CN102317483A - Cu-Zn-Sn alloy plate and tin-plated Cu-Zn-Sn alloy strip - Google Patents

Cu-Zn-Sn alloy plate and tin-plated Cu-Zn-Sn alloy strip Download PDF

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CN102317483A
CN102317483A CN2010800077130A CN201080007713A CN102317483A CN 102317483 A CN102317483 A CN 102317483A CN 2010800077130 A CN2010800077130 A CN 2010800077130A CN 201080007713 A CN201080007713 A CN 201080007713A CN 102317483 A CN102317483 A CN 102317483A
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alloy
texture
quality
utmost point
point density
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前田直文
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JX Nippon Mining and Metals Corp
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JX Nippon Mining and Metals Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • 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
    • C22C9/04—Alloys based on copper with zinc as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
    • C23C8/10—Oxidising
    • C23C8/12—Oxidising using elemental oxygen or ozone
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/30—Electroplating: Baths therefor from solutions of tin
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C25D7/0614—Strips or foils

Abstract

Provided are a Cu-Zn-Sn alloy plate and a tin-plated Cu-Zn-Sn alloy strip having not only excellent pressing processability, but also excellent strength, electrical conductivity, and bending processability. The Cu-Zn-Sn alloy plate comprises 2 to 12% by mass of Zn, 0.1 to 1.0% by mass of Sn, and Cu and unavoidable impurities as the remainder, wherein, when the crystal orientation is measured to a depth of 5 [mu]m from the surface of the plate by an X-ray diffraction method, the pole density of shear texture corresponding to a region of alpha=0+-10 DEG (alpha: an axis perpendicular to the rotation axis of a diffraction goniometer defined in the Schultz method) in a {111} pole figure is 2 to 8.

Description

Cu-Zn-Sn is that alloy sheets and Cu-Zn-Sn are alloy plating Sn bar
Technical field
For example the present invention relates to be suitable for, the Cu-Zn-Sn of electroconductibility spring materials such as junctor, terminal, rly., switch is that alloy sheets and Cu-Zn-Sn are alloy plating Sn bar.
Background technology
Terminal, junctor etc. are that Cu is the alloy sheets punch process and is shaped to required shape, and along with the miniaturized of electronic component, the dimensional precision behind the stamping-out is more important than in the past.In the punch process, along with the increase of stamping-out number of times, die wear, overlap raises, and therefore, along with the precision raising of parts, the frequency of maintenance of mould increases.This sagging, overlap still along with the raising of dimensional precision, require the Cu based material that sagging is little, overlap is low handling through the adjustment mould mostly in the past.
Under this background, developed texture, surface tissue through adjustment Cu based material, methods such as homodisperse miniaturization compound are improved the technology of punch process property.For example disclose for the copper base alloy that is selected from least a element among Sn, Ni, P, Zn, Si, Fe, Co, Mg, Ti, Cr, Zr, the Al that contains 0.01～30wt%; Working modulus Z% with regulation carries out cold rolling; Then carry out low-temperature annealing under the temperature of recrystallization temperature being lower than, the X ray strength ratio SND on surface is adjusted into the technology of SND=I{220} ÷ I{200} >=10.(patent documentation 1)
In addition, disclose in the X-ray diffraction intensity of material section, make 111} with { total diffraction intensity of 222} is the { copper base alloy more than 2 times of 200} diffraction intensity (patent documentation 2).Further, disclose on the copper alloy parts of the Sn that contains the Zn of 5～35wt%, 0.1～3wt% and to have formed semiconductor device that lamellated Pd forms with lead frame (patent documentation 3).
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2002-180165 communique
Patent documentation 2: TOHKEMY 2001-152303 communique
Patent documentation 3: japanese kokai publication hei 11-36027 communique
Summary of the invention
The problem that invention will solve
But, if improve punch process property and exceedingly adjust texture, surface tissue, then material behaviors such as intensity, electric conductivity, bendability reduce.
Therefore, the present invention proposes in order to solve above-mentioned problem, and its purpose is, provides that not only punch process property is excellent, and intensity is that alloy sheets and Cu-Zn-Sn are that alloy plates the Sn bar with the also excellent Cu-Zn-Sn of bendability.
Solve the means of problem
In order to achieve the above object; Cu-Zn-Sn of the present invention is that alloy sheets contains the Zn of 2～12 quality % and the Sn of 0.1～1.0 quality %; Rest part comprises Cu and unavoidable impurities; When measuring the slave plate surface to the crystalline orientation of the degree of depth of 5 μ m, be equivalent to through X-ray diffraction method α=0 ± 10 on the positive pole graph of 111} ° (wherein, α: perpendicular to the diffraction of Shu Erci (Schulz) law regulation with the turning axle of goniometer spool) the utmost point density of shearing texture in zone be 2～8.
Preferred oxygen concentration is that the thickness of the above surface oxide layer of 1 quality % is below the 0.5 μ m.
Preferred further containing adds up to being selected from more than at least a among Ni, Mg, Fe, P, Mn and the Cr of 0.005～0.5 quality %.
Cu-Zn-Sn of the present invention is an alloy plating Sn bar at above-mentioned Cu-Zn-Sn is that the surface thick Sn of plating 0.3～2 μ m of alloy sheets obtains, but is not limited thereto.For example be also included within above-mentioned Cu-Zn-Sn and be the Sn-plated material that each coating of forming Cu layer, Cu-Sn alloy layer and Sn layer on the alloy sheets successively forms, and be to form the Sn-plated material that each coating of Ni layer, Cu-Sn alloy layer, Sn layer forms on the alloy sheets successively at above-mentioned Cu-Zn-Sn.
The invention effect
According to the present invention, it is excellent to obtain not only punch process property, and intensity is that alloy sheets and Cu-Zn-Sn are that alloy plates the Sn bar with the also excellent Cu-Zn-Sn of bendability.
Description of drawings
[Fig. 1] is the synoptic diagram of utmost point density of the shearing texture of expression copper alloy plate of the present invention and copper alloy milled sheet in the past.
Embodiment
Below Cu-Zn-Sn that embodiment of the present invention is related to be that alloy sheets describes.
(composition)
[Zn and Sn]
The concentration that makes the Zn in the alloy sheets is that the concentration of 2～12 quality %, Sn is 0.1～1.0 quality %.Zn improves the intensity of alloy sheets, reduces the extent of exfoliation of Sn coating under heating.In addition, Sn has the effect that promotes the work hardening when rolling.
Zn was less than 2% o'clock, and the hardness of alloy sheets reduces.If surpassing the Zn composition of the sull on 12% alloy sheets surface, Zn increases (Zn enrichment), when alloy sheets is processed into male terminal and is installed to the through hole of printed base plate, and the wetting up property variation of lead-free solder.Sn can not get required work hardening characteristic less than 0.1% o'clock, if Sn surpasses 1.0%, then bendability and electroconductibility reduce.
[other adds element]
In alloy sheets, add up to being selected from more than at least a among Ni, Mg, P, Fe, Mn and the Cr of 0.005～0.5 quality % in order to improve intensity, thermotolerance, proof stress retentivity etc., can further to contain.The total amount of these elements can not get required characteristic less than 0.005% o'clock, if total amount surpasses 0.5 quality %, though then obtain required characteristic, electroconductibility, bendability reduce.
(shearing the utmost point density of texture)
Known usually in cold rolling; Along with the plastic deformation of material, carry out lattice and rotate, form texture; When rolling; There are differences with the formed texture of material central portion in zone, the top layer of the material that contacts with roller (going up city etc., Japanese metallography can will, p33,36 volumes, and 1972, the brave male volume of five bows, " Metal Forming progress ", p499, コ ロ Na society, 1978).This be because, at the material central part, the biaxial stress that the stress under compression through the thickness of slab direction and the tensile stress of rolling direction combine; Material deformation; And in material surface portion, with the influence of the frictional force of roller under, material shearing strain; Be referred to as surperficial texture (shearing texture), distinguish mutually with rolling texture.Can know that according to above-mentioned document for example for the Al plate, under optimum condition, the two sides of slave plate through thin transition layer, is sharply changed into interior tissue to the surperficial texture of each 30% formation of thickness of slab.
The inventor finds, is that to import the result of surperficial texture (shearing texture) in the alloy sheets initiatively be that alloy sheets is compared with in the past Cu at Cu-Zn-Sn, and overlap is low, and punch process property is good.Surface texture is so that { the 111} orientation is as the texture of staple, and common rolling texture is so that { the 110} orientation is as the texture of staple.In the uniaxial tensile test of known monocrystalline, { the 111} orientation is with { 110} compares in the orientation, and elongation at break is little, thinks that the reduction of the overlap that forms from the teeth outwards when elongation at break in the alloy sheets surface there are differences punch process in each orientation is influential.
In addition, as to Cu-Zn-Sn being the method that imports surperficial texture (shearing texture) in the alloy sheets on one's own initiative, the inventor changes final rolling condition when cold rolling, and the dependency of his-and-hers watches plane texture and rolling condition is investigated.The result is, through controlled rolling speed and rolling viscosity with oil, successfully makes the surperficial texture that in the past only is formed near surface be formed up to about 10～20% the degree of depth of thickness of slab.
Among the present invention; In the time of will measuring the slave plate surface to the crystalline orientation of the degree of depth of 5 μ m through X-ray diffraction method; Be equivalent to α=0 ± 10 on the positive pole graph of 111} ° (wherein, α: perpendicular to the diffraction of schultze method regulation with the turning axle of goniometer spool) the utmost point density of shearing texture in zone be controlled at 2～8.
Wherein, With the slave plate surface as the reason of object be to the 5 μ m degree of depth; Use the relation of Cu-Zn-Sn series copper alloy milled sheet his-and-hers watches plane texture of the present invention and punch process property to investigate the back discovery; If form the above surperficial texture of 5 μ m, then therefore punch process property generation significant difference will arrive this degree of depth as determination object.
In addition, be equivalent in the copper alloy of the present invention to shear texture the 111} orientation owing to be the zone of α=0 ± 10 in the positive pole graph of 111} °, therefore should the zone as the determination object of utmost point density.
As above measure the utmost point density of shearing texture.And known that carry out the stamping-out punch process as if the milled sheet that to the utmost point density of shearing texture is 2～8, the overlap that then produces behind the stamping-out lacks than material in the past.
If the utmost point density of the shearing texture of the degree of depth of distance plate surface 5 μ m less than 2, then fully forms and shears texture, so overlap raises, and punch process property does not improve.On the other hand, the utmost point density of shearing texture surpasses 8 and in industry, is difficult to realize, so the upper limit of utmost point density is set at 8.
In addition, when utmost point density is 2～3 scope, along with the utmost point density of shearing texture increases, punch process property raising (overlap reductions), but if utmost point density surpasses 3, the then improvement degree passivation of punch process property, if utmost point density is above 5, then punch process property does not find differences.In addition, in order to obtain surpassing 5 high utmost point density, be necessary to use high rolling of viscosity with oil or make the roll speed high speed, there is the trend of increase in the surfaceness of material.On the other hand, if utmost point density surpasses 4.5, then bending machining portion produces fold.Thus, preferred utmost point density is 2.2～5, more preferably 2.5～4.5.
In addition, under the situation of in the past copper alloy milled sheet, the high part of utmost point density of shearing texture is limited to the extremely surface of plate, so punch process property is insufficient.Fig. 1 schematically shows the utmost point density of the shearing texture of copper alloy plate of the present invention and copper alloy plate in the past.During copper alloy in the past was rolling, the extremely utmost point density of shearing texture on surface of plate was more than 2, but inner along with getting into, utmost point density sharply reduces, and during the degree of depth of distance plate surface 5 μ m, utmost point density is less than 2.
As the method that the slave plate surface is controlled at 2～8 to the utmost point density of the shearing texture of the degree of depth of 5 μ m; Can enumerate under and carry out full annealed, improve final roller and the method for the frictional force between the rolling blank of copper alloy when cold rolling corresponding to the annealing temperature of alloy composition.Specifically, can enumerate 1) improve the final rolling oil viscosity of use when cold rolling, 2) improve the roughness of final Rolling roller when cold rolling, 3) the final roll speed (reducing roller diameter) when cold rolling of raising.
Rolling use oil viscosity when usually, cold rolling is 0.03～0.06cm 2About/s, be 0.06cm through making the final rolling oil viscosity of using when cold rolling 2More than/the s, can make the utmost point density of shearing texture is 2～8.
(surface oxide layer)
In the copper alloy plate of the present invention, preferred oxygen concentration is that the thickness of the above surface oxide layer of 1 quality % is below the 0.5 μ m.This be because, usually the oxygen concn of parent phase is about 0.001～0.01 quality %, oxygen concn is that the above part of 1 quality % fully contains aerobic, performance is as the function to the influential layer of punching press processibility.
Even the inventor studies the phenomenon that the sample punch process property of under same rolling condition, making also produces difference; The result finds; If the surface oxide layer that forms in the annealing of before sample being processed into plate, bar, implementing thickens, then punch process property variation.Therefore, the atmosphere gas through when annealing control, temperature, time is the thickness optimization of surface oxide layer, thereby improves punch process property.
Surpass 0.5 μ m if oxygen concn is the thickness of the above surface oxide layer of 1 quality %, then die wear increases at interval, and overlap increases, and punch process property might reduce.Think that this is because surface oxide layer is harder than Cu mother metal, become the major cause of die wear, the frequency that produces friction between die steel during the thin more then material of surface oxide layer stamping-out and the zone of oxidation is more little, and punch process property is good.
In addition, if the oxygen concn in the annealing atmosphere gas is below 0.2%, the then thickness attenuation of surface oxide layer, therefore preferred.
(manufacturing)
Copper alloy plate of the present invention for example can be made as follows.At first, will be with electrolytic copper or oxygen free copper as main raw material, and add the composition that above-mentioned other chemical ingredients forms and melt with smelting furnace, make ingot.For ingot, for example carry out homogenizing anneal, hot rolling, surfacing, cold rolling, full annealed, final cold rolling processing successively, obtain milled sheet.When plating Sn, after will removing through electrolytic degreasing with oil attached to rolling in the milled sheet, for example carry out pickling, plate Sn with 10% aqueous sulfuric acid.
Copper alloy plate of the present invention can be processed various forms such as bar, paper tinsel.Through copper alloy bar of the present invention is processed, can it be applicable to electronic components such as junctor, plug (ピ Application), terminal, rly., switch.As junctor, go for the junctor of known arbitrary form, structure, but be used as the male terminal of the junctor that constitutes by public (socket (jack), plug (plug)) and female (socket (socket), socket (receptacle)) usually.
< embodiment >
Then enumerate embodiment the present invention is explained more specifically, but the invention is not restricted to them.
Embodiment 1
1. the manufacturing of sample
Melt electrolytic copper with high frequency induction furnace, after molten surface is covered with charcoal, add Zn (3 quality %) and Sn (0.2 quality %), liquation is adjusted into required alloy composition.Then, under 1200 ℃ of teeming temperatures, cast, with the ingot that obtains 850 ℃ down heating be hot-rolled down to thickness of slab 8mm after 3 hours, remove the oxide debris that the surface produces through surfacing.Then, process, finally be finish-machined to the milled sheet of 0.64mm with cold rolling, full annealed, cold rolling order.Full annealed carries out in the decomposed ammonia body, and annealing time is 30 minutes.The condition of full annealed, final cold rolling condition (roll speed and the rolling oil viscosity of using) and the material behavior that obtains are as shown in table 1.Change recrystallization condition and final cold rolling condition, the utmost point density of texture is sheared in adjustment.
2. shear the mensuration of the utmost point density of texture
With X-ray diffraction meter (RINT2500 that the リ ガ of society of Co., Ltd. Network is produced), carry out { the positive limit mensuration of 111}, making { the positive pole graph of 111} of each sample through reflection method.Wherein, In the reflection method; If X ray was measured with respect to shallow then being difficult to of the input angle of sample face; Therefore the angular range that in fact can measure on positive pole graph be 0 °≤α≤75 °, 0 °≤β≤360 ° (wherein, α: perpendicular to the diffraction of schultze method regulation with the turning axle of goniometer spool, β: the axle that is parallel to above-mentioned turning axle).
In the mensuration, making rotation interval delta α, the Δ β of α and β is 5 °, scans above-mentioned angular range, measures the X ray intensity that 16 * 73=1168 is ordered.At this moment, making the state (being that crystalline orientation is a state at random) with texture is 1, with the strength criterionization of the texture on the positive pole graph.With crystalline orientation is state at random, carry out the copper powder sample the positive limit of 111} is measured, and with it as 1.
As the x-ray bombardment condition, use Co pipe ball, making tube voltage is 30kV, tube current is 100mA, imposes a condition so that the degree of depth of X ray slave plate surface seepage to 5 μ m.
As above measure be equivalent to shear texture { utmost point density of the crystalline orientation of the scope of α=0 ± 10 on the positive pole graph of 111} ° is defined as the utmost point density of shearing texture with the peak of utmost point density in this scope.
3. the height of overlap
For each sample, what make mould is spaced apart 10%, and with the stamping-out speed of 250spm, stamping-out length is that 30mm, width are the lead-in wire of 0.5mm, takes the cross section of stamping-out material with confocal microscope.In photographic images, stamping-out is finished the height that the highest part of the height of face one side and the difference of altitude of highly minimum part are regarded as overlap.
If the height of overlap is that 15 μ m are low with next overlap, be judged to be good.
4. bendability
Stretch the technological standard T307 of copper association (JBMA) (1999) according to Japan, the bendability of each sample is estimated.Making bending radius is r=0.3, and it is crooked to implement Good Way.
Stretch the evaluation A～E of 5 grades of copper association (JBMA) technological standard corresponding to Japan, estimate by following benchmark.
Zero: the situation of the A (well) of copper association (JBMA) technological standard is stretched by Japan
△: the B (fold is little) and the C (fold is big) of copper association (JBMA) technological standard stretches in Japan
*: the D (crackle is little) and the E (crackle is big) of copper association (JBMA) technological standard stretches in Japan
5. tensile strength
For each sample, being parallel on the direction of rolling direction, carry out tension test according to JISZ2241, obtain tensile strength.If tensile strength is more than the 450MPa, be good then as spring material.
The result who obtains is as shown in table 1.
Figure BPA00001422109000081
Can know that by table 1 in invention example 1～9, because the overlap that punch process caused is low, bendability is also good.Therefore, punch process property is excellent, and tensile strength is also high.Wherein, oxygen concn is that the invention example 9 that the thickness of the above surface oxide layer of 1 quality % surpasses 0.5 μ m is compared with other invention example, and overlap is high, but the practical no problem of going up.
On the other hand, in the final comparative example 1 of roll speed less than 170mpm when cold rolling, the utmost point density of shearing texture is less than 2, and overlap is high, punch process property variation.
In addition, final rolling when cold rolling with oil viscosity less than 0.06cm 2In the comparative example 2 of/s, the utmost point density of shearing texture structure is less than 2, and overlap is high, punch process property variation.
The full annealed temperature is lower than in 380 ℃ the comparative example 3, and the utmost point density of shearing texture is less than 2, and overlap is high, punch process property variation.This is because because the full annealed temperature is low, sufficient recrystallization does not take place, because the influence of the rolling texture that full annealed formed in the past can not get required shearing texture.
The full annealed temperature surpasses in 430 ℃ the comparative example 4, and the utmost point density of shearing texture is more than 2, but because the full annealed temperature is too high, so thickization of crystallization particle diameter, tensile strength reduces.
In addition, the scope of suitable recrystallization temperature changes according to the composition of copper alloy plate, is not limited to 380～430 ℃ the TR that the present invention's example is adopted.
Embodiment 2
Melt electrolytic copper with high-frequency induction furnace, after molten surface was covered with charcoal, the composition interpolation alloying element with table 2 was adjusted into required alloy composition with liquation.Then, under 1200 ℃ of teeming temperatures, cast, heating is after 3 hours down at 850 ℃ with the ingot that obtains, and being hot-rolled down to thickness of slab is 8mm, removes the oxide debris that the surface produces through surfacing.Then, process, finally be finish-machined to the milled sheet of 0.64mm with cold rolling, full annealed, cold rolling order.Full annealed carries out in the decomposed ammonia body, and making oxygen concn is 0.1%, under the annealing temperature shown in the table 3, carries out 30 minutes.Making the roll speed of finish rolling is 200mpm, uses viscosity to be 0.1cm 2/ s's is rolling with oil.
For the sample that obtains, carry out the evaluation identical with embodiment 1, further, carry out the evaluation of the up property of following solder (は ん だ moistens れ and goes up Ga り property).
< the up property of solder >
The up property of solder of lead-free solder when the through hole mounting terminal of printed base plate is with following test simulation.
At first; After each the copper milled sheet that obtains among the embodiment 2 plated the Sn of 1.2 μ m; Add that to be pressed into plate wide for 0.64mm, length are the strip of 30mm, make end face produce the pressurization section after, at the atmosphere gas of 85 ℃ of relative humidity 85%, temperature exposure 24h (maturation process) down.Then, this rectangular plate is immersed in prescribed depth in 250 ℃ the lead-free solder (Sn-3%Ag-0.5%Cu) after 10 seconds, pulls out.When being immersed in sample in the lead-free solder, the solder sample, scolder rises from the dipping interface thus.Therefore, can pass through computes solder area occupation ratio (S).
S (%)=(total area of the solder attachment portion behind the dipping)/(initial area of the solder dipping portion during dipping) * 100
S surpasses at 100% o'clock, shows the wetting up phenomenon that produces scolder, and S is 110% when above, and the up property of above-mentioned solder is good.Therefore, with following benchmark the up property of solder is estimated.
○：S≥110％
×：S＜110％
The result who obtains is as shown in table 3.
[table 2]
[table 3]
Figure BPA00001422109000111
As shown in table 3, in the invention example 10～25, punch process property is excellent, and tensile strength is high, and the up property of solder is good.
On the other hand, in the comparative example 5 of Zn concentration less than 2 quality %, tensile strength reduces.Zn concentration surpasses in the comparative example 6 of 12 quality %, and punch process property, intensity are all good, but the up property of solder variation.In the comparative example 7 of Sn concentration less than 0.1 quality %, the work hardening when rolling is insufficient, and tensile strength reduces.Sn concentration surpasses in the comparative example 8 of 1.0 quality %, and bendability reduces.

Claims (4)

1.Cu-Zn-Sn be alloy sheets; Contain the Zn of 2～12 quality % and the Sn of 0.1～1.0 quality %; Rest part comprises Cu and unavoidable impurities; When measuring the slave plate surface to the crystalline orientation of the degree of depth of 5 μ m, be equivalent to through X-ray diffraction method α=0 ± 10 on the positive pole graph of 111} ° (wherein, α: perpendicular to the diffraction of schultze method regulation with the turning axle of goniometer spool) the utmost point density of shearing texture in zone be 2～8.
2. Cu-Zn-Sn as claimed in claim 1 is an alloy sheets, and wherein, oxygen concn is that the thickness of the above surface oxide layer of 1 quality % is below the 0.5 μ m.
3. according to claim 1 or claim 2 Cu-Zn-Sn is an alloy sheets, wherein, further contains and adds up to being selected from more than at least a among Ni, Mg, Fe, P, Mn and the Cr of 0.005～0.5 quality %.
4.Cu-Zn-Sn be alloy plating Sn bar, plating 0.3～2 μ m thick Sn in its surface that any described Cu-Zn-Sn is an alloy sheets in claim 1～3 obtains.
CN2010800077130A 2009-04-01 2010-03-25 Cu-Zn-Sn alloy plate and tin-plated Cu-Zn-Sn alloy strip Pending CN102317483A (en)

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JP2009-089343 2009-04-01
JP2009089343A JP5339995B2 (en) 2009-04-01 2009-04-01 Cu-Zn-Sn alloy plate and Cu-Zn-Sn alloy Sn plating strip
PCT/JP2010/055194 WO2010113749A1 (en) 2009-04-01 2010-03-25 Cu-Zn-Sn ALLOY PLATE AND TIN-PLATED Cu-Zn-Sn ALLOY STRIP

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