EP2752498A1 - Matériau en alliage de cuivre et son procédé de fabrication - Google Patents

Matériau en alliage de cuivre et son procédé de fabrication Download PDF

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Publication number
EP2752498A1
EP2752498A1 EP12828596.2A EP12828596A EP2752498A1 EP 2752498 A1 EP2752498 A1 EP 2752498A1 EP 12828596 A EP12828596 A EP 12828596A EP 2752498 A1 EP2752498 A1 EP 2752498A1
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European Patent Office
Prior art keywords
copper alloy
ratio
alloy material
mass
rolling
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EP12828596.2A
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German (de)
English (en)
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EP2752498A4 (fr
Inventor
Ryosuke Matsuo
Hiroshi Kaneko
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Furukawa Electric Co Ltd
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Furukawa Electric Co Ltd
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    • 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
    • C22C1/00—Making non-ferrous alloys
    • C22C1/10—Alloys containing non-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
    • C22C9/02—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
    • 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
    • C22C9/10—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
    • 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 material and a method of producing the same. More particularly, the present invention relates to a copper alloy material that is applied to lead frames, connectors, terminal materials, relays, switches, sockets, and the like of, for example, parts to be mounted on vehicles and surrounding infrastructures primarily for EV (electric vehicles) and HEV (hybrid electric vehicles), and solar photovoltaic power generation systems, and the present invention relates to a method of producing the copper alloy material.
  • Property items required in copper alloy materials that are used in applications include, for example, electrical conductivity, tensile strength, bending property, and stress relaxation resistance.
  • electrical conductivity tensile strength
  • bending property tensile strength
  • stress relaxation resistance tensile strength
  • stress relaxation resistance stress relaxation resistance
  • the environments in which terminals are used are exposed to higher temperature and higher voltage, and the demand for heat resistance is becoming stronger.
  • a contact pressure is applied to a terminal spring unit at a high temperature
  • the stress deteriorates with the lapse of time, and this causes a problem in the spring reliability.
  • the environment temperature increases every year. Further, not only the ambient environment but also spontaneous heat are also subjected to temperature increase and electrical current loss, which become problems.
  • terminals are required to have strong spring property and constant mechanical strength; however, on the other hand, if it is poor in workability in bending (bending property) that is applied to a contact area or a spring area, it is inconvenient in terms of design, and the design of necessary connectors becomes impossible to be achieved. Further, it is generally well known that bending property becomes poor by thickness increasing. However, increase of thickness of the sheet thickness cannot be avoided in large electrical current applications, and there is a problem that cracks occur even under bending at a level equivalent to that of conventional connector products.
  • Copper (Cu) in the state of pure metal, cannot be used as spring materials, since the spring strength of Cu does not reach a level that satisfies the required properties.
  • Mg or Sn is added to Cu to cause solid solution strengthening
  • Cr or Zr is added to Cu to cause precipitation strengthening
  • the resulting copper alloys can be utilized as a spring material.
  • a material with high electrical conductivity and excellent heat resistance is needed for applications under large electrical current.
  • Patent Literature 1 discloses that when Mg is added to a Cu-Cr-based alloy, stamping (press-punching) workability is improved.
  • Patent Literature 2 discloses that when Zr is added to a Cu-Cr-based alloy, bending property is improved.
  • Patent Literature 3 discloses that when Ti is added to a Cu-Cr-based alloy, stress relaxation resistance is improved. As shown in Patent Literatures 1 to 3, examples are known for the additional alloying elements and compositions in known highly electrically-conductive copper alloys.
  • Patent Literature 4 discloses that in a Cu-Cr-Zr-based alloy, when the ratio of coincidence boundary ⁇ 3 in the grain boundaries is 10% or more, bending property is excellent.
  • Patent Literature 5 discloses that in a Cu-Cr-Zr-based alloy, an improvement in bending property is achieved, by controlling orientation distribution density of Brass orientation to 20 or less, and by controlling the sum of orientation distribution density of Brass orientation, S orientation and Copper orientation to 10 to 50.
  • Patent Literatures 6 to 8 Cu-Mg-based alloys are known.
  • Patent Literature 6 discloses that when the surface grain size of a Cu-Mg-P-based alloy is controlled, mold abrasion upon stamping is reduced.
  • Patent Literature 7 discloses that by controlling the particle size of a Mg-P-based compound that is precipitated and dispersed in a Cu-Mg-P-based alloy, migration resistance is improved.
  • Patent Literature 8 discloses that by suppressing precipitation of coarse intermetallic compounds with particle size of 0.1 ⁇ m or more in a Cu-Mg-P-based alloy, the resultant copper alloy is high in electrical conductivity, and is improved in bending property.
  • Patent Literatures 1, 2 and 3 definitions of the alloying elements and definitions of the grain size of Cu-Cr-based alloys are provided, but they do not give any improvement in properties of the matrix itself by texture control (control of the texture or control of the grain boundary state) through production process conditions.
  • Patent Literature 4 when a Cu-Cr-Zr-based alloy is subjected to final cold-rolling at a particular high degree of working, dynamic recrystallization is induced, and the ratio of coincidence grain boundary ⁇ 3 is made to 10% or more, to improve bending property, but it does not give any improvement in stress relaxation resistance.
  • Patent Literature 5 when a Cu-Cr-Zr-based copper alloy is subjected to cold-rolling at a particular degree of working and to a heat treatment at a low temperature, the density of orientation distribution of Brass orientation is controlled to be 20 or less, and the sum of the density of orientation distribution of Brass orientation, S orientation and Copper orientation is controlled to be 10 to 50, to improve bending property, but it does not give any improvement in stress relaxation resistance.
  • the present invention is contemplated for providing a copper alloy material that is excellent in mechanical strength and electrical conductivity, and among them, in particular, that has favorable stress relaxation resistance and bending property in an excellently balanced manner of these two properties, and the present invention is contemplated for providing a method of producing the copper alloy material.
  • This copper alloy material is suitable for lead frames, connectors, and terminal materials of, for example, parts to be mounted on vehicles and surrounding infrastructures primarily for EVs and HEVs, and solar photovoltaic power generation systems; connectors and terminal materials of, for example, parts to be mounted on vehicles; relays, switches, sockets, and the like.
  • the inventors of the present invention have studied keenly, and have conducted research on copper alloys suitable for electrical or electronic part applications. As a result, the inventors found that, in the texture of Cu-Cr-based or Cu-Mg-based copper alloy materials having a specific alloy composition, when the Cube orientation ⁇ 100 ⁇ ⁇ 001> is accumulated at a ratio of 3% or more in the surface direction (ND) of a rolled sheet, and the ratio of coincidence grain boundary (CSL grain boundary) ⁇ 3 in grain boundaries is 20% or more, mechanical strength, electrical conductivity, as well as bending property and stress relaxation resistance can be simultaneously enhanced.
  • the present invention was made based on these findings.
  • the present invention it to provide the following means:
  • a first embodiment of the present invention means to include the Cu-Cr-based alloy materials described in the above items (1) to (3) and the method of producing the same described in the above item (4).
  • a second embodiment of the present invention means to include the Cu-Mg-based alloy materials described in the above items (5) to (7) and the method of producing the same described in the above item (8).
  • the present invention means to include both of the above first and second embodiments, unless otherwise specified.
  • the copper alloy material of a Cu-Cr-based primarily of the present invention is excellent in stress relaxation resistance and bending property, and has excellent mechanical strength and electrical conductivity, and the copper alloy material is suitable in lead frames, connectors, terminal materials, relays, switches, sockets and the like of, for example, parts to be mounted on vehicles and surrounding infrastructures primarily for EVs and HEVs, and solar photovoltaic power generation systems.
  • copper alloy material before working, having a predetermined alloy composition
  • copper alloy material means a product obtained after a copper alloy raw material is worked into a predetermined shape (for example, sheet, or strip).
  • a predetermined shape for example, sheet, or strip.
  • the copper alloy material of the present invention is one that properties thereof are defined, with the accumulation ratio of the texture in a predetermined direction of a rolled sheet, and a particular coincidence grain boundary in grain boundaries; however, this means that it is enough for a copper alloy material to have those properties, and the shape of the copper alloy material is not intended to be limited to a sheet material, and a strip material is also acceptable.
  • Cu-Cr-based alloys are used, as a copper alloy material having electrical conductivity, mechanical strength, bending property and stress relaxation resistance that are required in connectors of, for example, parts to be mounted on vehicles and surrounding infrastructures primarily for EVs and HEVs, and solar photovoltaic power generation systems.
  • the copper alloy material contains Cr in an amount of 0.1 to 0.8 mass%, and at least one selected from the group consisting of the additional alloying element group 1 and the additional alloying element group 2 in an amount of 0.01 to 0.5 mass% in total, respectively as an addition amount to Cu:
  • the copper alloy material contains at least one selected from the additional alloying element group 1 and at least one selected from the additional alloying element group 2 in an amount of 0.01 to 0.5 mass% in total. More preferably, the copper alloy material contains Cr in an amount of 0.15 to 0.5 mass%, and contains at least one selected from the additional alloying element group 1 and at least one selected from the additional alloying element group 2, in an amount of 0.1 to 0.5 mass% in total. This is because when the amounts to be added are defined to be in these ranges, since the matrix is in a state close to the pure copper texture, a balance can be achieved between acceleration of development of the Cube orientation and attainment of a state with lowered stacking fault energy caused by partial solid solution.
  • Cu-Mg-based alloys are used, as a copper alloy material having electrical conductivity, mechanical strength, bending property and stress relaxation resistance, which are required in connectors of, for example, parts to be mounted on vehicles and surrounding infrastructures primarily for EVs and HEVs, and solar photovoltaic power generation systems.
  • the copper alloy material contains Mg in an amount of 0.01 to 0.5 mass%, as an addition amount to Cu.
  • the copper alloy material may contain, in addition to Mg, at least one selected from the group consisting of Zn, Fe, Sn, Ag, Si and P, as an additional alloying element, in an amount of 0.01 to 0.3 mass% in total, and preferably, the copper alloy material may contain the additional alloying element in a total amount of 0.05 to 0.3 mass%.
  • the first embodiment of the present invention is directed to Cu-Cr-based alloys in order to secure mechanical strength and electrical conductivity.
  • the addition amount of Cr is 0.1 to 0.8 mass%, preferably 0.15 to 0.5 mass%.
  • a precipitate of the simple substance of Cr and/or a compound of Cr with another element is precipitated into the copper matrix, and thereby the matrix is brought to a state closer to pure copper with exhibiting precipitation strength, to accelerate nucleation and growth of the Cube orientation ⁇ 001 ⁇ ⁇ 100> in the sheet thickness direction (ND).
  • the term "compound” refers to a substance composed of two or more kinds of elements, and, for example, a substance composed of Cr or the like and one or more kinds of other elements (including Cu).
  • precipitate as used herein means to include precipitates or crystallization products in which these compounds exist within grains of the Cu matrix or on grain boundaries.
  • examples of Cr-based precipitates include not only the simple substance of Cr but also Cr-based compounds, such as Cr 3 Si and CrSi, when Si is added. These compounds vary depending on the alloying elements.
  • the copper alloy material contains, in addition to the Cr as a main alloying element, an additional alloying element of at least one selected from the group consisting of the additional alloying element group 1 and the additional alloying element group 2 described below, in an amount of 0.01 to 0.5 mass% in total.
  • the additional alloying elements are classified into two groups, from the viewpoint of their actions.
  • the additional alloying element group 1 at least one selected from the group consisting of Mg, Ti and Zr in an amount of 0.01 to 0.5 mass% in total
  • the additional alloying element group 2 at least one selected from the group consisting of Zn, Fe, Sn, Ag, Si and P in an amount of 0.005 to 0.5 mass% in total.
  • the copper alloy material contain at least one selected from the additional alloying element group 1 and at least one selected from the additional alloying element group 2 in an amount of 0.01 to 0.5 mass% in total.
  • the addition amount of Mg is preferably 0.01 to 0.5 mass%, more preferably 0.05 to 0.3 mass%.
  • the addition amount of Ti is preferably 0.01 to 0.2 mass%, more preferably 0.02 to 0.1 mass%.
  • the addition amount of Zr is preferably 0.01 to 0.2 mass%, more preferably 0.01 to 0.1 mass%.
  • the addition amount of Zn is preferably 0.05 to 0.3 mass%, more preferably 0.1 to 0.2 mass%.
  • the addition amount of Fe is preferably 0.05 to 0.2 mass%, more preferably 0.1 to 0.15 mass%.
  • the addition amount of Sn is preferably 0.05 to 0.3 mass%, more preferably 0.1 to 0.2 mass%.
  • the addition amount of Ag is preferably 0.05 to 0.2 mass%, more preferably 0.05 to 0.1 mass%.
  • the addition amount of Si is preferably 0.01 to 0.1 mass%, more preferably 0.02 to 0.05 mass%.
  • the addition amount of P is preferably 0.005 to 0.1 mass%, more preferably 0.005 to 0.05 mass%. If the addition amounts of those elements are smaller than the above, the effects of addition may not be obtained.
  • Mg forms a solid solution and improves the stress relaxation resistance. If the addition amount of Mg is too large, Mg-based compounds are formed and adversely affect melting, casting and hot-rolling, thereby conspicuously making manufacturability poor. Further, in addition to causing a lowering in electrical conductivity, nucleation and growth of the Cube orientation ⁇ 001 ⁇ ⁇ 100> in the ND are suppressed by an increase in the amount of solid solution, resulting in that bending property becomes insufficient.
  • Ti and Zr improve the stress relaxation resistance and mechanical strength through solid solution, precipitation and crystallization. If the amounts of addition of Ti and Zr are too large, Ti-based or Zr-based compounds are formed, to adversely affect melting, casting and hot-rolling, thereby conspicuously making manufacturability poor. Further, when the amounts of addition of Ti and Zr are too large so that Ti and Zr exist even in a solid solution state, Ti and Zr cause a lowering in electrical conductivity, and also, nucleation and growth of the Cube orientation ⁇ 001 ⁇ ⁇ 100> in the ND is suppressed by an increase in the amount of solid solution, resulting in that bending property becomes insufficient.
  • Fe exists in the predetermined addition amount in the range described above, Fe precipitates out finely into the matrix in the form of compound or simple substance. Simple substance precipitates out, to contribute to precipitation-hardening. Also, even Fe-based compounds also precipitate. In all cases, there is an effect of making grains fine by suppressing the growth of grains, and bending property is enhanced favorably, by improving the dispersed state of the grains of the Cube orientation ⁇ 001 ⁇ ⁇ 100>.
  • Sn accelerates solid-solution strengthening, and also work hardening upon rolling. Further, when Sn is added together with Mg, the stress relaxation resistance can be further improved than in the case of adding either one of the elements singly. If the addition amount of Sn is too large, Sn causes a lowering in electrical conductivity due to solid solution, and also, nucleation and growth of the Cube orientation ⁇ 001 ⁇ ⁇ 100> in the ND are suppressed by an increase in the amount of solid solution, resulting in that bending property becomes insufficient.
  • Ag exhibits an effect of improving the stress relaxation resistance even added singly, and when Ag is added together with Mg, Zr and/or Ti, the stress relaxation resistance can be further improved than in the case of adding either one of the elements singly. If the addition amount of Ag is too large, the effects are saturated, and particularly, the cost is largely affected, which is not preferable.
  • Si exhibits an effect of improving the stress relaxation resistance even added singly, and when Si is added together with Mg, Zr and/or Ti, the stress relaxation resistance can be further improved than in the case of adding either one of the elements singly. Further, Si has an effect of improving pressability. If the addition amount of Si is too large, Si causes a lowering in electrical conductivity due to solid solution, and also, nucleation and growth of the Cube orientation ⁇ 001 ⁇ ⁇ 100> in the ND are suppressed by an increase in the amount of solid solution, resulting in that bending property becomes insufficient.
  • P can make the metal flow at the time of melt-casting favorable, or can improve the stress relaxation resistance by added singly or in the form of a compound. If the addition amount of P is too large, P causes a lowering in electrical conductivity due to solid solution, and also, nucleation and growth of the Cube orientation ⁇ 001 ⁇ ⁇ 100> in the ND are suppressed by an increase in the amount of solid solution, resulting in that bending property becomes insufficient.
  • the second embodiment of the present invention contains Mg in an amount of 0.01 to 0.5 mass% as an essential alloying element.
  • the copper alloy material may further contain, as an optional alloying element, at least one selected from the group consisting of Zn, Sn, Ag, Si and P in an amount of 0.01 to 0.3 mass% in total.
  • Preferable ranges of the respective amounts of addition of these main alloying element and additional alloying elements are as follows.
  • the addition amount of Mg is preferably 0.01 to 0.3 mass%, more preferably 0.05 to 0.25 mass%.
  • the addition amount of Zn is preferably 0.05 to 0.3 mass%, more preferably 0.1 to 0.2 mass%.
  • the addition amount of Sn is preferably 0.05 to 0.2 mass%, more preferably 0.1 to 0.15 mass%.
  • the addition amount of Ag is preferably 0.01 to 0.15 mass%, more preferably 0.05 to 0.1 mass%.
  • the addition amount of Si is preferably 0.01 to 0.05 mass%, more preferably 0.02 to 0.03 mass%.
  • the addition amount of P is preferably 0.001 to 0.1 mass%, more preferably 0.005 to 0.05 mass%.
  • the unavoidable impurities that are included in the balance are usual ones, and examples thereof include O, F, S and C.
  • the content of each of the unavoidable impurities is preferably 0.001 mass% or less, respectively.
  • the analysis of the crystal orientation of the rolled face in the present invention is conducted using the EBSD method.
  • the EBSD method which stands for electron backscatter diffraction, is a technique of crystal orientation analysis using reflected electron Kikuchi-line diffraction (Kikuchi pattern) that occurs when a sample is irradiated with an electron beam under a scanning electron microscope (SEM).
  • a sample area which is measured 500 ⁇ m on each of the four sides and which contains 200 or more grains, is subjected to an analysis of the orientation, by scanning in a stepwise manner at an interval of 0.5 ⁇ m.
  • the area ratio of the Cube orientation ⁇ 001 ⁇ ⁇ 100> means the ratio of the area of grains having an orientation in which the deviation from an ideal orientation of the Cube orientation ⁇ 001 ⁇ ⁇ 100> is within 15° (a deviation angle of ⁇ 15° or less), to the total measured area.
  • the data obtained from the orientation analysis based on EBSD includes the orientation data to a depth of several tens nanometers, through which the electron beam penetrates into the sample. However, since the depth is sufficiently small as compared with the width to be measured, the data is described in terms of ratio of an area, i.e. area ratio, in the present specification.
  • the orientation distribution changes in the sheet thickness direction, it is preferable to carry out the orientation analysis by EBSD at several arbitrary points along the sheet thickness direction, to calculate the average.
  • the area ratio of a crystal plane having a certain crystal orientation is referred to the area ratio measured in this manner.
  • the area ratio of the Cube orientation ⁇ 001 ⁇ ⁇ 100> on a rolled face is 3% or more, preferably 6% or more.
  • the upper limit is not particularly limited, but is generally 90% or less.
  • coincidence grain boundaries are special grain boundaries with high geometric consistency, and the smaller value of ⁇ that is defined as a reciprocal of the coincident site lattice density means that this consistency is higher.
  • coincidence grain boundary ⁇ 3 is known to have less disorder of regularity in the grain boundaries and lower grain boundary energy. In particular, since there are fewer defects that accelerate stress relaxation in the texture, heat resistance is excellent.
  • the ratio of the coincidence grain boundary ⁇ 3 in the grain boundaries is 20% or more, preferably 30% or more, and more preferably 40% or more.
  • the upper limit is not particularly limited, but is generally 90% or less.
  • the ratio of the coincidence grain boundary ⁇ 3 is a value obtained by determining the sum of lengths of the coincidence grain boundary ⁇ 3 to the total sum of the lengths of grain boundaries on an observed plane analyzed by an ESBD method or the like, by the following formula: (sum of lengths of coincidence grain boundary E3)/(sum of lengths of the entire grain boundaries) x 100 (%).
  • the details of the coincidence grain boundary ⁇ 3 and the method for measuring the length thereof is given on the details of the coincidence grain boundary ⁇ 3 and the method for measuring the length thereof.
  • the analysis of the coincidence grain boundary ⁇ 3 is carried out via a CSL (coincidence site lattice boundary) analysis, using a software "Orientation Imaging Microscopy V5" (trade name) manufactured by EDAX TSL.
  • the coincidence grain boundary ⁇ 3 is a grain boundary in which, for example, adjoining grains are in a relationship of having an angle of rotation of 60° about the axis of rotation of ⁇ 111>.
  • a grain boundary corresponding to the coincidence grain boundary ⁇ 3 is analyzed from the orientation relationship of neighboring grain boundaries, using the software.
  • a measurement region which measures about 500 ⁇ m on each of the four sides and includes 200 or more grains
  • measurement is carried out via an EBSD method under the conditions of a scan step of 0.5 ⁇ m, and the length of the coincidence grain boundary ⁇ 3 and the total grain boundary length are measured using the software.
  • the orientation difference (deviation) of adjoining pixels is 15° or more is considered as a grain boundary
  • the coincidence grain boundary ⁇ 3 is determined from the orientation relationships of adjoining pixels.
  • the ratio of the sum of lengths of the coincidence grain boundary ⁇ 3 to the sum of lengths of the entire grain boundaries is calculated from the length of the entire grain boundaries and the length of the coincidence grain boundary ⁇ 3 on a rolled face, by the following formula: (sum of lengths of coincidence grain boundary E3)/(sum of lengths of entire grain boundaries) ⁇ 100, and this value is designated as the "ratio of the coincidence grain boundary E3 in the grain boundaries". In the present specification, this may be simply referred to as "ratio (%) of coincidence grain boundary ⁇ 3".
  • a Cu-Cr-based copper alloy can be produced by, in the following order: subjecting an ingot obtained by casting [Step 1-1] to homogenization heat treatment [Step 1-2]; making the resultant ingot into a thin sheet by hot-working [Step 1-3] (specifically, hot-rolling) and subsequent cold-working [Step 1-4] (specifically, cold-rolling); and further conducting intermediate heat treatment (intermediate annealing) [Step 1-5]; cold-working [Step 1-6] (specifically, cold-rolling); aging (aging-precipitation heat treatment) [Step 1-9]; and strain-relief annealing [Step 1-11].
  • the conditions for the steps of aging [Step 1-9], cold-working [Step 1-10] and strain-relief annealing [Step 1-11] are appropriately set, according to desired properties, such as mechanical strength and electrical conductivity.
  • a driving force for development of the Cube orientation is given via the hot-working [Step 1-3], and the coincidence grain boundary ⁇ 3 develops upon the aging [Step 1-9] and, if conducted, the heat treatment [Step 1-7], among the above series of steps.
  • the texture is roughly determined via the intermediate heat treatment [Step 1-5], and the texture is finally determined with rotation of the orientation that occurs in the cold-working (for example, cold-rolling) [Step 1-6], [Step 1-8] or [Step 1-10] that is conducted at the last.
  • the heat treatment [Step 1-7] and cold-working [Step 1-8] can be omitted. Although these steps are not carried out, if the aging [Step 1-9] is carried out under predetermined conditions, a desired texture can be obtained. When the heat treatment [Step 1-7] is carried out, the aging [Step 1-9] can be carried out in a shorter time period.
  • the cold-working [Step 1-6] has, in addition to an effect of adjusting the sheet thickness, an effect of giving a strain to the material and accelerating development of the coincidence grain boundary ⁇ 3 in the subsequent heat treatment.
  • any combination of cold-working and heat treatment, in the steps that follow the heat treatment [Step 1-7], may be freely carried out, in connection with, for example, making the material into a thin sheet by the cold-working [Step 1-8], precipitation-hardening and electrical-conductivity enhancement by the aging [Step 1-9] (enhancement of mechanical strength and restoration of electrical conductivity), mechanical-strength enhancement by the cold-working [Step 1-10] after the aging [Step 1-9], restoration of spring property and/or elongation by the strain-relief annealing [Step 1-11], and the like.
  • examples in the first embodiment of the present invention include the following representative examples of the heat treatment/working conditions and preferable conditions of the steps.
  • the homogenization heat treatment [Step 1-2] is preferably carried out at 600 to 1,025°C for 10 minutes to 10 hours.
  • the homogenization heat treatment time period may be set to 2 to 10 hours.
  • the hot-working [Step 1-3] is preferably carried out at a working temperature of 500 to 1,020°C at a working ratio of 30 to 98%.
  • the cold-working [Step 1-4] is preferably carried out at a working ratio of 50 to 99%. This working ratio may also be set to 50 to 95%.
  • the intermediate heat treatment (intermediate annealing) [Step 1-5] is preferably carried out at 300 to 1,000°C for 5 seconds to 180 minutes.
  • the cold-working [Step 1-6] is preferably carried out at a working ratio of 50 to 95%.
  • the heat treatment [Step 1-7] is preferably carried out at 650 to 1,000°C for 5 to 60 seconds.
  • the cold-working [Step 1-8] is preferably carried out at a working ratio of 10 to 60%.
  • the aging (aging-precipitation heat treatment) [Step 1-9] is preferably carried out at 400 to 650°C for 30 to 180 minutes.
  • the finish cold-working [Step 1-10] is preferably carried out at a working ratio of 0 to 70%.
  • a working ratio of 0% means that the relevant working is not conducted, and in this case, the cold-working [Step 1-10] is omitted.
  • the strain-relief annealing [Step 1-11] is preferably carried out at 550 to 700°C for 5 seconds to 10 minutes.
  • the strain-relief annealing time period may be set to 5 to 60 seconds.
  • pickling or surface-polishing may be conducted depending on the state of oxidation or roughness of the material surface, and/or a correction with a tension leveler may be conducted depending on the material shape.
  • a correction with a tension leveler may be conducted depending on the material shape.
  • Preferable examples of the combination of those steps in the first embodiment of the present invention include Production Method 1 to Production Method 4 in the example section described below.
  • the working ratio refers to a value calculated as in the following formula:
  • Working ratio % t 1 - t 2 / t 1 ⁇ 100 wherein, "t 1 " represents the sheet thickness before the rolling, and "t 2 " represents the sheet thickness after the rolling.
  • a Cu-Mg-based copper alloy can be produced by, in the following order: subjecting an ingot obtained by casting [Step 2-1] to homogenization heat treatment [Step 2-2]; making the resultant ingot into a thin sheet by hot-working [Step 2-3] (specifically, hot-rolling) and subsequent cold-working [Step 2-4] (specifically, cold-rolling); and further conducting intermediate heat treatment (intermediate annealing) [Step 2-5]; cold-working [Step 2-6] (specifically, cold-rolling); heat treatment [Step 2-7]; finish cold-working [Step 2-8] (specifically, cold-rolling); and strain-relief annealing [Step 2-9].
  • the conditions for the strain-relief annealing [Step 2-9] are appropriately set, according to desired properties, such as mechanical strength, electrical conductivity, elongation, and spring property (stress relaxation resistance).
  • the cold-working [Step 2-6] has, in addition to an effect of adjusting the sheet thickness, an effect of giving a strain to the material and accelerating development of the coincidence grain boundary ⁇ 3 in the subsequent heat treatment [Step 2-8].
  • any combination of cold-working and heat treatment, in the steps that follow the heat treatment [Step 2-7], may be freely carried out, in connection with, for example, making the material into a thin sheet by the cold-working [Step 2-8] together with mechanical-strength enhancement, restoration of spring property and/or elongation by the strain-relief annealing [Step 2-9], and the like.
  • examples in the second embodiment of the present invention include the following representative examples of the heat treatment/working conditions and preferable conditions of the steps.
  • the homogenization heat treatment [Step 2-2] is preferably carried out at 600 to 1,025°C for 10 minutes to 10 hours.
  • the homogenization heat treatment time period may be set to 1 to 5 hours.
  • the hot-working [Step 2-3] is preferably carried out at a working temperature of 500 to 1,020°C at a working ratio of 30 to 98%.
  • the cold-working [Step 2-4] is preferably carried out at a working ratio of 50 to 99%. This working ratio may also be set to 50 to 95%.
  • the intermediate heat treatment (intermediate annealing) [Step 2-5] is preferably carried out at 300 to 800°C for 5 seconds to 180 minutes.
  • the cold-working [Step 2-6] is preferably carried out at a working ratio of 50 to 95%.
  • the heat treatment [Step 2-7] is preferably carried out at 300 to 800°C for 5 seconds to 180 minutes.
  • This heat treatment temperature may be set at 300 to 600°C, 400 to 800°C, or 600 to 800°C.
  • This heat treatment time period may be set to 30 to 180 minutes, or 5 to 60 seconds.
  • the cold-working [Step 2-8] is preferably carried out at a working ratio of 10 to 80%.
  • the strain-relief annealing [Step 2-9] is preferably carried out at 300 to 600°C for 5 to 60 seconds.
  • pickling or surface-polishing may be conducted depending on the state of oxidation or roughness of the material surface, and/or a correction with a tension leveler may be conducted depending on the material shape.
  • a correction with a tension leveler may be conducted depending on the material shape.
  • Preferable examples of the combination of those steps in the second embodiment of the present invention include Production Method 10 to Production Method 14 in the example section described below.
  • the copper alloy material of the first embodiment of the present invention can satisfy the properties that are required in lead frames, connectors, terminal materials, and the like of, for example, parts to be mounted on vehicles and surrounding infrastructures primarily for EVs and HEVs, and solar photovoltaic power generation systems.
  • the copper alloy material satisfies an electrical conductivity of 75%IACS or higher, preferably 80%IACS or higher.
  • the copper alloy material satisfies a tensile strength of 400 MPa or higher. Bending property is evaluated by the value (R/t) obtained by dividing the minimum bending radius (R: unit mm) in 90° W bending in which bending is possible without cracking, by the sheet thickness (t: unit mm).
  • the bending property varies depending on the extent of tensile strength which the copper alloy material in interest has.
  • the stress relaxation resistance is evaluated by the stress relaxation ratio (SR) determined according to Japan Copper and Brass Association JCBA T309:2004 (method for testing stress relaxation by bending of thin sheet strips of copper and copper alloys), and the copper alloy material can satisfy a stress relaxation ratio of 35% or less.
  • SR stress relaxation ratio
  • the copper alloy material of the second embodiment of the present invention can satisfy the properties that are required in lead frames, connectors, terminal materials, and the like of, for example, parts to be mounted on vehicles and surrounding infrastructures primarily for EVs and HEVs, and solar photovoltaic power generation systems.
  • the copper alloy material satisfies an electrical conductivity of 75%IACS or higher, preferably 80%IACS or higher.
  • the copper alloy material satisfies a tensile strength of 250 MPa or higher. Bending property is evaluated by the value (R/t) obtained by dividing the minimum bending radius (R: unit mm) in which bending is possible without cracking, by the sheet thickness (t: unit mm).
  • the bending property varies depending on the extent of tensile strength which the copper alloy material in interest has.
  • the copper alloy material can satisfy the stress relaxation ratio (SR) of 35% or less.
  • SR stress relaxation ratio
  • the copper alloy material has favorable properties that are superior to: the results of the two properties of copper alloy materials, having the same composition as the present invention, produced via conventional methods; and a balance of the two properties.
  • Example 1-1 and Comparative Example 1-1 (Cu-Cr-based alloy)
  • the ingot was subjected to homogenization heat treatment [Step 1-2] at 600 to 1,025°C for 10 minutes to 10 hours, followed by hot-rolling [Step 1-3] at a working temperature of 500 to 1,020°C at a working ratio of 30 to 98%, and water-cooling; then, cold-rolling [Step 1-4] at a working ratio of 50 to 99%, and intermediate heat treatment [Step 1-5] at 300 to 1,000°C for 5 seconds to 180 minutes; and then, cold-rolling [Step 1-6] at a working ratio of 50 to 95%.
  • the steps heretofore are the upstream process.
  • the resultant sheet in this state was used as a supplied material, and sample specimens of copper alloy materials of Test Nos.
  • aging [Step 1-9] was carried out at 400 to 650°C for 30 to 180 minutes, followed by cold-rolling [Step 1-10] at a working ratio of 25%, and then strain-relief annealing [Step 1-11] of keeping the resultant sheet at 550 to 700°C for 5 to 60 seconds in a running furnace.
  • the homogenization heat treatment [Step 1-2] was carried out at 600 to 1,025°C for 2 to 10 hours, and the cold-rolling [Step 1-4] was carried out at a working ratio of 50 to 99%.
  • the heat treatment [Step 1-7] and cold-rolling [Step 1-8] were not carried out.
  • heat treatment [Step 1-7] was carried out at 650 to 1,000°C for 5 to 60 seconds, followed by cold-rolling [Step 1-8] at a working ratio of 25%, aging [Step 1-9] at 400 to 650°C for 30 to 180 minutes, and then strain-relief annealing [Step 1-11] of keeping the resultant sheet at 550 to 700°C for 5 to 60 seconds in a running furnace.
  • the cold-rolling [Step 1-10] was not carried out.
  • aging was carried out at 400 to 650°C for 30 to 180 minutes, followed by cold-rolling [Step 1-10] at a working ratio of 50%, and then strain-relief annealing [Step 1-11] of keeping the resultant sheet at 550 to 700°C for 5 to 60 seconds in a running furnace.
  • the heat treatment [Step 1-7] and cold-rolling [Step 1-8] were not carried out.
  • heat treatment was carried out at 650 to 1,000°C for 5 to 60 seconds, followed by cold-rolling [Step 1-8] at a working ratio of 30%, aging [Step 1-9] at 400 to 650°C for 30 to 180 minutes, and cold-rolling [Step 1-10] at a working ratio of 25%, and then strain-relief annealing [Step 1-11] of keeping the resultant sheet at 550 to 700°C for 5 to 60 seconds in a running furnace.
  • aging was carried out at 450 to 600°C for 30 to 180 minutes, followed by cold-rolling [Step 1-10] at a working ratio of 25%, and then strain-relief annealing [Step 1-11] of keeping the resultant sheet at 550 to 700°C for 5 to 60 seconds in a running furnace.
  • the hot-rolling [Step 1-3] was carried out at a working temperature of 300 to 450°C at a working ratio of 30 to 98%.
  • the heat treatment [Step 1-7] and cold-rolling [Step 1-8] were not carried out.
  • aging was carried out at 400 to 650°C for 30 to 180 minutes, followed by cold-rolling [Step 1-10] at a working ratio of 25%, and then strain-relief annealing [Step 1-11] of keeping the resultant sheet at 550 to 700°C for 5 to 60 seconds in a running furnace.
  • the cold-rolling [Step 1-6] was carried out at a working ratio of 30%.
  • the heat treatment [Step 1-7] and cold-rolling [Step 1-8] were not carried out.
  • aging was carried out at 300 to 350°C for 30 to 180 minutes, followed by cold-rolling [Step 1-10] at a working ratio of 25%, and then strain-relief annealing [Step 1-11] of keeping the resultant sheet at 550 to 700°C for 5 to 60 seconds in a running furnace.
  • the heat treatment [Step 1-7] and cold-rolling [Step 1-8] were not carried out.
  • the ingot was subjected to homogenization treatment (since the conditions in Patent Literature 4 are at 900°C or higher for 300 minutes or more, the conditions were set to at 950°C for 500 minutes). Then, the resultant ingot was subjected to hot-working and solution heat treatment, final cold-rolling to make the thickness to 0.15 mm, and aging.
  • the conditions for cold-rolling were set in accordance with the contents of the Patent Literature 4, and the degree of working in each pass was set to 20%, while the overall degree of working was set to 98%.
  • Patent Literature 4 has no description on hot-working conditions, the hot-rolling was conducted successfully, followed by water-cooling. Further, the solution heat treatment was carried out at 800°C for one hour. The aging was carried out at 400°C for about 30 minutes.
  • the ingot After casting to obtain an ingot, the ingot was heated to 950°C and was successfully subjected to hot-rolling to a thickness 8 mm, followed by water-cooling. Then, the resultant sheet was subjected to cold-rolling to a thickness 1 mm, followed by annealing at 800°C for 300 minutes (Patent Literature 5 describes simply that annealing is carried out, but has no description on a specific annealing time period, and the annealing time period was set to 300 minutes). Then, the resultant sheet was subjected to cold-working at a degree of working of 40%, followed by heat treatment at 500°C for one minute, which were repeated three times, to a thickness 0.22 mm.
  • the sample specimens produced via the Production Method 1 were examined on properties as described below.
  • the thickness of each of the sample specimens was set to 0.15 mm, unless otherwise specified.
  • the results of the Examples according to this invention are shown in Table 2-1, and the results of the Comparative Examples are shown in Table 2-2, respectively.
  • the results of the sample specimens produced via the Production Method 5, each of which were Comparative Examples, are shown in Table 3-1 and Table 3-2.
  • Table 4-1 shows the results of the sample specimens of the Examples according to this invention produced via the Production Methods 2 to 4, respectively, and Table 4-2 shows the results of the sample specimens of the Comparative Examples produced via the Production Methods 6 to 9, respectively.
  • the measurement was conducted with the EBSD method in a measurement region of about 500 ⁇ m on each of the four sides, under the conditions of a scan step of 0.5 ⁇ m.
  • the area of atomic planes of grains having a deviation angle from the Cube orientation within ⁇ 15° was determined, and the area ratio of the grains in the Cube orientation was obtained, by dividing the thus-determined area by the total measurement area. In the following tables, this is simply indicated as "Cube area ratio (%)".
  • the measurement was conducted with the EBSD method in a measurement region of about 500 ⁇ m on each of the four sides, under the conditions of a scan step of 0.5 ⁇ m.
  • the orientation difference between the two neighboring crystals (grains) was 15° or greater, it was defined a grain boundary in the measurement object, and the ratio of the sum of lengths of coincidence grain boundary ⁇ 3, to the sum of lengths of the entire grain boundaries, was calculated.
  • the values of: (sum of lengths of coincidence grain boundary E3)/(sum of lengths of the entire grain boundaries) ⁇ 100 is indicated as "Ratio of coincidence grain boundary ⁇ 3 (%)".
  • the bending property was tested and evaluated according to JIS Z 2248.
  • a test piece was taken, by cutting out from the respective sample specimen perpendicularly to the rolling direction, into a size with width 10 mm and length 25 mm.
  • the respective test piece was subjected to W-bending such that the axis of bending would be perpendicular to the rolling direction, which is designated as GW (Good Way), and separately subjected to W-bending such that the axis of bending would be parallel to the rolling direction, which is designated as BW (Bad Way).
  • the occurrence (i.e. whether occurred or not) of cracks at the thus-bent portion was examined, by observing the bent portion under an optical microscope with a magnification of 200x.
  • t represents the sheet thickness (mm)
  • R represents the minimum bending radius (mm) in 90° W bending.
  • a sample specimen was judged "good ( ⁇ )", in the case where it satisfied the conditions described above, it had other properties (tensile strength, electrical conductivity, and stress relaxation resistance) not conspicuously inferior to the conventional materials having the same alloy composition, and it was capable of being bent at a smaller bending radius R.
  • test pieces were cut out from the respective sample specimen in the direction parallel to the rolling direction, according to JIS Z2201-13B, followed by measuring, according to JIS Z2241, to obtain the average value as shown in the tables.
  • the electrical conductivity was calculated by using the four-terminal method to measure the specific resistance of the respective sample specimen in a thermostat bath that was maintained at 20°C ( ⁇ 0.5°C). The spacing between terminals was set to 100 mm. A sample specimen having an electrical conductivity (EC) of 75%IACS or higher was judged “fair (o)", and one with less than 75%IACS was judged “poor ( ⁇ )”.
  • EC electrical conductivity
  • the stress relaxation ratio (SR) was measured, according to Japan Copper and Brass Association JCBA T309:2004 (method for testing stress relaxation by bending of thin sheet strips of copper and copper alloys), under the conditions of maintaining at 150°C for 1,000 hours, as described below.
  • SR stress relaxation ratio
  • Figs. 1(a) and 1(b) each are a drawing explaining the method of testing the stress relaxation resistance, in which Fig. 1(a) shows the state before heat treatment, and Fig. 1(b) shows the state after the heat treatment.
  • Fig. 1(a) the position of a test piece 1 when the initial stress of 80% of the yield stress was applied to the test piece 1 cantilevered on a test bench 4, is defined as the distance ⁇ 0 from the reference position.
  • This test piece was kept in a thermostat at 150°C for 1,000 hours (which corresponds to the heat treatment at the state of the test piece 1).
  • the position of the test piece 2 after removing the load is defined as the distance H t from the reference position, as shown in Fig.
  • the reference numeral 3 denotes the test piece to which no stress was applied, and the position of the test piece 3 is defined as the distance H 1 from the reference position. Based on the relationships among those positions, the stress relaxation ratio (%) was calculated as: ⁇ (H t -H 1 )/( ⁇ 0 -H 1 ) ⁇ 100.
  • ⁇ 0 represents the distance from the reference position to the test piece 1
  • H 1 represents the distance from the reference position to the test piece 3
  • H t represents the distance from the reference position to the test piece 2.
  • a sample specimen having a stress relaxation ratio (SR) of less than 35% was judged “fair (o)", and a sample specimen having a stress relaxation ratio (SR) of 35% or higher was judged “poor ( ⁇ )”. Furthermore, a sample specimen of Example according to this invention was judged “good ( ⁇ )", in the case where it satisfied the conditions of a stress relaxation ratio (SR) of less than 35% as described above, it had other properties (tensile strength, electrical conductivity, and bending property) not conspicuously inferior to the conventional materials having the same alloy composition, and it had a smaller stress relaxation ratio (SR) Table 1-1 Alloy No.
  • Table 1-1 show copper alloys (Alloy Nos. 1 to 22) according to the present invention having alloy compositions in the range defined in the present invention
  • Table 1-2 show copper alloys (Alloy Nos. 23 to 50) of Comparative Examples having alloy compositions outside the range defined in the present invention.
  • the unit is mass%.
  • An empty cell means no addition of the alloying element.
  • the balance was Cu and unavoidable impurities.
  • Alloy properties are defined to include bending property, tensile strength, electrical conductivity, and stress relaxation resistance, and when an alloy satisfied favorable properties in which each of the properties had values that were the specified values according to the present invention or preferable values or more/or less, the alloy is judged to be favorable in the alloy properties. When even any one of the properties was not satisfied, the alloy is judged to be poor in the alloy properties.
  • any one or both of bending property and stress relaxation resistance were improved more than those of copper alloy materials having the same alloy composition and obtained with the conventional production method, the copper alloy material of the present invention is judged to be excellent that has not obtained conventionally.
  • the texture which are defined to include the area ratio of the Cube orientation and the ratio of coincidence grain boundary ⁇ 3 of the product
  • the texture is judged to fulfill the defined range, and when a copper alloy material did not satisfy even any one of these definitions, the texture is judged to be outside the defined range.
  • the production process conditions are judged to be in the range defined in the present invention.
  • Table 2-1 shows Examples according to this invention in which the alloy composition was in the range defined in the present invention, and the copper alloy material was produced via the production method in the range defined in the present invention. With respect to these Examples according to this invention, the copper alloy materials satisfied the texture defined in the present invention, and had favorable alloy properties.
  • Table 2-2 shows Comparative Examples in which the alloy composition was outside the range defined in the present invention, but the copper alloy material was produced via the production method in the range defined in the present invention. With respect to these Comparative Examples, any one or more of the alloy properties was poor, or cracking in the hot-working occurred in the middle course of the production, resulting in that it was impossible for the copper alloy material to be subjected to the subsequent process. It is understood that although the texture and the production conditions were in the ranges defined in the present invention, the copper alloy material, whose alloy composition was outside the range defined in the present invention, had alloy properties inferior to the desired alloy properties, or suffered problems in the production, resulting in giving defective products.
  • Table 3-1 shows Comparative Examples in which the alloy composition was in the range defined in the present invention, but the copper alloy material was produced via the production method outside the range defined in the present invention. Further, Table 3-2 shows Comparative Examples in which the alloy composition was outside the range defined in the present invention, and the copper alloy material was produced via the production method outside the range defined in the present invention.
  • Table 4-1 and Table 4-2 show the results of the alloy properties of the copper alloy materials produced via the Production Methods 2 to 5 and 6 to 9, respectively, for Alloy Nos. 3, 6, 9, 11, 15, 18, 20 and 22, respectively, as the representative alloy compositions.
  • the resultant copper alloy materials each satisfied the alloy properties.
  • the copper alloy material was produced via the production method in any of the Production Methods 6 and 7 outside the range defined in the present invention, any of the alloy properties was conspicuously inferior to the desired properties, or even if the resultant copper alloy material satisfied the desired properties, the properties were conspicuously inferior to the properties as compared to those of Examples according to this invention.
  • Example 2-1 and Comparative Example 2-1 (Cu-Mg-based alloy)
  • a copper alloy containing Mg as an essential alloying element, and containing, as an optional alloying element, at least one selected from the group consisting of Zn, Fe, Sn, Ag and Si, with the balance being Cu and unavoidable impurities, was melted in a high-frequency melting furnace, followed by casting [Step 2-1], to obtain an ingot.
  • the ingot was subjected to homogenization heat treatment [Step 2-2] at 600 to 1,025°C for 1 to 5 hours, followed by hot-rolling [Step 2-3] at a working temperature of 500 to 900°C at a working ratio of 30 to 98%, and water-cooling; then, cold-rolling [Step 2-4] at a working ratio of 50 to 99%, and intermediate heat treatment [Step 2-5] at 300 to 800°C for 5 seconds to 180 minutes; and then, cold-rolling [Step 2-6] at a working ratio of 50 to 95%.
  • the steps heretofore are the upstream process.
  • the resultant sheet in this state was used as a supplied material, and sample specimens of copper alloy materials of Test Nos.
  • heat treatment [Step 2-7] was carried out at 300 to 600°C for 30 to 180 minutes, followed by cold-rolling [Step 2-8] at a working ratio of 20%, and then strain-relief annealing [Step 2-9] of keeping the resultant sheet at 300 to 600°C for 5 to 60 seconds.
  • the cold-rolling [Step 2-4] was carried out at a working ratio of 50 to 95%.
  • heat treatment was carried out at 300 to 600°C for 30 to 180 minutes, followed by cold-rolling [Step 2-8] at a working ratio of 40%, and then strain-relief annealing [Step 2-9] of keeping the resultant sheet at 300 to 600°C for 5 to 60 seconds.
  • heat treatment was carried out at 600 to 800°C for 5 to 60 seconds, followed by cold-rolling [Step 2-8] at a working ratio of 20%, and then strain-relief annealing [Step 2-9] of keeping the resultant sheet at 300 to 600°C for 5 to 60 seconds.
  • heat treatment was carried out at 600 to 800°C for 5 to 60 seconds, followed by cold-rolling [Step 2-8] at a working ratio of 45%, and then strain-relief annealing [Step 2-9] of keeping the resultant sheet at 300 to 600°C for 5 to 60 seconds.
  • heat treatment was carried out at 400 to 800°C for 5 to 60 seconds, followed by cold-rolling [Step 2-8] at a working ratio of 75%, and then strain-relief annealing [Step 2-9] of keeping the resultant sheet at 300 to 600°C for 5 to 60 seconds.
  • heat treatment [Step 2-7] was carried out at 300 to 600°C for 30 to 180 minutes, followed by cold-rolling [Step 2-8] at a working ratio of 20%, and then strain-relief annealing [Step 2-9] of keeping the resultant sheet at 300 to 600°C for 5 to 60 seconds.
  • the hot-rolling [Step 2-3] was carried out at a working temperature of 300 to 500°C at a working ratio of 30 to 98%.
  • heat treatment [Step 2-7] was carried out at 300 to 600°C for 30 to 180 minutes, followed by cold-rolling [Step 2-8] at a working ratio of 40%, and then strain-relief annealing [Step 2-9] of keeping the resultant sheet at 300 to 600°C for 5 to 60 seconds.
  • the hot-rolling [Step 2-3] was carried out at a working temperature of 300 to 500°C at a working ratio of 30 to 98%.
  • heat treatment was carried out at 600 to 800°C for 5 to 60 seconds, followed by cold-rolling [Step 2-8] at a working ratio of 90%, and then strain-relief annealing [Step 2-9] of keeping the resultant sheet at 300 to 600°C for 5 to 60 seconds.
  • the sample specimens produced via the Production Method 10 were examined on properties as described below.
  • the thickness of each of the sample specimens was set to 0.15 mm, unless otherwise specified.
  • the results of the Examples according to this invention are shown in Table 6-1, and the results of the Comparative Examples are shown in Table 6-2, respectively.
  • the results of the sample specimens produced via the Production Method 15, each of which were Comparative Examples, are shown in Table 7-1 and Table 7-2.
  • Table 8-1 shows the results of the sample specimens of the Examples according to this invention produced via the Production Methods 11 to 14, respectively, and Table 8-2 shows the results of the sample specimens of the Comparative Examples produced via the Production Methods 16 to 17 or 8 to 9, respectively.
  • the bending property was tested and evaluated according to JIS Z 2248.
  • a test piece was taken, by cutting out from the respective sample specimen perpendicularly to the rolling direction, into a size with width 10 mm and length 25 mm.
  • the respective test piece was subjected to the bending such that the axis of bending would be perpendicular to the rolling direction, which is designated as GW (Good Way), and separately subjected to the bending such that the axis of bending would be parallel to the rolling direction, which is designated as BW (Bad Way).
  • the occurrence (i.e. whether occurred or not) of cracks at the thus-bent portion was examined, by observing the bent portion under an optical microscope with a magnification of 200x.
  • a sample specimen which had a favorable bending property without cracking under the respective conditions, was judged "fair (o)", and when cracks occurred, such a sample specimen was judged "poor (x)".
  • a sample specimen was judged "good ( ⁇ )", in the case where it satisfied the conditions described above, it had an improved bending property as compared to the conventional materials having the same alloy composition and a similar level of mechanical strength.
  • Table 5-1 show copper alloys (Alloy Nos. 2-1 to 2-10) according to the present invention having alloy compositions in the range defined in the present invention, and Table 5-2 show copper alloys (Alloy Nos. 2-11 to 2-18) of Comparative Examples having alloy compositions outside the range defined in the present invention.
  • the unit is mass%.
  • An empty cell means no addition of the alloying element.
  • the balance was Cu and unavoidable impurities.
  • Alloy properties are defined to include bending property, tensile strength, electrical conductivity, and stress relaxation resistance, and when an alloy satisfied favorable properties in which each of the properties had values that were the specified values according to the present invention or preferable values or more/or less, the alloy is judged to be favorable in the alloy properties. When even any one of the properties was not satisfied, the alloy is judged to be poor in the alloy properties.
  • any one or both of bending property and stress relaxation resistance were improved more than those of copper alloy materials having the same alloy composition and obtained with the conventional production method, the copper alloy material of the present invention is judged to be excellent that has not obtained conventionally.
  • the texture which are defined to include the area ratio of the Cube orientation and the ratio of coincidence grain boundary ⁇ 3 of the product
  • the texture is judged to fulfill the defined range, and when a copper alloy material did not satisfy even any one of these definitions, the texture is judged to be outside the defined range.
  • the production process conditions are judged to be in the range defined in the present invention.
  • Table 6-1 shows Examples according to this invention in which the alloy composition was in the range defined in the present invention, and the copper alloy material was produced via the production method in the range defined in the present invention. With respect to these Examples according to this invention, the copper alloy materials satisfied the texture defined in the present invention, and had favorable alloy properties.
  • Table 6-2 shows Comparative Examples in which the alloy composition was outside the range defined in the present invention, but the copper alloy material was produced via the production method in the range defined in the present invention. With respect to these Comparative Examples, any one or more of the alloy properties was poor, or cracking in the hot-working occurred in the middle course of the production, resulting in that it was impossible for the copper alloy material to be subjected to the subsequent process. It is understood that although the texture and the production conditions were in the ranges defined in the present invention, the copper alloy material, whose alloy composition was outside the range defined in the present invention, had alloy properties inferior to the desired alloy properties, or suffered problems in the production, resulting in giving defective products.
  • Table 7-1 shows Comparative Examples in which the alloy composition was in the range defined in the present invention, but the copper alloy material was produced via the production method outside the range defined in the present invention. Further, Table 7-2 shows Comparative Examples in which the alloy composition was outside the range defined in the present invention, and the copper alloy material was produced via the production method outside the range defined in the present invention.
  • Table 8-1 and Table 8-2 show the results of the alloy properties of the copper alloy materials produced via the Production Methods 11 to 14, 16 to 17, 8, and 9, respectively, for Alloy Nos. 2-4, 2-5, 2-7, 2-8, and 2-9, respectively, as the representative alloy compositions.
  • the resultant copper alloy materials each satisfied the alloy properties.
  • Comparative Examples 6-26 to 6-30 produced via the Production Method 17 since the copper alloy materials were worked with high deformation at an excessively high working ratio in the final cold-rolling [Step 2-8], grains underwent rotation, and the orientation relationships involving the area ratios of coincidence grain boundary ⁇ 3 and/or the Cube orientation were destroyed, resulting in poor stress relaxation resistance and poor bending property.
  • Comparative Examples 6-31 to 6-35 produced via the Production Method 8 when compared with the Examples according to the present invention in terms of the production conditions, no cold-rolling (corresponding to the [Step 2-4]) after the hot-rolling (corresponding to the [Step 2-3]) was carried out, and the working ratio in the final cold-rolling (corresponding to the [Step 2-6]) was too high.
  • the area ratio of the Cube orientation was too low, which was as low as less than 3%, and the ratio of coincidence grain boundary ⁇ 3 was too low, which was as low as less than 20%, resulting in poor stress relaxation resistance and poor bending property.
  • Comparative Examples 6-36 to 6-40 produced via the Production Method 9 when compared with the Examples according to the present invention in terms of the production conditions, there is a difference that the heating time period in the intermediate heat treatment (corresponding to the [Step 2-5]) was too long, and that a heat treatment (corresponding to the [Step 2-7]) was repeated three times. In the textures obtained in these Comparative Examples, the area ratio of the Cube orientation was too low, which was as low as less than 3%, resulting in poor bending property.
  • the copper alloy material of the present invention is suitable in lead frames, connectors, terminal materials, and the like of, for example, parts to be mounted on vehicles and surrounding infrastructures primarily for EVs and HEVs, and solar photovoltaic power generation systems.

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ITUA20163211A1 (it) * 2016-05-06 2017-11-06 De Angeli Prod S R L Conduttore elettrico per avvolgimenti elettrici, specialmente per cavo trasposto continuo
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EP3037561A1 (fr) * 2013-08-12 2016-06-29 Mitsubishi Materials Corporation Alliage à base de cuivre pour dispositifs électroniques/électriques, plaque mince en alliage à base de cuivre pour dispositifs électroniques/électriques, composant pour dispositifs électroniques/électriques, borne et barre omnibus
EP3037561A4 (fr) * 2013-08-12 2017-05-10 Mitsubishi Materials Corporation Alliage à base de cuivre pour dispositifs électroniques/électriques, plaque mince en alliage à base de cuivre pour dispositifs électroniques/électriques, composant pour dispositifs électroniques/électriques, borne et barre omnibus
US10392680B2 (en) 2013-08-12 2019-08-27 Mitsubishi Materials Corporation Copper alloy for electric and electronic devices, copper alloy sheet for electric and electronic devices, component for electric and electronic devices, terminal, and bus bar
US10522268B2 (en) 2014-03-31 2019-12-31 Furukawa Electric Co., Ltd. Rolled copper foil, method of manufacturing a rolled copper foil, flexible flat cable, and method of manufacturing a flexible flat cable
WO2016124322A1 (fr) * 2015-02-02 2016-08-11 Isabellenhütte Heusler Gmbh & Co. Kg Élément de liaison, notamment vis ou écrou
US10619232B2 (en) 2015-02-02 2020-04-14 Isabellenhuette Heusler Gmbh & Co. Kg Connecting element, in particular screw or nut
ITUA20163211A1 (it) * 2016-05-06 2017-11-06 De Angeli Prod S R L Conduttore elettrico per avvolgimenti elettrici, specialmente per cavo trasposto continuo
EP3242299A1 (fr) * 2016-05-06 2017-11-08 De Angeli Prodotti S.r.l. Conducteur électrique pour enroulements électriques, notamment pour conducteur transposé continuellement

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CN103534370A (zh) 2014-01-22
KR101914322B1 (ko) 2018-11-01
CN103534370B (zh) 2015-11-25
JP5307305B1 (ja) 2013-10-02
TWI571518B (zh) 2017-02-21
EP2752498A4 (fr) 2015-04-08
TW201311913A (zh) 2013-03-16
JPWO2013031841A1 (ja) 2015-03-23
WO2013031841A1 (fr) 2013-03-07
KR20140052997A (ko) 2014-05-07

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