (7) or cold rolling (9) that at least one is cold rolling.
Stress relief annealing (10) is that the recoveries such as the elastic limit value in order to make to reduce because this is cold rolling in the situation of carrying out cold rolling (9) are optionally carried out.No matter have or not stress relief annealing (10), all can obtain effect of the present invention.Stress relief annealing (10) can be carried out or not carry out.
Should illustrate, for operation (2), (6) and (8), can select Cu-Ni-Si to be associated common the creating conditions of gold.
Cu-Ni-Si of the present invention is associated gold can be processed as the various brass works of stretching, for example, plate, bar and paper tinsel, and then Cu-Ni-Si of the present invention is associated gold and can be used in electronic instrument parts such as lead frame, junctor, pin, terminal, rly., switch, secondary cell foil material etc.
In addition, the final thickness of slab (product thickness of slab) that Cu-Ni-Si of the present invention is associated gold is not particularly limited, and in the situation of the said products purposes, is generally 0.05～1.0mm.
Embodiment
Embodiments of the invention are shown below together with comparative example, but these embodiment provide in order to understand better the present invention and advantage thereof, and 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 %, and remainder by copper and the alloy that inevitably impurity forms as experiment material, the impact that the relation on preannealing, the second cold rolling degree of finish and the 3rd cold rolling rate of straining and crystalline orientation and n value and crystalline orientation and n value are brought product bendability is studied.
In argon atmospher, use the plumbago crucible of internal diameter 60mm, degree of depth 200mm with high-frequency melting stove, electrolytic copper 2.5kg is melted.Add alloying element for obtaining above-mentioned alloy composition, melt temperature is adjusted to after 1300 ℃, water the mold of the cast iron system of casting from, make the ingot casting of thickness 30mm, width 60mm, length 120mm.This ingot casting is heated 3 hours at 950 ℃, be hot-rolled down to thickness 10mm.The oxide skin grinding on hot-rolled sheet surface is removed with shredder.Thickness after grinding is 9mm.Then, implement rolling and thermal treatment according to following process sequence, make the product sample of thickness of slab 0.15mm.
(1) first is cold rolling: corresponding to the second cold rolling rolling degree of finish, be cold-rolled to the thickness of regulation.
(2) preannealing: sample is inserted and is adjusted in the electric furnace of specified temperature, keep, after the specified time, carrying out cooling under following 2 kinds of conditions: sample is put into tank and carry out cooling (water-cooled) or sample is placed in to atmosphere carrying out cooling (air cooling).
(3) second is cold rolling: under various rolling degree of finish, carry out cold rolling until thickness 0.18mm.
(4) solution treatment: sample is inserted in the electric furnace that is adjusted to 800 ℃, keep, after 10 seconds, sample being put into tank and carrying out cooling.
(5) ageing treatment: use electric furnace 450 ℃, in Ar atmosphere, heat 5 hours.
(6) the 3rd is cold rolling: with various rate of straining, be cold-rolled to 0.15mm 17% time at degree of finish from 0.18mm.
(7) stress relief annealing: sample is inserted in the electric furnace that is adjusted to 400 ℃, keep, after 10 seconds, sample being placed in to atmosphere and carrying out cooling.
To the sample after preannealing and product sample (now for stress relief annealing finishes), carry out following evaluation.
(the softening degree evaluation in preannealing)
For the sample before preannealing and after preannealing, use tensile testing machine, measure abreast tensile strength according to JIS Z 2241 with rolling direction, using value separately as σ 0and σ.In addition, make 900 ℃ of annealing samples according to above-mentioned steps (insert in the stove of 950 ℃, carry out water-cooled in the time that sample reaches 900 ℃), and similarly measure abreast tensile strength with rolling direction, obtain σ 900.By σ 0, σ, σ 900, obtain softening degree S according to following formula,
S＝（σ 0-σ）/（σ 0-σ 900）。
(crystalline orientation of product is measured)
By EBSD(Electron Back-Scatter Diffraction: Electron Back-Scattered Diffraction) measure the area occupation ratio of Cube orientation, Copper orientation and Brass orientation.
During EBSD measures, to the square Area of Sample of 500 μ m that comprises more than 200 crystallization crystal grain, with stepping, 0.5 μ m scans, and analyzes orientation.For the angle departing from from ideal orientation, centered by common axis of rotation, calculate rotation angle, as deviation angle.For example, with respect to S orientation (2 3 1) ［ 6-4 3 ］, (1 2 1) ［ 1-1 1 ］ is the relation that is oriented to 19.4 ° of turning axle rotations with (20 10 17), using this angle as deviation angle.Common axis of rotation adopts the turning axle that can show with minimum angle of deviation degree.Calculate this deviation angle with respect to all measuring points, and take one decimal place as significant figure, depart from separately 10 ° of areas with the crystallization crystal grain of interior orientation divided by total area of measuring, as area occupation ratio by having from Cube orientation, Copper orientation, Brass orientation.Although utilize the information of gained in the orientation analysis of EBSD comprise electron rays penetrate sample until the orientation information of the number 10nm degree of depth is very little with respect to the scope of measuring, be therefore designated as area occupation ratio.
(tension test of product)
Use tensile testing machine to carry out abreast tension test according to JIS Z 2241 with rolling direction, obtain stress-strain curve.Obtain tensile strength and 0.2% yield strength by this curve.And then, stress-strain curve is converted to true stress-true strain curve, read n value.
(pliability test of product)
Carry out the W pliability test of record in JIS H 3130 in the parallel direction with respect to rolling direction time, obtain and do not produce the minimum bending radius (MBR, unit: mm) of breaking, measure the ratio (MBR/t) with thickness of slab (t, unit: mm).
Table 1 illustrates test conditions and evaluation result.Example is manufactured under condition given to this invention, and crystalline orientation and n value meet regulation of the present invention, and having obtained MBR/t is the good bendability below 0.5.
Comparative example 1 is due to the softening degree less than 0.25 in preannealing, thereby the area occupation ratio of Copper orientation exceedes the area occupation ratio less than 5% of 20%, Cube orientation.Comparative example 2 is because the softening degree in preannealing exceedes 0.75, thereby the area occupation ratio of Brass orientation exceedes the area occupation ratio less than 5% of 20%, Cube orientation.The degree of finish of the second rolling of comparative example 3 and 4 departs from regulation of the present invention, and the area occupation ratio of Cube orientation becomes less than 5%.The rate of straining of the 3rd rolling of comparative example 5 departs from regulation of the present invention, and n value exceedes 0.2.In above comparative example, MBR/t is 1, and bendability is poor.
Should illustrate, comparative example 5 is to carry out under the scope of the condition of recommending at patent documentation 3, and its crystalline orientation meets the regulation of patent documentation 2.
[table 1]
(embodiment 2)
Being associated the golden effect of improving that whether can obtain the bendability shown in embodiment 1 for different compositions with the Cu-Ni-Si creating conditions is studied.
With the method identical with embodiment 1 cast, hot rolling and surfacing, obtain 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, make the product sample of thickness of slab 0.15mm.
(1) first is cold rolling: corresponding to the second cold rolling rolling degree of finish, be cold-rolled to the thickness of regulation.
(2) preannealing: sample is inserted and is adjusted in the electric furnace of specified temperature, keep, after the specified time, carrying out cooling under following 2 kinds of conditions: sample is put into tank and carry out cooling (water-cooled) or sample is placed in to atmosphere carrying out cooling (air cooling).
(3) second is cold rolling: under various rolling degree of finish, carry out cold rolling until thickness 0.18mm.
(4) solution treatment: sample is inserted and is adjusted in the electric furnace of specified temperature, keep, after 10 seconds, sample being put into tank and carrying out cooling.Select this temperature take the mean diameter of recrystal grain as the scope of 5～25 μ m scopes.
(5) ageing treatment: use electric furnace, heat 5 hours under specified temperature, in Ar atmosphere.Select this temperature take the tensile strength after timeliness as maximum mode.
(6) the 3rd is cold rolling: with various rate of straining, be cold-rolled to 0.15mm 17% time at degree of finish from 0.18mm.
(7) stress relief annealing: sample is inserted and is adjusted in the electric furnace of specified temperature, keep, after 10 seconds, sample being placed in to atmosphere and carrying out cooling.
For the sample after preannealing and product sample, carry out the evaluation identical with embodiment 1.Table 2 and 3 illustrates respectively test conditions and evaluation result.While not carrying out stress relief annealing, in its temperature one hurdle, be designated as " nothing ".
The Ni that alloy of the present invention contains defined concentration of the present invention and Si manufacture under defined condition of the present invention, and crystalline orientation and n value meet regulation of the present invention, and having obtained MBR/t is the good bendability below 0.5.
On the other hand, the rate of straining of the 3rd rolling of comparative example 6 departs from regulation of the present invention, and therefore n value exceedes 0.2, and its bendability is poor.Softening degree in the preannealing of comparative example 7,8 and 9 departs from regulation of the present invention, and therefore the degree of finish of the second rolling of comparative example 10 and 11 departs from regulation of the present invention, so its crystalline orientation departs from regulation of the present invention, bendability is poor.The Ni of comparative example 12 and Si concentration are lower than regulation of the present invention, although its bendability is good, 0.2% yield strength 500MPa does not reach yet.
[table 2]
[table 3]
Figure 77770DEST_PATH_IMAGE003

Claims (6)

1.Cu-Ni-Si is associated gold, the Si of the Ni that it contains 1.0～4.5 quality % and 0.2～1.0 quality %, and remainder is made up of copper and inevitable impurity, carrying out EBSD(Electron Back-Scatter Diffraction: Electron Back-Scattered Diffraction) when measuring and analyzing crystalline orientation, the area occupation ratio of Cube orientation { 001 } < 100 > is more than 5%, the area occupation ratio of Brass orientation { 110 } < 112 > is below 20%, the area occupation ratio of Copper orientation { 112 } < 111 > is below 20%, work hardening exponent is below 0.2.
2. Cu-Ni-Si claimed in claim 1 is associated gold, its contain with total amount count among Sn, Zn, Mg, Fe, Ti, Zr, Cr, Al, P, Mn, Co, Cr and the Ag of 0.005～2.5 quality % more than a kind.
3. the Cu-Ni-Si described in claim 1 or 2 is associated golden manufacture method, wherein, the ingot casting that the Si of the Ni that making contains 1.0～4.5 quality % and 0.2～1.0 quality % and remainder are made up of copper and inevitable impurity, by after described slab hot-rolling, carry out cold rollingly, carry out, after the thermal treatment of softening degree 0.25～0.75, carrying out the cold rolling of degree of finish 7～50%, then carry out solution treatment, then carry out ageing treatment and rate of straining 1 × 10 with random order -4(1/ second) following cold rolling.
4. Cu-Ni-Si claimed in claim 3 is associated golden manufacture method, wherein, described ingot casting contain with total amount count among Sn, Zn, Mg, Fe, Ti, Zr, Cr, Al, P, Mn, Co, Cr and the Ag of 0.005～2.5 quality % more than a kind.
5. stretch brass work, it possesses profit and requires the copper alloy described in 1 or 2.
6. electronic instrument part, it possesses the copper alloy described in claim 1 or 2.
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