EP2221391A1 - Kupferlegierungsblechmaterial - Google Patents
Kupferlegierungsblechmaterial Download PDFInfo
- Publication number
- EP2221391A1 EP2221391A1 EP08847798A EP08847798A EP2221391A1 EP 2221391 A1 EP2221391 A1 EP 2221391A1 EP 08847798 A EP08847798 A EP 08847798A EP 08847798 A EP08847798 A EP 08847798A EP 2221391 A1 EP2221391 A1 EP 2221391A1
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- EP
- European Patent Office
- Prior art keywords
- mass
- sheet material
- copper alloy
- alloy sheet
- particles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000463 material Substances 0.000 title claims abstract description 64
- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 35
- 238000005452 bending Methods 0.000 claims abstract description 36
- 239000000956 alloy Substances 0.000 claims abstract description 19
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 17
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 17
- 239000010949 copper Substances 0.000 claims abstract description 16
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 15
- 239000012535 impurity Substances 0.000 claims abstract description 11
- 229910052718 tin Inorganic materials 0.000 claims abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 6
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 6
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 5
- 229910052709 silver Inorganic materials 0.000 claims abstract description 5
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 5
- 239000002245 particle Substances 0.000 claims description 64
- 239000000203 mixture Substances 0.000 claims description 12
- 239000000470 constituent Substances 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 6
- 239000010936 titanium Substances 0.000 abstract description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract 2
- 239000011651 chromium Substances 0.000 abstract 2
- 239000011777 magnesium Substances 0.000 abstract 2
- 239000011572 manganese Substances 0.000 abstract 2
- 239000010703 silicon Substances 0.000 abstract 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract 1
- 229910017052 cobalt Inorganic materials 0.000 abstract 1
- 239000010941 cobalt Substances 0.000 abstract 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract 1
- 239000011574 phosphorus Substances 0.000 abstract 1
- 239000004332 silver Substances 0.000 abstract 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 43
- 238000000034 method Methods 0.000 description 30
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- 150000001875 compounds Chemical class 0.000 description 5
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- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 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 4
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 4
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 4
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- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 3
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 3
- 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 3
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 3
- 238000011835 investigation Methods 0.000 description 3
- 238000000691 measurement method Methods 0.000 description 3
- 229910001369 Brass Inorganic materials 0.000 description 2
- 229910017876 Cu—Ni—Si Inorganic materials 0.000 description 2
- 239000010951 brass Substances 0.000 description 2
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- 230000008018 melting Effects 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- IHCCLXNEEPMSIO-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 IHCCLXNEEPMSIO-UHFFFAOYSA-N 0.000 description 1
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- 229910018098 Ni-Si Inorganic materials 0.000 description 1
- 229910018529 Ni—Si Inorganic materials 0.000 description 1
- FHKPLLOSJHHKNU-INIZCTEOSA-N [(3S)-3-[8-(1-ethyl-5-methylpyrazol-4-yl)-9-methylpurin-6-yl]oxypyrrolidin-1-yl]-(oxan-4-yl)methanone Chemical compound C(C)N1N=CC(=C1C)C=1N(C2=NC=NC(=C2N=1)O[C@@H]1CN(CC1)C(=O)C1CCOCC1)C FHKPLLOSJHHKNU-INIZCTEOSA-N 0.000 description 1
- JAWMENYCRQKKJY-UHFFFAOYSA-N [3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-ylmethyl)-1-oxa-2,8-diazaspiro[4.5]dec-2-en-8-yl]-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]methanone Chemical compound N1N=NC=2CN(CCC=21)CC1=NOC2(C1)CCN(CC2)C(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F JAWMENYCRQKKJY-UHFFFAOYSA-N 0.000 description 1
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- 238000007796 conventional method Methods 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
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- 230000008023 solidification Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Images
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
- C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/04—Alloys based on copper with zinc as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
-
- 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
-
- 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
Definitions
- the present invention relates to a copper alloy sheet material.
- Characteristics that are required for copper alloy sheet material that is used for electrical / electronic equipment include for example, constant electrical conductivity, constant tensile strength, constant bending workability, and constant stress relaxation resistance.
- electrical conductivity constant electrical conductivity
- constant tensile strength constant tensile strength
- constant bending workability constant stress relaxation resistance
- Cu-Ni-Si system alloys that are strengthened by precipitating microscopic Ni and Si compounds into Cu (for example, CDA70250, which is a registered alloy of the CDA (Copper Development Association); refer to patent documents 1 and 2) are increasingly being used in the market.
- solution heat treatment is employed as an intermediate process for solidifying the solution of solute atoms.
- the temperature of this process differs depending on the alloy system and the solute concentration, however, is a high temperature of about 750 °C. Since the temperature of this solution heat treatment is a high temperature, there is a problem in that the grain size of the material becomes coarse. When the grain size is coarse, problems occur such as cracking due to the promotion of localized deformation during bending, concentration of electric current when bent sections are used as contacts due to large creases on the surface of the bent sections, or cracking of plating that is coated on the surface of the material.
- the inventors performed research of copper alloys suitable for use in electrical / electronic equipment, and by focusing their attention on methods of dispersing second-phase particles in order to greatly improve the bending workability and strength of Cu-Ni-Si series copper alloys, developed the present invention after much dedicated study.
- the inventors found the best modes of the present invention by discovering added elements that function to improve the strength and stress relaxation resistance characteristics without impairing electrical conductivity.
- the second-phase particles referred to here are precipitates and crystallized matter.
- the tensile strength of the copper alloy sheet material of the present invention is 730 to 820 MPa. More preferably, it is 740 to 800 MPa.
- the bending workability is such that under rigid conditions such as when the product of the material sheet width W (mm) and the material sheet thickness T (mm) is 0.16 (mm 2 ) or less, 180° tight bending is possible. It is preferred that this product of width W and thickness T be 0.14 or less.
- the minimum value of this product of width W and thickness T is not especially limited, however is normally 0.01 or greater.
- an electrical conductivity of 30% IACS is preferred, and it is also preferred for the stress relaxation resistance that when the material is maintained for 3000 hours or more at 165 °C, the stress relaxation rate be 30% or less.
- Suitable dispersion of second-phase particles is effective against grain coarsening during solutionization that causes bending workability to worsen. This is because it is considered that when grain is grown, a gain in energy occurs at the interface between the dispersed particles and grain boundary when the grain boundary passes the second-phase particles and suppresses grain boundary migration.
- the obtained grain size is preferably 10 ⁇ m or less, and more preferably 8 ⁇ m or less, and yet even more preferably 6 ⁇ m or less.
- the minimum value of grain size is not particularly limited, however, normally is 2 ⁇ m or more.
- the grain size is measured according to the Japanese Industrial Standard JIS H 0501 (cutting method).
- the second-phase particles that exist on the grain boundary should exist at a density of 10 4 to 10 8 particles/mm 2 . In this case, it is further preferred that the density be 5 x 10 5 to 5 x 10 7 particles/mm 2 .
- the value of the ratio r/f of the particle size r (unit: ⁇ m) of all of the second-phase particles inside the grain and on the grain boundary and the volume fraction f of the particles should be 1 to 100.
- the particle size r of the second-phase particles is the arithmetic mean value of the particle size of all of the measured particles.
- the notation f 0.005 for the volume fraction f indicates 0.5 vol%.
- the stress relaxation phenomenon is considered to be caused by dislocations inside the grain moving to the grain boundary, or by grain boundary slippage occurring in part of the grain boundary, with the strain inside the elastic limit changing to permanent strain.
- the particles existing inside the grain function to suppress moving of dislocations, and the particles existing at the grain boundary suppress slipping movement of the grain boundary.
- the percentage of particles that include Cr as a constituent element be 50% or greater. This is because when Cr is included, the particles can exist as stable compounds without entering the solid solution of Cu even at high temperature. This contributes to a higher density of second-phase particles and increases the effect of suppressing the growth of grain. It is even more preferable that this percentage be 70% or greater. The maximum value of this percentage is not particularly limited, however normally is 90% or less.
- the contained amount of Ni be 1.8 to 3.3 mass%, and more preferably 2.0 to 3.0 mass%
- the contained amount of Si be 0.4 to 1.1 mass%, and more preferably 0.5 to 1.0 mass%. Too large of an amount of these elements leads to a drop in electrical conductivity, and causes cracking at the grain boundary by the precipitation at the grain boundary during bending. However, too small of an amount of these elements leads to the insufficient strength.
- Cr precipitates as the second-phase particle with Ni or Si, and is effective in controlling the grain size. Furthermore, Cr per se performs precipitation hardening. It is preferred that the contained amount of Cr be 0.01 to 0.5 mass%, and more preferably 0.03 to 0.4 mass%. When the amount is too small, the effect is not obtained, and when the amount is to large, adverse effects occur in that the Cr crystallizes out as coarse crystallized matter during solidification, which causes the plating characteristics to worsen, and promotes starting points for cracking as well as the propagation of cracking during plastic working.
- At least one kind of element that is selected from among (1) at least one of Sn, Mg, Ag, Mn, Ti, Fe and P for a total of 0.01 to 1 mass%, (2) Zn at 0.01 to 10 mass %, and (3) Co at 0.01 to 1.5 mass% can be added in order to improve the alloy characteristics.
- These elements improve the strength and the stress relaxation resistance characteristic, and especially Sn and Mg are very effective for that.
- Zn and Sn function to improve solder joinability
- Co functions to improve electrical conductivity
- Mn functions to improve hot workability.
- the stress relaxation rate be 30% or less when the material is kept at 165 °C for 3000 hours, and more preferably 25% or less.
- the copper alloy sheet material of the present invention can, for example, be manufactured by a method comprising the steps of casting, (homogenization) heat treatment, hot working (for example, hot rolling) and cold working (for example, cold rolling) (1), solution heat treatment, cold working (for example, cold rolling) (2), (aging precipitation) heat treatment, cold working (for example cold rolling) (3) and (strain relief) annealing.
- rapid cooling and facing be performed after heat treatment and before cold working (1).
- the copper alloy material is prepared by combining all of the elements so that the specified alloy constituent composition is achieved, with the remaining part being Cu and inevitable impurities, and this is melted using a high-frequency melting furnace.
- Casting is performed at a preferable cooling rate of 0.1 to 100 °C/sec (more preferably, 0.5 to 50 °C/sec) to obtain an ingot.
- Heat treatment is performed by preferably maintaining the ingot at 900 to 1050 °C for 0.5 to 10 hours (more preferably, for 0.8 to 8 hours).
- Hot working is preferably performed at a reduction percentage (rolling reduction) of 50% or greater (more preferably, 60 to 98%), and a processing temperature of 600 °C or greater (more preferably, 620 to 1000 °C) to form a sheet.
- Rapid cooling for example, water cooling
- This hot rolled sheet can be faced according to a conventional method.
- Cold working (cold rolling) (1) is preferably performed with a reduction percentage of 90% or greater (more preferably, 92 to 99%).
- Solution heat treatment is preferably performed by maintaining the material at 720 to 860 °C for 3 sec to 2 hours (more preferably 5 sec to 0.5 hours).
- treatment be performed within a range of rising temperature from 400 °C to 700 °C and a rate of temperature increase of 0.1 °C/sec to 200 °C/sec (more preferably, 0.5 to 100 °C/sec).
- Cold working (cold rolling) (2) is preferably performed with a reduction percentage of 5 to 50% (more preferably, 7 to 45%).
- Aging precipitation heat treatment is preferably performed by maintaining the material at 400 °C to 540 °C for 5 min to 10 hours (more preferably, at 410 to 520 °C for 10 min to 8 hours).
- Cold working (cold rolling) (3) is preferably performed with a reduction percentage of 10% or less (meaning greater than 0% but not exceeding 10%).
- Strain relief annealing is preferably performed by maintaining the material at 200 °C to 600 °C for 15 sec to 10 hours (more preferably, 250 to 570 °C for 20 sec to 8 hours). When there is sufficient strength after aging precipitation heat treatment, cold working (3) and strain relief annealing do not need to be performed after that and can be omitted.
- the specified preferred metallic structure for the copper alloy sheet material of the present invention can be obtained.
- the casting speed cooling speed during casting
- the temperature range and time during which the material is maintained at that temperature during hot rolling it is possible to suppress coarse precipitation during hot rolling, and suitable precipitation can be performed in a later process.
- the second-phase particles that suppress coarsening of the grain mainly precipitate out during the temperature rise of the solution heat treatment, however, in order to effectively induce that precipitation, it is preferred that processing be performed such that both the processing rate of the cold working (1) process, which is the process prior to the solution heat treatment process, and the rate of temperature rise during the solution heat treatment be within the aforementioned preferred conditions. Furthermore, by employing the cold working (2) process before the aging precipitation heat treatment process, it is possible to induce higher density of microscopic precipitate that contributes to precipitation hardening, and suppress the coarsening of second-phase particles that remain at the time of solutionization during aging precipitation heat treatment.
- the copper alloy sheet material of the present invention has excellent strength and bending workability, and is suitable for use in electrical / electronic equipment.
- the preferred copper alloy sheet material of this present invention also has excellent electrical conductivity and stress relaxation resistance.
- the copper alloy sheet of the present invention can also be suitably used in lead frames, connectors, and terminals of electrical / electronic equipment, and is particularly suitable for use in connectors, terminals, relays, switches and sockets that are used in automobiles.
- by having increased strength makes it possible to make the copper alloy material thinner, thus contributing to a reduction in the amount of global resources used.
- Solution heat treatment was performed such that the rate of temperature rise during a temperature rise at 400 °C to 700 °C was in the range of 0.1 °C/sec to 200 °C/sec.
- cold working (2) was performed at a reduction percentage of 5 to 50%
- aging precipitation heat treatment was performed by maintaining the material at 400 °C to 540 °C for 5 min to 10 hours
- cold working (3) was performed at a reduction percentage of 10% or less
- strain relief annealing was performed by maintaining the material at 200 °C to 600 °C for 15 sec to 10 hours to obtain material to be used as test material.
- the cold working (3) and strain relief annealing after that aging precipitation heat treatment were not performed.
- the electrical conductivity was calculated by using the four-terminal method to measure the specific resistance of the material in an isothermal bath that was maintained at 20 °C ( ⁇ 0.5 °C). The spacing between terminals was 100 mm.
- Bending work was performed according to JIS Z2248. After preliminary bending was performed using a 0.4 mm R 90° bending die, tight bending was performed using a compression testing machine. The bending location was observed by using a 50x optical microscope to visually inspect whether or not there was cracking on the outside of the bent section.
- the sheet width W and sheet thickness T conditions of the test piece are indicated in mm.
- GW (Good way) indicates testing in the case where the bending axis is perpendicular to the rolling direction
- BW (Bad way) indicates testing in the case where the bending axis is parallel to the rolling direction.
- the observation results are indicated as “O (Good)” when no cracking occurred, and as “X (Bad)” when cracking occurred.
- Observation test pieces were formed by punching the test material into 3 mm diameter pieces, and polishing the pieces to a thin film by using a twin-jet polishing method. Using a transmission electron microscope having an accelerating voltage of 300 kV, 5000x photographs were taken arbitrarily every ten fields of view, and the particle size r ( ⁇ m) and distribution density ⁇ (particles/mm 2 ) were measured on the photographs.
- the particle size r of the second-phase particles was found by first, finding the particle size of each particle, then, for all of the measured particles, finding the calculated average value of the particle sizes of all of the particles.
- the particle size of each particle was taken to be the calculated average value of the long diameter and short diameter of the particle.
- the thickness of an observed test piece was measured from the thickness contours, and of the total volume of an observed field of view, the percentage of the volume occupied by the second-phase particles was taken to be the volume fraction f.
- the stress relaxation resistance was measured according to the Japan Electronics and Information Technology Industries Association standards EMAS-3003 under conditions of 165 °C for 3000 hours.
- FIG. 1 is a drawing explaining the method for testing the stress relaxation, where (a) of FIG. 1 shows the state before heat treatment, and (b) of FIG. 1 shows the state after heat treatment.
- the stress relaxation rate (%) was calculated as (H t - H 1 )/ ⁇ 0 ⁇ 100.
- the average grain size was measured according to JIS H 0501 (cutting method). Measurement was performed for a cross-section that is parallel to the rolling direction, and a cross-section that is perpendicular to the rolling direction, and the average of both was taken. Observation of the metallic structure was done by chemically edging a mirror polished material surface and performing SEM reflection electron imaging.
- invention examples 1-1 to 1-8 have excellent strength, electrical conductivity, bending workability and stress relaxation resistance characteristics. However, when some of the elements of the present invention are not satisfied, some characteristics may become inferior.
- comparative examples 1-1 to 1-4 are all examples in which the bending workability is inferior. In comparative examples 1-1, 1-2 and 1-4, the density of precipitate on the grain boundary is low, and the grain size becomes coarse. Moreover, in comparative example 1-3, the density of precipitate on the grain boundary is high, and it was observed that cracking occurred at the grain boundary.
- examples 1 The same investigation as was performed for examples 1 was performed for a copper alloy comprising the composition shown in Table 2 with the remaining part being Cu and inevitable impurities.
- the manufacturing method and measurement method were the same as for examples 1.
- the comparative examples given below that are presented with the examples were made outside the range of these manufacturing conditions in order to be separated from the range of examples of the present invention. Details of the comparative examples are given below.
- invention examples 2-1 to 2-8 have excellent strength, electrical conductivity, bending workability and stress relaxation resistance characteristics. However, when some of the elements of the present invention are not satisfied, some characteristics may become inferior.
- comparative example 2-1 is an example in which the tensile strength became inferior. In this comparative example 2-1, the solutionization temperature was lowered and grain size was made small, however, precipitation hardening was thought to be insufficient and there was not enough strength.
- Comparative examples 2-2 and 2-4 are examples in which the bending workability became inferior. In these comparative examples 2-2 and 2-4, it was found that the precipitation fraction was small, so the r/f value became large and the grain size became coarse.
- Comparative example 2-3 is an example in which bending workability was inferior. In this comparative example 2-3, it was found that the size of the second-phase particles was small, so the r/f value became small, and because the grain could not be effectively controlled, the grain size became coarse.
- invention examples 3-1 to 3-4 in which the contained amounts of Ni and Si are especially within the preferred range, have excellent strength, electrical conductivity, bending workability, and stress relaxation resistance characteristics. However, when the added amounts of Ni and Si are not especially within the preferred range, some characteristics may become inferior.
- comparative example 3-1 is an example in which the amounts of Ni and Si were inadequate, so there was insufficient strength.
- Comparative example 3-2 is an example in which the amounts of Ni and Si were large, so precipitation occurred at the grain boundary, causing the bending workability to become somewhat inferior.
- Ni and Si are not necessary for the contained amounts of Ni and Si to be especially within the preferred range, however, when outside this range, examples are seen in which characteristics become inferior, so it is preferred that when possible, the amount of Ni be within the range 1.8 to 3.3 mass%, and that the amount of Si be within the range 0.4 to 1.1 mass%.
- invention examples 4-1 to 4-4 in which the contained amounts of other added elements (secondary added elements) other than Ni and Si were especially within the preferred range, have excellent electrical conductivity, bending workability and stress relaxation resistance characteristics.
- the contained amounts of those other added elements are not especially within the preferred range, some of the characteristics may become inferior.
- comparative example 4-1 is an example in which the bending workability became inferior.
- Comparative example 4-2 is an example in which the mechanical strength became inferior.
- the copper alloy sheet material of the present invention can be suitably applied for use in lead frames, connectors and terminal materials for electrical / electronic equipment, for example, connectors, terminal materials, relays, switches and sockets for use in automobiles.
Applications Claiming Priority (2)
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JP2007287066 | 2007-11-05 | ||
PCT/JP2008/070139 WO2009060873A1 (ja) | 2007-11-05 | 2008-11-05 | 銅合金板材 |
Publications (3)
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EP2221391A1 true EP2221391A1 (de) | 2010-08-25 |
EP2221391A4 EP2221391A4 (de) | 2012-06-27 |
EP2221391B1 EP2221391B1 (de) | 2014-04-30 |
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EP08847798.9A Not-in-force EP2221391B1 (de) | 2007-11-05 | 2008-11-05 | Kupferlegierungsblech |
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US (1) | US20110038753A1 (de) |
EP (1) | EP2221391B1 (de) |
JP (1) | JP4785092B2 (de) |
KR (1) | KR101515668B1 (de) |
CN (1) | CN101849027B (de) |
WO (1) | WO2009060873A1 (de) |
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JP5690169B2 (ja) * | 2011-02-25 | 2015-03-25 | 株式会社神戸製鋼所 | 銅合金 |
JP5690170B2 (ja) * | 2011-02-25 | 2015-03-25 | 株式会社神戸製鋼所 | 銅合金 |
JP6154997B2 (ja) * | 2012-07-13 | 2017-06-28 | 古河電気工業株式会社 | 強度およびめっき性に優れる銅合金材およびその製造方法 |
JP6154996B2 (ja) * | 2012-07-13 | 2017-06-28 | 古河電気工業株式会社 | 高強度銅合金材およびその製造方法 |
CN103643079B (zh) * | 2013-11-29 | 2016-05-11 | 国网河南省电力公司平顶山供电公司 | 一种大功率发电机转子槽楔用合金及其生产工艺 |
CN104561643A (zh) * | 2014-12-25 | 2015-04-29 | 春焱电子科技(苏州)有限公司 | 一种电子材料用微合金 |
CN108823466B (zh) * | 2018-06-14 | 2020-10-13 | 北京科技大学 | 一种多元复合析出强化型高强高导铜合金及其制备方法 |
US20210130931A1 (en) * | 2018-07-12 | 2021-05-06 | Materion Corporation | Copper-nickel-silicon alloys with high strength and high electrical conductivity |
CN109112351B (zh) * | 2018-08-27 | 2020-12-11 | 山东光韵智能科技有限公司 | 一种高弹性模量的黄铜合金材料及其制备方法 |
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EP0949343A1 (de) * | 1998-03-26 | 1999-10-13 | KABUSHIKI KAISHA KOBE SEIKO SHO also known as Kobe Steel Ltd. | Bleche aus Kupferlegierung für Elektronikbauteile |
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US4191601A (en) * | 1979-02-12 | 1980-03-04 | Ampco-Pittsburgh Corporation | Copper-nickel-silicon-chromium alloy having improved electrical conductivity |
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JPH05156392A (ja) * | 1991-12-03 | 1993-06-22 | Furukawa Electric Co Ltd:The | ダンパ用屈曲部材 |
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JP4729680B2 (ja) | 2000-12-18 | 2011-07-20 | Dowaメタルテック株式会社 | プレス打ち抜き性に優れた銅基合金 |
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- 2008-11-05 JP JP2009540067A patent/JP4785092B2/ja active Active
- 2008-11-05 EP EP08847798.9A patent/EP2221391B1/de not_active Not-in-force
- 2008-11-05 WO PCT/JP2008/070139 patent/WO2009060873A1/ja active Application Filing
- 2008-11-05 KR KR1020107012166A patent/KR101515668B1/ko active IP Right Grant
- 2008-11-05 CN CN2008801147025A patent/CN101849027B/zh active Active
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Also Published As
Publication number | Publication date |
---|---|
KR101515668B1 (ko) | 2015-04-27 |
WO2009060873A1 (ja) | 2009-05-14 |
KR20100095431A (ko) | 2010-08-30 |
JP4785092B2 (ja) | 2011-10-05 |
EP2221391A4 (de) | 2012-06-27 |
CN101849027A (zh) | 2010-09-29 |
JPWO2009060873A1 (ja) | 2011-03-24 |
CN101849027B (zh) | 2013-05-15 |
EP2221391B1 (de) | 2014-04-30 |
US20110038753A1 (en) | 2011-02-17 |
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