EP2508632B1 - Kupferlegierungsfolie - Google Patents

Kupferlegierungsfolie Download PDF

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Publication number
EP2508632B1
EP2508632B1 EP20100834574 EP10834574A EP2508632B1 EP 2508632 B1 EP2508632 B1 EP 2508632B1 EP 20100834574 EP20100834574 EP 20100834574 EP 10834574 A EP10834574 A EP 10834574A EP 2508632 B1 EP2508632 B1 EP 2508632B1
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Prior art keywords
rolling
copper alloy
cold
sheet material
alloy sheet
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French (fr)
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EP2508632A1 (de
EP2508632A4 (de
Inventor
Koji Sato
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
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H01B1/026—Alloys based on copper

Definitions

  • the present invention relates to an excellent copper alloy sheet material, and specifically to a copper alloy sheet material excellent in mechanical strength and bending property, which copper alloy sheet material is suitable for connection parts, such as connectors and terminals for use in automobiles.
  • Corson alloy is an alloy in which the solid solution limit of nickel silicide (Ni 2 Si) compound to copper varies depending upon the temperature, and is a precipitation hardening-type alloy that is hardened by an aging precipitation treatment, and is favorable in heat resistance, electrical conductivity, and mechanical strength.
  • the inventors of the present invention having studied the mechanism of bending in a Corson-based copper alloy, have confirmed that the shear band that occurs at the sheet surface upon bending is a cause of cracks. Further, we have confirmed that this shear band can be reduced by accumulating the Cube orientation, but we also found a problem that, at the same time, tensile strength is lowered. As a cause for this lowering of mechanical strength, we presume that, since the Cube orientation is small in the work hardening coefficient upon deforming, deformation occurs even with relatively low mechanical strength, and fracture occurs, without enhancing mechanical strength sufficiently.
  • the present invention is contemplated for providing a copper alloy sheet material for electrical or electronic equipments, which is excellent in bending property and mechanical strength, and which is favorable for lead frames, connectors, terminal materials, and the like, for electrical or electronic equipments, and in particular for connectors, for example, to be mounted on automobile vehicles, or terminal materials, relays, switches, and the like.
  • the inventors of the present invention found that, when the area ratio of grains with crystals oriented having a deviation angle within 15° to 30° from the Cube orientation is defined to be within a specific range, a balance between excellent bending property and high mechanical strength can be achieved.
  • the present invention has been attained based on this finding.
  • the present invention is the following means:
  • the copper alloy sheet material of the present invention has high mechanical strength and favorable bending property, and exhibits high electrical conductivity. Furthermore, the above-described properties of the copper alloy sheet material can be further enhanced, by adding other additive elements. Moreover, the copper alloy sheet material can also realize an enhancement of migration resistance or heat resistant peelability upon soldering, or an enhancement of stress relaxation resistance or workability upon hot-rolling.
  • copper alloy material means a product obtained after a copper alloy base material is worked into a predetermined shape (for example, sheet, strip, foil, rod, or wire).
  • a sheet material refers to a material which has a specific thickness, is stable in the shape, and is extended in the plane direction, and in a broad sense, the sheet material is meant to encompass a strip material.
  • the term "surface layer of the material (or material surface layer)” means the “sheet surface layer,” and the term “position of a depth of the material” means the “position in the sheet thickness direction.”
  • the thickness is preferably 8 to 800 ⁇ m, and more preferably 50 to 70 ⁇ m.
  • the characteristics are defined by the accumulation ratio of the atomic plane in a predetermined direction of a rolled sheet, but this will be considered enough if the copper alloy sheet material has such characteristics.
  • the shape of the copper alloy sheet material is not intended to be limited to a sheet material or a strip material, and it is noted that in the present invention, a tube material can also be construed and treated as a sheet material.
  • the average grain size of the copper alloy sheet material of the present invention is preferably set to 50 ⁇ m or less.
  • the shear band that would become a cause of cracking is not easily occurred in both the cases of Good Way (GW) bending and Bad Way (BW) bending, which is preferable.
  • GW Good Way
  • BW Bad Way
  • the grain size is determined, according to JIS H 0501 (cutting method).
  • the crystal texture of the copper alloy sheet material of the present invention has, particularly in order to achieve a good balance between mechanical strength and bending property, a crystal texture in which from the results of an analysis according to a SEM-EBSD method (which will be described below), the area ratio of grains having a deviation angle (orientation shift) of less than 15° from the Cube orientation is less than 10%, and the area ratio of grains having a deviation angle of 15° to 30° from the Cube orientation is 15% or greater, preferably equal to or greater than 20% and less than 50%.
  • the material mainly forms crystal textures called the Cube orientation, the Goss orientation, the Brass orientation, the Copper orientation, the S orientation, and the like, which will be described below, and has crystal faces corresponding to those orientations, respectively.
  • crystal textures of a material are indicated by planes and directions, such that a plane is expressed in the form of ⁇ A B C ⁇ , and a direction is expressed in the form of ⁇ D E F>.
  • the method of indicating the crystal orientation in the present specification is such that a Cartesian coordinate system is employed, representing the rolling direction (RD) of the material in the X-axis, the transverse direction (TD) in the Y-axis, and the direction normal to the rolling direction (ND) in the Z-axis, various regions in the material are indicated in the form of (h k I) [u v w], using the index (h k I) of the crystal plane that is perpendicular to the Z-axis and the index [u v w] in the crystal direction parallel to the X-axis.
  • the respective orientations are expressed as follows.
  • the Cube orientation ⁇ 001 ⁇ ⁇ 100> The Goss orientation ⁇ 011 ⁇ ⁇ 100>
  • the Rotated-Goss orientation ⁇ 011 ⁇ ⁇ 011> The Brass orientation ⁇ 011 ⁇ ⁇ 211>
  • the Copper orientation ⁇ 112 ⁇ ⁇ 111> The S orientation ⁇ 123 ⁇ ⁇ 634>
  • the crystal texture of a conventional copper alloy sheet material is composed of quite many orientation factors, as explained above. However, when the constitutional proportions of these crystal faces is changed, the plastic behavior of the material, such as a sheet material, changes, to change the workability in, for example, bending.
  • the crystal texture of a conventional Corson-based high-strength copper alloy sheet material is such that, when the sheet material is produced according to a usual method, the S orientation ⁇ 1 2 3 ⁇ ⁇ 6 3 4> and/or the Brass orientation ⁇ 0 1 1 ⁇ ⁇ 2 1 1 > exists as a main component, in addition to the Cube orientation ⁇ 0 0 1 ⁇ ⁇ 1 0 0>, as presented in the examples that will be described below, and the proportion of the Cube orientation is decreased. For this reason, a shear band is apt to occur, particularly in the BW bending, to deteriorate the bending property. On the other hand, when the bending property is improved by increasing the accumulation of grains having a deviation angle of less than 15° from the Cube orientation, there is a problem that mechanical strength is lowered.
  • the crystal texture of the copper alloy sheet material of the present invention has a crystal texture excellent in mechanical strength and bending property, in which the area ratio of grains having a deviation angle of 15 to 30% from the Cube orientation ⁇ 0 0 1 ⁇ ⁇ 1 0 0> is 15% or greater.
  • the area ratio of grains having a deviation angle of 15° to 30° from the Cube orientation is 15% or greater, the existence of other orientations as sub-orientations is allowable.
  • the measurement of the degree of accumulation of orientation grains having a deviation angle of 15° to 30° from the Cube orientation ⁇ 0 0 1 ⁇ ⁇ 1 0 0> in the crystal texture of a copper alloy sheet material is achieved by conducting an orientation analysis based on the data obtained by analyzing an electron micrographic texture by SEM with EBSD, by using the crystal orientation distribution function (ODF).
  • ODF crystal orientation distribution function
  • a sample area measured 1,200 ⁇ m on each of the four sides and containing 400 or more grains, is subjected to an analysis of the orientation, by scanning in a stepwise manner at an interval of 0.5 ⁇ m. Since these orientation distributions vary in the thickness direction of the material, it is preferable to analyze the orientation distribution at any several points in the thickness direction, to determine the orientation distribution by taking an average of the data thus obtained.
  • This SEM-EBSD method is an abbreviation of the Scanning Electron Microscopy-Electron Back Scattered Diffraction Pattern method. That is, the method involves irradiating individual grains described in a scanning electron microscope (SEM) image with an electron beam, and identifying the individual crystal orientations from the diffracted electrons.
  • SEM scanning electron microscope
  • an angle of rotation around the axis of common rotation is calculated, and the angle of rotation is designated as the deviation angle.
  • the orientation (1 2 1) [1 -1 1] is in a relationship of being rotated by 19.4° around the (20 10 17) direction as the axis of rotation, and this angle is designated as the deviation angle.
  • the common axis of rotation one that can be represented by the smallest deviation angle is employed. This deviation angle is calculated for all measurement points, and the number including up to the first decimal place is designated as the effective number.
  • the area of grains having an orientation of less than 15° from, or within 15° to 30° from the Cube orientation is divided by the total measured area, and the resultant value is designated as the ratio of the area.
  • the analysis is conducted, after mirror polishing of the substrate surface, with polishing particles of colloidal silica after mechanical polishing.
  • orientations that can be measured by the method of X-ray diffraction include only five kinds of planes which satisfy the Bragg's diffraction condition and can give sufficient diffraction intensities, namely, ND//(1 1 1), (2 0 0), (2 2 0), (3 1 1), and (4 2 0) planes, and the orientations whose deviation angles from the Cube orientation correspond to 15° to 30°, for example, the crystal orientations indicated with higher indexes, such as ND//(5 1 1) plane or ND//(9 5 1) plane, cannot be measured.
  • the EBSD analysis by employing the EBSD analysis, for the first time, information on those orientations is obtained, and the relationship between the metal texture to be specified by the orientations and the actions/effects thereof are made clear.
  • the second feature is that X-ray diffraction analyzes the quantity of the crystal orientation that is included in the range of about ⁇ 0.5° with respect to ND// ⁇ h k l ⁇ .
  • the EBSD analysis which utilizes Kikuchi patterns, makes it possible to obtain a huge variety of comprehensive information on metal textures that are not limited to particular crystal faces, thereby to clarify those states that cannot be easily specified by X-ray diffraction in the overall alloy material.
  • the results of EBSD are results obtained in connection with the ND direction of a copper alloy sheet material.
  • Ni is set to 0.5 to 5.0%.
  • Ni is an element that is contained together with Si, which will be described below, to form a Ni 2 Si phase that is precipitated by an aging treatment, to contribute to enhancement of the mechanical strength of the resultant copper alloy sheet material. If the content of Ni is too small, the Ni 2 Si phase is insufficient, and the tensile strength of the copper alloy sheet may not be enhanced. On the other hand, if the content of Ni is too large, the electrical conductivity lowers, and the hot-rolling workability is deteriorated. Thus, the content of Ni is set to the range of 0.5 to 5.0%, preferably 1.5 to 4.0%.
  • the content of Co is set to 0.5 to 5.0%.
  • Co is an element that is contained together with Si, to form a Co 2 Si phase that is precipitated by the aging treatment as in the case of Ni, to contribute to enhancement of the mechanical strength of the resultant copper alloy sheet material. If the content of Co is too small, the Co 2 Si phase is insufficient, and the tensile strength of the copper alloy sheet may not be enhanced. On the other hand, if the content of Co is too large, the electrical conductivity lowers, and the hot-rolling workability is deteriorated.
  • the content of Co is set to the range of 0.5 to 5.0%, preferably 0.8 to 3.0%.
  • Ni and Co may be contained in a total amount for both elements of 0.5 to 5.0%.
  • both Ni 2 Si and Co 2 Si are precipitated upon the aging treatment, to enhance the aging strength. If the total content of Ni and Co is too small, the tensile strength may not be enhanced, and if the total content is too large, electrical conductivity and hot-rolling workability are deteriorated.
  • the total content of Ni and Co is set in the range of 0.5 to 5.0%, preferably 0.8 to 4.0%.
  • Si is contained together with the Ni and/or Co, to form the Ni 2 Si phase and/or Co 2 Si phase that are(is) precipitated by the aging treatment, to contribute to enhancement of the mechanical strength of the copper alloy sheet material.
  • the content of Si is set such that the ratio Ni/Si as a stoichiometric ratio is set to 4.2, and the ratio Co/Si as a stoichiometric ratio is set to 4.2, the balance between electrical conductivity and mechanical strength is most favorably achieved.
  • the tensile strength of the copper alloy sheet material can be enhanced, but the excess amount of Si is made into a solid solution in the matrix of copper, to lower the electrical conductivity of the copper alloy sheet material. Further, if Si is contained in excess, the casting property in casting, and/or hot- and cold-rolling workability are also deteriorated, to result in being apt to occurring casting cracks or rolling cracks. On the other hand, if the content of Si is outside this range and too small, the precipitated phase of Ni 2 Si and/or Co 2 Si is insufficiently formed, and the tensile strength of the sheet may not be enhanced.
  • the copper alloy may also contain Cr in an amount of 0.01 to 0.5%.
  • Cr has an effect of making grains in the alloy finer, to contribute to enhancement of the mechanical strength and/or bending property of the copper alloy sheet material. If the content is too small, the effect is not obtained, and if the content is too large, crystallized products are formed upon casting, to lower the aging strength.
  • a preferred content of Cr is 0.05 to 0.3%.
  • the high-strength copper alloy sheet material of the present invention may contain, as an additive element(s) in addition to the above-mentioned basic composition, one, two or more of Sn: 0.05 to 1.0%, Zn: 0.01 to 1.0%, Ag: 0.01 to 1.0%, Mn: 0.01 to 1.0%, Zr: 0.1 to 1.0%, and Mg: 0.01 to 1.0%, each in terms of mass%.
  • Sn 0.05 to 1.0%
  • Zn 0.01 to 1.0%
  • Ag 0.01 to 1.0%
  • Mn 0.01 to 1.0%
  • Zr 0.1 to 1.0%
  • Mg 0.01 to 1.0%
  • Sn is an element that mainly enhances the mechanical strength of the resultant copper alloy sheet material, and in the case where the sheet is utilized in applications where these characteristics are regarded as important, Sn is selectively contained. If the content of Sn is too small, the strength enhancing effect is insufficient. On the other hand, when Sn is contained, the electrical conductivity of the copper alloy sheet tends to lower. In particular, if the content of Sn is too large, it is difficult to attain the electrical conductivity of the copper alloy sheet material to be 20 %IACS or higher. Thus, when contained, it is preferable to set the content of Sn to the range of 0.01 to 1.0%.
  • the content of Zn By containing Zn, it becomes possible to enhance the migration resistance or heat resistant peelability upon soldering. If the content of Zn is too small, the effects are insufficient. On the other hand, when Zn is contained, the electrical conductivity of the copper alloy sheet tends to lower, and if the content of Zn is too large, it is difficult to attain the electrical conductivity of the copper alloy sheet to be 20 %IACS or higher. Thus, it is preferable to set the content of Zn to the range of 0.01 to 1.0%.
  • Ag contributes to enhancement of the mechanical strength of the copper alloy sheet material. If the content of Ag is too small, the effects are insufficient. On the other hand, even if Ag is contained in excess, the effects are saturated, which is not preferable. Thus, when Ag is contained, it is preferable to set the content of Ag to the range of 0.01 to 1.0%.
  • Mn mainly enhances workability in hot-rolling of the alloy. If the content of Mn is too small, the effects are insufficient. On the other hand, if the content of Mn is too large, the melt fluidity in casting of the copper alloy is deteriorated, thereby to lower the casting yield. Thus, when Mn is contained, the content of Mn is set to the range of 0.01 to 1.0%.
  • Zr mainly makes grains finer, to enhance the mechanical strength and/or bending property of the copper alloy sheet. If the content of Zr is too small, the effects are insufficient. On the other hand, if the content of Zr is too large, compounds are formed, and the workability upon rolling or the like of the copper alloy sheet is deteriorated. Thus, when Zr is contained, the content of Zr is set to the range of 0.01 to 1.0%.
  • Mg enhances the stress relaxation resistance.
  • Mg is selectively contained in an amount in the range of 0.01 to 1.0%. If the content of Mg is too small, the target effect is insufficient, and if the content is too large, an impediment of lowering of the electrical conductivity is caused, which is not preferable.
  • the Corson alloy sheet material of the present invention is produced through the steps of: casting, hot-rolling, cold-rolling 1, intermediate annealing, cold-rolling 2, solution heat treatment, cold-rolling 3, aging heat treatment, finish cold-rolling, and low-temperature annealing.
  • the method of producing the copper alloy sheet material of the present invention itself may be seen achievable by the similar method as in the case of conventional Corson alloy.
  • the production conditions in each step need to be limited, and in particular, in order to produce the copper alloy sheet material of the present invention, it is preferable to strictly control the conditions in the intermediate annealing and cold-rolling 3.
  • casting is carried out to a molten copper alloy having its components set to any of the composition ranges described above. Then, the resultant ingot is face-milled, followed by subjecting to heating or a homogenization heat treatment at 800 to 1,000°C, hot-rolling, and then water-cooling the thus-hot-rolled sheet.
  • the surface is face-milled, followed by cold-rolling 1.
  • the rolling ratio of this cold-rolling 1 is sufficiently high, even if production proceeds to obtain final products, the Brass orientation, the S orientation, and the like do not excessively develop, and the area ratio of grains having a deviation angle of 15° to 30° from the Cube orientation can be sufficiently increased. For that reason, the rolling ratio of the cold-rolling 1 is preferably 70% or higher.
  • One feature of the method for the copper alloy material of the present invention is to add the cold-rolling 2 at a rolling ratio of 3 to 80% between the cold-rolling 1 and the solution heat treatment, subsequently to the intermediate annealing at 300 to 800°C for 5 seconds to 2 hours.
  • the intermediate annealing a heat treatment is carried out at a temperature lower than the temperature of the solution heat treatment, and thereby a sub-annealed texture can be obtained, which is obtained not by complete recrystallization of the material but by partial recrystallization.
  • microscopically nonuniform strain can be introduced into the material, by rolling at a relatively low working ratio.
  • a desired crystal orientation can be obtained, in the recrystallized crystal texture obtained by the solution heat treatment.
  • a more preferred range of the intermediate annealing is 10 seconds to 1 minute at 400 to 700°C, and an even more preferred range is 15 seconds to 45 seconds at 500 to 650°C.
  • a more preferred range of the working ratio of the cold-rolling 2 is 5 to 55%, and an even more preferred range is 7 to 45%.
  • the heat treatment such as the intermediate annealing is carried out, to recrystallize the material to lower the mechanical strength, in order to reduce the load at rolling in the subsequent step.
  • rolling is intended to make the sheet thickness small, and with the capacity of conventional rolling machines, it is general to employ a working ratio of higher than 80%.
  • the purpose of the intermediate annealing and cold working according to the present invention is to impart the preferentiality to the crystal orientation after recrystallization, which is different from the conventional purposes of those steps.
  • the solution treatment is carried out at 600 to 1,000°C for 5 seconds to 300 seconds. Since the necessary temperature conditions vary depending on the concentration of Ni and/or Co, it is necessary to select appropriate temperature conditions according to the Ni and/or Co concentrations. When the solution temperature is equal to or higher than the lower limit, mechanical strength is sufficiently maintained in the aging treatment step. When the solution treatment is equal to or lower than the upper limit, the material is not softened more than necessary, and the shape control is suitably realized, which is preferable. At this time, it is preferable to set the area ratio of grains having a deviation angle of 15° to 30° from the Cube orientation, to 15 to 50%.
  • the cold-rolling 3 at a working ratio of 5 to 40% is carried out.
  • the crystal texture falls in the range of the present invention, which is preferable.
  • the findings of the inventors of the present invention when rolling with different friction is carried out with rolls different in roughness from each other of the rolls for the cold-rolling, the grains having a deviation angle of less than 15° from the Cube orientation undergo slight rotation of orientation, to make it possible to accumulate at the orientation having a deviation angle of 15 to 30° from the Cube orientation.
  • the plastic constraint is different between the upper surface and the lower surface of the rolled material, and this difference in the plastic constraint causes the introduction of slight shear deformation.
  • the roughness of the rolls may be controlled, by roughening the surfaces of the rolls with grinding paper.
  • the cold-rolling 3 has an effect of increasing the amount of aging precipitation, to contribute to enhancement in the mechanical strength.
  • the aging treatment is carried out in the range of at 400 to 600°C for 0.5 hours to 8 hours. Since the necessary temperature conditions vary depending on the concentration of Ni and/or Co, it is necessary to select appropriate temperature conditions according to the Ni and/or Co concentrations. When the temperature of the aging treatment is equal to or higher than the lower limit, the amount of aging precipitation does not decrease, and sufficient mechanical strength is maintained. Further, when the temperature of the aging treatment is equal to or lower than the upper limit, the resultant precipitate does not become coarse, and the mechanical strength is maintained.
  • the working ratio of the finish cold-rolling after the solution treatment it is preferable to set the working ratio of the finish cold-rolling after the solution treatment to 0 to 20% or less. If the working ratio is too high, the cube grains of crystal orientations may undergo rotation in orientation to the Brass orientation, the S orientation, the Copper orientation, or the like, and the resultant crystal texture may fall outside the range of the present invention.
  • the confirmation of characteristics of the copper alloy sheet produced according to the present invention can be made by verifying whether the texture of the copper alloy sheet is within the defined range, through an EBSD analysis.
  • Copper alloys having the compositions shown in Table 1 were cast, to produce copper alloy sheets, and characteristics, such as mechanical strength, electrical conductivity, and bending property, were evaluated.
  • casting was conducted by a DC (direct chill) method, to obtain ingots with thickness 30 mm, width 100 mm, and length 150 mm. Then, these ingots were heated to 900°C, followed by maintaining at this temperature for one hour, hot-rolling to thickness 14 mm, and rapid cooling. Then, the respective surface of each of the thus-rolled sheets were face-milled respectively by 1 mm to remove oxide layer, followed by subjecting to cold-rolling 1 at a rolling ratio of 90 to 98%. Then, a heat treatment at 600 to 700°C for 1 hour was carried out, followed by cold-rolling 2 at a cold-rolling ratio of 5 to 20%.
  • DC direct chill
  • solution treatment was carried out under any of conditions of 700 to 950°C, immediately followed by cooling at a cooling speed of 15°C/sec or higher.
  • cold-rolling 3 was carried out at a rolling ratio of 5 to 40%.
  • rolls were used which had a difference in the surface roughness Ra between the upper roll and the lower roll of 0.05 to 3.0 ⁇ m.
  • an aging treatment at 400 to 600°C for 2 hours was conducted, under an inert gas atmosphere, followed by finish rolling at a rolling ratio of 20% or less.
  • the final sheet thickness was aligned to 0.15 mm.
  • the finish rolling the materials were subjected to low-temperature annealing at 400°C for 30 seconds, and evaluations of characteristics were carried out.
  • OIM5.0 HIKARI manufactured by TSL Solutions, Ltd.
  • Examples 1 to 31 of Table 1 indicate the examples according to the present invention.
  • Examples 1 to 31 had the crystal textures within the range according to the present invention, and were excellent in the mechanical strength and bending property.
  • Table 2 shows Comparative examples against the present invention. Comparative Examples 1, 2, and 5 were too small in the content of Ni or/and Co as compared with the range defined by the present invention, and the tensile strength was conspicuously low. Comparative examples 3, 4, 6, and 7 were too large in the content of Ni or/and Co, and cracks occurred upon the hot-rolling, to stop the production.
  • Table 3 presents examples, in which the effects on the crystal texture of the difference in the average roughness Ra between the upper and lower rolling rolls in the cold-rolling 3, were examined, using the same ingots as those in the examples of Table 1.
  • the crystal textures were fallen in the range of the examples according to the present invention, and the samples were excellent in the mechanical strength and bending property.
  • Comparative Examples 10-2, 22-2, and 29-2 since the difference of Ra was too small, the area ratio of grains having a deviation angle of less than 15° from the Cube orientation was too high, and the mechanical strength was poor.
  • Comparative Examples 10-3, 22-3, and 29-3 since the difference of R was too large, the area ratio of grains having a deviation angle within 15° to 30° from the Cube orientation was too low, and the bending property was poor.
  • the surface roughness, Ra, of the roll was measured, according to JIS B 0601. Table 1 No. Ni Co Si Cr Other elements Area ratio 1 *1 Area ratio *2 Electrical conductivity
  • C Ex means Comparative Example.
  • Table 3 Ni Co Si Cr Difference in Ra between upper and lower rolls Area ratio *1 Area ratio 2 *2 Electrical conductivity
  • Tensile strength (MPa) R/t Ex 10-2 3.8 0.9 0.1 0.08 ⁇ m 9 23 38 880 1 C Ex 0.02 ⁇ m 13 10 38 840 1 Ex 10-3 3.8 0.9 0.1 2.7 ⁇ m 3 25 38 890 1 C Ex 3.4 ⁇ m 5 11 38 875 1.5 Ex 22-2 1.3 0.8 0.5 0.1 0.08 ⁇ m 7 23 50 835 0.5 C Ex 0.02 ⁇ m 17 6 50 810 0.5 Ex 22-3 1.3 0.8 0.5 0.1 2.7 ⁇ m 5 26 50 840 0.5 C Ex 3.4 ⁇ m 2 7 50 840 1 Ex 29-2 2.3 0.5 0.08 ⁇ m 8 16 55 860 0.67 C Ex 0.02 ⁇ m
  • Example 1-1 An alloy formed by blending the same metal elements as those in Example 1-1, with the balance of Cu and inevitable impurities, was melted in a high-frequency melting furnace, followed by casting at a cooling speed of 0.1 to 100°C/sec, to obtain an ingot.
  • the resultant ingot was maintained at 900 to 1,020°C for 3 minutes to 10 hours, followed by subjecting to hot working, quenching in water, and then surface milling to remove oxide scale.
  • the production steps included one, two times or more solution heat treatments.
  • the steps were divided into those before and after the final solution heat treatment, so that the steps up to the intermediate solution treatment are designated as Step A-3, while the steps after the intermediate solution treatment are designated as Step B-3.
  • Step A-3 Cold working at a cross-sectional area reduction ratio of 20% or greater, a heat treatment at 350 to 750°C for 5 minutes to 10 hours, cold working at a cross-sectional area reduction ratio of 5 to 50%, and a solution heat treatment at 800 to 1,000°C for 5 seconds to 30 minutes.
  • Step B-3 Cold working (without any different friction) at a cross-sectional area reduction ratio of 50% or less, a heat treatment at 400 to 700°C for 5 minutes to 10 hours, cold working at a cross-sectional area reduction ratio of 30% or less, and temper annealing at 200 to 550°C for 5 seconds to 10 hours.
  • test specimen c01 thus obtained was different from those in the examples according to this invention, in terms of the rolling with different friction, whether conducted or not conducted, in connection with the production conditions, and resulted in not satisfying the required level on the tensile strength.
  • Comparative Example 102 ⁇ Conditions described in JP-A-2006-283059
  • a copper alloy having the same composition as in Example 1-1 according to this invention was melted in the air under charcoal coating with an electric furnace, to judge whether the copper alloy was able to be cast or not.
  • the resultant ingot produced by melting was hot rolled, to finish to thickness 15 mm. Then, this hot-rolled sheet was subjected to cold-rollings and heat treatments (cold-rolling 1 ⁇ solution continuous annealing ⁇ cold-rolling 2 (without any different friction) ⁇ aging ⁇ cold-rolling 3 ⁇ short-time annealing), to produce a copper alloy sheet (c02) with a predetermined thickness.
  • test specimen c02 thus obtained was different from that in Example 1 according to this invention, in terms of the intermediate annealing and the cold-rolling 2, whether conducted or not conducted, and the rolling with different friction, whether conducted or not conducted, in connection with the production conditions, and resulted in not satisfying the bending property.
  • Comparative Example 103 ⁇ Conditions described in JP-A-2006-152392
  • Example 1-1 An alloy having the same composition as in Example 1-1 according to this invention was melted in the air under charcoal coating in a kryptol furnace, followed by casting in a book mold made of cast iron, to produce an ingot with a size of thickness 50 mm, width 75 mm, and length 180 mm. Then, the surface of the ingot was surface milled, followed by hot rolling at a temperature of 950°C until that the thickness became 15 mm, and then quenching in water from a temperature of 750°C or higher. Then, oxide scale was removed, followed by cold-rolling, to give a sheet with a predetermined thickness.
  • the resultant sheet was subjected to a solution treatment by heating at the temperature for 20 seconds, in a salt bath furnace, followed by quenching in water, and then finish cold-rolling (without any different friction) of the second half, to produce a cold-rolled sheet with any of various thicknesses.
  • cold-rolled sheets (c03) were obtained by changing the working ratio (%) in these cold-rollings.
  • These cold-rolled sheets were subjected to aging by changing the temperature (°C) and the time period (hr) as shown below.
  • test specimen c03 thus obtained was different from that in Example 1 according to this invention, in terms of the intermediate annealing and the cold-rolling 2, whether conducted or not conducted, and the rolling with different friction, whether conducted or not conducted, in connection with the production conditions, and resulted in not satisfying the bending property.
  • Comparative Example 104 ⁇ Conditions described in JP-A-2008-223136
  • the copper alloy shown in Example 1 was melted, followed by casting with a vertical continuous casting machine. From the thus-obtained ingot (thickness 180 mm), a sample with thickness 50 mm was cut out, and this sample was heated to 950°C, followed by extracting, and then starting hot-rolling. At that time, the pass schedule was set to the rolling ratio in the temperature range of 950 to 700°C to be 60% or higher, and to conduct rolling even in the temperature range of lower than 700°C. The final pass temperature of hot-rolling was between 600°C and 400°C. The total hot-rolling ratio from the ingot was about 90%. After the hot-rolling, the oxide layer at the surface layer was removed by mechanical polishing (surface milling).
  • the sample was subjected to a solution treatment.
  • the temperature change at the time of the solution treatment was monitored with a thermocouple attached to the sample surface, and the time period for temperature rise from 100°C to 700°C in the course of temperature rising was determined.
  • the end-point temperature was adjusted in the range of 700 to 850°C, depending on the alloy composition, so that the average grain size (a twin boundary was not regarded as the grain boundary) after the solution treatment would be 10 to 60 ⁇ m, and the retention time period in the temperature range of 700 to 850°C was adjusted in the range of 10 sec to 10 min.
  • the sheet material obtained after the solution treatment was subjected to intermediate cold-rolling (without any different friction) at the rolling ratio, followed by aging.
  • the aging temperature was set to a material temperature of 450°C, and the aging time period was adjusted to the time period at which the hardness reached the maximum upon the aging at 450°C, depending on the alloy composition.
  • the optimum solution treatment conditions and the optimum aging time period had been found by preliminary experiments in accordance with the alloy composition.
  • finish cold-rolling was conducted at the rolling ratio. Samples that had been subjected to the finish cold-rolling were then further subjected to low-temperature annealing of placing the sample in a furnace at 400°C for 5 minutes. Thus, test specimens c04 were obtained. Surface milling was conducted in the mid course, as necessary, and thus the sheet thickness of the test specimens was set to 0.2 mm.
  • the principal production conditions are as described below. [Conditions of Example 1 of JP-A-2008-223136 ]
  • test specimens c04 thus obtained were different from that in Example 1 according to this invention, in terms of the intermediate annealing and the cold-rolling 2, whether conducted or not conducted, and the rolling with different friction, whether conducted or not conducted, in connection with the production conditions, and resulted in not satisfying the bending property.

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Claims (3)

  1. Kupferlegierungsblechmaterial für elektrische oder elektronische Bauteile, das aus einer Kupferlegierungszusammensetzung besteht, die, jeweils in Massen-%, ein beliebiges oder beide von Ni oder Co in einer Menge von 0,8 bis 5%, Si in einer Menge von 0,2 bis 1,5%, optional Cr in einer Menge von 0,05 bis 0,5%, und optional mindestens eines, ausgewählt aus der Gruppe, bestehend aus Zn, Sn, Mg, Ag, Mn, und Zr in einer Menge von insgesamt 0,01 bis 1,0%, enthält, wobei der Ausgleich aus Cu und unvermeidlichen Verunreinigungen besteht,
    wobei ein Flächenverhältnis der Körner, die einen Abweichungswinkel von weniger als 15° von der Würfel-Orientierung aufweisen, weniger als 10% beträgt, und ein Flächenverhältnis der Körner, die einen Abweichungswinkel von 15° bis 30° von der Würfel-Orientierung aufweisen, 15% oder größer beträgt, und
    wobei das Kupferlegierungsblechmaterial ausgezeichnete mechanische Festigkeit und Biegeeigenschaft aufweist.
  2. Verbindungsstück, das aus dem Kupferlegierungsblechmaterial für elektrische oder elektronische Bauteile nach Anspruch 1 zusammen gesetzt ist.
  3. Verfahren zum Herstellen des Kupferlegierungsblechmaterials für elektrische oder elektronische Bauteile nach Anspruch 1 oder 2, umfassend die folgenden Schritte in dieser Reihenfolge:
    Unterziehen einer geschmolzenen Kupferlegierung, die die Elemente aufweist, die auf den Zusammensetzungsbereich nach Anspruch 1 eingestellt sind, einem Gießen in einen Barren;
    Unterziehen des Barrens einem Planfräsen, gefolgt von Heizen oder einer Homogenisierungswärmebehandlung bei 800 bis 1000°C, Heißwalzen, und Wasserkühlen des so heiß gewalzten Blechs;
    Durchführen von Planfräsen der Oberfläche des heiß gewalzten Blechs, gefolgt von Kaltwalzen 1 mit einem Walzverhältnis von 70% oder höher;
    Durchführen eines Zwischenausglühens bei 300 bis 800°C für 5 Sekunden bis 2 Stunden, gefolgt von Kaltwalzen 2 mit einem Walzverhältnis von 3 bis 80%;
    Durchführen einer Lösungsbehandlung bei 600 bis 1000°C für 5 Sekunden bis 300 Sekunden;
    Durchführen von Kaltwalzen mit unterschiedlicher Reibung mit Walzen, bei denen eine Differenz bezüglich der mittleren Mittellinien Rauheit Ra zwischen einer oberen Walze und einer unteren Walze 0,05 bis 3,0 µm beträgt, als Kaltwalzen 3, bei einem Bearbeitungsverhältnis von 5 bis 40%;
    Durchführen einer Alterungsbehandlung bei 400 bis 600°C für 0,5 Stunden bis 8 Stunden; und
    Durchführen eines abschließenden Kaltwalzens bei einem Bearbeitungsverhältnis von 0 bis 20%, gefolgt von einem Niedertemperaturausglühen.
EP20100834574 2009-12-02 2010-12-01 Kupferlegierungsfolie Active EP2508632B1 (de)

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PCT/JP2010/071494 WO2011068124A1 (ja) 2009-12-02 2010-12-01 銅合金板材

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JP6196757B2 (ja) * 2012-07-12 2017-09-13 Ｊｘ金属株式会社 コルソン合金及びその製造方法
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EP3088542A4 (de) * 2013-12-27 2017-08-16 Furukawa Electric Co., Ltd. Folienmaterial aus kupferlegierung, verbinder und herstellungsverfahren für folienmaterial aus kupferlegierung
CN105118570A (zh) * 2015-08-14 2015-12-02 太仓安托建筑材料有限公司 一种铜排制造工艺
CN105154714A (zh) * 2015-09-02 2015-12-16 太仓顺如成建筑材料有限公司 一种合金铜排
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JP6166414B1 (ja) * 2016-03-30 2017-07-19 株式会社神戸製鋼所 ベーパチャンバー用銅又は銅合金条
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CN108149062B (zh) * 2018-02-10 2019-09-20 中南大学 一种超高强高导电性铜合金及其制备方法
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CN111647768A (zh) * 2020-06-10 2020-09-11 铜陵高铜科技有限公司 高强度铜合金板材及其制造方法
KR102403910B1 (ko) * 2021-11-29 2022-06-02 주식회사 풍산 강도, 전기전도도 및 굽힘가공성이 우수한 자동차 또는 전기전자 부품용 동합금판재의 제조 방법 및 이로부터 제조된 동합금판재
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KR20120104548A (ko) 2012-09-21
EP2508632A1 (de) 2012-10-10
WO2011068124A1 (ja) 2011-06-09
JP4934759B2 (ja) 2012-05-16
CN102639732B (zh) 2017-08-04
KR101419149B1 (ko) 2014-07-11
CN102639732A (zh) 2012-08-15
EP2508632A4 (de) 2013-12-18

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