EP2653574B1 - Kupferlegierung und herstellungsverfahren für die kupferlegierung - Google Patents
Kupferlegierung und herstellungsverfahren für die kupferlegierung Download PDFInfo
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- EP2653574B1 EP2653574B1 EP11848127.4A EP11848127A EP2653574B1 EP 2653574 B1 EP2653574 B1 EP 2653574B1 EP 11848127 A EP11848127 A EP 11848127A EP 2653574 B1 EP2653574 B1 EP 2653574B1
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- copper alloy
- mass
- electrical conductivity
- phase
- high strength
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- 229910000906 Bronze Inorganic materials 0.000 description 3
- 229910017876 Cu—Ni—Si Inorganic materials 0.000 description 3
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- 239000010974 bronze Substances 0.000 description 3
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 2
- 229910019819 Cr—Si Inorganic materials 0.000 description 2
- 229910018098 Ni-Si Inorganic materials 0.000 description 2
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
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- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 2
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- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910017870 Cu—Ni—Al Inorganic materials 0.000 description 1
- 229910018104 Ni-P Inorganic materials 0.000 description 1
- 229910003217 Ni3Si Inorganic materials 0.000 description 1
- 229910018536 Ni—P Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- RZJQYRCNDBMIAG-UHFFFAOYSA-N [Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Zn].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn] Chemical class [Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Zn].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn] RZJQYRCNDBMIAG-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- DMFGNRRURHSENX-UHFFFAOYSA-N beryllium copper Chemical compound [Be].[Cu] DMFGNRRURHSENX-UHFFFAOYSA-N 0.000 description 1
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- 229910052791 calcium Inorganic materials 0.000 description 1
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- 238000001816 cooling Methods 0.000 description 1
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- 229910001873 dinitrogen Inorganic materials 0.000 description 1
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- 238000004453 electron probe microanalysis Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
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- 238000010191 image analysis Methods 0.000 description 1
- KHYBPSFKEHXSLX-UHFFFAOYSA-N iminotitanium Chemical compound [Ti]=N KHYBPSFKEHXSLX-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 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
- 229910001000 nickel titanium Inorganic materials 0.000 description 1
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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
- C22C9/02—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
- 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
- C22C9/01—Alloys based on copper with aluminium 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
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/05—Alloys based on copper with manganese 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
- C22C9/06—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
- 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
- H01B1/026—Alloys based on copper
Definitions
- the present invention relates to a copper alloy having the high strength and high electrical conductivity which is applied to a lead frame, a connector, a terminal material and the like for electric and electronic instruments and a process for producing a copper alloy, which produces this copper alloy.
- An aging hardening-type copper alloy is a copper alloy which, by aging-treating a supersaturated solid solution which has been solution-treated, contributes to improvement in strength property such as a proof stress or a spring limit value by uniform precipitation of fine particles, and improvement in electrical conductivity by decrease in a solid solution element amount.
- an aging hardening-type copper alloy such as a Cu-Ni-Si alloy (Colson) and beryllium copper is used.
- Patent Literature 1 discloses a copper alloy material containing 1.0 to 5.0 mass% of Ni, 0.2 to 1.0 mass% of Si, 1.0 to 5.0 mass% of Zn, 0.1 to 0.5 mass% of Sn, and 0.003 to 0.3 mass% of P, with the remainder consisting of Cu and incidental impurities, which is obtained by a first cold rolling step of cold rolling to a thickness which is 1.3 to 1.7-fold of an objective final plate thickness, a first heat-treating step of heating a material after the first cold rolling to 700 to 900°C and, thereafter, cooling the material to 300°C or lower at a temperature lowering rate of 25°C or more per minute, a second cold rolling step of cold-rolling a material after the first heat treatment to a final plate thickness, a second heat-treating step of heating
- Patent Literature 2 describes a copper alloy for electronic materials containing Ni: 1.0 to 4.5 mass%, Si: 0.50 to 1.2 mass%, and Cr: 0.0030 to 0.3 mass% (provided that a weight ratio of Ni and Si is 3 ⁇ Ni/Si ⁇ 5.5), with the remainder being composed of Cu and incidental impurities, in which a Cr-Si compound having a size of 0.1 ⁇ m or more and 5 ⁇ m or less, which is dispersed in a material is such that an atomic concentration ratio of Cr relative to Si in the dispersed particle is 1 to 5, and a dispersion density thereof is 1 ⁇ 10 6 /mm 2 or less.
- this alloy improves the strength of a Ni-Si intermetallic compound, and there is a limit regarding the high strength and high electrical conductivity.
- Patent Literature 7 describes a copper alloy for electric and electronic instruments containing 1 to 3 mass% of Ni and 0.2 to 1.4 mass% of Ti, in which a ratio (Ni/Ti) of a mass percentage of the Ni and the Ti is 2.2 to 4.7, containing 0.02 to 0.3 mass% of one or both of Mg and Zr, and 0.1 to 5 mass% of Zn, with the remainder consisting of Cu and incidental impurities, in which the copper alloy contains at least one of an intermetallic compound consisting of Ni, Ti and Mg, an intermetallic compound consisting of Ni, Ti and Zr, or an intermetallic compound consisting of Ni, Ti, Mg, and Zr, a distribution density of the intermetallic compounds is 1 ⁇ 10 9 to 1 ⁇ 10 13 /mm 2 , the tensile strength is 650 MPa or more, electrical conductivity is 55 IACS% or more, and a stress relaxation ratio when held at 150°C for 1000 hours is 20% or less.
- Patent Literature 8 discloses a beryllium-free precipitation hardenable copper alloy comprising 2-9% by weight nickel, 0.05-2% by weight of aluminium, chromium and silicon, with the balance being copper and impurities.
- the copper alloy possesses sufficient electrical conductivity to be useful in electrical applications.
- the present invention was done in view of the aforementioned problems, and an object thereof is to provide a copper alloy which is excellent in workability in spite of the high strength, and is of high electrical conductivity, and a process for producing such the copper alloy.
- Another object of the present invention is to provide a copper alloy which is excellent in workability in spite of the high strength, and has high electrical conductivity, and which can control physical property, and a process for producing such the copper alloy.
- the present inventors studied in order to obtain a high strength copper alloy and, as a result, found out that it is effective to finely precipitate a ⁇ ' phase of the L1 2 structure with Ni 3 Al in a parent phase of the FCC structure, in a Cu-Ni-Al alloy. Further, it was found out that the copper alloy is further highly strengthened by adding Si.
- the copper alloy of the present invention is a copper alloy including Ni, Al and Si in which a ⁇ ' phase of the L1 2 structure is precipitated at an average particle diameter of 100 nm or less, and an area fraction of the ⁇ ' phase of 5 to 40%, with Ni 3 (A1, Si), wherein an atom positioned at a corner is Al and Si, and an atom positioned at a face centre is Ni, in a parent phase of the copper alloy, and the high strength copper alloy has an electrical conductivity of 8.5 IACS or more, and has a Vickers hardness of 220 Hv or more.
- the process for producing a high strength copper alloy of the present invention is characterized in that raw materials are integrated, melted and mixed, and hot-worked and cold-worked and, thereafter, the mixture is solution heat-treated in a range of 700 to 1020°C for 0.1 to 10 hours and, thereafter, this is aging-treated in a range of 400 to 650°C and 0.1 to 48 hours.
- the process for producing a high strength copper alloy of the present invention is further characterized in that, before or after the aging treatment, cold working at a working rate of 10 to 95% is performed.
- High electrical conductivity was studied by the copper alloy of the present invention which is the means to solve the problems and, as a result, it was found out that both of the strength and electrical conductivity are satisfied in a region A and a region B.
- a high strength copper alloy having, particularly, high electrical conductivity and excellent workability can be obtained and, in the region B, particularly, a high strength copper alloy having the high strength can be obtained.
- Fig. 1 is a photograph of a transmission electron microscope in which an upper side shows a crystal structure L1 2 of a precipitate according to electron beam diffraction, and a lower shows the state of a precipitate.
- the copper alloy of the present invention is a copper alloy of the FCC structure containing Ni: 3.0 to 29.5 mass%, Al: 0.5 to 7.0 mass%, and Si: 0.1 to 1.5 mass%, with the remainder consisting of Cu and incidental impurities, in which a ⁇ ' phase of the L1 2 structure is precipitated at an average particle diameter of 100 nm or less with Ni a Al including Si, in a parent phase of the copper alloy.
- the L1 2 structure can be confirmed, for example, by an arrangement structure of an electron beam diffraction image.
- Fig. 1 is a photograph of a transmission electron microscope in which an upper side shows a crystal structure L1 2 of a precipitate by electron beam diffraction, and a lower side shows the state of a precipitate.
- the present photograph is a composition of Ni: 12.3 mass%-Al: 1.0 mass%-Si: 0.3 mass%-Cu, and the composition has been subjected to solution treatment: 900°C 10 minutes-cold working 30%-aging treatment 500°C 6 hours.
- electron beam diffraction is directed to a regular phase having a diffraction plane 110.
- the ⁇ ' phase is an intermetallic compound, and has a regularized FCC structure in which an atom positioning at a corner is Al and Si, and an atom positioning at a face center is Ni.
- these copper of a parent phase having the FCC structure and ⁇ ' phase having the L1 2 structure are both of the FCC structure, they are good in integrity, they contribute to improvement in the strength and, at the same time, a solute element concentration of a parent phase is decreased by precipitating the ⁇ ' phase, and they also contribute to improvement in electrical conductivity.
- the copper alloy of the present invention is a copper alloy while it has the FCC structure.
- the FCC structure is a structure in which metal elements are laminated most closely, and is suitable as a parent phase alloy of the high strength and high electrical conductivity. Therefore, copper having the FCC structure is excellent in workability, and an objective shape can be easily made.
- inclusion of Ni: 3.0 to 29.5 mass%, Al: 0.5 to 7.0 mass%, and Si: 0.1 to 1.5 mass% is necessary for satisfying the high intensity and high electrical conductivity.
- Ni and Al precipitate an intermetallic compound of Ni 3 Al to form a ⁇ ' phase in Cu of a parent phase. Further, since Al and Si together with Ni form a Ni 3 (Al, Si) intermetallic compound, Al and Si together are required at an amount adapted for this system, and form not a system of Ni 3 Al or Ni 3 Si alone, but one Ni 3 (Al, Si) intermetallic compound while it resides in mixture at a corner of the FCC structure in the L1 2 type.
- the ⁇ ' phase having the L1 2 structure in the copper alloy of the present invention is an intermetallic compound, and has a regularized FCC structure in which an atom positioning at a corner is Al and Si, and an atom positioning at a face center is Ni.
- these copper of a parent phase having the FCC structure and ⁇ ' phase having the L1 2 structure are both of the FCC structure, they are good in integrity, contribute to improvement in the strength and, at the same time, a solute element concentration of a parent phase is decreased by precipitating the ⁇ ' phase, and they also contribute to improvement in electrical conductivity.
- the ⁇ ' phase of the L1 2 structure belongs to the GCP (Geometrically close packing) phase, has ductility due to a closed packed structure thereof, and further, is high in integrity, a ⁇ + ⁇ ' structure is formed, in which a ⁇ ' phase being a fine structure is precipitated, thereby, a copper alloy having high workability with toughness can be obtained.
- This ⁇ ' phase is precipitated finely and spherically in a ⁇ phase containing mainly copper being parent phase. Since the ⁇ ' phase is spherical, a highly workable copper alloy with toughness can be obtained without stress concentration at an interface between the ⁇ ' phase and the ⁇ phase.
- an average particle diameter of the ⁇ ' phase By controlling an average particle diameter of the ⁇ ' phase small, it is possible to improve the strength more. By reducing an average particle diameter of the ⁇ ' phase, a pinning site of moving rearrangement is increased in the number, and the high tensile strength can be obtained.
- the ⁇ ' phase is an intermetallic compound, its own hardness is high, and the tensile strength is also high. Therefore, by preventing rearrangement from moving in the ⁇ ' phase, it can contribute to a hardness and the tensile strength of a copper alloy.
- electrical conductivity is lowered as a concentration of a solute element which forms a solid solution in copper, but since a solute element concentration in a parent phase is decreased as compared with the solutionized state of a ⁇ monophase by heat-treating an alloy at a low temperature to precipitate a ⁇ ' phase, precipitation of the ⁇ ' phase also contributes to improvement in electrical conductivity.
- electrical conductivity of the ⁇ ' phase is lower than electrical conductivity of pure Cu, movement of electrons is reduced by a portion corresponding to a volumetric ratio occupied by this ⁇ ' phase, but high electrical conductivity can be maintained by adopting an area fraction of a suitable amount of the ⁇ ' phase.
- the copper alloy greatly contributes to mechanical property such as a hardness, the tensile strength and the like without considerably deteriorating ductility such as cold workability and the like, and as a second phase having the effect of improving electrical conductivity, the ⁇ ' phase is suitable. Thereupon, the area fraction of the ⁇ ' phase is 5 to 40%.
- This area fraction can be obtained by comparing an area of each metal structure of a certain cross section of a copper alloy.
- an area fraction and a volume fraction if areas of sections when two three dimensional-objects are cut with a plane parallel with a certain plane are equal in accordance with Cavalieri principle, volumes of two three dimensional-objects are equal. Therefore, there is no problem that this area fraction is grasped as a volume fraction.
- the area fraction can be measured with a metal microscope, an electron microscope (SEM, TEM), EPMA (X-ray analysis apparatus) or the like.
- the average particle diameter of this ⁇ ' phase is 100 nm or less.
- a smaller average particle diameter is preferable, but it is difficult to control a practical precipitation size finer than 1 nm due to coarsening by heat treatment, and when the size is 1 nm or more and 100 nm or less, the sufficient strength can be obtained.
- An average particle diameter of the ⁇ ' phase is obtained by measuring diameters of a plurality of ⁇ ' phases by image analysis from structural observation with an electron microscope, and averaging them.
- an intermetallic compound such as Ni 2 (Al, Si), NiAl, Ni 5 Si 2 and the like other than the ⁇ ' phase of an intermetallic compound of Ni 3 Al is precipitated by added Ni, Al and Si, in some cases.
- Ni 2 (Al, Si) is smaller in a precipitation amount as compared with that of Ni 3 (Al, Si), and influences little on a mechanical nature and an electric nature of a copper alloy.
- An intermetallic compound of a ⁇ phase represented by NiAl is precipitated.
- This ⁇ phase is of the B2 structure of the BCC regular structure, but a compositional range at which precipitation occurs, is narrow, and if precipitated, an amount thereof is smaller as compared with that of Ni 3 (Al, Si), and the ⁇ phase influences little on a mechanical nature and an electric nature of a copper alloy.
- Ni 5 Si 2 an intermetallic compound of Ni 5 Si 2 is precipitated in some cases.
- This Ni 5 Si 2 is also smaller in a precipitation amount as compared with that of Ni 3 (Al, Si), and influences little on a mechanical nature and an electric nature of a copper alloy.
- Si has the effect of reducing a concentration of a solute element in a matrix, and has the effect of increasing a volume fraction of the ⁇ ' phase and, at the same time, enhancing electrical conductivity.
- the copper alloy of the present invention has a compositional range containing Ni: 3.0 to 14.0 mass%, Al: 0.5 to 4.0 mass%, and Si: 0.1 to 1.5 mass%, and has electrical conductivity of 8.5 IACS% or more.
- electrical conductivity can be made to be 8.5 IACS% or more.
- the copper alloy as a copper alloy having high electrical conductivity is applied to a lead frame, a connector, a terminal material and the like of electronic instruments and the like.
- the copper alloy of the present invention by adopting this compositional range to precipitate the ⁇ ' phase of 100 nm or less, further, cold workability can be made to be 10 to 95%.
- Cold workability is defined as a reduction ratio of a maximum thickness at which rolling is possible with no cracking without performing annealing in the case of rolling implemented at a temperature of 20°C, and is defined as a maximum area reduction ratio at which wire drawing is possible with no cracking without performing annealing in the case of wire drawing.
- Ni 3 (Al, Si) intermetallic compound of the ⁇ ' phase has lower workability than that of pure Cu, a working ratio cannot be increased by a portion corresponding to a ratio of a volume occupied by this Ni 3 (Al, Si) intermetallic compound.
- a precipitation amount of the ⁇ ' phase can be controlled to adjust cold workability at 10 to 95% while electrical conductivity is maintained high.
- cold workability is preferably in a range of 10 to 95%, further preferably 20 to 90%.
- the copper alloy as a copper alloy having the high strength is applied to a lead frame, a connector, a terminal material and the like of electronic instruments and the like.
- the copper alloy of the present invention can afford high electrical conductivity and high cold workability by residing in a range of this region A and adopting 5 to 20% of a volume fraction at which the ⁇ ' phase is precipitated.
- the copper alloy as a contact material can reduce abrasion even when the material is contacted and sliding-rubbed frequently.
- the copper alloy can be applied to a lead frame, a connector, a terminal material and the like of electronic instruments and the like, as a copper alloy having high electrical conductivity and high cold workability.
- Ni: 9.5 to 29.5 mass%, Al: 1.5 to 7.0 mass%, and Si: 0.1 to 1.5 mass% are contained, and a Vickers hardness is in a range of 220 to 450 Hv.
- an average particle diameter of the ⁇ ' phase is preferably 100 nm or less like the above.
- a smaller average particle diameter is preferable, but it is difficult to perform practical precipitation completely uniformly, and the sufficient strength can be obtained at an average particle diameter of 1 nm or more and 100 nm or less, and 30 nm or less is more preferable.
- the copper alloy of the present invention since as electrical conductivity in this compositional range, electrical conductivity of approximately 7 to 15 IACS% can be obtained, abrasion is little, and durability is good, the copper alloy can stand use for a long term, even when applied to a lead frame, a connector, a terminal material and the like of electronic instruments and the like, by possession of a high Vickers hardness together.
- the copper alloy of the present invention can further have the high strength represented by a Vickers hardness by residing in a range of this region B and adjusting a volume fraction at which the ⁇ ' phase is precipitated, at 25 to 40%. This is derived from that the ⁇ ' phase is an intermetallic compound, and the strength is very high. However, when an area ratio of the ⁇ ' phase is increased, there is a demerit that electrical conductivity is reduced.
- the copper alloy can be also provided with a high Vickers hardness, while high electrical conductivity is obtained.
- the copper alloy can be widely applied to a lead frame, a connector, a terminal material and the like of electronic instruments and the like.
- a total amount of 0.01 to 5.0 mass% of one or two or more elements selected from the group consisting of Co, Ti, Sn, Cr, Fe, Zr, Mg and Zn can be contained as an addition element.
- Co, Ti, Cr and Zr stabilize the ⁇ ' phase and promote precipitation thereof, they contribute to improvement in the strength, and since they also have the effect of decreasing a concentration of a solute element in Cu, they also contribute to improvement in electrical conductivity.
- Sn, Mg and Zn have the effect of improving stress relaxation resistance property and, at the same time, dissolve in Cu, they contribute to improvement in the strength.
- Fe has the effect of miniaturization of a crystal grain by dispersion of a fine grain of Fe in Cu, and contributes to improvement in the strength and improvement in heat resistance.
- An addition amount of an addition element is so that selected one or two more addition elements are contained at a total amount of 0.01 to 5.0 mass%.
- a total amount of selected one or two or more addition elements is less than 0.01 mass%, there is a problem that this does not contribute to improvement in electrical conductivity and improvement in the strength, for a copper alloy.
- a total amount of addition elements exceeds 5.0 mass%, this contributes to improvement in electrical conductivity and improvement in the strength, but there is a problem that it becomes impossible to control electric property such as electrical conductivity and the like, and mechanical property such as a Vickers hardness and the like in a suitable range.
- the copper alloy of the present invention can further contain a total amount of 0.001 to 0.5 mass% of one or two or more elements selected from the group consisting of C, P and B as an addition element.
- C is thought to have the effect on miniaturization of a crystal grain, and contributes to improvement in the strength. Further, C reduces solid solubility of a solute element in Cu, and contributes to improvement in electrical conductivity.
- P is used as a deoxidant, has the effect of decreasing a concentration of impurities of Cu, and contributes to improvement in electrical conductivity.
- B has the effect of suppressing growth of a crystal grain and, therefore, has the effect of miniaturizing a crystal grain to improve the strength. B can improve heat resistance.
- An addition amount is such that selected one or two or more addition elements are contained at a total amount of 0.001 to 0.5 mass%.
- a total amount of addition elements is less than 0.001 mass%, there is a problem that addition elements do not contribute to improvement in electrical conductivity and improvement in the strength, for a copper alloy.
- a total amount of addition elements exceeds 0. 5 mass%, there is a problem that addition elements contribute to improvement in electrical conductivity and improvement in the strength, but it becomes impossible to control electric property such as electrical conductivity and the like and mechanical property such as a Vickers hardness and the like in a suitable range.
- raw materials are integrated, melted, mixed and cast and, thereafter, the cast product is formed into a shape such as a plate material, a wire material, a tube material and the like by hot working such as hot forging and, if necessary, cold working such as cold rolling, cold wire drawing and the like.
- the formed material is heat-treated in a range of 700 to 1020°C and 0.1 to 10 hours and, thereafter, aging-treated in a range of 400 to 650°C and 0.1 to 48 hours.
- the process for producing a copper alloy of the present invention has (a) a step of integrating, melting and mixing Ni: 3.0 to 29.5 mass%, Al: 0.5 to 7.0 mass%, Si: 0.1 to 1.5 mass% and Cu to form a copper alloy material as an ingot, (b) a step of performing solution treatment of heat-treating the copper alloy material at a temperature in a range of 700°C to 1020°C for a time in a range of 0.1 to 10 hours, after the material is formed by hot working and, if necessary, cold working, and (c) a step of performing aging treatment of heating the copper alloy material after solution treatment at a temperature in a range of 400°C to 650°C for a time in a range of 0.1 to 48 hours.
- a total amount of 0.01 to 5.0 mass% of one or two or more elements selected from the group consisting of Co, Ti, Sn, Cr, Fe, Zr, Mg and Zn can be also further added as an addition element.
- a total amount of 0.001 to 0.5 mass% of one or two or more elements selected from the group consisting of C, P and B can be also added.
- a deoxidant such as calcium boride and the like
- a bubbling treatment may be performed using an argon gas or a nitrogen gas
- melting may be performed in vacuum in a vacuum container.
- a method of melting is not particularly limited, but a raw material may be heated at a temperature of a melting point of a copper alloy raw material or higher using the known apparatus such as a high frequency melting furnace and the like.
- a copper alloy material is heat-treated at a temperature in a range of 700°C to 1020°C for a time in a range of 0.1 to 10 hours.
- a method of heating is not particularly limited, but heating may be performed according to the known method.
- a copper alloy material is aging-treated at 400 to 650°C, for a time in a range of 0.1 to 48 hours.
- the ⁇ ' phase cannot be precipitated at lower than 400°C and/or for shorter than 0.1 hour.
- a problem arises that the ⁇ ' phase is grown, an average particle diameter exceeds 100 nm, and desired electrical conductivity and working ratio cannot be obtained. Therefore, in order to obtain desired electrical conductivity and hardness, such the aging treatment becomes essential requirement.
- the process for producing a high strength copper alloy of the present invention is further characterized in that, before or after the aging treatment, cold working of 10 to 95% is performed.
- a lattice defect such as a crystal grain boundary, rearrangement, a lamination defect and the like is formed to miniaturize and working-cure a crystal grain and, at the same time, thereafter, disperse and precipitate a number of ⁇ ' phases of Ni 3 (Al, Si), thereby, an average particle diameter of the ⁇ ' phase can be made to be 100 nm or less and, at the same time, a temperature of aging treatment can be lowered, and a time of aging treatment can be shortened.
- a method of cold working is not particularly limited, but the method may be performed by the known method such as rolling with a roller and the like.
- the material can be highly strengthened.
- working is performed at a working ratio in a range of 10 to 95%.
- the working ratio is less than 10%, introduction of a defect is little, and the aforementioned effect of working is not sufficiently obtained.
- the working ratio exceeds 95%, a burden on a processing facility becomes great, raising a problem.
- low temperature aging may be performed in a range of 100 to 400°C.
- a method of low temperature aging is not particularly limited, but the method can be performed according to the known method.
- a copper alloy obtained by such the production process can precipitate a sufficient amount of a fine ⁇ ' phase while suppressing coarsening of a ⁇ ' phase of the L1 2 structure precipitating in a copper alloy, electric property such as electrical conductivity and the like, and mechanical property such as cold workability, a Vickers hardness and the like can be easily controlled.
- copper alloy materials of compositions of Examples 1 to 57 were integrally placed into a high frequency induction melting furnace, fused, melted and mixed. This was formulated into a cast ingot (as-cast).
- Heat treatment condition is representative production condition, and is hot rolling (900°C, rolling reduction 90%)-solutionizing (900°C, 10 minutes)-cold rolling (20°C, rolling reduction 30%)-aging precipitation treatment (500°C, 18 hours).
- Copper alloy materials of compositions of Examples 58 to 70 were integrally placed into a high frequency induction melting furnace, fused, melted and mixed. This was formulated into a cast ingot (as-cast).
- Heat treatment condition is representative production condition, and is hot rolling (900°C, rolling reduction 90%)-solutionizing (900°C, 10 minutes)-cold rolling (20°C, rolling reduction 30%)-aging precipitation treatment (500°C, 18 hours).
- Copper alloy materials of compositions of Examples 71 to 76 were integrally placed into a high frequency induction melting furnace, fused, melted and mixed. This was formulated into a cast ingot (as-cast). Thereafter, a ⁇ ' phase of the L1 2 structure was precipitated in a parent phase of Cu of the FCC structure.
- compositions of Examples 71 to 76 are shown in the following Table 7. [Table 7] Alloy No. Addition element (mass%) 71 Sn:0.2 72 Sn:0.2 73 Sn:1.0 74 Sn:0.2 75 (62) Sn:0.5 76 Sn:1.0 *71 ⁇ 73 Ni13Al2Si1 *74 ⁇ 76 Ni13Al1Si1
- Heat treatment condition is representative production condition, and is hot rolling (900°C, rolling reduction 90%)-solutionizing (900°C, 10 minutes)-cold rolling (20°C, rolling reduction 30%)-aging precipitation treatment (500°C, 18 hours).
- a Vickers hardness was 220 Hv or more.
- Copper alloy materials of compositions of Examples 77 to 82 were integrally placed into a high frequency induction melting furnace, fused, melted and mixed. This was formulated into a cast ingot (as-cast). Thereafter, a ⁇ ' phase of the L1 2 structure was precipitated in a parent phase of Cu of the FCC structure.
- Heat treatment condition is representative production condition, and is hot rolling (900°C, rolling reduction 90%)-solutionizing (900°C, 10 minutes)-cold rolling (20°C, rolling reduction 30%)-aging precipitation treatment (500°C, 18 hours).
- Copper alloy materials of compositions of Examples 83 to 88 were integrally placed into a high frequency induction melting furnace, fused, melted and mixed. This was formulated into a cast ingot (as-cast). Thereafter, a ⁇ ' phase of the L1 2 structure was precipitated in a parent phase of Cu of the FCC structure.
- compositions of Examples 83 to 88 are shown in the following Table 11. [Table 11] Alloy No. Addition element (mass%) 83 Zr:0.2 84 Zr:0.5 85 Zr:1.0 0 86 Zr:0.2 87 (64) Zr:0.5 88 Zr:1.0 0 *83 ⁇ 85 Ni13Al2Si1 *86 ⁇ 88 Ni13Al1Si1
- Heat treatment condition is representative production condition, and is hot rolling (900°C, rolling reduction 90%)-solutionizing (900°C, 10 minutes)-cold rolling (20°C, rolling reduction 30%)-aging precipitation treatment (500°C, 18 hours).
- Copper alloy materials of compositions of Examples 89 to 94 were integrally placed into a high frequency induction melting furnace, fused, melted and mixed. This was formulated into a cast ingot (as-cast). Thereafter, a ⁇ ' phase of the L1 2 structure was precipitated in a parent phase of Cu of the FCC structure.
- Heat treatment condition is representative production condition, and is hot rolling (900°C, rolling reduction 90%)-solutionizing (900°C, 10 minutes)-cold rolling (20°C, rolling reduction 30%)-aging precipitation treatment (500°C, 18 hours).
- Copper alloy materials of compositions of Examples 95 to 100 were integrally placed into a high frequency induction melting furnace, fused, melted and mixed. This was formulated into a cast ingot (as cast). Thereafter, a ⁇ ' phase of the L1 2 structure was precipitated in a parent phase of Cu of the FCC structure.
- compositions of Examples 95 to 100 are shown in the following Table 15. [Table 15] Alloy No. Addition element (mass%) 95 Fe:0.2 96 (65) Fe:0.5 97 Fe:1.0 98 Fe:0.2 99 Fe:0.5 100 Fe:1.0 *95 ⁇ 97 Ni13Al2Si1 *98 ⁇ 100 Ni13Al1Si1
- Heat treatment condition is representative production condition, and is hot rolling (900°C, rolling reduction ratio 90%)-solutionizing (900°C, 10 minutes)-cold rolling (20°C, rolling reduction 30%)-aging precipitation treatment (500°C, 18 hours).
- Copper alloy materials of compositions of Examples 101 to 106 were integrally placed into a high frequency induction melting furnace, fused, melted and mixed. This was formulated into a cast ingot (as-cast). Thereafter, a ⁇ ' phase of the L1 2 structure was precipitated in a parent phase of Cu of the FCC structure.
- compositions of Examples 101 to 106 are shown in the following Table 17. [Table 17] Alloy No. Addition element (mass%) 101 P:0.01 102 P:0.05 103 P:0.1 104 P:0.01 105 P:0.05 106 (68) P:0.1 *101 ⁇ 103 Ni13Al2Si1 *104 ⁇ 106 Ni13Al1Si1
- Heat treatment condition is representative production condition, and is hot rolling (900°C, rolling reduction 90%)-solutionizing (900°C, 10 minutes)-cold rolling (20°C, rolling reduction 30%)-aging precipitation treatment (500°C, 18 hours).
- Copper alloy materials of compositions of Examples 107 to 112 were integrally placed into a high frequency induction melting furnace, fused, melted and mixed. This was formulated into a cast ingot (as-cast). Thereafter, a ⁇ ' phase of the L1 2 structure was precipitated in a parent phase of Cu of the FCC structure.
- compositions of Examples 107 to 112 are shown in the following Table 19. [Table 19] Alloy No. Addition element (mass%) 107 Zn:0.2 108(67) Zn:0.5 109 Zn:1.0 110 Zn,:0.2 111 Zn:0.5 112 Zn:1.0 *107 ⁇ 109 Ni13Al2Si1 *110 ⁇ 112 Ni13Al1Si1
- Heat treatment condition is representative production condition, and is hot rolling (900°C, rolling reduction 90%)-solutionizing (900°C, 10 minutes)-cold rolling (20°C, rolling reduction 30%)-aging precipitation treatment (500°C, 18 hours).
- Copper alloy materials of compositions of Examples 113 to 118 were integrally placed into a high frequency induction melting furnace, fused, melted and mixed. This was formulated into a cast ingot (as-cast). Thereafter, a ⁇ ' phase of the L1 2 structure was precipitated in a parent phase of Cu of the FCC structure.
- Heat treatment condition is representative production condition, and is hot rolling (900°C, rolling reduction 90%)-solutionizing (900°C, 10 minutes)-cold rolling (20°C, rolling reduction 30%)-aging precipitation treatment (500°C, 18 hours).
- Copper alloy materials of compositions of Examples 119 to 122 were integrally placed into a high frequency induction melting furnace, fused, melted and mixed. This was formulated into a cast ingot (as-cast). Thereafter, a ⁇ ' phase of the L1 2 structure was precipitated in a parent phase of Cu of the FCC structure.
- Heat treatment condition is representative production condition, and is hot rolling (900°C, rolling reduction 90%)-solutionizing (900°C, 10 minutes)-cold rolling (20°C, rolling reduction 30%)-aging precipitation treatment (500°C, 18 hours).
- Copper alloy materials of compositions of Examples 123 to 128 were integrally placed into a high frequency induction melting furnace, fused, melted and mixed. This was formulated into a cast ingot (as-cast). Thereafter, a ⁇ ' phase of the L1 2 structure was precipitated in a parent phase of Cu of the FCC structure.
- Heat treatment condition is representative productive condition, and is hot rolling (900°C, rolling reduction 90%)-solutionizing (900°C, 10 minutes)-cold rolling (20°C, rolling reduction 30%)-aging precipitation treatment (500°C, 18 hours).
- the copper alloy of the present invention is a copper alloy having a predetermined composition, which is obtained by a predetermined production process, and since the copper alloy can precipitate a sufficient amount of a fine ⁇ ' phase while coarsening of a ⁇ ' phase of the L1 2 structure which is precipitated in a copper alloy is suppressed, it was seen that it can easily control electric property such as electrical conductivity and the like, and mechanical property such as cold workability, a Vickers hardness and the like.
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Claims (6)
- Hochfeste Kupferlegierung der FCC-Struktur, enthaltend 3,0 bis 29,5 Masse-% Ni, 0,5 bis 7,0 Masse-% Al und 0,1 bis 1,5 Masse-% Si, gegebenenfalls ferner enthaltend eine Gesamtmenge von 0,01 bis 5,0 Masse-% von einem oder zwei oder mehr Elementen, die aus der Gruppe ausgewählt sind, welche aus Co, Ti, Sn, Cr, Fe, Zr, Mg und Zn besteht, als Zusatzelement und gegebenenfalls ferner enthaltend eine Gesamtmenge von 0,001 bis 0,5 Masse-% von einem oder zwei oder mehr Elementen, die aus der Gruppe ausgewählt sind, welche aus C, P und B besteht, als Zusatzelement, wobei der Rest aus Cu und zufälligen Verunreinigungen besteht, wobei:eine γ'-Phase der intermetallischen Verbindung Ni3 (Al, Si) mit einer Struktur von L12 und einem FCC ausgefällt wird, wobei es sich bei einem an einer Ecke positionierten Atom um Al und Si handelt und es sich bei einem im vorderen Zentrum positionierten Atom um Ni handelt, wobei der durchschnittliche Teilchendurchmesser 100 nm oder weniger beträgt und ein Flächenanteil der γ'-Phase in einer Ausgangsphase der Kupferlegierung 5 bis 40 % beträgt; unddie hochfeste Kupferlegierung eine elektrische Leitfähigkeit von 8,5 IACS% oder mehr aufweist und eine Vickershärte von 220 Hv oder mehr aufweist.
- Hochfeste Kupferlegierung nach Anspruch 1,
wobei die hochfeste Kupferlegierung 3,0 bis 14,0 Masse-% Ni, 0,5 bis 4,0 Masse-% Al und 0,1 bis 1,5 Masse-% Si enthält, und eine elektrische Leitfähigkeit von 10 bis 25 IACS% aufweist. - Hochfeste Kupferlegierung nach Anspruch 1 oder 2,
wobei die Kaltformbarkeit im Bereich von 10 bis 95 % liegt. - Hochfeste Kupferlegierung nach Anspruch 1,
wobei die hochfeste Kupferlegierung 9,5 bis 29,5 Masse-% Ni, 1,5 bis 7,0 Masse-% Al und 0,1 bis 1,5 Masse-% Si enthält, und Vickershärte von 220 bis 450 Hv und eine elektrische Leitfähigkeit von 8,5 bis 15 IACS% aufweist. - Verfahren zum Herstellen der hochfesten Kupferlegierung nach einem der Ansprüche 1 bis 4, wobei das Verfahren das Einarbeiten, Schmelzen, Mischen, Heißformen und Kaltformen von Rohmaterialien, dann Lösungsglühen des geformten Produkts in einem Bereich von 700 bis 1020 °C und für 0,1 bis 10 Stunden und anschließendes Auslagern des geformten Produkts in einem Bereich von 400 bis 650 °C und für 0,1 bis 48 Stunden umfasst.
- Verfahren zum Herstellen der hochfesten Kupferlegierung nach Anspruch 5,
wobei vor oder nach dem Auslagern eine Kaltformung bei einem Formungsanteil von 10 bis 95 % durchgeführt wird.
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2011
- 2011-12-13 US US13/993,642 patent/US20130333812A1/en not_active Abandoned
- 2011-12-13 KR KR1020137015270A patent/KR101576715B1/ko active IP Right Grant
- 2011-12-13 WO PCT/JP2011/078786 patent/WO2012081573A1/ja active Application Filing
- 2011-12-13 CN CN201180059926.2A patent/CN103328665B/zh active Active
- 2011-12-13 EP EP11848127.4A patent/EP2653574B1/de active Active
- 2011-12-13 JP JP2012548789A patent/JP5743165B2/ja active Active
Also Published As
Publication number | Publication date |
---|---|
WO2012081573A1 (ja) | 2012-06-21 |
US20130333812A1 (en) | 2013-12-19 |
CN103328665B (zh) | 2016-04-13 |
CN103328665A (zh) | 2013-09-25 |
JP5743165B2 (ja) | 2015-07-01 |
KR101576715B1 (ko) | 2015-12-10 |
EP2653574A1 (de) | 2013-10-23 |
KR20130089661A (ko) | 2013-08-12 |
JPWO2012081573A1 (ja) | 2014-05-22 |
EP2653574A4 (de) | 2014-09-10 |
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