WO2002053790A1 - Alliage de cuivre haute resistance ayant une excellente aptitude au pliage et son procede de fabrication, terminal et connecteur comportant cet alliage - Google Patents
Alliage de cuivre haute resistance ayant une excellente aptitude au pliage et son procede de fabrication, terminal et connecteur comportant cet alliage Download PDFInfo
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- WO2002053790A1 WO2002053790A1 PCT/JP2001/011483 JP0111483W WO02053790A1 WO 2002053790 A1 WO2002053790 A1 WO 2002053790A1 JP 0111483 W JP0111483 W JP 0111483W WO 02053790 A1 WO02053790 A1 WO 02053790A1
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- copper alloy
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- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 106
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 28
- 238000000137 annealing Methods 0.000 claims abstract description 72
- 238000005097 cold rolling Methods 0.000 claims abstract description 53
- 229910000906 Bronze Inorganic materials 0.000 claims abstract description 39
- 239000010974 bronze Substances 0.000 claims abstract description 38
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 claims abstract description 38
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000000463 material Substances 0.000 claims abstract description 34
- 238000005096 rolling process Methods 0.000 claims abstract description 19
- 239000010949 copper Substances 0.000 claims abstract description 11
- 229910052802 copper Inorganic materials 0.000 claims abstract description 4
- 238000005452 bending Methods 0.000 claims description 89
- 239000013078 crystal Substances 0.000 claims description 78
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 14
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- 239000002244 precipitate Substances 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 229910052749 magnesium Inorganic materials 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 229910052725 zinc Inorganic materials 0.000 claims description 9
- 239000012535 impurity Substances 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 229910052790 beryllium Inorganic materials 0.000 claims description 7
- 229910052791 calcium Inorganic materials 0.000 claims description 7
- 229910052804 chromium Inorganic materials 0.000 claims description 7
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- 229910052758 niobium Inorganic materials 0.000 claims description 7
- 229910052709 silver Inorganic materials 0.000 claims description 7
- 229910052727 yttrium Inorganic materials 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 229910052738 indium Inorganic materials 0.000 claims description 5
- 238000005275 alloying Methods 0.000 claims 1
- 239000000956 alloy Substances 0.000 abstract description 11
- 229910045601 alloy Inorganic materials 0.000 abstract description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 3
- 230000002301 combined effect Effects 0.000 abstract description 2
- 230000002787 reinforcement Effects 0.000 abstract 2
- 238000011835 investigation Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 27
- 230000000694 effects Effects 0.000 description 25
- 238000005482 strain hardening Methods 0.000 description 19
- 238000005728 strengthening Methods 0.000 description 18
- 238000001953 recrystallisation Methods 0.000 description 13
- 230000007423 decrease Effects 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 239000006104 solid solution Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 239000011651 chromium Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 239000012467 final product Substances 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000037303 wrinkles Effects 0.000 description 3
- 229910001369 Brass Inorganic materials 0.000 description 2
- DMFGNRRURHSENX-UHFFFAOYSA-N beryllium copper Chemical compound [Be].[Cu] DMFGNRRURHSENX-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000010951 brass Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- 229910017526 Cu-Cr-Zr Inorganic materials 0.000 description 1
- 229910017810 Cu—Cr—Zr Inorganic materials 0.000 description 1
- 229910017876 Cu—Ni—Si Inorganic materials 0.000 description 1
- 229910009038 Sn—P Inorganic materials 0.000 description 1
- 229910008651 TiZr Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- ZTXONRUJVYXVTJ-UHFFFAOYSA-N chromium copper Chemical compound [Cr][Cu][Cr] ZTXONRUJVYXVTJ-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- IUYOGGFTLHZHEG-UHFFFAOYSA-N copper titanium Chemical compound [Ti].[Cu] IUYOGGFTLHZHEG-UHFFFAOYSA-N 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- UREBDLICKHMUKA-CXSFZGCWSA-N dexamethasone Chemical compound C1CC2=CC(=O)C=C[C@]2(C)[C@]2(F)[C@@H]1[C@@H]1C[C@@H](C)[C@@](C(=O)CO)(O)[C@@]1(C)C[C@@H]2O UREBDLICKHMUKA-CXSFZGCWSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- MOFOBJHOKRNACT-UHFFFAOYSA-N nickel silver Chemical compound [Ni].[Ag] MOFOBJHOKRNACT-UHFFFAOYSA-N 0.000 description 1
- 239000010956 nickel silver Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- 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
- C22C9/02—Alloys based on copper with tin 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
Definitions
- the present invention relates to a high-strength copper alloy excellent in bending workability, particularly high-strength phosphor bronze used for electronic components such as terminals and connectors, and a method for producing the same, and to a terminal-to-connector using them. .
- Phosphor bronze strips such as C5210 and C 5191 (according to JISH 3110 and JISH 3130 ') and copper alloy materials such as C 2600 (according to JISH 3100) have excellent workability and mechanical strength, and are therefore electronic components. Widely used in terminal-connector applications.
- high-strength copper alloys such as beryllium copper and titanium copper, and Corson alloy (Cu-Ni-Si) -based and chromium copper-based (Cu-Cr) , Cu—Cr—Zr, Cu—Cr—Sn).
- these high-strength copper alloys which are relatively new as copper alloys for electronic components, do not yet have general versatility, so they are not suitable for market supply and demand and distribution. For example, there is a problem that it is not widely used in a market where priority is placed on standard. Also, these high-strength copper alloys are not preferable because they are more expensive than conventional copper alloys such as phosphor bronze.
- an object of the present invention is to develop a technology that combines high strength and bending workability of a solid solution strengthened copper alloy, particularly a versatile phosphor bronze.
- solid-solution strengthened copper alloys especially general-purpose phosphor bronze
- grain boundary strengthening and dislocation strengthening that is, heat treatment and rolling
- grain boundaries cannot be revealed in the final product.
- various deformation bands such as a shear band and a micro band appear. Due to these deformation zones, the grain boundaries formed by recrystallization before cold working become discontinuous, and their cross sections are etched and observed with an optical microscope. The crystal structure becomes unclear even if it is observed.
- the present inventors adjusted the cold rolling and annealing conditions of phosphor bronze and investigated the correlation between the characteristic values after final rolling, and found that the combined effect of grain boundary strengthening and dislocation strengthening was We succeeded in obtaining stable improvements.
- the present invention provides a high strength copper alloy with excellent bendability, which can be defined by the following properties:
- the average crystal grain size (mG S) after the bending is 5 ⁇ or less and the standard deviation (a GS) of the average crystal grain size is 1 Z 3 X m GS or less.
- Copper alloy is Sn: l ⁇ l lma ss o / o , P: 0.03 ⁇ 0.35ma ss%, and Fe, Ni, Mg, Si, Zn, Cr , Ti, Zr, Nb, Al, Ag , Be, Ca, Y, Mn, and one or more of In: Phosphor bronze consisting of 0.05 to 2.0 mass% in total, with the balance being Cu and unavoidable impurities.
- Copper alloy is Sn: l ⁇ l lma ss o / o , P: 0.03 ⁇ 0.35ma ss%, and Fe, Ni, Mg ⁇ Si, Zn, Cr, TiZr , Nb, Al, Ag, Be, Ca, Y, Mn, and one or more of In: 0.05 to 2.
- the present invention also provides a method for producing a high-strength copper alloy having excellent bending workability based on the following conditions:
- mGS average grain size
- aGS standard deviation of the grain size
- TS is the tensile strength after the final cold rolling with a work ratio of X (%).
- the cold-rolled material (MP a), tensile strength TS a (MP a) is TS a rather TS.
- the above methods (6) to (8) can be applied as the above-mentioned methods (1) to (5) for producing a copper alloy.
- the present invention further provides a method for producing a high-strength copper alloy having excellent bending workability based on the following conditions:
- the present invention also provides
- the invention of claim 1 is directed to a copper alloy having a strength characteristic in which a difference between a tensile strength and a 0.2% proof stress is within 8 OMPa, wherein the copper alloy has an average crystallinity after an annealing test at 425 ° C for 10,000 seconds. It defines that the particle size (mGS) is 5 ⁇ or less, and the standard deviation ( ff GS) of the crystal particle size is 1/3 mGS or less.
- the crystal grain size is measured by a cutting method according to JISH0501. Specifically, the number of crystal grains completely cut by a line segment of a predetermined length is counted, and the average value of the cut lengths is used as the crystal grain size.
- the standard deviation which is an index of the variation, is It is not the standard deviation but the standard deviation of the grain size.
- the copper alloy of the present invention is basically cold rolled at a workability of 45% or more, and finally annealed to have an average grain size (mGS) of 3 ⁇ or less and a standard deviation (GS) of the grain size of 2 / m or less, followed by final cold rolling at a work ratio of 10 to 45% or the average grain size (mGS) is 2 ⁇ or less and the standard deviation ( ⁇ GS) of the grain size is 1 ⁇ m
- the product was manufactured by performing the following cold rolling at a working ratio of 20 to 70%. As mentioned above, if grain boundary strengthening and dislocation strengthening, ie, heat treatment and rolling, are used to increase the strength, grain boundaries cannot be revealed in the final product.
- the present invention relates to a copper alloy having a strength characteristic in which the difference between the tensile strength and the 0.2% proof stress is within 8 OMPa, the average crystal grain size when annealed at 425 ° C for 10,000 seconds.
- An object of the present invention is to provide a copper alloy having excellent bendability due to crystal grain characteristics having an (mGS) of 5 / xm or less and a standard deviation ( ff GS) of its crystal grain size of 1 / 3mGS or less.
- the difference between the tensile strength and 0.2% proof stress decreases as the degree of cold working increases, but at the same time, ductility decreases and bending occurs. Cracking easily occurs during processing.
- the present invention has found that by adjusting the final annealing conditions before the final rolling and the cold working conditions before the final rolling, the reduction of the total 14 can be reduced.
- the difference between the tensile strength and the 0.2% proof stress is within 80 MPa. A remarkable effect can be expected in a high-strength copper alloy having the following characteristics.
- the average crystal grain size is maintained at 5 jum or less.
- the product is produced by setting the average grain size (mGS) to 2 ⁇ m or less and the standard deviation GS) of the crystal grain size to 1 ⁇ m or less, and then performing final cold rolling at a workability of 20 to 70%.
- the copper alloy of the present invention has an ultrafine crystal structure in which a grain boundary cannot appear in the final product, but such a fine crystal structure is subjected to calcination at 425 ° C for 10,000 seconds.
- it has the unique property that crystals do not grow and the average grain size is maintained at 5 ⁇ or less, and by using this property, it is distinguished from other copper alloys to define the copper alloy of the present invention. You can do it.
- This product of copper alloys has low ductility reduction due to final cold working, and has both high strength and excellent bending workability when the products are manufactured.
- the average crystal grain size after annealing at 425 ° C. for 1.0000 seconds is 3 ⁇ m or less, the relationship between tensile strength and bending workability is further improved.
- the production method must be strictly controlled to achieve a uniform microstructure.
- the allowable range of the variation must be less than l / 3mGS, expressed as the standard deviation of the crystal grain size. This is because when the standard deviation ((JGS)) exceeds 1/3 mGS, the effect of improving bending workability is small.
- the present invention limits the copper alloy to phosphor bronze, which has a high tensile strength.
- phosphor bronze to which tin is added as a solid solution strengthening element has a work hardening characteristic that differs depending on the tin concentration.
- the range in which the present invention is particularly effective as a high-strength material is considered.
- the tensile strength is shown as TS Sn (MPa)> 500 + 15 XSn (tin mass% concentration).
- the copper alloy is limited to phosphor bronze, and the average grain size (mGS: ⁇ ) after annealing at 425 ° C. for 1000 seconds and the tin concentration (S n: ma ss%) are determined.
- the relationship is mG S ⁇ 2.7 X exp (0.04 3 6 XS n)
- the crystal grains so as to satisfy (0.043 6 X Sn).
- This standard covers the processing conditions, properties (strength and bending workability) and 425 ° CX 10000 for phosphor bronze containing 1 to 11%, especially 2% to 10% tin.
- This is an empirical formula that correlates the crystal grain size after heat treatment for a second. If the mGS is above the specified value, the effect of grain refinement is low, and high strength cannot be achieved unless the degree of rolling is increased, and the ductility of the high-strength material is greatly reduced. The performance is not improved.
- the relationship between crystal grain size and strength (proof stress) is a force mainly due to the effect of grain refinement described by the generally known formula of Ha11-P etch After recrystallization. It has been found that the subsequent work hardening ability itself is increased by the crystal grain size.
- this feature enables high strength to be achieved by low work rolling.
- the lower limit is not specified, if the average crystal grain size (mGS) after final annealing is reduced to less than 0.4 ⁇ , the ductility reduced by cold rolling before final annealing cannot be fully recovered. Since the final cold rolling further reduces ductility, desirably, mGS should be 0.4 / zm or more. preferable.
- the present invention relates to the above identified copper alloys, especially phosphor bronze, for the Fe, Ni, Mg, Si and Zn groups and for the Cr, Ti, Zr, Nb, Al, Ag, Be , Ca, Y, Mn, and In are added in a total of 0.05 to 2. Omass%.
- the addition of trace amounts of Fe, Ni, Mg, and Si to the copper alloy is phosphor bronze means that these elements and P, etc., form intermetallic compounds and disperse in the matrix.
- the present invention is to improve the characteristics of the bronze manufactured mainly by grain boundary strengthening and solid solution strengthening.
- intermetallic compounds such as Fe-P are precipitated and dispersed in these combinations, the strength of the alloy itself is enhanced by the precipitation strengthening function, and the effect of pinning the crystal grain boundaries by residual particles of precipitates or crystallized substances This makes it difficult for crystal grains to grow and facilitates grain refinement.
- 0.05 ma s s% is necessary, and if it exceeds 2. O mas s s%, it is harmful rather than electrical conductivity.
- Zn is an element that suppresses the thermal delamination of tin and solder when added to a copper alloy.
- Zn is added at about 0.5 ss% or more, its effect is exhibited, but when it exceeds 0.5 ss%, The improvement effect saturates and the electrical conductivity decreases.
- Fe, Ni, Mg, Si, and Zn are additive elements that enhance the strength of phosphor bronze or improve the heat-peelability of tin and soldering, and it is recommended to add them.
- the amount of addition is determined in consideration of bending workability and electrical conductivity, and the total amount is 0.05 to 2. Omass%. The reason is that if the total amount is less than 0.05 mass ° / o, the strength does not improve, and there is no effect of improving the heat-peeling resistance of the plating, and if it exceeds 2.0 mass%, the bending workability deteriorates and the electrical conductivity Is also reduced.
- the decrease in electrical conductivity is particularly significant for low-tin high-conductivity phosphor bronze with a tin concentration of about 1 to 4 mass%.
- Zn may be set to 0.1 to 0.5mass%. desirable.
- These elements are elements that strengthen the copper alloy by solid solution strengthening and precipitation strengthening, and, as in the case of Fe, Ni, Mg, Si, and Zn, do not deteriorate the bending workability, and the total amount is 1. Addition of Omass% or less enables higher strength.
- the present invention in the invention of claim 4, further defines the distribution of precipitates and crystals of the alloy element.
- the particles that actually contribute to the nucleation of crystal grains and the pinning effect of grain boundaries in grain refinement include those with smaller diameters, but are observed at the level of a scanning electron microscope.
- an excellent crystal grain refinement effect is observed in the state of the cross-sectional structure of the particle distribution described above. In other words, the substitute properties of grain refinement and Then, the distribution of the precipitates and crystals is specified.
- the present invention relates to a method for producing a high-strength copper alloy having excellent bending workability. More specifically, in copper alloys manufactured by repeating cold rolling and annealing, the final cold rolling, the final annealing before that, and the excellent bending workability that defines the previous cold rolling process It relates to a method for producing a high-strength copper alloy '.
- These inventions also basically aim at the effect of crystal grain refinement after final annealing and before final rolling.
- T The material thickness before cold rolling.
- X (t 0-1 ) t, where t is the material thickness after cold rolling.
- X 100 (%) Defined degree of cold rolling before final annealing X is set to 45% or more.If it is less than 45%, even after adjusting the heat treatment conditions for final annealing, after final annealing, This is a force that makes it difficult for the crystal grain size to be reduced.
- the crystal grain size is not normally distributed, but if the average crystal grain size (mGS) is 3 / ⁇ and its standard deviation (aGS) is 2 / zm, It means that 99% or more of the crystal grain size is less than mGS + 3 ⁇ GS, that is, 9 ⁇ or less.
- crystal grains having a diameter of 8 ⁇ m or more are mixed in the recrystallized structure, and for that purpose, the standard deviation of the crystal grain diameter is desirably 1.5 ⁇ m or less.
- the effect of the degree of cold rolling before final annealing on the recrystallized structure after final annealing is such that as the degree of work is increased, the grain size of the recrystallized structure after annealing tends to decrease, but at the same time, nucleation and subsequent Secondary recrystallization behavior greatly varies, and the particles tend to be mixed.
- the tendency is strong in a copper alloy having a pure copper type recrystallized structure having a high copper concentration.
- 30m ass ° /.
- brass containing Zn or phosphor bronze containing 411 3% or more of 311 as described above recrystallized grains after relatively strong working are easily sized.
- the standard deviation of the crystal grain size is preferably 2; ⁇ or less, but the average crystal grain size is 2 ⁇ m or less, and the standard deviation is 1 ⁇ m or less. If the variation in crystal grain size is reduced, the workability of final cold rolling is further increased due to the effect of uniform and fine grain size, and even if it is set to 20 to 70%, bending workability is not deteriorated. A high strength copper alloy is obtained.
- the present invention is to perform strain relief annealing after final rolling on the above-mentioned copper alloy, and to specify the amount of decrease in tensile strength in the strain relief annealing. . (MP a), the tensile strength after stress relief annealing as TS a (MP a), TS a rather TS. X (the final cold rolling work ratio (%)).
- Phosphor bronze, nickel silver, etc. may be subjected to strain relief annealing. Unlike recrystallization annealing performed before final rolling, strain relief annealing is intended to restore ductility (workability) after cold working and to improve spring properties, for example.
- strain relief annealing is intended to restore ductility (workability) after cold working and to improve spring properties, for example.
- phosphor bronze for springs C5 210: commonly used in JISH 310).
- the copper alloy according to the present invention has higher strength and superior bending workability even after strain relief annealing than alloys manufactured by conventional techniques.
- this material is subjected to strain relief annealing, and subjected to strain relief annealing to less than 67 OMPa. Can be obtained.
- claims 6 to 8 are applicable to the production method of high-strength copper alloys, particularly, phosphor bronze described in claims 1 to 5. The description is as described above.
- Hinaaki provides a high-strength copper alloy excellent in bending workability and a method of manufacturing the same for solid-solution strengthened copper alloys, particularly phosphor bronze-based copper alloys, and has a small and excellent bending property. Applicable to terminals-connectors that require high strength and high strength.
- Example 1 (Example relating to the inventions according to claims 1 to 3)
- Phosphor bronze with the composition shown in Table 1 was coated with charcoal in the air, dissolved, An agglomerate with a size of mm w X 4 Omm 1 X 15 Omm 1 was prepared.
- the lump was homogenized and annealed at 700 in a 75% N 2 + 25% H 2 atmosphere at 700 for 1 hour, and the tin segregation layer on the surface was polished with a grinder and removed.
- cold rolling and recrystallization annealing are repeated a plurality of times as necessary, and in particular, the cold rolling degree before the final annealing, the final recrystallization annealing, and the final cold rolling degree are adjusted.
- a plate having a thickness of mm was obtained.
- Table 1 shows the characteristics.
- Tensile strength (TS: MPa) and 0.2% resistance (YS: MPa) were determined by taking a 13B test piece (JISZ 2201) in parallel with the rolling direction and performing a tensile test (JISZ 2241). .
- the crystal grain size is calculated by the cutting method (JISH 0501), by counting the number of crystal grains completely cut by a line segment of a predetermined length, taking the average of the cut lengths as the crystal grain size, and the standard deviation of the crystal grain size ( aGS) is the standard deviation of the grain size. That is, the cross-sectional structure in the direction perpendicular to the rolling direction was magnified 4000 times with a scanning electron microscope image (SEM image), and the number of intersections between the line and the grain boundary was 50 in the line segment with a length of 50. Is the crystal grain size, and the average of each grain size obtained by measuring 10 line segments is the average grain size (mGS) in this application, and the standard deviation of each grain size is The standard deviation (crGS) in this application was used.
- Table 1 shows Inventive Example 18 and Comparative Examples I to 4 which are conventional materials, and Examples A to E in which the parameters were further changed for the purpose of explaining the effect of the present invention (ratio: comparative example, small: book) (Indicating invention)) is shown separately for convenience.
- Comparative examples 14 are examples of conventional materials, and when these examples and the present invention examples I to D were subjected to fefeT, they had the same composition and the same strength, but the present invention examples 1 to 4 and D It can be seen that r zt is small and the bending force tri property is improved.
- Example D of the present invention is an example in which TS-YS is large in the scope of claim 1. (This is an example for the purpose of clarifying the definition of S-YS ⁇ 80. Indicates that the bending workability has been improved.)
- Inventive Examples 5 to 8 are examples in which the crystal grain size is further reduced in Inventive Examples 1 to 4, but according to the tin concentration in accordance with mGS, 2.7 XeXp (0.0436 XSn). By adjusting the crystal grain size, the strength is improved, the shear force and rZt are equal or smaller, and the bending process is good.
- Comparative Example B is an example in which mGS and ff GS satisfy claim 1, but TS-YS does not satisfy claim 1. Although the crystal grains after annealing are fine, the strength is low due to the large TS-YS, and the strength and bending workability are the same as those of conventional material C, and no improvement is observed.
- Comparative Example C is an example for the purpose of comparison with Comparative Example B.
- Comparative example E is an example for the purpose of comparison with inventive example D.
- test piece was prepared in the same manner as in Example 1 with a composition to which iron, nickel, and the like were added based on the component of phosphor bronze.
- the recrystallization sintering was adjusted while adjusting the crystal grains and observing the coarse precipitates, the residual state of the crystallized substances, and the growth of the precipitates.
- the precipitates and crystals were analyzed for the number of particles in a cross section with a diameter of 0.1 ⁇ m or more using an energy dispersive analyzer of a field emission scanning electron microscope (FESEM) and observed.Table 2 shows the results. is there. From the comparison with the present invention C u- S n-P-based alloy Table 1, C u- S n - by the addition of other elements to P-based alloy trace, CxGS decreases, the further the crystal grain size It can be seen that the miniaturization can be stably performed, and further, by dispersing the particles composed of these elements, the strength is further improved and the bendability is excellent.
- FESEM field emission scanning electron microscope
- 'Comparative Example H is an example in which the sum of the sub-components exceeds 2.Omass%, and has poor bending workability.
- Example 3 Examples of Verification of Inventions According to Claims 6, 7, 9, and 10.
- the compositions of Examples 17 to 20 of the present invention correspond to Tables 1 to 4 in Example 1.
- Comparative Examples 5 to 8 are examples of conventional materials.
- Examples A to F ratio: comparative example, present: present the present invention in which the parameters are further changed for the purpose of explaining the effect of the present surprise are separately classified for convenience.
- the test method was in accordance with Example 1. Table 3 shows the results.
- Comparative Example 58 is an example of a conventional material, in which the degree of cold rolling before final annealing and the average crystal grain size in final annealing deviate from the present invention, but Examples 17 to 20 of the present invention are comparative examples.
- Example 58 Higher strength, lower r / t and better bending workability than the conventional material of Example 8.
- the present invention Example A the crystal grain size after recrystallization annealing of the present invention Example ⁇ 9 2. And 6, but satisfy the claim 6 is an example not satisfying the claim 7, the crystal grain size fine Example ⁇ Nine is slightly stronger.
- Example B of the present invention is an example in which the final cold work degree satisfies claim 6 but does not satisfy claim 7, and the workability is low, that is, the strength is low V, and the bending workability is good.
- Comparative Example D is an example in which the workability of rolling and mGS satisfy claims 6 and 7, but the temperature history during recrystallization firing is poor and ⁇ GS is not satisfied. Is bad.
- Comparative Example ⁇ is an example in which the final cold rolling degree is low, but the strength is almost the same as that of the conventional material of Comparative Example F, and since the strength is low, no improvement effect is recognized.
- Comparative example F is a conventional material example as described above (TS is about the same as ⁇ and rZt is the same).
- 21 to 28 of the examples of the present invention correspond to the above examples of the present invention No. 2, 3, 4, 7, 8, 15, 16, and 20, respectively, as described above, and comparative examples (conventional materials).
- Nos. 9 to 12 correspond to Comparative Examples Nos. 3, 4, 7, and 8 described above.
- Comparative Examples A and B are for the purpose of showing a case where TS lowered by strain relief annealing is small, and correspond to Examples 16 and 20 of the present invention.
- test pieces were subjected to strain relief annealing under various final cold rolling reduction conditions to evaluate their properties.
- the amount of decrease in tensile strength (TS) due to strain relief annealing is also shown.
- Invention Example No. 21 is a material having a tin concentration of 6.2 mass%, a tensile strength ( TS ) of 570 MPa, and a bending or raw ( r / t) of 0.
- Inventive Examples Nos. 22, 24, 26, Comparative Examples Nos. 9 and 11, which are conventional materials, are tin-rich / gears of 8.0 to 8.2 mass%.
- is (TS) is 6 5 2 ⁇ 7 6 0MP a
- bending workability ⁇ chi / t) is 0 to 2.0
- Comparative example The tensile strength (TS) was 650 ⁇ 6981 ⁇ ? & And the r / t force was 1.5 ⁇ 2.5, indicating that the present invention has high strength and good bending workability.
- inventive examples Nos. 23, 25, 27, and 28 and the comparative examples No. 10 and 12 are materials having a tin concentration of 10.0 to 10.2 mass%, but the tensile strength (TS) of the inventive examples was Whereas, while the bending workability (r / t) is 1.5 to 3.0, the tensile strength (TS) force is 06 to 762 MPa and the r / t force is S3. 0 indicates that the present invention has high strength and good bending workability.
- the material of the present invention subjected to the strain relief annealing can clearly achieve higher strength and improved bending workability than the conventional material of the comparative example. In other words, if the strength is the same, the bendability is significantly improved, and if the bendability is the same, the strength is greatly increased.
- the copper alloy particularly the phosphor bronze alloy
- the copper alloy can be strengthened without deteriorating the bending workability, and the characteristics required for the copper alloy for terminals and connectors for electronic components can be improved.
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Abstract
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JP2002554288A JP4177104B2 (ja) | 2000-12-28 | 2001-12-26 | 曲げ加工性に優れた高強度銅合金及びその製造方法及びそれを用いた端子・コネクタ |
KR10-2003-7007183A KR100535737B1 (ko) | 2000-12-28 | 2001-12-26 | 굽힘가공성이 우수한 고강도 동합금과 그 제조방법 및그것을 사용한 단자ㆍ커넥터 |
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JP2000-400837 | 2000-12-28 | ||
JP2000400837 | 2000-12-28 |
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WO2002053790A1 true WO2002053790A1 (fr) | 2002-07-11 |
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PCT/JP2001/011483 WO2002053790A1 (fr) | 2000-12-28 | 2001-12-26 | Alliage de cuivre haute resistance ayant une excellente aptitude au pliage et son procede de fabrication, terminal et connecteur comportant cet alliage |
Country Status (6)
Country | Link |
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US (2) | US20030188814A1 (fr) |
JP (1) | JP4177104B2 (fr) |
KR (1) | KR100535737B1 (fr) |
CN (1) | CN1250756C (fr) |
TW (1) | TW526272B (fr) |
WO (1) | WO2002053790A1 (fr) |
Cited By (4)
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WO2006093233A1 (fr) * | 2005-03-02 | 2006-09-08 | The Furukawa Electric Co., Ltd. | Alliage de cuivre et procede de production de celui-ci |
JP2006274445A (ja) * | 2005-03-02 | 2006-10-12 | Furukawa Electric Co Ltd:The | 銅合金とその製造方法 |
WO2008126681A1 (fr) * | 2007-03-26 | 2008-10-23 | The Furukawa Electric Co., Ltd. | Alliage de cuivre pour un dispositif électrique/électronique et son procédé de fabrication |
WO2010071220A1 (fr) | 2008-12-19 | 2010-06-24 | 古河電気工業株式会社 | Matériau à base d'alliage de cuivre pour composants électriques ou électroniques et procédé de fabrication associé |
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- 2001-12-26 WO PCT/JP2001/011483 patent/WO2002053790A1/fr active IP Right Grant
- 2001-12-26 KR KR10-2003-7007183A patent/KR100535737B1/ko active IP Right Grant
- 2001-12-26 TW TW090132285A patent/TW526272B/zh active
- 2001-12-26 JP JP2002554288A patent/JP4177104B2/ja not_active Expired - Fee Related
- 2001-12-26 US US10/380,291 patent/US20030188814A1/en not_active Abandoned
- 2001-12-26 CN CNB018195121A patent/CN1250756C/zh not_active Expired - Fee Related
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2008
- 2008-04-11 US US12/082,531 patent/US20080210353A1/en not_active Abandoned
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JPH07331363A (ja) * | 1994-06-01 | 1995-12-19 | Nikko Kinzoku Kk | 高力高導電性銅合金 |
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Publication number | Priority date | Publication date | Assignee | Title |
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WO2006093233A1 (fr) * | 2005-03-02 | 2006-09-08 | The Furukawa Electric Co., Ltd. | Alliage de cuivre et procede de production de celui-ci |
JP2006274445A (ja) * | 2005-03-02 | 2006-10-12 | Furukawa Electric Co Ltd:The | 銅合金とその製造方法 |
WO2008126681A1 (fr) * | 2007-03-26 | 2008-10-23 | The Furukawa Electric Co., Ltd. | Alliage de cuivre pour un dispositif électrique/électronique et son procédé de fabrication |
JP2008266783A (ja) * | 2007-03-26 | 2008-11-06 | Furukawa Electric Co Ltd:The | 電気・電子機器用銅合金およびその製造方法 |
WO2010071220A1 (fr) | 2008-12-19 | 2010-06-24 | 古河電気工業株式会社 | Matériau à base d'alliage de cuivre pour composants électriques ou électroniques et procédé de fabrication associé |
Also Published As
Publication number | Publication date |
---|---|
US20080210353A1 (en) | 2008-09-04 |
US20030188814A1 (en) | 2003-10-09 |
JPWO2002053790A1 (ja) | 2004-05-13 |
KR100535737B1 (ko) | 2005-12-09 |
TW526272B (en) | 2003-04-01 |
KR20030057561A (ko) | 2003-07-04 |
JP4177104B2 (ja) | 2008-11-05 |
CN1250756C (zh) | 2006-04-12 |
CN1476486A (zh) | 2004-02-18 |
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