WO2011068134A1 - 低ヤング率を有する銅合金板材およびその製造法 - Google Patents
低ヤング率を有する銅合金板材およびその製造法 Download PDFInfo
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- WO2011068134A1 WO2011068134A1 PCT/JP2010/071517 JP2010071517W WO2011068134A1 WO 2011068134 A1 WO2011068134 A1 WO 2011068134A1 JP 2010071517 W JP2010071517 W JP 2010071517W WO 2011068134 A1 WO2011068134 A1 WO 2011068134A1
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- WIPO (PCT)
- Prior art keywords
- copper alloy
- alloy sheet
- rolling
- modulus
- electronic parts
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- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 100
- 239000000463 material Substances 0.000 title claims abstract description 59
- 238000004519 manufacturing process Methods 0.000 title claims description 22
- 239000000956 alloy Substances 0.000 claims abstract description 61
- 238000005096 rolling process Methods 0.000 claims abstract description 43
- 238000005452 bending Methods 0.000 claims abstract description 28
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 239000010949 copper Substances 0.000 claims abstract description 14
- 239000012535 impurity Substances 0.000 claims abstract description 4
- 238000005097 cold rolling Methods 0.000 claims description 44
- 238000000137 annealing Methods 0.000 claims description 30
- 238000005098 hot rolling Methods 0.000 claims description 26
- 230000032683 aging Effects 0.000 claims description 22
- 230000035882 stress Effects 0.000 claims description 21
- 238000001816 cooling Methods 0.000 claims description 18
- 238000001887 electron backscatter diffraction Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 14
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 239000013078 crystal Substances 0.000 description 30
- 239000000243 solution Substances 0.000 description 25
- 238000012360 testing method Methods 0.000 description 14
- 230000000694 effects Effects 0.000 description 13
- 238000005259 measurement Methods 0.000 description 13
- 230000007423 decrease Effects 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 10
- 229910052802 copper Inorganic materials 0.000 description 10
- 230000009467 reduction Effects 0.000 description 10
- 238000005266 casting Methods 0.000 description 9
- 239000011701 zinc Substances 0.000 description 9
- 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 8
- 229910001369 Brass Inorganic materials 0.000 description 7
- 239000010951 brass Substances 0.000 description 7
- 238000010583 slow cooling Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000012545 processing Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 229910000906 Bronze Inorganic materials 0.000 description 2
- 229910020711 Co—Si Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000010974 bronze Substances 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 230000008520 organization Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 239000013598 vector Substances 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- 229910017876 Cu—Ni—Si Inorganic materials 0.000 description 1
- -1 FCC metals Chemical class 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000006061 abrasive grain Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000003483 aging Methods 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
-
- 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
- C22C9/10—Alloys based on copper with silicon as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
- B21B2003/005—Copper or its alloys
Definitions
- the present invention relates to a copper alloy sheet having high strength and high conductivity suitable as materials for electric and electronic parts such as connectors, and further having a low Young's modulus, and a method for producing the same.
- the tensile strength in the rolling direction (RD) is 500MPa or more as the strength not to be deformed during insertion and removal or bending, and furthermore, the electrical conductivity is 30% IACS to suppress the generation of Joule heat due to energization. The above is preferable.
- the connector be miniaturized and that a large Young's modulus of the connector material be obtained so that a large stress can be obtained with a small displacement.
- the dimensional accuracy of the terminal itself becomes severe, and management standards such as die technology and press operation management, or variations in plate thickness and residual stress of connector materials become strict, which in turn causes an increase in cost. Therefore, recently, a connector material having a small Young's modulus is used, a structure in which the displacement of the spring is large, and a design that can tolerate variations in dimensions are being sought. Therefore, it is required that the Young's modulus in the rolling direction is 110 GPa or less, preferably 100 GPa or less.
- brass, phosphor bronze and the like have been generally used as connector materials.
- the Young's modulus in the rolling direction of both brass and phosphor bronze is about 110 to 120 GPa, which is smaller than the Young's modulus 128 GPa of pure copper, and is widely used as a low Young's modulus material.
- these copper alloys have a conductivity of 30% IACS or less, a low conductivity, and can not be used as a connector in applications where a large current flows. Therefore, Corson alloys having moderate conductivity have been attracting attention, and the amount used has been increasing. However, this Corson alloy has a Young's modulus of about 130 GPa, and in this point, the Young's modulus of the connector material is reduced. It has been demanded.
- the connector may be designed not with Young's modulus but with a bending deflection coefficient (longitudinal elastic modulus at the time of bending test), and therefore, a low bending deflection coefficient is required.
- Young's modulus represents the longitudinal elastic modulus under tensile stress
- flexural deflection coefficient represents the longitudinal elastic modulus under complex stress of compression and tension at bending
- the values of Young's modulus and flexural deflection coefficient are Although different, when the Young's modulus is low, the bending deflection coefficient tends to be a low value.
- the low Young's modulus and the low flexural deflection are achieved not only by adding zinc (Zn) and phosphorus (P) to copper but also by controlling the crystal orientation.
- Zn zinc
- P phosphorus
- the Young's modulus decreases and the flexibility becomes good.
- the Corson alloy it is difficult to control the Young's modulus by simply increasing the cold rolling ratio before recrystallization without increasing the Cube orientation.
- the present invention is a copper alloy sheet material for electrical and electronic components such as a connector which can simultaneously satisfy high strength, high conductivity and low Young's modulus required for materials for electrical and electronic components such as connectors with the development of electronics industry. And its purpose is to provide its manufacturing method.
- the area ratio of the (111) plane facing in the rolling direction obtained by analyzing using EBSD of the copper alloy sheet is 15% or less, as described in (1) or (2).
- Copper alloy sheet for electrical and electronic parts is (4)
- a connector comprising the copper alloy sheet material for electric and electronic parts according to any one of (1) to (6).
- the copper-based alloy material according to the present invention or the copper alloy material obtained by the production method of the present invention has high strength and high required for materials for electrical and electronic parts such as connectors, as compared with conventional Corson-based alloys. It has a low Young's modulus without impairing the conductivity, and is suitable as a copper alloy material for electrical and electronic parts such as connectors.
- copper alloy material means one obtained by processing a copper alloy material into a predetermined shape (e.g., plate, strip, foil, bar, wire, etc.).
- a plate material refers to a plate having a specific thickness, being stable in shape and having a spread in the surface direction, and in a broad sense, it includes a bar material.
- material surface layer means “plate surface layer”
- depth position of material means “position in the plate thickness direction”.
- the thickness of the plate is not particularly limited, but is preferably 8 to 800 ⁇ m, more preferably 50 to 70 ⁇ m, in consideration of the fact that the effects of the present invention are more apparent and suitable for practical applications.
- the copper alloy sheet material of the present invention defines its characteristics by the accumulation ratio of atomic planes in a predetermined direction of the rolled sheet, it has the characteristics as the present invention as a copper alloy sheet material.
- the shape of the copper alloy plate is not limited to the plate and the strip, and in the present invention, the tube can be interpreted as a plate and handled.
- the alloy composition of the copper alloy material of the present invention (a typical shape is a plate material), which is a precipitation type copper alloy material such as Corson type having a low Young's modulus and a low flexural deflection coefficient, Describe the organization.
- Ni is an element which is contained together with Si to be described later, forms an Ni 2 Si phase precipitated by aging treatment, and contributes to the improvement of the strength of the copper alloy material.
- the Ni 2 Si phase is insufficient, and the tensile strength of the copper alloy material can not be increased.
- the Ni content is in the range of 0.5 to 5.0%, preferably 1.5 to 4.0%.
- Co 0.5 to 5.0%
- Co is an element which is contained together with Si to form a Co 2 Si phase precipitated by aging treatment and contributes to the improvement of the strength of the copper alloy material.
- the content of Co is too low, the Co 2 Si phase runs short, and the tensile strength of the copper alloy material can not be increased.
- the content of Co is too large, the conductivity decreases. In addition, the hot rolling processability is deteriorated. Therefore, the Co content is in the range of 0.5 to 5.0%, preferably 0.8 to 3.0%, and more preferably 1.1 to 1.7%.
- Ni and Co may contain both, but the total content thereof is 0.5 to 5.0%.
- both Ni 2 Si and Co 2 Si can be precipitated during the aging treatment to enhance the aging strength. If the total content is too small, the tensile strength can not be increased, and if too large, the electrical conductivity and the hot-rolling processability decrease. Therefore, the total content of Ni and Co is in the range of 0.5 to 5.0%, preferably 0.8 to 4.0%.
- (Si) Si is contained together with the Ni and Co to form a Ni 2 Si or Co 2 Si phase precipitated by the aging treatment, and contributes to the improvement of the strength of the copper alloy material.
- the content of Si is 0.2 to 1.5%, preferably 0.2 to 1.0%.
- the tensile strength of the copper alloy material can be increased, but the excess of Si forms a solid solution in the copper matrix and the conductivity of the copper alloy material Decreases.
- Si is excessively contained, castability in casting and rolling workability in hot and cold also decrease, and casting cracking and rolling cracking easily occur.
- precipitation phases of Ni 2 Si or Co 2 Si will be insufficient, and the tensile strength of the material can not be increased.
- Cr In addition to the above composition, 0.05 to 0.5 mass% of Cr may be contained. Cr has the effect of refining the crystal grains in the alloy and contributes to the improvement of the strength and bending workability of the copper alloy material. When the amount is too small, the effect is small, and when the amount is too large, a crystallized product is formed during casting and the aging strength is reduced.
- (Other alloying elements) In the copper alloy material of the present invention, Sn: 0.01 to 1.0%, Zn: 0.01 to 1.0%, Ag: 0.01 to 10% by mass as an additive element in addition to the above basic composition. One or two or more of 1.0%, Mn: 0.01 to 1.0%, Zr: 0.1 to 1.0%, Mg: 0.01 to 1.0% in total It can be contained as needed in an amount of 1.0%.
- Each of these elements has a common effect of improving either the high strength, conductivity or low Young's modulus that the copper alloy material of the present invention is intended to play, in addition to or instead of this. It is an element that further improves other properties (such as stress relaxation resistance). Below, the characteristic effect of each element and the significance of the content range are described.
- (Sn) Sn is an element that mainly improves the strength of the copper alloy material, and is selectively contained when used in applications that place importance on these properties.
- the content of Sn is too small, the strength improvement effect is small.
- the conductivity of the copper alloy material is lowered.
- the amount of Sn is too large, it becomes difficult to make the conductivity of the copper alloy material 30% IACS or more. Therefore, when it is contained, the content of Sn is in the range of 0.01 to 1.0%.
- Zn The addition of Zn can improve the thermal peelability and migration resistance of the solder. If the content of Zn is too low, the effect is small. On the other hand, when Zn is contained, the conductivity of the copper alloy material is lowered, and when Zn is too much, it is difficult to set the conductivity of the copper alloy material to 30% IACS or more. Therefore, the content of Zn is in the range of 0.01 to 1.0%.
- (Ag) Ag contributes to the increase in strength. If the content of Ag is too small, the effect is small. On the other hand, even if a large amount of Ag is contained, the strength increase effect is only saturated. Therefore, when it is contained, the content of Ag is in the range of 0.01 to 1.0%.
- (Mn) Mn mainly improves the workability in hot rolling.
- the content of Mn is too small, the effect is small.
- the amount of Mn is too large, the fluidity of the copper alloy during ingot formation deteriorates, and the ingot retention decreases. Therefore, when it is contained, the content of Mn is in the range of 0.01 to 1.0%.
- (Zr) Zr mainly refines crystal grains to improve the strength and bending workability of the copper alloy material. If the content of Zr is too small, the effect is small. On the other hand, when the amount of Zr is too large, a compound is formed, and the workability such as rolling of a copper alloy material is reduced. Therefore, when it is contained, the content of Zr is in the range of 0.01 to 1.0%.
- Mg improves the stress relaxation resistance. Therefore, when stress relaxation resistance is required, it is selectively contained in the range of 0.01 to 1.0%. When the amount is too small, the effect of addition is small, and when the amount is too large, the conductivity decreases. Therefore, when it is contained, the content of Mg is in the range of 0.01 to 1.0%.
- Mg, Sn, and Zn improve the stress relaxation resistance by adding them to Cu-Ni-Si, Cu-Ni-Co-Si, and Cu-Co-Si copper alloys. The stress relaxation resistance is further improved by the synergetic effect when they are added together as compared to when each of them is added alone. In addition, it has the effect of significantly improving solder embrittlement.
- the conductivity realized by the copper alloy sheet material of the present invention is 30% IACS or more, preferably 35% IACS or more, and more preferably 45% IACS or more. There is no particular upper limit, but it is practical that it is 60% IACS or less. Further, a preferable range as a 0.2% proof stress in the rolling direction realized by the copper alloy material of the present invention is 500 MPa or more, preferably 650 MPa or more, and more preferably 800 MPa or more. There is no particular upper limit, but it is practical that it is 1100 MPa or less.
- the bending deflection coefficient is preferably 105 GPa or less, more preferably 100 GPa or less. There is no particular lower limit, but it is practical that it is 60 GPa or more.
- the Young's modulus is 110 GPa or less, more preferably 100 GPa or less. There is no particular lower limit, but it is practical that it is 70 GPa or more.
- the texture of the copper alloy material of the present invention is, in particular, a surface (100) facing RD in the analysis result from the rolling direction (RD) by the SEM-EBSD method in order to realize a low Young's modulus and a low flexural deflection coefficient. It is preferable to have a texture having an area ratio of 30% or more. Note that all crystal grains having an orientation in which the angle between the sheet rolling direction (RD) and the normal to the surface is 10 ° or less has a (100) plane facing the RD.
- a texture called Cube orientation, Goss orientation, Brass orientation, Copper orientation, S orientation, etc. is formed, and a crystal plane corresponding to them is present.
- the material rolling direction (RD) is taken along the X axis, the plate width direction (TD) as the Y axis, and the rolling normal direction (ND) as the Z axis orthogonal coordinate system.
- the angle between two vectors of the plane orientation ⁇ eg the normal to the (100) plane ⁇ and RD is 10 ° or less
- the area ratio of the crystal plane is preferably 30% or more, and thereby, it is possible to have a texture with a low Young's modulus and a low flexural deflection coefficient.
- the area ratio of the (100) plane facing the RD is more preferably 40% or more, more preferably 50% or more.
- the Young's modulus can be 110 GPa or less
- the bending deflection coefficient can be 105 GPa or less.
- the area ratio of the crystal face toward RD having a low Young's modulus and a low flexural modulus (100) increases.
- the Young's modulus can be reduced by decreasing the area ratio of the crystal face to the RD of (111) having a high Young's modulus and a high bending deflection coefficient.
- the area ratio of the (111) plane facing RD is preferably 15% or less, more preferably 10% or less.
- the measurement of the area ratio of the (100) plane facing RD in the texture of the copper alloy sheet can be obtained by analyzing the electron microscopic structure by SEM using EBSD.
- a range including 400 or more crystal grains was scanned at 1 ⁇ m steps to analyze the orientation.
- direction distribution is changing to the plate
- the SEM-EBSD method is an abbreviation of Scanning Electron Microscopy-Electron Back Scattered Diffraction Pattern method. That is, the individual crystal grains appearing on the SEM screen are irradiated with an electron beam, and the individual crystal orientations are identified from the diffracted electrons.
- the crystal orientation display method in this specification takes the rectangular coordinate system of the rolling direction (RD) of the material as the X axis, the sheet width direction (TD) as the Y axis, and the rolling normal direction (ND) as the Z axis.
- the ratio of the area where the (100) plane faces is defined by the area ratio.
- a region having an atomic plane in which the angle between the normal to the (100) plane and the RD is 10 ° or less Regarding accumulation of atomic planes facing the rolling direction (RD) of the rolled sheet, that is, facing the RD, the (100) plane itself with the rolling direction (RD) of the rolled sheet being the ideal direction as a normal
- the region (the sum of these areas) is a combination of each of the atomic planes in which the angle between the normal of R and the angle formed by RD is 10 ° or less.
- the features of the EBSD measurement will be described as a comparison with the X-ray diffraction measurement.
- the first point mentioned is the crystal orientation which can not be measured by X-ray diffraction measurement, which is the S orientation and the BR orientation. In other words, by adopting EBSD, for the first time, information on S orientation and BR orientation can be obtained, and the relationship between the specified alloy structure and action can be clarified.
- the second point is that X-ray diffraction measures the amount of crystal orientation included in ⁇ 0.5 ° of ND // ⁇ hkl ⁇ .
- EBSD measures the amount of crystal orientation included in ⁇ 10 ° from the orientation. Therefore, EBSD measurement provides an order of magnitude comprehensive information on the alloy structure comprehensively, and it becomes clear that it is difficult to identify the entire alloy material by X-ray diffraction. As described above, the information obtained by EBSD measurement and X-ray diffraction measurement differs in the content and nature thereof. In addition, unless otherwise indicated in this specification, the result of EBSD is performed to the ND direction of a copper alloy plate material.
- the copper alloy material of the present invention is, for example, each step of casting, hot rolling, slow cooling, cold rolling 1, intermediate annealing, cold rolling 2, solution heat treatment, aging heat treatment, finish cold rolling, low temperature annealing, Manufactured through.
- the copper alloy material of the present invention can be manufactured with almost the same equipment as a conventional Corson alloy. In order to obtain predetermined physical properties and further a texture, it is necessary to appropriately adjust the manufacturing conditions of each process. In this respect, the copper alloy material of the present invention is manufactured by performing processing after hot rolling or at least one of cold rolling and intermediate annealing before solution treatment under predetermined conditions. Can.
- the casting is performed by casting a molten copper alloy having its components adjusted to the above composition range. Then, the ingot is chamfered, heated or homogenized at 800 to 1000 ° C., and hot rolled.
- the steel is rapidly quenched by a method such as water cooling immediately after hot rolling.
- the quenching is not carried out in order to increase the (100) surface facing RD after the hot rolling, and it is characterized by slow cooling. I assume.
- the cooling rate at the time of slow cooling is preferably 5 K / s or less.
- the direction in which the (100) plane faces RD has a recovery phenomenon at low temperature as compared with other directions, and the area ratio of the direction in which the (100) face faces RD can be increased in the hot-rolled structure.
- the area ratio of the orientation in which the face of (100) faces in RD in the subsequent solutionizing step It can be enhanced. Since a change in structure does not occur if the temperature upon cooling is less than 350 ° C., after the temperature is cooled to less than 350 ° C., quenching may be performed by a method such as water cooling to reduce production time.
- the surface is cut and cold rolling 1 is performed. If the rolling reduction ratio of the cold rolling 1 is too low, even if the final product is manufactured, the brass orientation and the S orientation develop, and it becomes difficult to increase the (100) area ratio. Therefore, it is preferable that the rolling reduction rate of the cold rolling 1 be 70% or more.
- intermediate annealing is applied at 300 to 800 ° C. for 5 seconds to 2 hours.
- cold rolling 2 with a rolling reduction of 3 to 60% is performed. Repeating the intermediate annealing and the cold rolling 2 can further increase the area ratio of the (100) plane facing RD. Therefore, in the second preferred embodiment of the method for producing a copper alloy material of the present invention, the intermediate annealing and the cold rolling 2 are repeated twice or more.
- the solution treatment is performed at 600 to 1000 ° C. for 5 seconds to 300 seconds. Since the necessary temperature conditions change depending on the concentrations of Ni and Co, it is necessary to select an appropriate temperature condition according to the Ni and Co concentrations. If the solution treatment temperature is too low, the strength is insufficient in the aging treatment step, and if the solution treatment temperature is too high, the material softens more than necessary and the shape control becomes difficult, which is not preferable.
- the aging treatment is performed at 400 to 600 ° C. for 0.5 to 8 hours. Since the necessary temperature conditions change depending on the concentrations of Ni and Co, it is necessary to select an appropriate temperature condition according to the Ni and Co concentrations. When the temperature of the aging treatment is too low, the amount of aging precipitation decreases and the strength is insufficient. In addition, when the temperature of the aging treatment is too high, the precipitates become coarse and the strength decreases.
- the working ratio of finish cold rolling after solution treatment it is preferable to set the working ratio of finish cold rolling after solution treatment to 50% or less.
- the crystal grains having (100) orientation such as Cube orientation can be prevented from rotating in orientation to Brass, S, Copper orientation, etc., and the physical properties of the obtained copper alloy material In addition, it is possible to achieve the desirable state of the texture.
- Low temperature annealing is performed at 300 to 700 ° C. for 10 seconds to 2 hours. This annealing can improve the stress relaxation resistance and the spring limit value required for the connector material.
- the steps of both the first embodiment and the second embodiment are performed, that is, until the temperature range of at least less than 350 ° C. after hot rolling. Is not rapid cooling but gradual cooling (preferably with a cooling rate of 5 K / sec or less), and intermediate annealing and cold rolling 2 are repeated twice or more.
- the copper alloy material of the present invention manufactured by the above method has predetermined properties, it is verified by EBSD analysis whether the physical properties of the copper alloy material and the texture are within the predetermined range. do it.
- the copper alloy of each composition shown in the following Tables 1 and 2 was cast to manufacture a copper alloy plate, and each characteristic such as strength (0.2% proof stress), conductivity, Young's modulus was evaluated.
- casting was performed by a DC (Direct Chill) method to obtain an ingot having a thickness of 30 mm, a width of 100 mm, and a length of 150 mm.
- these ingots were heated to 950 ° C., held at this temperature for 1 hour, hot-rolled to a thickness of 14 mm, gradually cooled at a cooling rate of 1 K / s, and cooled to 300 ° C. or less.
- the both surfaces were subjected to 2 mm face milling to remove the oxide film, and then cold rolling 1 with a rolling ratio of 90 to 95% was applied. Thereafter, cold rolling 2 was performed at an intermediate annealing temperature of 350 to 700 ° C. for 30 minutes and a cold rolling ratio of 10 to 30%.
- solution treatment was performed at 700 to 950 ° C. under various conditions for 5 seconds to 10 minutes, and immediately cooled at a cooling rate of 15 ° C./second or more.
- aging was performed at 400 to 600 ° C. for 2 hours, and then finish rolling was performed at a rolling reduction of 50% or less, and the final plate thickness was made 0.15 mm.
- finish rolling a low temperature annealing treatment was performed at 400 ° C. for 30 seconds to obtain a copper alloy sheet of each alloy composition.
- the sum of the areas of the (100) planes of the crystal grains having the normal to the (100) plane such that the angle between the plate material sample and the rolling direction (RD) makes 10 ° or less is determined
- the area ratio (%) of the (100) plane facing RD was obtained by dividing the sum of the areas by the total measurement area.
- the crystal grains having the above-mentioned angle of 10 ° or less were the same orientation grains.
- the area ratio (%) of the (111) plane facing RD was similarly determined.
- (2) 0.2% proof stress The 0.2% proof stress was determined in accordance with JIS Z 2241 by cutting a No. 5 test piece described in JIS Z 2201 from each test material. The 0.2% proof stress is shown by rounding to an integral multiple of 5 MPa.
- Table 1 shows an example of the present invention.
- the texture was within the preferable range of the present invention, and all of 0.2% proof stress, conductivity, Young's modulus and bending deflection coefficient were excellent.
- Table 2 shows a comparative example to the present invention. Comparative Examples 1, 2 and 5 were inferior in 0.2% proof stress because the content of Ni and / or Co and the content of Si were too smaller than the range of the present invention. In Comparative Examples 3, 4, 6, and 7, since the content of Ni and / or Co was too high, cracking occurred during hot rolling, and the production was stopped. In Comparative Example 8, the conductivity was inferior because the concentration of Si was too high.
- the following comparative example is an example using the same ingot as Example 2.
- Comparative Example 2-2 is an example in which water cooling was immediately performed after hot rolling, intermediate annealing and cold rolling 2 were omitted, and the others were prepared in the same manner as in Example 2, but the (100) plane is suitable for RD The area ratio of (111) was low, and the area ratio of (111) plane was high, and the Young's modulus and bending deflection coefficient were higher than those of the inventive example.
- Comparative Example 2-3 is an example produced similarly to Example 2 except that water cooling is immediately performed after hot rolling, but the area ratio of the (100) plane facing RD is low, and the Young's modulus is an example of the present invention It was higher than that.
- Table 3 shows another embodiment.
- Examples 10-2, 18-2 and 25-2 of Table 3 the same ingot as that of Examples 10, 18 and 25 of Table 1 was used, and water cooling was immediately performed after hot rolling, and intermediate annealing and cooling were performed. This is an example in which the inter-rolling 2 was repeated twice, and the others were produced in the same manner as in each example of Table 1 and the respective characteristics were similarly evaluated.
- the area ratio of the (100) plane facing RD is within the preferable range of the present invention, and the strength, the conductivity, the Young's modulus, and the bending deflection coefficient are excellent.
- Examples 10-3, 18-3, and 25-3 using the same ingots as those of Examples 10, 18, and 25 in Table 1, intermediate annealing and cold rolling 2 are repeated twice, and the others are It is the example which produced similarly to each Example of Table 1, and evaluated each characteristic similarly. These had a particularly high area ratio of (100) face toward RD, a Young's modulus was particularly low at 100 GPa or less, a bending deflection coefficient was particularly low at 90 GPa, and 0.2% proof stress and conductivity were excellent. .
- Comparative Example 101 Condition of JP 2009-007666 A metal element similar to that of the invention example 1-1 was blended, and an alloy composed of Cu and incidental impurities with the balance was melted in a high frequency melting furnace, This was cast at a cooling rate of 0.1 to 100 ° C./sec to obtain an ingot. After holding this at 900 ° C. to 1020 ° C. for 3 minutes to 10 hours, it was hot-worked and then water-quenched to carry out facing for oxide scale removal. In the subsequent steps, a copper alloy c01 was produced by the treatment of steps A-3 and B-3 described below.
- the manufacturing process includes one or more solution heat treatment, in which the steps are classified before and after the last solution heat treatment, and the steps up to intermediate solution treatment are designated as A-3, It was designated as B-3 step in the step after intermediate solution treatment.
- Step A-3 Cold work with a reduction in area of 20% or more, heat treatment for 5 minutes to 10 hours at 350 to 750 ° C., cold work with a reduction in area of 5 to 50%, 800 A solution heat treatment is performed at about 1000 ° C. for 5 seconds to 30 minutes.
- Step B-3 Cold work with a reduction in area of 50% or less, heat treatment at 400 to 700 ° C. for 5 minutes to 10 hours, cold work with a reduction in area of 30% or less, Apply temper annealing at 550 ° C. for 5 seconds to 10 hours.
- the obtained test body c01 differs from the above example in terms of the presence or absence of slow cooling to 350 ° C. after hot rolling with respect to manufacturing conditions, and the area ratio of the (111) plane facing RD is high, Young's modulus and bending The deflection coefficient did not meet the required characteristics.
- Comparative Example 102 Condition of Japanese Patent Application Laid-Open No. 2006-283059
- the copper alloy having the composition of the above-mentioned inventive example 1-1 was dissolved in the atmosphere with an electric furnace under charcoal coating, and the possibility of casting was judged. .
- the molten ingot was hot-rolled and finished to a thickness of 15 mm.
- cold rolling and heat treatment (cold rolling 1 ⁇ solution annealing continuous annealing ⁇ cold rolling 2 ⁇ aging treatment ⁇ cold rolling 3 ⁇ short time annealing) are applied to the hot-rolled material, and a predetermined thickness is obtained.
- Copper alloy sheet (c02) was produced.
- the obtained test body c02 is different from the above-mentioned Example 1 in the presence or absence of slow cooling to 350 ° C. after hot rolling and the presence or absence of intermediate annealing before solution treatment and cold rolling with respect to production conditions.
- the area ratio of the (111) plane facing to was high, and the result was not satisfied with the Young's modulus and bending deflection coefficient.
- Comparative Example 103 Condition of JP-A-2006-152392 The alloy having the composition of the above-mentioned invention example 1-1 is melted under charcoal covering in the atmosphere in a krypton furnace and cast in a cast iron book mold. Thus, an ingot having a thickness of 50 mm, a width of 75 mm and a length of 180 mm was obtained. Then, after the surface of the ingot was chamfered, it was hot rolled at a temperature of 950 ° C. to a thickness of 15 mm, and quenched into water from a temperature of 750 ° C. or more. Next, after removing the oxide scale, cold rolling was performed to obtain a plate having a predetermined thickness.
- the obtained test body c03 is different from the above-mentioned Example 1 in the presence or absence of slow cooling to 350 ° C. after hot rolling and the presence or absence of intermediate annealing before solution treatment and cold rolling with respect to production conditions.
- the area ratio of the (111) plane facing to was high, and the result was not satisfied with the Young's modulus and bending deflection coefficient.
- Comparative Example 104 Condition of JP-A-2008-223136 The copper alloy shown in Example 1 was melted and cast using a vertical continuous casting machine. A sample of 50 mm in thickness was cut out from the obtained slab (180 mm in thickness), heated to 950 ° C., extracted, and hot rolling was started. At this time, a pass schedule was set so that the rolling reduction in a temperature range of 950 to 700 ° C. would be 60% or more and rolling could be performed in a temperature range of less than 700 ° C. The final pass temperature for hot rolling is between 600 and 400 ° C. The total hot-rolling rate from the slab is about 90%. After hot rolling, the surface oxide layer was removed by mechanical polishing (face grinding).
- the aging treatment temperature was set to 450 ° C., and the aging time was adjusted to a time at which the hardness peaked at 450 ° C. aging depending on the alloy composition.
- the optimum solution treatment conditions and aging treatment time are grasped by preliminary experiments according to such alloy composition.
- finish cold rolling was performed at a rolling ratio.
- the final cold-rolled product was further subjected to low-temperature annealing for 5 minutes in a 400 ° C. furnace.
- the test material c04 was obtained.
- the main production conditions are described below.
- the obtained test body c04 is different from the above-mentioned Example 1 in the presence or absence of slow cooling up to 350 ° C. after hot rolling and the presence or absence of intermediate annealing before solution treatment and cold rolling with respect to production conditions.
- the area ratio of the (111) plane facing to was high, and the result was not satisfied with the Young's modulus and bending deflection coefficient.
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Abstract
Description
(1)NiとCoのどちらか一方または両方の合計で0.5~5.0質量%、Siを0.2~1.5質量%含有し、残部がCuおよび不可避不純物からなる合金組成を有してなり、圧延方向の0.2%耐力が500MPa以上、導電率が30%IACS以上、ヤング率が110GPa以下、曲げたわみ係数が105GPa以下であることを特徴とする電気・電子部品用銅合金板材。
(2)前記銅合金板材のEBSDを用いて解析することによって得られる圧延方向に向く(100)面の面積率が30%以上であることを特徴とする(1)に記載の電気・電子部品用銅合金板材。
(3)前記銅合金板材のEBSDを用いて解析することによって得られる圧延方向に向く(111)面の面積率が15%以下であることを特徴とする(1)又は(2)に記載の電気・電子部品用銅合金板材。
(4)さらに、Crを0.05~0.5質量%含有することを特徴とする(1)~(3)のいずれかに記載の電気・電子部品用銅合金板材。
(5)さらに、Zn、Sn、Mg、Ag、MnおよびZrからなる群から選ばれる1種または2種以上を合計で0.01~1.0質量%含有することを特徴とする(1)~(4)のいずれかに記載の電気・電子部品用銅合金板材。
(6)コネクタ用材料であることを特徴とする(1)~(5)のいずれか1項に記載の電気・電子部品用銅合金板材。
(7)(1)~(6)のいずれか1項に記載の電気・電子部品用銅合金板材からなるコネクタ。
(8)(1)~(7)のいずれか1項に記載の電気・電子部品用銅合金板材を製造する方法であって、前記合金組成を与える銅合金に、鋳造、熱間圧延、冷間圧延1、中間焼鈍、冷間圧延2、溶体化熱処理、時効熱処理、仕上げ冷間圧延、低温焼鈍の各工程をこの順に施し、さらに、下記[1]と[2]の少なくともいずれか一方または両方の処理を行うことを特徴とする電気・電子部品用銅合金板材の製造方法。
[1]上記熱間圧延後に350℃までは徐冷する工程
[2]前記中間焼鈍と冷間圧延2とを2回以上繰り返して行う工程
なお、本発明の銅合金板材は、その特性を圧延板の所定の方向における原子面の集積率で規定するものであるが、これは銅合金板材として本発明のような特性を有していれば良いのであって、銅合金板材の形状は板材や条材に限定されるものではなく、本発明では、管材も板材として解釈して取り扱うことができるものとする。
上記の、低ヤング率および低曲げたわみ係数を有するコルソン系などの析出型銅合金材料である本発明の銅合金材料(代表的な形状としては、板材)について、まずその合金組成を、次いでその組織を説明する。
高強度を有するための前提となる、本発明の銅合金材料における化学成分組成の限定理由を説明する(ここで記載する含有量「%」は全て「質量%」である)。
Niは後述するSiと共に含有されて、時効処理で析出したNi2Si相を形成して、銅合金材料の強度の向上に寄与する元素である。Niの含有量が少なすぎる場合は、前記Ni2Si相が不足し、銅合金材料の引張強さを高めることができない。一方、Niの含有量が多すぎると、導電率が低下する。また、熱間圧延加工性が悪化する。したがって、Ni含有量は0.5~5.0%の範囲とし、好ましくは1.5~4.0%である。
CoはSiと共に含有されて、時効処理で析出したCo2Si相を形成して、銅合金材料の強度の向上に寄与する元素である。導電性を高めたい場合は、Niを含まずCoを単独で含有させることが好ましい。Coの含有量が少なすぎる場合は、前記Co2Si相が不足し、銅合金材料の引張強さを高めることができない。一方、Coの含有量が多すぎると、導電率が低下する。また、熱間圧延加工性が悪化する。したがって、Co含有量は0.5~5.0%の範囲とし、好ましくは0.8~3.0%、さらに好ましくは1.1~1.7%である。
Siは前記Ni、Coと共に含有されて、時効処理で析出したNi2SiまたはCo2Si相を形成して、銅合金材料の強度の向上に寄与する。Siの含有量は、0.2~1.5%とし、好ましくは0.2~1.0%である。Siの含有量は化学量論比でNi/Si=4.2、Co/Si=4.2とするのが最も導電率と強度のバランスがよい。そのためSiの含有量は、Ni/Si、Co/Si、(Ni+Co)/Siが3.2~5.2の範囲となるようにするのが好ましく、より好ましくは3.5~4.8である。
上記組成に加えて、Crを0.05~0.5質量%含有してもよい。Crは合金中の結晶粒を微細化する効果があり、銅合金材料の強度や曲げ加工性の向上に寄与する。少なすぎるとその効果が小さく、多すぎると鋳造時に晶出物を形成し時効強度が低下する。
本発明の銅合金材料は、上記基本組成の他に添加元素として、質量%で、Sn:0.01~1.0%、Zn:0.01~1.0%、Ag:0.01~1.0%、Mn:0.01~1.0%、Zr:0.1~1.0%、Mg:0.01~1.0%の一種または二種以上を合計で0.01~1.0%の量で、必要に応じて含有することができる。これらの元素は、いずれも本発明の銅合金材料が奏しようとする高い強度や導電率あるいは低いヤング率のいずれかを向上させる共通の効果があるか、これに加えてあるいはこれに代えて、さらに他の性質(耐応力緩和特性など)を向上させる元素である。以下に、各元素の特徴的な作用効果と含有範囲の意義を記載する。
Snは主に銅合金材料の強度を向上させる元素であり、これらの特性を重視する用途に使用する場合には、選択的に含有させる。Snの含有量が少なすぎるとその強度向上効果が小さい。一方、Snを含有させると銅合金材料の導電率が低下する。特に、Snが多すぎると、銅合金材料の導電率を30%IACS以上とすることが難しくなる。したがって、含有させる場合には、Snの含有量を0.01~1.0%の範囲とする。
Zn添加により、半田の耐熱剥離性や耐マイグレーション性を向上させることができる。Znの含有量が少なすぎるとその効果が小さい。一方、Znを含有させると銅合金材料の導電率が低下し、Znが多すぎると、銅合金材料の導電率を30%IACS以上とすることが難しくなる。したがって、Znの含有量を0.01~1.0%の範囲とする。
Agは強度の上昇に寄与する。Agの含有量が少なすぎるとその効果が小さい。一方、Agを多く含有させても、強度上昇効果が飽和するだけである。したがって、含有させる場合には、Agの含有量を0.01~1.0%の範囲とする。
Mnは主に熱間圧延での加工性を向上させる。Mnの含有量が少なすぎるとその効果が小さい。一方、Mnが多すぎると、銅合金の造塊時の湯流れ性が悪化して造塊歩留まりが低下する。したがって、含有させる場合には、Mnの含有量を0.01~1.0%の範囲とする。
Zrは主に結晶粒を微細化させて、銅合金材料の強度や曲げ加工性を向上させる。Zrの含有量が少なすぎるとその効果が小さい。一方、Zrが多すぎると、化合物を形成し、銅合金材料の圧延などの加工性が低下する。したがって、含有させる場合には、Zrの含有量を0.01~1.0%の範囲とする。
Mgは耐応力緩和特性を向上させる。したがって、耐応力緩和特性が必要な場合には、0.01~1.0%の範囲で選択的に含有させる。少なすぎると、添加した効果が小さく、多すぎると導電率が低下する。したがって、含有させる場合には、Mgの含有量を0.01~1.0%の範囲とする。
なお、Mg、Sn、Znは、Cu-Ni-Si系、Cu-Ni-Co-Si系、Cu-Co-Si系銅合金に添加することで、いずれも耐応力緩和特性が向上する。それぞれを単独で添加した場合よりも併せて添加した場合に相乗効果によってさらに耐応力緩和特性が向上する。また、半田脆化を著しく改善する効果がある。
また、本発明の銅合金材料で実現される圧延方向の0.2%耐力として好ましい範囲は500MPa以上であり、650MPa以上であることが好ましく、更に好ましい範囲は800MPa以上である。上限は特にないが1100MPa以下であることが実際的である。
曲げたわみ係数は、105GPa以下であることが好ましく、100GPa以下であることがより好ましい。下限は特にないが60GPa以上であることが実際的である。
ヤング率は110GPa以下であり、100GPa以下であることがより好ましい。下限は特にないが70GPa以上であることが実際的である。
本発明の銅合金材料の集合組織は、特に、低ヤング率および低曲げたわみ係数を実現するために、SEM-EBSD法による圧延方向(RD)からの解析結果で、RDに向く(100)面の面積率が30%以上である集合組織を有するものとすることが好ましい。なお、板材圧延方向(RD)と当該面の法線とのなす角の角度が10°以下の方位を有する結晶粒はすべて当該RDに向く(100)面を有するものとする。
Cube方位 {001}<100>
Rotated-Cube方位 {012}<100>
Goss方位 {011}<100>
Rotated-Goss方位 {011}<011>
Brass方位 {011}<211>
Copper方位 {112}<111>
S方位 {123}<634>
P方位 {011}<111>
すなわち、本発明において、圧延板の圧延方向(RD)に向く原子面の集積に関し、(100)面の法線とRDのなす角の角度が10°以下である原子面を有する領域とは、圧延板の圧延方向(RD)に向く、つまりRDに対向する原子面の集積に関して、理想方位である圧延板の圧延方向(RD)を法線とする(100)面自体と、(100)面の法線とRDのなす角の角度が10°以下である原子面の各々とを合わせた領域(これらの面積の和)をいう。以下、これらの面を合わせて、RDに向く(100)面ともいい、また、これらの領域を、単に、RDに(100)面が向く原子面の領域ともいう。また、RDに向く(111)面についても同様である。
ここで、EBSD測定の特徴について、X線回折測定との対比として説明する。まず1点目に挙げられるのは、X線回折測定によったのでは測定することができない結晶方位があり、それがS方位及びBR方位である。換言すれば、EBSDを採用することにより、初めて、S方位及びBR方位に関する情報が得られ、それにより特定される合金組織と作用との関係が明らかになる。2点目は、X線回折はND//{hkl}の±0.5°程度に含まれる結晶方位の分量を測定している。一方、EBSDは当該方位から±10°に含まれる結晶方位の分量を測定している。したがって、EBSD測定によれば桁違いに広範な合金組織に関する情報が網羅的に得られ、合金材料全体としてX線回折では特定することが難しい状態が明らかになる。以上のとおり、EBSD測定とX線回折測定とで得られる情報はその内容及び性質が異なる。なお、本明細書において特に断らない限り、EBSDの結果は、銅合金板材のND方向に対して行ったものである。
次に、本発明の銅合金材料の好ましい製造条件について以下に説明する。本発明の銅合金材料は、例えば、鋳造、熱間圧延、徐冷、冷間圧延1、中間焼鈍、冷間圧延2、溶体化熱処理、時効熱処理、仕上げ冷間圧延、低温焼鈍、の各工程を経て製造される。本発明の銅合金材料は、従来のコルソン系合金とほぼ同様の設備で製造できる。所定の物性とさらには集合組織を得るには、各工程の製造条件を適宜調整する必要がある。この点、本発明の銅合金材料は、熱間圧延後の処理か、溶体化処理前の冷間圧延と中間焼鈍の、少なくともいずれかの処理もしくは加工を所定の条件で行なうことで製造することができる。
銅合金板試料の組織について、RDに向く(100)面の面積率を次のように求めた。
すなわち、RD方向からEBSD解析したときの(100)面の法線がRDとなす角についてその角度が10°以下の結晶方位を有する結晶粒を、RDに向く(100)面を有する粒とした。前記RDに向く(100)面の面積率は、具体的には次のように求めた。EBSD法により、約800μm四方の試料測定領域で、スキャンステップが1μmの条件で測定を行った。測定面積は結晶粒を400個以上含むことを基準として調整した。上記の通り、板材試料の圧延方向(RD)とのなす角が10°以下となるような(100)面の法線を有する結晶粒の(100)面についてその面積の和を求めて、該面積の和を全測定面積で割ることでRDに向く(100)面の面積率(%)を得た。ここで、前記なす角が10°以下の結晶粒については同一方位粒とした。
また、RDに向く(111)面の面積率(%)についても同様に求めた。
(2)0.2%耐力
0.2%耐力は、各供試材からJIS Z 2201記載の5号試験片を切り出して、JIS Z 2241に準拠して求めた。0.2%耐力は5MPaの整数倍に丸めて示した。
(3)導電率
導電率はJIS H 0505に準拠して求めた。
(4)ヤング率
ヤング率は、幅20~30mmの短冊状試験片を用い、引張試験機にて0.2%耐力以下の強度領域のヤング率を、ひずみゲージを用いて測定した。なお、試験片は圧延方向に対して平行に採取した。
(5)曲げたわみ係数
曲げたわみ係数は、日本伸銅協会(JCBA)技術標準に準拠して測定した。試験片の幅は10mm、長さ15mmとし、片持ち梁の曲げ試験を行い、荷重とたわみ変位から、たわみ係数を測定した。
これらの結果を表1、2に示す。
以下の比較例は実施例2と同一の鋳塊を用いた例である。
・比較例2-2は、熱間圧延後ただちに水冷し、中間焼鈍と冷間圧延2を省略し、その他については実施例2と同様に作製した例であるが、RDに向く(100)面の面積率が低く、また(111)面の面積率が高く、ヤング率および曲げたわみ係数が本発明例よりも高くなった。
・比較例2-3は、熱間圧延後ただちに水冷すること以外は実施例2と同様に作製した例であるが、RDに向く(100)面の面積率が低く、ヤング率が本発明例よりも高くなった。
実施例10-3、18-3、25-3は、表1の実施例10、18、25とそれぞれ同一の鋳塊を用いて、中間焼鈍と冷間圧延2を2度繰り返し、その他については表1の各実施例と同様に作製し、同様に各特性を評価した例である。これらはRDに向く(100)面の面積率が特に高く、ヤング率が100GPa以下と特に低く、曲げたわみ係数が90GPaと特に低く、かつ、0.2%耐力と導電率が優れるものであった。
上記本発明例1-1と同様の金属元素を配合し、残部がCuと不可避不純物から成る合金を高周波溶解炉により溶解し、これを0.1~100℃/秒の冷却速度で鋳造して鋳塊を得た。これを900~1020℃で3分から10時間の保持後、熱間加工を行った後に水焼き入れを行い、酸化スケール除去のために面削を行った。この後の工程は、次に記載する工程A-3,B-3の処理を施すことによって銅合金c01を製造した。
製造工程には、1回または2回以上の溶体化熱処理を含み、ここでは、その中の最後の溶体化熱処理の前後で工程を分類し、中間溶体化までの工程でA-3工程とし、中間溶体化より後の工程でB-3工程とした。
工程B-3:断面減少率が50%以下の冷間加工を施し、400~700℃で5分~10時間の熱処理を施し、断面減少率が30%以下の冷間加工を施し、200~550℃で5秒~10時間の調質焼鈍を施す。
上記本発明例1-1の組成の銅合金を、電気炉により大気中にて木炭被覆下で溶解し、鋳造可否を判断した。溶製した鋳塊を熱間圧延し、厚さ15mmに仕上げた。つづいてこの熱間圧延材に対し、冷間圧延及び熱処理(冷間圧延1→溶体化連続焼鈍→冷間圧延2→時効処理→冷間圧延3→短時間焼鈍)を施し、所定の厚さの銅合金薄板(c02)を製造した。
上記本発明例1-1の組成をもつ合金について、クリプトル炉において大気中で木炭被覆下で溶解し、鋳鉄製ブックモールドに鋳造し、厚さが50mm、幅が75mm、長さが180mmの鋳塊を得た。そして、鋳塊の表面を面削した後、950℃の温度で厚さが15mmになるまで熱間圧延し、750℃以上の温度から水中に急冷した。次に、酸化スケールを除去した後、冷間圧延を行い、所定の厚さの板を得た。
溶体化処理温度: 900℃
人工時効硬化処理温度×時間: 450℃×4時間
板厚: 0.6mm
実施例1に示す銅合金を溶製し、縦型連続鋳造機を用いて鋳造した。得られた鋳片(厚さ180mm)から厚さ50mmの試料を切り出し、これを950℃に加熱したのち抽出して、熱間圧延を開始した。その際、950~700℃の温度域での圧延率が60%以上となり、かつ700℃未満の温度域でも圧延が行われるようにパススケジュールを設定した。熱間圧延の最終パス温度は600~400℃の間にある。鋳片からのトータルの熱間圧延率は約90%である。熱間圧延後、表層の酸化層を機械研磨により除去(面削)した。
700℃未満~400℃での熱間圧延率: 56%(1パス)
溶体化処理前 冷間圧延率: 92%
中間冷間圧延 冷間圧延率: 20%
仕上げ冷間圧延 冷間圧延率: 30%
100℃から700℃までの昇温時間: 10秒
Claims (9)
- NiとCoのどちらか一方または両方の合計で0.5~5.0質量%、Siを0.2~1.5質量%含有し、残部がCuおよび不可避不純物からなる合金組成を有してなり、圧延方向の0.2%耐力が500MPa以上、導電率が30%IACS以上、ヤング率が110GPa以下、曲げたわみ係数が105GPa以下であることを特徴とする電気・電子部品用銅合金板材。
- 前記銅合金板材のEBSDを用いて解析することによって得られる圧延方向に向く(100)面の面積率が30%以上であることを特徴とする請求項1に記載の電気・電子部品用銅合金板材。
- 前記銅合金板材のEBSDを用いて解析することによって得られる圧延方向に向く(111)面の面積率が15%以下であることを特徴とする請求項1又は2に記載の電気・電子部品用銅合金板材。
- さらに、Crを0.05~0.5質量%含有することを特徴とする請求項1~3のいずれかに記載の電気・電子部品用銅合金板材。
- さらに、Zn、Sn、Mg、Ag、MnおよびZrからなる群から選ばれる1種または2種以上を合計で0.01~1.0質量%含有することを特徴とする請求項1~4のいずれか1項に記載の電気・電子部品用銅合金板材。
- 前記銅合金板材のEBSDを用いて解析することによって得られる圧延方向に向く(111)面の面積率が15%以下であることを特徴とする請求項1~5のいずれか1項に記載の電気・電子部品用銅合金板材。
- コネクタ用材料であることを特徴とする請求項1~6のいずれか1項に記載の電気・電
子部品用銅合金板材。 - 請求項1~6のいずれか1項に記載の電気・電子部品用銅合金板材からなるコネクタ。
- 請求項1~6のいずれか1項に記載の電気・電子部品用銅合金板材を製造する方法であって、前記合金組成を与える銅合金に、鋳造、熱間圧延、冷間圧延1、中間焼鈍、冷間圧延2、溶体化熱処理、時効熱処理、仕上げ冷間圧延、低温焼鈍の各工程をこの順に施し、さらに、下記[1]と[2]の少なくともいずれか一方または両方の処理を行うことを特
徴とする電気・電子部品用銅合金板材の製造方法。
[1]上記熱間圧延後に350℃までは徐冷する工程
[2]前記中間焼鈍と冷間圧延2とを2回以上繰り返して行う工程
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2010
- 2010-12-01 JP JP2011513179A patent/JP4809935B2/ja active Active
- 2010-12-01 EP EP10834584.4A patent/EP2508634B1/en not_active Not-in-force
- 2010-12-01 KR KR1020127013066A patent/KR20120104553A/ko active Search and Examination
- 2010-12-01 WO PCT/JP2010/071517 patent/WO2011068134A1/ja active Application Filing
- 2010-12-01 CN CN201080053121.2A patent/CN102630251B/zh active Active
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2012
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Also Published As
Publication number | Publication date |
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US20120241056A1 (en) | 2012-09-27 |
CN102630251B (zh) | 2017-03-15 |
JP4809935B2 (ja) | 2011-11-09 |
CN102630251A (zh) | 2012-08-08 |
EP2508634B1 (en) | 2017-08-23 |
EP2508634A1 (en) | 2012-10-10 |
EP2508634A4 (en) | 2016-01-06 |
KR20120104553A (ko) | 2012-09-21 |
JPWO2011068134A1 (ja) | 2013-04-18 |
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