CN102666891A - Cu-ni-si based alloy with excellent bendability - Google Patents
Cu-ni-si based alloy with excellent bendability Download PDFInfo
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- CN102666891A CN102666891A CN2011800045219A CN201180004521A CN102666891A CN 102666891 A CN102666891 A CN 102666891A CN 2011800045219 A CN2011800045219 A CN 2011800045219A CN 201180004521 A CN201180004521 A CN 201180004521A CN 102666891 A CN102666891 A CN 102666891A
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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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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
- H01B1/026—Alloys based on copper
Abstract
Disclosed is a Cu-Ni-Si alloy strip which contains 0.8-4.6 mass% Ni and 0.3-1.6 mass% Si and may contain one or more optional elements selected from Sn, Zn, Fe, Co, Cr, Mg, and Mn in a total amount of 2.0 mass% or less, and in which the number of shear bands in the surface layer is up to 1.0 time the number of shear bands in the sheet-thickness center part. The alloy strip has high strength and has an excellent appearance after being bent. Preferably, the number of shear bands in the surface layer is 10 or less per 10,000 [mu]m2, and the number of 1-10 [mu]m precipitate particles in the surface layer is 1.0102 or less per mm2, the number of 1-10 [mu]m precipitate particles in the surface layer being up to 1.0 time the number thereof in the center part.
Description
Technical field
The present invention relates to a kind of high strength copper alloy that is used for electronic materials such as lead frame, junctor, vehicle-mounted junctor with terminal etc.In detail, the present invention relates to the high strength copper alloy that bend outward appearance after a kind of bending machining can not produce gauffer or crackle, demonstrate good bendability and bend outward appearance.
Background technology
In recent years, the high-density installationization of electronics such as mobile telephone, digital camera, pick up camera and vehicle-mounted junctor just constantly develops, and it is frivolous, short and small that its parts obviously become.Employed material also obviously has the tendency of thin-walled property, for material requirements high-strength materials more.In addition; The shape of parts is also complicated; Implement than the situation increase of more harsh bending machining in the past; Require better bendability, even it is also equal with current material for example to carry out high strength, toughness, perhaps being not only the crooked even laggard line bend of extrusion processing (つ ぶ processing) that reduce thickness of slab of box-bending or 180 degree driving fits does not have crackle etc. yet.
These electronicss are the good Corson alloys (Cu-Ni-Si series copper alloy) of balance of intensity and electroconductibility and toughness with the parts use.In general, if improve the intensity of alloy, toughness variation then, and the intensity of the good alloy of toughness is low.Therefore, many improvement that take into account intensity and toughness have been carried out.For example disclosed a kind of Corson alloy that contains the element-specific of specified amount in the patent documentation 1 and 2; In this alloy; Through precipitate that is made up of Ni and Si and precipitate particle diameter and the number separately that contains element-specific are controlled, thereby tensile strength and bendability and proof stress relaxation property are good.In the patent documentation 3, when making the Corson alloy surface smoothingization, apply compressive residual stress, make its antagonism, thereby suppress the generation of crackle because of the crooked tensile stress that produces of product.
The prior art document
Patent documentation
Patent documentation 1: Japanese Patent Laid is opened the 2006-161148 communique
Patent documentation 2: Japanese Patent Laid is opened the 2006-265731 communique
Patent documentation 3: Japanese Patent Laid is opened the 2005-48262 communique
Summary of the invention
Invent technical problem to be solved
The outward appearance of bend outward appearance, the particularly bending axis of Corson alloy and the vertical bending of rolling direction (GW) is poorer than the outward appearance of phosphor bronze, has the big characteristic of surface irregularity (the waste れ of flesh).If terminal cracks, then the desired characteristic of terminal is that electroconductibility and elasticity can be lost, and influences reliability of products, therefore carries out the visual inspection of product bend usually.But; For example with the naked eye be difficult to confirm the state of appearance of the bend of subminiature terminal foremost; Use reading lens to estimate in the inspection operation of the situation after confirming crooked pressurization of having to, or rely on anchor clamps (smelting tool) or the machinery of confirming etc. with the surface examining device that adopts the CCD camera.During this inspection, though in fact do not ftracture, under the serious situation that is difficult to separate with cracked zone of the surface irregularity of bend outward appearance, inspection is confirmed to expend time in, and checking efficiency reduces.Therefore, for the Corson alloy that uses in the subminiature electronic equipment material, be not as long as bend does not crack, but require the surface irregularity of bend little yet.
But; Among the embodiment of patent documentation 1,2; Even the best person of toughness also be MBR/t (following of situation about not cracking can be crooked minimum bending radius and the ratio of thickness of slab) be 0.5; Do not break away from the intensity of the Corson alloy that all the time just has and the relation of toughness, can't tackle desired in recent years harsh bending machining.In addition,, therefore think that the gauffer of bend is also big, be not suitable for requiring the subminiature bonder terminal purposes of harsh bending machining and visual inspection thereof because the best MBR/t of toughness is more than 0.5 among this embodiment.
Though patent documentation 3 in order to improve for the fatigue characteristic of alternating bending and be conceived to the product surface roughness, is not the purpose that is improved as with the bend outward appearance after the bending machining.Therefore, only estimated the preceding surfaceness of bending machining, for estimating after the bending machining.
The good toughness that the objective of the invention is the gloomy series copper alloy of section; In detail, the objective of the invention is not only to improve the cracking situation, also improve the surface irregularity of the bend that did not in the past receive publicity after the bending machining of GW (good way).
The means that the technical solution problem is adopted
The inventor studies for the toughness that improves GW and the surface irregularity of bend; The result finds; The part that foreign matter or defective etc. is become the starting point of uneven pulling is got rid of near surface; Thereby suppress to be in a ratio of the formation of the shear zone on top layer (playing from material surface till 1/6 degree of depth of thickness of slab) with thickness of slab central part (part beyond the following top layer); Can under the situation that keeps mechanical characteristicies such as the original tensile strength of material, 0.2% ys, elastic limit value, improve the surface irregularity of the bend of GW by this, thereby accomplish the present invention.
The present invention has following formation.
(1) the also good Cu-Ni-Si of outward appearance after a kind of HS and the bending machining is an alloy bar; It is characterized in that; It is in quality percentage (%) (following note is made %) contain Ni:0.8～4.6% and Si:0.3～1.6% and count with total amount among any composition Sn, Zn, Fe, Co, Cr, Mg and the Mn of 2.0% following scope more than a kind; The copper alloy that surplus branch is made up of Cu and unavoidable impurities; Wherein, the ratio Ss/Sc of the lines radical Sc of the shear zone of the part (following note is made the thickness of slab central part) beyond the lines radical Ss of the shear zone of (following note is done the top layer) and the material surface is below 1.0 till material surface plays 1/6 degree of depth of thickness of slab.
(2) (1) described Cu-Ni-Si is an alloy bar, it is characterized in that, the lines radical of the shear zone of material surface is 10/10000 μ m
2Below.
(3) (1) or (2) described Cu-Ni-Si is an alloy bar, it is characterized in that, at material surface, particle diameter is that the number of the precipitate of 1～10 μ m is 1.0 * 10
2Individual/mm
2Below, and the particle diameter on top layer is that the particle diameter of number Ns and thickness of slab central part of the precipitate of 1～10 μ m is that the ratio Ns/Nc of number Nc of the precipitate of 1～10 μ m is below 1.0.
The effect of invention
The present invention can provide a kind of high strength copper alloy, and this copper alloy demonstrates the good bendability of copper alloy for electronic material such as being suitable as terminal, junctor and non-wrinkled bend outward appearance.
Description of drawings
Fig. 1 be to the skin section of the thickness of slab section parallel of the alloy bar of processing among the embodiment 4 with rolling direction take and optical microscope photograph (800 times).(before the flexural deformation)
Fig. 2 be to the thickness of slab central part of the alloy bar of product of the present invention take and optical microscope photograph (800 times).(before the flexural deformation, reference drawing)
Fig. 3 be to embodiment 4 (on) and comparative example 34 (descending) in after the alloy bar processed carries out the bendability evaluation test, to the thickness of slab section parallel with rolling direction take and optical microscope photograph (200 times on a left side, right 400 times).
Embodiment
Describe in the face of specific factor of the present invention down.
(1) composition of copper alloy
Ni:Ni and Si reaction generate Ni
2The compound that Si forms is separated out in Cu matrix, suppresses the reduction of electroconductibility and significantly improves intensity.Ni addition in the copper alloy of the present invention is 0.8～4.6% (quality %, down together), during less than 0.8%; The amount of separating out is few, can't obtain enough intensity, if surpass 4.6%; Then casting or can generate during hot-work and be helpless to the precipitate that intensity improves not only can't obtain the intensity that is complementary with addition, also can cause detrimentally affect to hot workability and bendability; And thickization of precipitate given prominence to from the lead frame end face, makes the adaptation variation of precious metal plating.
Si:Si generates Ni can not causing electroconductibility under the dysgenic situation with the Ni reaction
2The compound that Si forms.Therefore, if the addition of Ni is definite, just can confirm best Si addition.Si addition in the copper alloy of the present invention is 0.3～1.6%, during less than 0.3%, likewise can't obtain enough intensity with the situation of Ni, if surpass 1.6%, then produces the same variety of issue of situation with Ni.
Sn:, can expect that intensity improves through containing Sn.But, as a rule, with the electronic materials such as junctor of having implemented plating Sn as waste recovery, when utilizing again with low cost without smelting procedure; Sn can be included in inevitably and utilize in the Cu alloy material again; If surpass 2.0 quality %, then specific conductivity reduces, and is limited to 2.0 quality % on therefore.
Zn:Zn improves the thermotolerances such as heat-resisting separability that copper alloy is carried out the tin coating when zinc-plated, if but surpass 2.0 quality %, then specific conductivity reduces, and is limited to 2.0 quality % on therefore.
Mg:Mg improves stress relaxation characteristics, but makes the composition of the heat-resisting separability variation of coating, if surpass 2.0 quality %, then the heat-resisting separability of coating reduces.
Fe, Co, Cr, Mn:Fe and Co and Si reaction form silicide and separate out, and help to improve intensity.Cr and Mn also have the hot pressing of improvement ductile effect.Therefore its reason is that the affinity of these elements and sulphur is strong, forms compound with the sulphur that is present in inevitably in the alloy, alleviates as the segregation to the ingot casting crystal boundary of the sulphur of hot calender rimose reason.The addition more than a kind of these elements is counted below 2.0% with total amount, if surpass 2.0%, then can cause the reduction of electroconductibility, and is therefore undesirable.
(2) reason of crooked gauffer
In general, when material was carried out bending machining, the bend most peripheral can be endowed strain.In the bending machining, though material surface is stretched to specific strain value equably, be the boundary with specific strain value, stretching can reduce partly, produces crooked gauffer.Along with the carrying out of bending machining, be that starting point cracks with this gauffer.The stretching part takes place reduce (calling uneven pulling in the following text) though the strain limit value of phenomenon also depends on the mechanical characteristics of material to a great extent; If but exist foreign matter or defective etc. to become the material of the starting point of uneven pulling in the material; Then with uneven pulling takes place easily below the corresponding strain limit value of the mechanical characteristics of material itself, have the gauffer of bend to become big tendency.Therefore, through reducing the starting point that these produce uneven pulling, can reduce crooked gauffer.
In addition, if there is the starting point that produces uneven pulling in material internal, though then not as being present in the starting point of material surface, therefore it also can impact material surface, therefore for material internal, also hopes to reduce the starting point that produces uneven pulling.
As the factor of the starting point that becomes uneven pulling, the roughness of the material surface of can giving an example, be present in the precipitate on top layer.Though the roughness of material surface can reduce through the existing methods such as surface grinding on final stack surface, only depends on this method can't tackle the up-to-date desired bending machining of subminiature terminal.
(3) shear zone in the metal structure
In general, copper alloy can wait and strengthen through the particle diameter (crystal miniaturization) of adjustment Metallic Solids and amount, particle diameter, the distribution (precipitation strength) of precipitate, also can strengthen (work strengthening) through adjusting the degree of finish that prolongs of finally colding pressing.During calendering, for bearing the tensile material in the longitudinal direction, utilize the stack applying load from vertical direction, material is out of shape (calendering) gradually.In this when calendering, the property sheared distortion is concentrated partly, and the grain structure destruction that deforms irrespectively forms the banded structure that is called as shear zone with crystalline orientation.
The lines of shear zone of the present invention are meant: to when the thickness of slab section parallel with rolling direction of the material of rolling processing observed, confirm, be arranged in parallel with rolling direction and and lines that exist crossing with flat grain structure with about 10～60 ° angle.For example, in the part of irising out with ellipse of Fig. 2, can confirm to have to be extended to many upper right shear zones down from a left side and to be arranged in parallel.
Shear zone is the tissue of distortion concentration of local, i.e. strain is built up and the part of dislocation desity increase in a large number, compares with tissue on every side to be difficult to distortion.Therefore, existing in the material of shear zone, is starting point generation uneven pulling with the shear zone when carrying out bending machining, produces gauffer or crackle when uneven pulling arrives the surface.But, if till shear zone forms, do not carry out rolling processing, then can't work strengthening, can't reach desired alloy strength, the product inside of delaying of therefore finally colding pressing certainly exists shear zone.
The inventor is conceived to the distribution of shear zone, finds: near the shear zone the material surface is few more, be difficult to more produce the uneven pulling that arrives the surface, so crackle or gauffer is few more.That is, compare with the thickness of slab central part, under the strain situation of specializing with the form of shear zone still less on top layer, be difficult to during bending machining crack or gauffer.Particularly; If the ratio Ss/Sc of the lines radical Sc of the shear zone of the lines radical Ss of the observed shear zone of material surface after final calendering and thickness of slab central part (part beyond the top layer) is below 1.0, is preferably below 0.95; Even then when violent bending machining, the generation of crooked gauffer also reduces.
Also have, if the lines radical of the shear zone of the material surface after the final calendering is preferably 10/10000 μ m
2Below, 5/10000 μ m more preferably
2Below, then the generation of crooked gauffer is still less.
Total degree of finish when reducing final calendering and the shear zone that fully do not carry out work strengthening, material surface and thickness of slab central part all under seldom the situation, can't obtain high-intensity alloy bar of the present invention.
Here; The shear zone observation that can be described below: after the thickness of slab section parallel with rolling direction carried out mechanical mill; Make it impregnated in acidic aqueous solutions such as dilute sulphuric acid or rare nitric acid and carry out etching; After crystal boundary and shear zone are shown, observe (with reference to Fig. 1～3) with about 200～800 times multiplying power with opticmicroscope.The lines of shear zone are to have with respect to rolling direction to be about 10～60 ° slope, lines more than the length 5 μ m that an above position and crystal boundary intersect.The stock size of shear zone is following, long 5～30 μ m of wide 1 μ m.
In the photo shown in Fig. 1～3, both direction oppositely rolls (リ バ one ス calendering) towards the left and right sides, so shear zone also forms respectively with respect to all directions, and the lines angle of shear zone is both direction towards the left and right sides.
(4) particle diameter of precipitate and quantity
Shear zone is easy to generate the part of building up in strain.In addition, strain is built up in organizing discontinuous part easily, that is, gloomy in section is in the alloy, and strain is built up in precipitate particulate periphery easily partly.Therefore, precipitate particulate density is low more, and the strained localization also is suppressed more, also is difficult to produce shear zone more.Here; " precipitate " of the present invention is general name, comprising: the metallic compounds such as precipitate of in Cu matrix mother metal, separating out when process of cooling after the process of cooling after oxide compound that generates through reaction in the liquation the when crystallization precipitate that produces in the process of setting during casting, fusing and sulfide etc., ingot bar solidify, the hot calender, after the solutionizing processing and timeliness are handled.Therefore, the existing particle that constitutes by Ni and Si of precipitate particle, also have in this particle further add add alloying element and particle and do not contain among Ni and the Si any one or do not comprise the two particle.
The observation that can be described below of the particle diameter of precipitate and quantity: with material with the ferric chloride in aqueous solution etching after, observe with about 200～2000 times multiplying power with FE-SEM (field-emission scanning electron microscope).Measure composition with grain size analysis software and EDS (energy dispersion type X-ray analysis), the particle that will be made up of the composition different with the mother metal composition is judged to be precipitate.Measure precipitate particle diameter separately, count its number.Here, with the external circular diameter of precipitate particle diameter as precipitate.
Though the present invention is not constituted restriction in theory, in the top layer till 1/6 degree of depth of thickness of slab is played on the surface of the material after the ageing treatment, be 1.0 * 10 if particle diameter is the number of the precipitate of 1～10 μ m
2Individual/mm
2Below, the density of precipitate that then becomes the starting point that produces shear zone is low, so the generation of the shear zone of top layer part reduces, and the gauffer that bend produced also can reduce.On the other hand, if surpass 1.0 * 10
2Individual/mm
2, then the generation of the shear zone in the top layer increases, and the gauffer that bend produced increases.The particle diameter on top layer is that the number of the precipitate of 1～10 μ m is preferably 1 * 10
-6Individual/mm
2More than, should value if not enough, then material monolithic is in and separates out few state, has can't obtain intensity and improve effect, tendency that electroconductibility is also low.
If the particle diameter on top layer is the particle diameter of precipitate particulate number Ns and the thickness of slab central part of 1～10 μ m is that the ratio Ns/Nc of the precipitate particulate number Nc of 1～10 μ m is below 1.0; Be preferably below 0.95; Even then after violent bending machining, the generation of gauffer also reduces.Its reason is, compare with the thickness of slab central part, the precipitate particulate number on top layer still less, so strain can not build up in the top layer, shear zone reduces, and is difficult to during bending machining crack or gauffer.
In the Corson alloy, owing to fine precipitate exists equably, so visual intensity raising effect, but being the above precipitate of 1 μ m, particle diameter can cause the distribution density of precipitate and the reduction of grain boundary area, therefore not satisfactory from the angle consideration of intensity raising.But, among the present invention, be conceived to make the strain localization that produces in the rolling processing easily and the particle diameter that becomes the reason that forms shear zone is the precipitate of 1～10 μ m, adjust its distribution and reached target property.
Though the precipitate particle of particle diameter less than 1 μ m helps precipitation strength, almost be helpless to the strained localization, for the almost not influence of generation of shear zone, therefore the gauffer to bend does not have influence yet.Whether in addition, the precipitate particle of particle diameter less than 0.5 μ m is too little, to such an extent as to can't be the composition judgement of precipitate.On the other hand, in the integral body that comprises top layer and thickness of slab central part, the precipitate that particle diameter surpasses 10 μ m becomes the rimose reason, so its number is preferably 1/mm
2Below, 0/mm more preferably
2
(5) method of manufacture of alloy bar of the present invention
Then, the method for manufacture that is used to obtain alloy of the present invention is described.
In general, the manufacturing of the ingot bar of Corson alloy adopts the semicontinuous casting method to carry out.Temperature, time and the speed of cooling of preferred control casting condition make that can not generate thick Ni-Si in the process of setting when casting is precipitate.To be precipitate strengthen through the heating to the hot calender of carrying out after the casting Ni-Si below certain size; Can be solid-solubilized in the Cu matrix; If but improve Heating temperature in the matrix for all thick precipitates all are solid-solubilized in; The body of heater refractory body lost of life of process furnace then if prolong heat-up time, produces setup time then that (リ one De タ イ system) increases, productivity becomes problems such as extreme difference.
If carry out making end temp in the hot calender more than 650 ℃ after more than 1 hour, then in castingprocesses, separate out or certain precipitate below the size that crystallization is separated out is solid-solubilized in the Cu matrix in heating under the temperature more than 800 ℃.At this moment; If heating at high temperature; The precipitate that casting the time is separated out or crystallization is separated out is solid-solubilized in the Cu matrix; But the Heating temperature before the hot calender can produce a large amount of incrustation, the problems such as crackle when producing hot calender more than 1000 ℃ the time, so the Heating temperature before the hot calender is preferably more than 800 ℃ and is lower than 1000 ℃.
Corson alloy is mostly made through the operation that solutionizing processing, ageing treatment, calendering combine; It is after above-mentioned hot calender processing, to heat that said solutionizing is handled, and making the Ni-Si that separates out in casting or the hot calender is that precipitate is solid-solubilized in the Cu matrix; Said ageing treatment is under the temperature that is lower than the solutionizing treatment temp, to heat-treat, and the Ni and the Si of solid solution in the solutionizing processing are separated out; Said calendering is before and after ageing treatment, to process curing.In general, make with the operation of solutionizing processing, calendering, ageing treatment, calendering, stress relief annealing.About the calendering before and after the ageing treatment, consider mechanical characteristics and bendabilities such as desired tensile strength and 0.2% ys, can omit the calendering together arbitrarily of timeliness front and back.
At this moment, the solutionizing treatment temp is high more, and Ni, the solid solution capacity of Si in Cu matrix increase, and the intermetallics of Ni-Si system is separated out from matrix when ageing treatment, and intensity is improved.The solutionizing treatment temp that is used to obtain this effect is more than 700 ℃, is preferably 800～950 ℃.If copper alloy of the present invention is in about 950 ℃; Then Ni, Si fully are solid-solubilized in the matrix; But surpassing under 950 ℃ the temperature; The degree of oxidation of material surface is serious when the solutionizing heat treated, and the load that is used to remove the pickling process of zone of oxidation increases, therefore preferred treatment temp below 950 ℃.
In order to keep the solid solution condition of Ni and Si as far as possible, in the solutionizing treatment process, carry out quenching usually.Among the present invention; Be conceived to carry out quenching all can have the Ni-Si intermetallics of to a certain degree measuring roughly to separate out this point equably at material internal in the process of cooling that solutionizing is handled in fact anyway; Speed of cooling in the solutionizing treatment process that slows down conversely; In the process of cooling of solutionizing, between top layer and thickness of slab central part, create thermograde by this; Making particle diameter is that the precipitate number of 1～10 μ m changes with the mode that increases gradually from the top layer to the thickness of slab central part, reduces the top layer shear zone radical of finally colding pressing and delaying, even obtain after bending machining, also demonstrating the alloy bar of good appearance.Though the present invention is not constituted restriction in theory, think that through the speed of cooling that slows down the difference of the speed of cooling of top layer and thickness of slab central part increases, by quenching, precipitate reduces near the top layer, and the thickness of slab central part is slowly cooled, and precipitate increases.
Average cooling rate till solutionizing temperature to 400 ℃ is preferably below 500 ℃/minute, is preferably 500～300 ℃/minute, most preferably is 500～400 ℃/minute.If in above-mentioned scope, then the top layer is by quenching, so particle diameter is that the above precipitate number of 1 μ m reduces, and central part is slowly cooled, and therefore produces the precipitate that particle diameter is 1～10 μ m.If surpass 500 ℃/minute, then roughly separate out equably at material internal, so the appearance poor after toughness and the bending machining.If 300 ℃/minute of less thaies, thickization of precipitate of thickness of slab central part then can't fully obtain the precipitating reinforcing effect of timeliness.
Average cooling rate till from 400 ℃ to 70 ℃ is preferably below 300 ℃/minute, more preferably 300～100 ℃/minute.If surpass 300 ℃/minute, then roughly separate out equably at material internal, so the appearance poor after the bending machining.On the other hand, if 100 ℃/minute of less thaies, thickization of precipitate of thickness of slab central part then can't fully obtain the precipitating reinforcing effect of timeliness.But also expend time in, undesirable in industry.
Among the present invention, from the process of cooling that the solutionizing temperature begins, in fact be difficult to make speed of cooling to keep constant, therefore adopt average cooling rate.Average cooling rate of the present invention be with solutionizing temperature and 400 ℃ or 400 ℃ and 70 ℃ difference divided by the spent time of cooling the result.
Theoretical solutionizing temperature changes according to the content of Ni and Si, and actual solutionizing is handled at Cu-Ni
2Each Ni of the state graph of Si
2Implement in the scope of solid solubility limit temperature+50～200 of Si concentration ℃.
Ageing treatment obtains required intensity and electroconductibility in order to make growth in the material of fine precipitate after solutionizing is handled and carries out.Aging temperature is preferably 300～700 ℃, more preferably 400～650 ℃.Its reason is that when being lower than 300 ℃, ageing treatment expends time in, and is uneconomical, if surpass 650 ℃, then thickization of Ni-Si particle surpasses 700 ℃ if also have, then Ni and Si solid solution, and intensity and electroconductibility can not improve.When in 300～700 ℃ scope, carrying out ageing treatment,, then can obtain enough intensity and electroconductibility if the ageing treatment time is 1～10 hour.
Shear zone produces because of the localization of the strained in the transfer material.As stated; Be adjusted in skin section few and for the number that with particle diameter is the precipitate of 1～10 μ m at the many materials of thickness of slab central part; If top layer and thickness of slab central part are applied distortion (calendering) equably; Then shear zone produces in the top layer on a small quantity, and produces in a large number at the thickness of slab central part, reaches the degree that is enough to carry out work strengthening.
The Yanzhong of finally colding pressing, the calendering load of every 1mm length of material width direction is preferably 50～150kg/mm, more preferably 70～150kg/mm.If not enough 50kg/mm then can't fully depress.On the other hand, if surpass 150kg/mm, then strain concentrates on material surface easily, and the shear zone on top layer increases.
In order in the process of prolonging of finally colding pressing, to produce machining deformation equably on top layer and central part, the calendering oil viscosity is low more good more.The calendering oil viscosity is preferably 11～7cST, more preferably 10～8cST.If not enough 7cST then can't be fully engaging-in between roller and the material, can't play the effect of rolling oil.On the other hand, if surpass 11cST, the engaging-in material surface of rolling oil when then rolling, surface smoothing property variation, and strain builds up in the top layer, and the shear zone radical on top layer increases.
The total degree of finish that prolongs of colding pressing is 15～80%, can at random select according to mechanical characteristicies such as desired tensile strength, 0.2% ys and bendability.The degree of finish of per 1 passage is higher than 5%, is preferably more than 10%.If below 5%, then the road number of times increases, and the shear zone radical on top layer increases.
Copper alloy of the present invention can be heat-treated (stress relief annealing) finally colding pressing to delay also.
Copper alloy of the present invention will be estimated the variation of the appearance after the bending machining, so the material surface outward appearance is very important.The adjustment of surfaceness can through for example roll, method such as grinding carries out.In the actually operating, can use stack of adjusting surfaceness etc. to roll, adjust the surfaceness of copper alloy by this.In addition, in the operation after the calendering.Also can be to material surface embodiment such as mesh (Japanese: the polishing grinding that roughness order) is different, adjustment sheet surface roughness by this.
Surface average roughness Ra after the following bending machining evaluation of alloy bar of the present invention is below the 2.0 μ m, is preferably below the 1.5 μ m.
Embodiment
Be depicted as Cu-Ni-Si of the present invention below and be the manufacturing example of alloy and the result of testing of characteristic, but should be understood that they provide in order to understand the present invention and advantage thereof better, and do not mean that the present invention is limited.
(method of manufacture)
With the copper alloy that the various one-tenth of high frequency melting furnace melting are grouped into, cast the ingot casting of thick 20mm, wide 50mm, long 150mm.Then, being solid-solubilized in fully in the matrix in order to make Ni and Si, in Heating temperature more than 800 ℃ and be lower than under 900 ℃ the temperature heating more than 2 hours, is that condition more than 650 ℃ is carried out hot calender according to end temp, with this ingot casting till thickness 8mm then.Then, implement building up by welding, be calendered to the thickness of slab of regulation then for the incrustation (scale) of removing the surface.
Then; According to thickness of slab after the solutionizing of carrying out under 850～950 ℃ the temperature 10 minutes is handled; On one side each average cooling rate in solutionizing temperature～400 ℃ and 400 ℃～70 ℃ scopes is adjusted to the speed of regulation; Cool off on one side, the particle diameter of adjustment top layer and thickness of slab central part is the number of the precipitate of 1～10 μ m.
Then, for embodiment 1～29, comparative example 32～45, form the ageing treatment that the temperature (400～600 ℃) that can obtain maximum intensity through precipitation strength was carried out 5 hours, then colding pressing is extended down to 0.25mm with each.Various calendering loads and rolling oil viscosity are selected in the Yanzhong of colding pressing, the shear zone radical on adjustment sample top layer.Used rolling oil is system trade(brand)name Tiffany stainless steel oil (ダ Off ニ one ス テ Application レ ス オ イ Le, DAPHNE STAINLESS OIL) X-60 (viscosity 9.5cST) of the emerging product of bright dipping society or the system trade(brand)name Tiffany stainless steel oil X-3K (viscosity 12cST) of the emerging product of bright dipping society.In the rolling oil of the rolling oil of viscosity 12cST or viscosity 9.5cST, add MO and adjust the calendering oil viscosity.
For embodiment 30 and 31, after likewise carrying out above-mentioned solutionizing and handle with embodiment 1～29, comparative example 32～45, colding pressing is extended down to 0.25mm.Various calendering loads and rolling oil viscosity are selected in the Yanzhong of colding pressing, the shear zone radical on adjustment sample top layer.Used rolling oil is the same.Then, form the ageing treatment that the temperature (400～600 ℃) that can obtain maximum intensity through precipitation strength was carried out 5 hours with each.
Change the road number of times of the final calendering in embodiment 1～31, the comparative example 32～43 according to degree of finish, for example total degree of finish be 15～30% o'clock be 1 passage, total degree of finish be 30～50% o'clock be 2 passages, total degree of finish is 3 passages more than it the time.Therefore, the working modulus minimum of per 1 passage is also more than 10%.
In the present embodiment, embodiment 1～29, comparative example 32～45 have carried out colding pressing prolonging after ageing treatment, therefore implement stress relief annealing (550 ℃, 15 seconds) subsequently.Among the present invention, also can before ageing treatment, roll, can omit the stress relief annealing after the timeliness this moment.Omitted the stress relief annealing after the timeliness among the embodiment 30 and 31.The time-delay of colding pressing before and after the ageing treatment is carried out stress relief annealing finally colding pressing to delay.
(evaluation method)
In embodiment 1～29, the comparative example 32～45,, carry out shear zone radical, precipitate particulate number, crystal median size, intensity, electroconductibility, bendability evaluation, tension test, conductivity test for the sample after the stress relief annealing.
Among the embodiment 30 and 31,, carry out same test for the sample after the ageing treatment.
(a) shear zone radical
The observation of shear zone is described below and carries out: for the parallel thickness of slab section of calendering; After carrying out mechanical mill with the Buddha's warrior attendant gypsum of 3 μ m; In the solution of iron(ic)chloride 5g+ hydrochloric acid 30ml+ water 100ml, flood about 5～15 seconds; After crystal boundary and shear zone are shown, in the scope till 1/6 degree of depth that plays thickness of slab from the surface, select to amount to 2mm at random
2The visual field, with 800 times observation by light microscope.Likewise observe the thickness of slab central part (scope till 1/6 degree of depth of thickness of slab plays 5/6 degree of depth) beyond the top layer.Shear zone is evaluated as the angle that becomes 10～60 ° with rolling direction, across the crystal boundary more than 1, lines more than the long 5 μ m.
(b) precipitate particulate number
For the parallel and thickness of slab orthogonal cross-section of calendering; With the ferric chloride in aqueous solution etching at room temperature of 47 Baumes (ボ one メ) after 2 minutes, from the top layer (from the surface play thickness of slab 1/6 till the degree of depth) and thickness of slab central part (part beyond the said top layer) select to amount to 2mm at random
2The visual field; With FE-SEM (field-emission scanning electron microscope; The system model XL30/SFEG/TMP of PHILIPS Co. (Off イ リ Star プ ス society)) secondary electron image in the above-mentioned visual field of shooting uses incidental grain size analysis software, at first with precipitate part and part binaryzation in addition thereof; Use EDS (energy dispersion type X-ray analysis) to measure composition again, identify the precipitate that constitutes by the composition different with the mother metal composition.Using grain size analysis software (the system EDS of Phonex Corp. (Off エ ニ Star Network ス society) particle/facies analysis software) is that the number of 1～10 μ m is counted to particle diameter in these precipitate particles that identify.In addition, in all embodiment and the comparative example, top layer and thickness of slab central part do not exist particle diameter to surpass the precipitate of 10 μ m.
(c) average crystalline particle diameter
Crystal particle diameter is measured based on the process of chopping (JISH0501) of JIS defined.Particularly; Sample is carried out resin embedding; Sightingpiston is met at right angles with respect to rolling direction; After through mechanical mill sightingpiston being carried out mirror finish, be in the solution that forms of the mixed of 10 capacity parts, dissolve the iron(ic)chloride of 5% weight of this solution weight at hydrochloric acid by the water of 100 capacity parts, concentration 36%.Sample was flooded for 10 seconds in the solution of processing as stated, metal structure is shown.Then; For above-mentioned metal structure; Amplify 1000 times with opticmicroscope and take pictures,, on photo, mark 5 lines parallel and 5 vertical lines of the plate width direction with sample, 10 the line segment of 200mm altogether with the interval of 25mm respectively with the plate width direction of sample through the process of chopping (JIS H0501) of JIS defined; Number of die n to being cut out by above-mentioned line segment counts, and obtains through formula (200mm * 10/ (n * 1000)).The visual field number of observing is in a selected arbitrarily visual field of thickness of slab central part for each sample.
(d) tension test
With JIS Z 2241 is benchmark, uses JIS 13B tension test sheet, carries out tension test abreast with rolling direction, obtains tensile strength (tensile strength, MPa).Cu-Ni-Si of the present invention is in the alloy bar, and HS is meant that the tensile strength in the said determination method is generally more than the 680MPa, is preferably more than the 780MPa, more preferably more than the 800MPa.
(e) specific conductivity
Specific conductivity (%IACS) is through with JIS H 0505 being the four-terminal method mensuration of benchmark.Be preferably more than the 44.0%IACS, more preferably more than the 45.0%IACS.
(f) bendability evaluation
Carry out GOOD WAY bending machining (R=0.125, R/t=0.5) according to JIS Z 2248, observe curved surface.Observational technique is described below: HD100 takes curved surface with laser technology company (レ one ザ one テ Star Network society) system confocal microscope, with incidental software mensuration average roughness Ra and compare.In addition, with the specimen surface before the confocal microscopy sem observation bending machining, the result fails to confirm concavo-convex.When the surface average roughness Ra after the bending machining surpasses 2.0 μ m, be evaluated as the appearance poor after the bending machining.Among the present invention, " outward appearance after the bending machining is good " is meant that the surface average roughness Ra after the above-mentioned bending machining is below the 2.0 μ m.
Create conditions and the characteristic of the material of processing as stated are shown in table 1～3.In the table 1; Embodiment 1～16th, do not add the alloy bar of the present invention of other metal ingredient; In the table 2; Embodiment 17～31st, in scope, are added with the example of other any metal ingredient, and the top layer of shear zone radical/thickness of slab central part ratio Ss/Sc is less than 1.0, and the shear zone radical Ss on top layer is 10/10000 μ m
2Below.Therefore the outward appearance of the surface element after the bending machining is good.Embodiment 30 and 31 rolls with timeliness after solutionizing successively, does not implement the example of final stress relief annealing, can know through the shear zone radical Ss on top layer, Ss/Sc etc. are adjusted in the scope of the invention, can obtain and the same characteristic of the present invention.
In the table 3, comparative example 32 is because the addition of Ni and Si is few, though so with the same condition of embodiment under make, tensile strength is still very low, is 643MPa.In the comparative example 33, owing to the Ni that is added with 5.0%, therefore serious cracking taking place when hot calender, can't carry out subsequent handling.
Comparative example 34 is that the average cooling rate till solutionizing temperature to 400 ℃ is accelerated the example to 650 ℃/minute.The particle diameter on top layer be the ratio Ns/Nc of number of precipitate of number and thickness of slab central part of precipitate of 1～10 μ m greater than 1, consequently, the shear zone radical on top layer is more than central part, the bend appearance after the bending machining is poor.Comparative example 35 is will slow to 100 ℃/minute example from the average cooling rate till the solutionizing temperature to 400 ℃ conversely; Because the precipitate number on top layer is more; The shear zone radical on top layer is many; Therefore crooked texture is poor, and tensile strength is low, and this possibly be because the influence of thickization of precipitate.
Comparative example 36 and 37 is examples of the average cooling rate till changing from 400 ℃ to 70 ℃.Comparative example 36 has been accelerated average cooling rate; Consequently, the particle diameter on top layer is that the ratio Ns/Nc of number of precipitate of number and thickness of slab central part of precipitate of 1～10 μ m is greater than 1, consequently; The shear zone radical on top layer is more than central part, and the bend appearance after the bending machining is poor.In the comparative example 37, because speed of cooling is slow excessively, so the particle diameter on top layer is that the number of precipitate of 1～10 μ m is many.And the precipitate of thickness of slab central part condenses, thickization.Consequently, the particle diameter on top layer be the ratio Ns/Nc of number of precipitate of number and thickness of slab central part of precipitate of 1～10 μ m greater than 1, the shear zone radical on top layer increases, the bend appearance poor.And tensile strength is low, and this possibly be because the influence of thickization of precipitate.
In the comparative example 38 and 39, the average cooling rate till solutionizing temperature～70 ℃ is constant, but in the comparative example 38; Average cooling rate till from 400 ℃ to 70 ℃ is fast, in the comparative example 39, the average cooling rate till the solutionizing temperature to 400 ℃ and from 400 ℃ to 70 ℃ till average cooling rate all fast; Therefore both compare with the thickness of slab central part, and the particle diameter on top layer is that the precipitate amount of 1～10 μ m is all a lot, consequently; The shear zone radical on top layer increases, the bend appearance poor.
In the comparative example 40, because the calendering load is excessive, so the shear zone radical on top layer is many, the bend appearance poor.In the comparative example 41,,, also can't be calendered to the thickness of slab of regulation, be judged as and be not suitable for industrial application, interrupt halfway estimating even therefore calendering road number of times reaches 20 passages because calendering load is little, to depress power little.
In the comparative example 42, because the calendering oil viscosity is too high, so the shear zone radical on top layer is many, the bend appearance poor.In the comparative example 43,, produce slit between material and the stack, thereby cause the material surface major injury, therefore do not carry out follow-up evaluation because the calendering oil viscosity is low.
Comparative example 44 is that the degree of finish of per 1 passage when finally rolling is 5% example.Owing to reduced the degree of finish of per 1 passage, so the road number of times is more than 10 times, and productivity is poor.And applied viscous deformation because the top layer concentrates, so nearly 31 of the shear zone radicals on top layer, the roughness after the bending machining is big.Comparative example 45 be with the same condition of comparative example 44 under stress relief annealing condition after finally rolling become 600 ℃ * 1 minute example; Though the precipitate number on top layer is reduced to 42 slightly; But the shear zone radical on top layer still reaches 30, the bend appearance poor.
As stated, utilize the present invention, can obtain the high strength copper alloy that bend outward appearance after the bending machining does not produce the good bend outward appearance of demonstrating of gauffer or crackle, be suitable as copper alloy for electronic material such as terminal, junctor.
[table 1]
[table 2]
[table 3]
Claims (3)
1. the also good Cu-Ni-Si of outward appearance after HS and the bending machining is an alloy bar; It is characterized in that; It is contain Ni:0.8～4.6% and Si:0.3～1.6% and count with total amount among any composition Sn, Zn, Fe, Co, Cr, Mg and the Mn of 2.0% following scope more than a kind; The copper alloy that surplus branch is made up of Cu and unavoidable impurities; Wherein, the ratio Ss/Sc of the lines radical Sc of the shear zone of the part (following note is made the thickness of slab central part) beyond the lines radical Ss of the shear zone of (following note is done the top layer) and the material surface is below 1.0 till material surface plays 1/6 degree of depth of thickness of slab; Said % is a quality percentage.
2. the described Cu-Ni-Si of claim 1 is an alloy bar, it is characterized in that, the lines radical of the shear zone of material surface is 10/10000 μ m
2Below.
3. claim 1 or 2 described Cu-Ni-Si are alloy bar, it is characterized in that, at material surface, particle diameter is that the number of the precipitate of 1～10 μ m is 1.0 * 10
2Individual/mm
2Below, and the particle diameter on top layer is that the particle diameter of number Ns and thickness of slab central part of the precipitate of 1～10 μ m is that the ratio Ns/Nc of number Nc of the precipitate of 1～10 μ m is below 1.0.
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| JP2010083736A JP5281031B2 (en) | 2010-03-31 | 2010-03-31 | Cu-Ni-Si alloy with excellent bending workability |
| JP2010-083736 | 2010-03-31 | ||
| PCT/JP2011/057441 WO2011125558A1 (en) | 2010-03-31 | 2011-03-25 | Cu-ni-si alloy with excellent bendability |
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| WO2011125558A1 (en) | 2011-10-13 |
| KR20120053087A (en) | 2012-05-24 |
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| TW201202445A (en) | 2012-01-16 |
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