CN102666890A - Cu-co-si-based alloy sheet, and process for production thereof - Google Patents
Cu-co-si-based alloy sheet, and process for production thereof Download PDFInfo
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- CN102666890A CN102666890A CN2011800035931A CN201180003593A CN102666890A CN 102666890 A CN102666890 A CN 102666890A CN 2011800035931 A CN2011800035931 A CN 2011800035931A CN 201180003593 A CN201180003593 A CN 201180003593A CN 102666890 A CN102666890 A CN 102666890A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
- H01B1/026—Alloys based on copper
Abstract
Disclosed is a Cu-Co-Si-based alloy sheet which can be used suitably for various electronic components and can be plated satisfactorily and homogeneously. Specifically disclosed is a copper alloy sheet for an electronic material, which comprises 0.5 to 3.0 mass% of Co, 0.1 to 1.0 mass% of Si, and a remainder made up by Cu and unavoidable impurities, wherein the average crystal particle diameter at the thicknesswise center part of the sheet is 20 [mu]m or less and crystal particles that are in contact with the surface of the sheet and have a longer diameter of 45 [mu]m or less exist at a density of 5 particles or less per mm of the length of the sheet in the rolling direction.
Description
Technical field
The present invention relates to as the Cu-Co-Si that is preferred for the precipitation hardening type copper alloy of various electronic units is alloy sheets, and the excellent Cu-Co-Si of homogeneous tack that particularly relates to plating is an alloy sheets.
Background technology
For the copper alloy for electronic material that uses in the various electronic units such as junctor, switch, rly., pin, terminal, lead frame, require to have concurrently HS and high conductivity (or thermal conductivity) as fundamental characteristics.In recent years, corresponding along with the highly integrated of electronic unit and miniaturized thinning develop hastily with it, require level also increasingly high to the copper alloy that uses in the e-machine parts.
From the viewpoint of HS and high conductivity, as copper alloy for electronic material, replace the solution strengthening type copper alloy of representatives such as phosphor bronze, brass in the past, the usage quantity of precipitation hardening type copper alloy increases.In the precipitation hardening type copper alloy, through the supersaturated solid solution through solution treatment is carried out ageing treatment, fine precipitate disperses equably, and when alloy strength increased, the solid solution element amount in the copper reduced, electroconductibility improves.Thereby, can obtain mechanical properties excellences such as intensity, elasticity and electroconductibility, the good material of thermal conductivity.
In the precipitation hardening type copper alloy, the Ni-Si series copper alloy that is commonly referred to as Corson alloy is the representative copper alloy that has high electrical conductivity, intensity and bendability concurrently, is one of alloy of developing actively at present in the industry cycle.In this copper alloy, in copper matrix, separate out, can realize the raising of intensity and electric conductivity through making fine Ni-Si series intermetallic compound particle.
With the characteristic of Corson alloy further rise to purpose, the interpolation of the alloying constituent beyond various technological development: Ni and the Si below having carried out, characteristic is caused the eliminating of dysgenic composition, the optimization of crystal structure, the optimization of precipitation particles etc.For example, knownly separate out the second phase particle to the parent phase through adding Co or control, characteristic increases, and as the nearest improving technology of Ni-Si-Co series copper alloy, can enumerate following technology.
Show in the 2005-532477 communique (patent documentation 1) in order to obtain the excellent Ni-Si-Co series copper alloy of bendability, electric conductivity, intensity and stress relaxation-resistant property the Japan spy; Ni, Si, Co amount and relation each other thereof are controlled, the average crystallite particle diameter below the 20 μ m is also put down in writing.And, it is characterized in that in its manufacturing process, the first aging anneal temperature is higher than the 2nd aging anneal temperature (paragraph 0045～0047).
In the TOHKEMY 2007-169765 communique (patent documentation 2), be the purpose distribution of controlling the 2nd phase particle, thickization that suppresses crystal grain with the bendability that improves the Ni-Si-Co series copper alloy.In this patent documentation; For the copper alloy that in Corson alloy, has added cobalt; The precipitate of clear and definite effect with thickization of crystal grain when suppressing high-temperature heat treatment and the relation of its distribution improve intensity, electroconductibility, stress relaxation characteristics, bendability (paragraph 0016) through the crystallization control particle diameter.The crystallization particle diameter is more little preferred more, improves bendability (paragraph 0021) to get off through reaching 10 μ m.
Disclose in the TOHKEMY 2008-248333 communique (patent documentation 3) and suppressed the copper alloy for electronic material that the second thick phase particle in the Ni-Si-Co series copper alloy produces.In this patent documentation, when suppressing the generation of the thick second phase particle, can realize the excellent specific property (paragraph 0012) of target through carrying out hot rolling and solution treatment under given conditions.
The prior art document
Patent documentation
Patent documentation 1: Japan special table 2005-532477 communique
Patent documentation 2: TOHKEMY 2007-169765 communique
Patent documentation 3: TOHKEMY 2008-248333 communique.
Summary of the invention
The technical problem that invention will solve
Usually many enforcements have plating Au on the copper alloy for electronic material plate that in various electronic units such as junctor, switch, rly., pin, terminal, lead frame, uses, but implement to plate Ni usually as substrate this moment.For this Ni substrate plating, its also further attenuation along with the lightweight thinning of parts in recent years.
Thereby, bad in the past, specifically promptly plate Ni bad obviousization that become of inhomogenous situation that partly become for the situation of the plating Ni of problem.
The copper alloy that above-mentioned patent documentation 1～3 is put down in writing is all put down in writing the crystallization particle diameter, but does not recognize the inequality of the crystallization particle diameter on the depth direction fully, particularly is formed at the relation of tack of thick crystallization and the plating on surface.
Problem of the present invention is to provide the substrate plating, particularly plates the Cu-Co-Si that Ni can adhere to equably is alloy sheets.
The method that is used for the technical solution problem
The inventor studies in order to solve the problems of the technologies described above repeatedly, and it is that to process Cu-Co-Si be alloy through Ni being replaced as Co in the alloy sheets that the result finds at Cu-Ni-Si, can pursue the adaptation of further improvement and substrate plating.And find that this Cu-Co-Si is that the top layer of alloy sheets is compared with inner (thickness of slab center), the crystallization particle diameter is easy to partly that there are thickization crystallization in thickization, surface, even if thereby the average crystallite particle diameter of integral body is little, plating (homogeneous adheres to) property also can reduce.The present invention has following formation.
(1) a kind of copper alloy for electronic material plate; It is to contain the copper alloy for electronic material plate that Co:0.5～3.0 quality %, Si:0.1～1.0 quality %, remainder are made up of Cu and unavoidable impurities; It is characterized in that; The average crystallite particle diameter at thickness of slab center is below the 20 μ m, with respect to rolling direction length 1mm, joins with the surface and major diameter is that crystal grain more than the 45 μ m is below 5.
(2) (1) described copper alloy for electronic material plate, it also contains the Cr of maximum 0.5 quality %.
(3) (1) or (2) described copper alloy for electronic material plate, its also contain amount to maximum 2.0 quality % be selected among Mg, P, As, Sb, Be, B, Mn, Sn, Ti, Zr, Al, Fe, Zn and the Ag more than a kind or 2 kinds.
The method of manufacture of each described copper alloy for electronic material plate of (4) (1)～(3), it comprises and carries out following operation successively:
Operation with the ingot casting melting and casting;
Making material temperature is to carry out hot rolling after heating more than 1 hour more than 950 ℃ and below 1050 ℃, and the hot rolling end temp is the operation more than 700 ℃;
With final passage is the intermediate rolling operation before the solid solution carried out of the degree of finish more than 8%;
Making material temperature is more than 850 ℃ and 0.5 minute～1 hour middle solid solution operation of heating below 1050 ℃;
More than 400 ℃ and the timeliness operation that heats below 600 ℃; With
The final rolling process of degree of finish 10～50%.
Description of drawings
[Fig. 1] is the microphotograph (multiplying power: * 200) of the coating surface of the copper alloy plate of the present invention (invention example 1) of having implemented plating Ni.
[Fig. 2] is the microphotograph (multiplying power: * 200) of the coating surface of the comparative example copper alloy plate (comparative example 11) of having implemented plating Ni.
[Fig. 3] is the zoom microscope photo (multiplying power: * 2500) of the coating surface of Fig. 2.
Embodiment
(1) addition of Co and Si
Co that is added and Si form intermetallic compound through implementing suitable thermal treatment in copper alloy, even if exist the interpolation element beyond the copper that electric conductivity is worsened, can realize high strength through precipitating reinforcing effect.
The addition of Co and Si is respectively Co: less than 0.5 quality %, Si: during less than 0.1 quality %, can't obtain desirable strength.On the contrary, as Co: surpass 3.0 quality %, Si: when surpassing 1.0 quality %, though can realize that the high strength electric conductivity obviously reduces and hot workability worsens.Thereby the addition of Co and Si is Co:0.5～3.0 quality %, Si:0.1～1.0 quality %.The addition of Co and Si is preferably Co:0.5～2.0 quality %, Si:0.1～0.5 quality %.
(2) addition of Cr
In the process of cooling of Cr when melting and casting owing to preferentially separate out at crystal boundary, thereby be difficult for producing slight crack can strengthen crystal boundary, hot-work the time, the qualification rate in the time of can suppressing to make reduces.That is, Cr that crystal boundary separates out takes place when melting and casting through solution treatment etc. solid solution again takes place, then when timeliness is separated out, produce with Cr be principal constituent the bcc structure precipitation particles or with the compound (silicide) of Si.In the Si that in common Ni-Si series copper alloy, the adds amount, it is residual in the state of parent phase with solid solution timeliness not to be separated out acting Si, becomes the reason that electric conductivity descends.Thereby, through adding Cr, making and timeliness is not separated out acting Si and further separate out, can reduce solid solution Si amount as silicide as the silicide forming element, prevent that under the situation of not damaging intensity electric conductivity from descending.But, when Cr concentration surpasses 0.5 quality %, owing to be easy to form the second thick phase particle, thereby can damage product performance.Therefore, Cu-Co-Si involved in the present invention is the Cr that can add maximum 0.5 quality % in the alloy.But, thereby preferably add 0.01～0.5 quality %, more preferably 0.09～0.3 quality % because its effect is little during less than 0.01 quality %.
The addition of (3) the 3rd elements
A) addition of Mg, Mn, Ag and P
Mg, Mn, Ag and P under the situation of not damaging electric conductivity, improve product performances such as intensity, stress relaxation characteristics through the interpolation of trace.Additive effect mainly is able to performance through the solid solution in parent phase, but through containing in the second phase particle, also can further bring into play effect.But when the total concn of Mg, Mn, Ag and P surpassed 2.0 quality %, not only to improve effect saturated for characteristic, and can damage manufacturing property.Therefore, Cu-Co-Si involved in the present invention is in the alloy sheets, preferred add amount to maximum 2.0 quality % be selected among Mg, Mn, Ag and the P more than a kind or 2 kinds.But because its effect is little during less than 0.01 quality %, thus more preferably add amount to 0.01～2.0 quality %, further preferred the interpolation amounts to 0.02～0.5 quality %, typically adds and amount to 0.04～0.2 quality %.
B) addition of Sn and Zn
Sn and Zn also improve product performances such as intensity, stress relaxation characteristics, plating property under the situation of not damaging electric conductivity through the interpolation of trace.Additive effect mainly is able to performance through the solid solution in parent phase.But when Sn and Zn totalled over 2.0 quality %, not only to improve effect saturated for characteristic, and can damage manufacturing property.Therefore, Cu-Co-Si involved in the present invention is in the alloy sheets, preferred a kind or 2 kinds among Sn and the Zn that is selected from that amounts to maximum 2.0 quality % that adds.But because its effect is little during less than 0.05 quality %, thereby preferred the interpolation amounts to 0.05～2.0 quality %, more preferably adds and amount to 0.5～1.0 quality %.
C) addition of As, Sb, Be, B, Ti, Zr, Al and Fe
Among As, Sb, Be, B, Ti, Zr, Al and the Fe,, improve product performances such as electric conductivity, intensity, stress relaxation characteristics, plating property through adjusting addition according to desired product performance.Additive effect mainly is able to performance through the solid solution in parent phase, through containing in the second phase particle or forming the brand-new second phase particle of forming, can also bring into play further effect.But when these elements totalled over 2.0 quality %, not only to improve effect saturated for characteristic, and can damage manufacturing property.Therefore, Cu-Co-Si involved in the present invention is in the alloy sheets, can add amount to maximum 2.0 quality % be selected among As, Sb, Be, B, Ti, Zr, Al and the Fe more than a kind or 2 kinds.But because its effect is little during less than 0.001 quality %, thereby preferred the interpolation amounts to 0.001～2.0 quality %, more preferably adds and amount to 0.05～1.0 quality %.
When the addition of above-mentioned Mg, P, As, Sb, Be, B, Mn, Sn, Ti, Zr, Al, Fe, Zn and Ag totals over 2.0 quality %; Make property owing to be easy to infringement, thereby preferably make them add up to below the 2.0 quality %, more preferably below the 1.5 quality %, further be preferably below the 1.0 quality %.
(4) crystallization particle diameter
The crystallization particle diameter is little then can to obtain HS, and this is known in the past, and among the present invention, the average crystallite particle diameter at the thickness of slab center in rolling direction cross section also is below the 20 μ m.Here, the average crystallite particle diameter at thickness of slab center is measured according to JIS H 0501 (intercept method).The average crystallite particle diameter at the thickness of slab center of copper alloy plate of the present invention can not take place in the final rolling front and back of degree of finish 10～50% significantly to change relatively.Thereby, so long as final be the average crystallite particle diameter below the 20 μ m before rolling, then still keep the more fine crystalline texture of sample copper alloy after rolling than average crystallite particle diameter 20 μ m final.Therefore; Even if crystalline texture is too fine, can't numerically correctly measure final average crystallite particle diameter after rolling; Through with under the same conditions to final before rolling be the sample of average crystallite particle diameter 20 μ m to carry out final rolling product be that standard compares, can judge that also whether the average crystallite particle diameter is above 20 μ m.Explain that " thickness of slab center average crystallite particle diameter 20 μ m below " of the present invention are used for confirming the high-intensity regulation identical with prior art, " the thickness of slab " center " is to be used to represent the term that locates.
In the prior art, the thickization crystallization on the inequality of crystallization particle diameter, particularly surface is paid close attention to especially, and the thickization crystal grain on surface is unknown fully to the detrimentally affect that the homogeneous tack of plating is caused.But the top layer is the easiest in rolling process accumulates strain energy, under common creating conditions compared to inner (thickness of slab center), crystallization more is prone to thickization partly.In addition, in heat treatment step, top layer and inner thermal history condition of different are arranged also,, also have crystallization that the situation of thickization takes place partly compared to inner (thickness of slab center).At this moment, explain that said " top layer " is the scope of the surperficial 25 μ m of distance here.
Discoveries such as the inventor are through reducing crystal grain that Cu-Co-Si is thickization on alloy sheets surface, can obtaining the copper alloy for electronic material plate that plating adheres to equably.
Specifically, with respect to the length 1mm of rolling direction, join with the surface and final major diameter after rolling be crystal grain more than the 45 μ m be below 5, be preferably below 4, more preferably below 2.When surpassing 5, plating can not adhere to, become the substandard products that smudgy state takes place when detecting by an unaided eye coating surface equably.
In addition; The crystal grain number is that (multiplying power: the crystal grain number more than the 45 μ m that * 400) surface with the cross section of rolling direction joined is measured at microphotograph; With the total length of crystal grain number, as 1mm unit divided by length 2000 mu m ranges on surface in a plurality of (10 times) mensuration visual field.
Copper alloy plate of the present invention is because the crystal grain that go up more than the major diameter 45 μ m on the surface is below 5, thereby the homogeneous tack of plating is excellent.Copper alloy plate of the present invention can be suitable for various coating materials, for example can enumerate normally used Ni substrate plating or Cu substrate plating, plating Sn in the substrate of plating Au.
Even if plated thickness of the present invention under the thickness of normally used 2～5 μ m is being certain sufficient homogeneous tack that under the thickness of 0.5～2.0 μ m, also shows.
(5) method of manufacture
The method of manufacture of copper alloy plate of the present invention is used ME common in the copper alloy plate (melting and casting → hot rolling → centre cold rolling → middle solid solution → finally cold rolling → timeliness), but adjusts the copper alloy plate that following condition is come manufacturing objective at its in-process.Explain, for intermediate rolling, middle solid solution, also can carry out several as required repeatedly.
Strictly control hot rolling among the present invention, middle condition cold rolling, middle solution treatment is important.Its reason is, in copper alloy plate of the present invention, adds the Co that the second phase particle is easy to thickization, maintenance temperature and speed of cooling when the generation of the second phase particle and growth rate can influence thermal treatment greatly.
In the melting and casting operation with raw materials such as electrolytic copper, Si, Co fusings, obtain the fused solution of required composition.Then this fused solution is cast as ingot casting.After hot rolling in, what be necessary is the crystallization things such as Co-Si that carry out the thermal treatment of homogeneous, remove in the casting to be produced as far as possible.For example, after keeping more than 1 hour under 950 ℃～1050 ℃, carry out hot rolling.Maintenance temperature before the hot rolling is during less than 950 ℃, and solid solution is insufficient; And when surpassing 1050 ℃, material might fuse.
In addition, the temperature when hot rolling finishes is less than 700 ℃ situation, and being processed under 700 ℃ of several time that is meant the final passage of hot rolled or comprises final passage carried out.Temperature when hot rolling finishes is during less than 700 ℃, the crystalline state of attaching most importance in inside that then can become, and to be the state that bears processing deformation finish down on the top layer.Under this state through cold rolling, when under common condition, carrying out solid solution, then become inner and form thickization crystal grain for normal recrystallization tissue top layer.Therefore, for the thickization crystalline that prevents the top layer forms, it is desirable to more than 700 ℃, preferably finish hot rolling more than 850 ℃, it is desirable to after hot rolling finishes, carry out quenching.Quenching can be reached through water-cooled.
After the hot rolling, in target zone, suitably select number of times and order to carry out intermediate rolling and middle solid solution.The degree of finish of the final passage of intermediate rolling is less than 5% o'clock, owing to only accumulate the processing deformation energy at material surface, thereby can produce thick crystal grain on the top layer.Particularly, preferably making the intermediate rolling degree of finish of final passage is more than 8%.In addition, the speed of control employed rolling oil viscosity of intermediate rolling and intermediate rolling is effective to applying the processing deformation energy equably also.
Crystallization particle when middle solid solution is used to make melting and casting or the precipitation particles solid solution after the hot rolling, remove precipitate such as thick Co-Si as far as possible and carry out fully.For example, solid solution temperature is during less than 850 ℃, and solid solution is insufficient, can't obtain required intensity.And solid solution temperature then has material that the possibility of fusion takes place when surpassing 1050 ℃.Therefore, preferably carry out material temperature is heated to 850 ℃～1050 ℃ solution treatment.The time of solution treatment is preferably 0.5 minute～and 1 hour.
Explain, as the relation of temperature and time, in order to obtain identical thermal effectiveness (for example identical crystallization particle diameter), on the general knowledge be must shorten the pyritous following time of situation, the cryogenic following time of situation must prolong.For example, among the present invention, it is desirable under 950 ℃ the situation 1～2 minute, under 1000 ℃ situation, it is desirable to 0.5～1 minute.
For the speed of cooling after the solution treatment, generally, can carry out quenching for the separating out of the second phase particle that prevents solid solution.
Then, carrying out ageing treatment more than 400 ℃ and under the temperature condition below 600 ℃, the second fine phase particle is separated out equably.Aging temp is during less than 400 ℃, and separating out of the second phase particle is insufficient, has the problem that can't obtain desirable strength and electric conductivity; And when surpassing 600 ℃, thickization then can take place in the second phase particle of separating out, and has the problem that can't obtain desirable strength.Aging temp is preferably more than 450 ℃ and below 550 ℃.
Final rolling degree of finish is preferably 10～50%, more preferably 30～50%.Less than 10% o'clock, can't obtain required intensity.And surpass at 50% o'clock, bendability variation then.
Copper alloy plate of the present invention is not because there is thick crystalline particle in the surface, thereby the homogeneous tack of plating is excellent, can be used for lead frame, junctor, pin, terminal, rly., switch, secondary cell aptly with electronic units such as foil material.
Embodiment
Below with comparative example embodiments of the invention are shown together, but these embodiment provide in order to understand the present invention and advantage thereof better, and are not intended to limit invention.
(1) measuring method
(a) the crystallization particle diameter at thickness of slab center: after solution treatment, the average crystallite particle diameter of making final rolling thickness of slab center preceding, rolling direction is the standard model (Co:1.0 quality %, Si:0.66 quality %, remainder are copper) of 20 μ m.The average crystallite particle diameter is measured according to JIS H 0501 (process of chopping).Standard model is carried out finally cold rolling (degree of finish 15%), take the optical microscope photograph (multiplying power: at the thickness of slab center in rolling direction cross section * 400) as benchmark.Then; The optical microscope photograph (with the same multiplying power of benchmark) at the thickness of slab center after each embodiment of visual comparison (invention example and comparative example) final cold rolling and the size of benchmark are expressed as when big greater than 20 μ m (＞20 μ m), equal or hour meter and are shown 20 μ m following (≤20 μ m).
(b) near the observation of the crystal grain the top layer
For the top layer; Use the microphotograph in cross section, rolling direction top layer; On the position of table of distances layer depth 10 μ m, draw the line that is parallel to the surface, try to achieve the number of the crystallization particle diameter more than the 45 μ m that join with a surface even a part when obtaining the length of line through segment method, in 10 visuals field, carry out; Total number of the crystallization particle diameter more than the 45 μ m divided by total segment, is tried to achieve the number with respect to the crystallization particle diameter more than the 45 μ m of 1mm.
(c) the plating homogeneity of adhering to
(electrolytic degreasing order)
In alkali aqueous solution, be that negative pole carries out electrolytic degreasing with the sample.
Use 10 quality % aqueous sulfuric acids to carry out pickling.
(Ni substrate plating condition)
Plating is bathed and is formed: single nickel salt 250g/L, nickelous chloride 45g/L, boric acid 30g/L
Plating bath temperature: 50 ℃
Current density: 5A/dm
2
Plating Ni thickness utilizes electrodeposition time adjustment, is made as 1.0 μ m.Plated thickness is measured and is used CT-1 type electrolyzing film thickness gauge (electrical measurement Co., Ltd. system) to use the system electrolytic solution R-54 of コ ク ー Le society to carry out.
(plating adheres to the homogeneity evaluation)
Take the optical microscope photograph (multiplying power: * 200, visual field area 0.1mm of coating surface
2), measure the number and the distribution of observing the island plating.Evaluation is described below.
S: do not have,
A: the number of island plating is 50/mm
2Below,
B: the number of island plating is 100/mm
2Below,
C: the number of island plating surpasses 100/mm
2
Explain, Fig. 1 for the optical microscope photograph of the coating surface of the present invention example 1, be equivalent to " S " level, Fig. 2 for the optical microscope photograph of the coating surface of comparative example 11, be equivalent to " C " level.Fig. 3 is the enlarged photograph (multiplying power: * 2500), make such island be shaped as 1 and measure the number of the island plating in the visual field of observed on coating surface " island plating ".
(d) intensity
Be rolled the tension test of parallel direction, measure 0.2% ys (YS:MPa).
(e) electric conductivity (EC; %IACS)
Volume resistance mensuration through utilizing double bridge is tried to achieve.
(f) bendability
According to JIS H 3130, carry out the W pliability test of Badway (bending axis and rolling direction are same direction), measure the ratio MBR/t value of the minimum radius (MBR) of fracture with respect to thickness of slab (t) do not take place.Bendability is estimated through following benchmark.
MBR/t≤2.0 are good
2.0＜MBR/t is bad
(2) method of manufacture
Utilize the high frequency calciner at 1300 ℃ of following each copper alloys that become to be grouped into of smelting table 1 record, cast the ingot casting of thick 30mm.Then, this ingot casting of heating was hot-rolled down to thickness of slab 10mm as hot rolling end temp (end temp) after 3 hours under the condition of table 1 record, after hot rolling finishes promptly water-cooled to room temperature.Then, in order to remove the scale on surface, implement surfacing to thickness 9mm, the degree of finish that suitably carries out final passage is cold rolling, 900 ℃ of middle solid solution operations of following 0.5 minute～1 hour of material temperature of 5～15%, processes the plate of thickness 0.15mm.Solution treatment is cooled to room temperature through water-cooled rapidly after finishing.Then, in inert environments, carry out 3 hours ageing treatment under 520 ℃.Carry out each test film of final cold rolling manufacturing of degree of finish 15% then.The mensuration result of each test film is shown in table 1.
[table 1]
With respect to the degree of finish 15% of the intermediate rolling in the final passage of invention example 1, in the invention of the same composition example 2 since low reach 10% thus produce oversize particle on the surface, plating homogeneous tack is poor slightly.The relation of invention example 4 and 5 too.
With respect to 750 ℃ of the end temps (temperature when hot rolling finishes) of invention example 1, in the invention example 3 of same composition because low to reach 700 ℃ thereby plating homogeneous tack poor.The relation of invention example 4 and 6 too.
Hot rolling with respect to invention example 1 begins 950 ℃ of temperature, 750 ℃ of end temps, in the comparative example 11 of same composition since low reach 800 ℃ and 500 ℃ thereby produce oversize particle on the surface, plating homogeneous tack is poor.Explain that when on the copper alloy surface of comparative example 11, implementing plating Ni with 3.0 μ m thickness, the island plating on the surface behind the plating becomes not obvious, becomes the state near " S " level.
The relation of invention example 4 and comparative example 14 too.
With respect to the degree of finish 15% of the intermediate rolling in the final passage of comparative example 11, in the comparative example 12 of same composition since low reach 5% thus produce oversize particle on the surface, plating homogeneous tack is poor.
Begin the degree of finish 15% of the intermediate rolling in 950 ℃ of temperature, 750 ℃ of end temps, the final passage with respect to the hot rolling of invention example 7; In the comparative example 17 of same composition because all lower, be 800 ℃, 500 ℃ and 5%, thereby produce oversize particle on the surface, plating homogeneous tack is poor.The relation of invention example 8 and comparative example 18 too.
Claims (4)
1. copper alloy for electronic material plate; It is to contain the copper alloy for electronic material plate that Co:0.5～3.0 quality %, Si:0.1～1.0 quality %, remainder are made up of Cu and unavoidable impurities; It is characterized in that; The average crystallite particle diameter at thickness of slab center is below the 20 μ m, with respect to rolling direction length 1mm, joins with the surface and major diameter is that crystal grain more than the 45 μ m is below 5.
2. copper alloy for electronic material plate according to claim 1, it also contains the Cr of maximum 0.5 quality %.
3. copper alloy for electronic material plate according to claim 1 and 2, its also contain amount to maximum 2.0 quality % be selected among Mg, P, As, Sb, Be, B, Mn, Sn, Ti, Zr, Al, Fe, Zn and the Ag more than a kind or 2 kinds.
4. according to the method for manufacture of each described copper alloy for electronic material plate of claim 1～3, it comprises and carries out following operation successively:
Operation with the ingot casting melting and casting;
Making material temperature is to carry out hot rolling after heating more than 1 hour more than 950 ℃ and below 1050 ℃, and the hot rolling end temp is the operation more than 700 ℃;
With final passage is the intermediate rolling operation before the solid solution carried out of the degree of finish more than 8%;
Making material temperature is more than 850 ℃ and 0.5 minute～1 hour middle solid solution operation of heating below 1050 ℃;
More than 400 ℃ and the timeliness operation that heats below 600 ℃; With
The final rolling process of degree of finish 10～50%.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010127943A JP4708497B1 (en) | 2010-06-03 | 2010-06-03 | Cu-Co-Si alloy plate and method for producing the same |
| JP2010-127943 | 2010-06-03 | ||
| PCT/JP2011/057216 WO2011152104A1 (en) | 2010-06-03 | 2011-03-24 | Cu-co-si-based alloy sheet, and process for production thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102666890A true CN102666890A (en) | 2012-09-12 |
| CN102666890B CN102666890B (en) | 2014-05-07 |
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| CN201180003593.1A Active CN102666890B (en) | 2010-06-03 | 2011-03-24 | Cu-Co-Si-based alloy sheet, and process for production thereof |
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| Country | Link |
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| US (1) | US20130092297A1 (en) |
| EP (1) | EP2578708A4 (en) |
| JP (1) | JP4708497B1 (en) |
| CN (1) | CN102666890B (en) |
| TW (1) | TWI422693B (en) |
| WO (1) | WO2011152104A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106414811A (en) * | 2014-05-30 | 2017-02-15 | 古河电气工业株式会社 | Electric contact material, electric contact material manufacturing method, and terminal |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP5437519B1 (en) | 2013-07-31 | 2014-03-12 | Ｊｘ日鉱日石金属株式会社 | Cu-Co-Si-based copper alloy strip and method for producing the same |
| JP5437520B1 (en) * | 2013-07-31 | 2014-03-12 | Ｊｘ日鉱日石金属株式会社 | Cu-Co-Si-based copper alloy strip and method for producing the same |
| JP6294037B2 (en) * | 2013-09-18 | 2018-03-14 | 株式会社Maruwa | Composite noise filter |
| JP6306632B2 (en) | 2016-03-31 | 2018-04-04 | Ｊｘ金属株式会社 | Copper alloy for electronic materials |
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| CN1793394A (en) * | 2004-12-24 | 2006-06-28 | 株式会社神户制钢所 | Copper alloy having bendability and stress relaxation property |
| CN101146920A (en) * | 2005-03-24 | 2008-03-19 | 日矿金属株式会社 | Copper alloy for electronic material |
| CN101646791A (en) * | 2007-03-30 | 2010-02-10 | 日矿金属株式会社 | Cu-Ni-Si-Co-based copper alloy for electronic material, and method for production thereof |
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| US7182823B2 (en) | 2002-07-05 | 2007-02-27 | Olin Corporation | Copper alloy containing cobalt, nickel and silicon |
| JP2007169765A (en) | 2005-12-26 | 2007-07-05 | Furukawa Electric Co Ltd:The | Copper alloy and its production method |
| JP5085908B2 (en) * | 2006-10-03 | 2012-11-28 | Ｊｘ日鉱日石金属株式会社 | Copper alloy for electronic materials and manufacturing method thereof |
| CN101952465B (en) * | 2008-01-31 | 2012-09-19 | 古河电气工业株式会社 | Copper alloy material for electric/electronic component and method for manufacturing the copper alloy material |
| JP4596490B2 (en) * | 2008-03-31 | 2010-12-08 | Ｊｘ日鉱日石金属株式会社 | Cu-Ni-Si-Co-based copper alloy for electronic materials and method for producing the same |
| EP2319947A4 (en) * | 2008-07-31 | 2011-11-23 | Furukawa Electric Co Ltd | Copper alloy material for electrical and electronic components, and manufacturing method therefor |
| JPWO2010016428A1 (en) * | 2008-08-05 | 2012-01-19 | 古河電気工業株式会社 | Copper alloy material for electrical and electronic parts |
| JP5619389B2 (en) * | 2008-08-05 | 2014-11-05 | 古河電気工業株式会社 | Copper alloy material |
| JP5261161B2 (en) * | 2008-12-12 | 2013-08-14 | Ｊｘ日鉱日石金属株式会社 | Ni-Si-Co-based copper alloy and method for producing the same |
-
2010
- 2010-06-03 JP JP2010127943A patent/JP4708497B1/en active Active
-
2011
- 2011-03-24 US US13/581,715 patent/US20130092297A1/en not_active Abandoned
- 2011-03-24 WO PCT/JP2011/057216 patent/WO2011152104A1/en active Application Filing
- 2011-03-24 EP EP11789514.4A patent/EP2578708A4/en not_active Withdrawn
- 2011-03-24 CN CN201180003593.1A patent/CN102666890B/en active Active
- 2011-04-18 TW TW100113320A patent/TWI422693B/en active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1793394A (en) * | 2004-12-24 | 2006-06-28 | 株式会社神户制钢所 | Copper alloy having bendability and stress relaxation property |
| CN101146920A (en) * | 2005-03-24 | 2008-03-19 | 日矿金属株式会社 | Copper alloy for electronic material |
| CN101646791A (en) * | 2007-03-30 | 2010-02-10 | 日矿金属株式会社 | Cu-Ni-Si-Co-based copper alloy for electronic material, and method for production thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106414811A (en) * | 2014-05-30 | 2017-02-15 | 古河电气工业株式会社 | Electric contact material, electric contact material manufacturing method, and terminal |
| CN106414811B (en) * | 2014-05-30 | 2019-05-28 | 古河电气工业株式会社 | Electric contact material, the manufacturing method of electric contact material and terminal |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102666890B (en) | 2014-05-07 |
| EP2578708A1 (en) | 2013-04-10 |
| TWI422693B (en) | 2014-01-11 |
| JP2011252216A (en) | 2011-12-15 |
| JP4708497B1 (en) | 2011-06-22 |
| US20130092297A1 (en) | 2013-04-18 |
| WO2011152104A1 (en) | 2011-12-08 |
| EP2578708A4 (en) | 2014-04-09 |
| TW201200606A (en) | 2012-01-01 |
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