EP2695956B1 - Kupferlegierungsblech - Google Patents

Kupferlegierungsblech Download PDF

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Publication number
EP2695956B1
EP2695956B1 EP13005147.7A EP13005147A EP2695956B1 EP 2695956 B1 EP2695956 B1 EP 2695956B1 EP 13005147 A EP13005147 A EP 13005147A EP 2695956 B1 EP2695956 B1 EP 2695956B1
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Prior art keywords
orientation
copper alloy
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sheet
alloy sheet
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English (en)
French (fr)
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EP2695956A3 (de
EP2695956A2 (de
Inventor
Yasuhiro Aruga
Daisuke Hashimoto
Koya Nomura
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Kobe Steel Ltd
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Kobe Steel Ltd
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Priority claimed from JP2007205630A external-priority patent/JP4324627B2/ja
Priority claimed from JP2007232641A external-priority patent/JP4210703B1/ja
Priority claimed from JP2007252036A external-priority patent/JP4210705B1/ja
Priority claimed from JP2007252037A external-priority patent/JP4210706B1/ja
Application filed by Kobe Steel Ltd filed Critical Kobe Steel Ltd
Publication of EP2695956A2 publication Critical patent/EP2695956A2/de
Publication of EP2695956A3 publication Critical patent/EP2695956A3/de
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R13/00—Details of coupling devices of the kinds covered by groups H01R12/70 or H01R24/00 - H01R33/00
    • H01R13/02—Contact members
    • H01R13/03—Contact members characterised by the material, e.g. plating, or coating materials
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/02—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
    • C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R13/00—Details of coupling devices of the kinds covered by groups H01R12/70 or H01R24/00 - H01R33/00
    • H01R13/02—Contact members
    • H01R13/10—Sockets for co-operation with pins or blades
    • H01R13/11—Resilient sockets
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R43/00—Apparatus or processes specially adapted for manufacturing, assembling, maintaining, or repairing of line connectors or current collectors or for joining electric conductors
    • H01R43/16—Apparatus or processes specially adapted for manufacturing, assembling, maintaining, or repairing of line connectors or current collectors or for joining electric conductors for manufacturing contact members, e.g. by punching and by bending

Definitions

  • the present invention relates to a cold rolled copper alloy sheet. More specifically, the present invention relates to a copper alloy sheet having properties suitable for a connection component such as automotive terminal or connector.
  • connection component such as automotive terminal or connector recently requires a performance enough to ensure reliability in a high-temperature environment such as engine room.
  • One of most important properties for the reliability in a high-temperature environment is a contact-fitting force maintaining characteristic, that is, a stress relaxation resistance characteristic.
  • Fig. 2 shows a structure of a box-type connector (female terminal 3) representative of a connection component such as automotive terminal or connector.
  • Fig. 2(a) is an elevational view and Fig. 2(b) is a cross-sectional view.
  • the female terminal 3 has a pressing strip 5 cantilever-supported in an upper holder part 4 and when a male terminal (tab) 6 is inserted into the holder, the pressing strip 5 is elastically deformed and the male terminal (tab) 6 is fixed by the reaction force.
  • 7 is a wire connecting part and 8 is an anchoring tongue strip.
  • the stress relaxation resistance characteristic is such a resistance characteristic against high temperatures as not allowing great reduction in the contact-fitting force of the spring-shaped component composed of a copper alloy sheet even when the connection component is kept standing in a high-temperature environment.
  • Figs. 1(a) and (b) each shows a tester for the stress relaxation resistance characteristic according to this standard. Using this tester, a test specimen 1 cut out into a strip shape is fixed at one end to a rigid test board 2, warped by lifting another end in a cantilever manner (d: warpage size), kept standing at a predetermined temperature for a predetermined time, and then unloaded at room temperature, and the warpage size after unloading (permanent distortion) is determined as ⁇ .
  • the stress relaxation ratio of a copper alloy sheet has anisotropy and takes a different value according to the direction in which the longitudinal direction of the test specimen runs with respect to the rolling direction of the copper alloy sheet.
  • the connection component such as automotive terminal or connector must have a stress relaxation ratio of 15% or less in the direction used as a spring, that is, in either one direction parallel or orthogonal to the rolling direction of the sheet.
  • a Cu-Ni-Si-based alloy, a Cu-Ti-based alloy, a Cu-Be-based alloy and the like have been heretofore widely known, but in recent years, a Cu-Ni-Sn-P-based alloy having a relatively small additive element content has been used.
  • This Cu-Ni-Sn-P-based alloy allows for ingot making in a shaft furnace which is a large-scale melting furnace with the opening being widely opened to the atmosphere, and because of its high productivity, a great cost down can be achieved.
  • Patent Documents 1 and 2 disclose a technique of uniformly and finely dispersing an Ni-P intermetallic compound in a Cu-Ni-Sn-P-based alloy matrix to enhance the electrical conductivity and at the same time, enhance the stress relaxation resistance characteristic and the like
  • Patent Documents 2 and 3 disclose a technique of decreasing the P content of a Cu-Ni-Sn-P-based alloy to obtain a solid solution-type copper alloy reduced in the precipitation of an Ni-P compound.
  • Patent Documents 4 and 5 disclose a technique of specifying the substantial temperature and holding time in finish annealing at the production of a Cu-Ni-Sn-P-based alloy sheet to enhance the electrical conductivity and at the same time, enhance the stress relaxation resistance characteristic and the like.
  • JP 2006-083465 A discloses a copper alloy sheet which contains, by mass%, 0.01 to 3.0% Fe and 0.01 to 0.3% P having a texture that the orientation distribution density of Brass orientation is 20 or less, and a sum of the orientation distribution density of the Brass orientation, S orientation and Copper orientation is 10 to 50%, measured by X-ray diffraction method.
  • the stress relaxation ratio of a rolled copper alloy sheet (obtained by rolling) has anisotropy and takes a different value according to the direction in which the longitudinal direction of the female terminal 3 in Fig. 2 runs with respect to the rolling direction of the raw material copper alloy sheet.
  • the measurement of the stress relaxation ratio and the measured stress relaxation ratio takes a different value according to the direction in which the longitudinal direction of a test specimen runs with respect to the rolling direction of the raw material copper alloy sheet. Accordingly, the stress relaxation ratio is liable to be low in the orthogonal direction than in the parallel direction with respect to the rolling direction of the copper alloy sheet.
  • blanking is sometimes performed such that the longitudinal direction of the female terminal 3 (the longitudinal direction of the pressing strip 5) runs in the direction orthogonal to the rolling direction.
  • a high stress relaxation resistance characteristic is usually required for the bending (elastic deformation) in the length direction of the pressing strip 5. Accordingly, when blanking is performed to allow for running in the direction orthogonal to the rolling direction, it is required to have a high stress relaxation resistance characteristic not in the parallel direction but in the orthogonal direction with respect to the rolling direction of the copper alloy sheet.
  • the stress relaxation resistance characteristic as a terminal or connector can be satisfied irrespective of the blanking direction of the raw material copper alloy sheet.
  • the conventional Cu-Ni-Sn-P-based copper alloy enhanced in the stress relaxation resistance characteristic is not excellent in bendability or press punchability.
  • the working of a copper alloy sheet into a terminal or connector sometimes involves a severe bending work such as contact bending or 90° bending after notching or a stamping work such as press punching of the sheet, and bendability high enough to withstand such a working or excellent press punchability is becoming required.
  • an object of the present invention is to provide a Cu-Ni-Sn-P-based copper alloy sheet satisfying, as a terminal or connector, the requisite properties such as stress relaxation resistance characteristic and bendability.
  • the gist of the copper alloy sheet excellent in the stress relaxation resistance characteristic and bendability is a cold rolled copper alloy sheet with a 0.2%-proof stress of 500 MPa or more consisting of, in terms of mass%, 0.3 to 3.0% of Ni, 0.01 to 3.0% of Sn and 0.01 to 0.3% of P, and optionally at least one member selected from the group consisting of, in terms of mass%, 0.3% or less of Fe, 0.05% or less of Zn, 0.1% or less of Mn, 0.1% or less of Si and 0.3% or less of Mg, optionally at least one member selected from the group consisting of Ca, Zr, Ag, Cr, Cd, Be, Ti, Co, Au and Pt, in a total amount of 1.0 mass% or less, and optionally at least one member selected from the group consisting of Hf, Th, Li, Na, K, Sr, Pd, W, S, C, Nb, Al,
  • the formation of this texture differs according to the working or heat-treatment method even in the same crystal system.
  • the texture of a sheet material obtained by rolling is indicated by the rolling plane and rolling direction.
  • the rolling plane is expressed by ⁇ ABC ⁇
  • the rolling direction is expressed by ⁇ DEF>. Based on these expressions, each orientation is expressed as follows.
  • the texture of a normal copper alloy sheet is composed of a fairly large number of orientation factors and when the constituent ratio of these factors is varied, the plastic anisotropy of the sheet material changes.
  • the properties such as stress relaxation resistance characteristic and bendability are greatly changed.
  • the distribution density of Brass orientation (B orientation) needs to be reduced.
  • the sum of distribution densities of B orientation, S orientation and Cu orientation also needs to be controlled to a specific range.
  • the alloy system differs, there is conventionally a case, for example, where, in a Cu-Fe-P-based copper alloy sheet, the orientation density of Cube orientation [hereinafter sometimes referred to as D(Cube)] is controlled to an appropriate range with an attempt to enhance and stabilize the bendability.
  • D(Cube) the orientation density of Cube orientation
  • such control of the Cube orientation cannot enhance the bendability particularly of a high-strength Cu-Ni-Sn-P-based copper alloy sheet with a 0.2%-proof stress of 500 MPa or more, which is enhanced in the stress relaxation resistance characteristic.
  • the distribution density of B orientation and the sum of distribution densities of B orientation, S orientation and Cu orientation are measured by a crystal orientation analysis method using an electron backscatter diffraction pattern EBSP through a field emission scanning electron microscope FESEM.
  • the orientation density of each of these orientations is measured by a crystal orientation analysis method using EBSP, because for enhancing the stress relaxation resistance characteristic or bendability while maintaining high strength, this is affected by the texture (aggregate texture) in a more microscopic region of the sheet (sheet surface).
  • the texture in a microscopic region can be quantified.
  • a texture (aggregate texture) in a relatively macroscopic region is measured as compared with the crystal orientation analysis method using EBSP. Accordingly, the texture (aggregate texture) in a microscopic region cannot be measured accurately.
  • the crystal orientation analysis method using an electron backscatter diffraction pattern EBSP the crystal orientation is analyzed based on the electron backscatter diffraction pattern (Kikuchi pattern) generated when an electron beam is obliquely applied to the sample surface.
  • This method is also known as a high-resolution crystal orientation analysis (FESEM/EBSP) method for the analysis of crystal orientation of a diamond thin film, a copper alloy or the like.
  • FESEM/EBSP high-resolution crystal orientation analysis
  • a measurement region of a material to be measured is usually partitioned into hexagonal regions or the like, and the partitioned regions each is determined for a Kikuchi pattern from the reflected electron of an electron beam injected into the sample surface.
  • an electron beam is two-dimensionally scanned on the sample surface and the crystal orientation is measured at predetermined pitch intervals, whereby the orientation distribution in the sample surface can be measured.
  • the obtained Kikuchi pattern is analyzed to determine the crystal orientation at the electron beam incident position. That is, the obtained Kikuchi pattern is compared with a known crystal structure data, and the crystal orientation at the measurement point is determined. The crystal orientation at a measurement point adjacent to the measurement point above is determined in the same manner, and those where the orientation difference between crystals adjacent to each other is within ⁇ 15° (slippage within ⁇ 10° from the crystal plane) are taken (regarded) as belonging to the same crystal plane.
  • a test specimen for the observation of texture is sampled from the produced copper alloy sheet and after mechanical polishing and buff polishing, the surface is regulated by electrolytic polishing.
  • the orientation of each grain is judged using, for example, FESEM manufactured by JEOL Ltd. and the EBSP measurement/analysis system OIM (Orientation Imaging Macrograph) manufactured by TSL and using an analysis software (software name: "OIM Analysis”) for the system, and the orientation density in the measured view is determined.
  • the range of measured view is a fine (microscopic) region of about 500 ⁇ m ⁇ 500 ⁇ m and is an extremely fine region as compared with the measuring range of X-ray diffraction. Accordingly, the orientation density of the texture in a more microscopic region of the sheet, which affects the stress relaxation resistance characteristic or bendability, can be measured in greater detail with higher precision as described above than in the measurement of orientation density by the X-ray diffraction.
  • the connection component such as automotive terminal or connector is a thin sheet having a thickness of about 0.1 to 0.3 mm and therefore, the value measured with the sheet thickness may be directly evaluated.
  • the distribution density of B orientation is reduced and at the same time, the sum of distribution densities of B orientation, S orientation and Cu orientation is controlled to a specific range.
  • the texture of the copper alloy sheet is specified such that the distribution density of B orientation is 40% or less and the sum of distribution densities of B orientation, S orientation and Cu orientation is 30 to 90%.
  • the Cu-Ni-Sn-P-based copper alloy sheet in a normal sheet made to have high strength by increasing the work-hardened amount in the heavy working of cold rolling, excessive development of the rolled texture inevitably results and therefore, the distribution density of B orientation is necessarily liable to become large and exceed 40%. Incidentally, this development of the rolled texture also affects other orientation densities such as Cube orientation. However, particularly, in the region of a high-strength Cu-Ni-Sn-P-based copper alloy sheet with a 0.2%-proof stress of 500 MPa or more, the effect of development of Cu orientation, B orientation and S orientation on the bendability is by far higher than the effect of other orientations such as Cube orientation.
  • the component composition of the copper alloy according to the embodiment of the present invention is described below.
  • the component composition of the copper alloy is, as described above, a Cu-Ni-Sn-P-based alloy allowing for ingot making in a shaft furnace and because of its high productivity, enabling a great cost down.
  • the copper alloy fundamentally comprises 0.3 to 3.0% of Ni, 0.01 to 3.0% of Sn, and 0.01 to 0.3% of P, with the balance being copper and inevitable impurities.
  • the % indicative of the content of each element means mass%.
  • Ni is an element necessary for enhancing the strength or stress relaxation resistance characteristic by being present as a solid solution in the copper alloy matrix or forming a fine precipitate or compound with other alloy elements such as P.
  • An Ni content of less than 0.1% causes, even by an optimal production method, shortage in the absolute amount of a fine Ni compound of 0.1 ⁇ m or less or of Ni contained as a solid solution. Accordingly, a content of 0.1% or more is necessary for effectively bringing out those effects of Ni.
  • Ni is excessively contained to exceed 3.0%, a compound such as oxide, crystallized product or precipitate of Ni is coarsened or a coarse Ni compound increases, as a result, the amount of a fine Ni compound or the amount of Ni contained as a solid solution rather decreases.
  • the coarsened Ni compound becomes a starting point of fracture and leads to reduction in the strength or bendability. Accordingly, the Ni content is specified to be 0.3 to 3.0%, preferably 0.3 to 2.0%.
  • Sn is contained as a solid solution in the copper alloy matrix and thereby enhances the strength. Also, Sn contained as a solid solution suppresses the softening due to recrystallization during annealing. If the Sn content is less than 0.01%, the amount of Sn is too small and the strength cannot be enhanced, whereas if the Sn content exceeds 3.0%, not only the electrical conductivity is significantly decreased but also Sn contained as a solid solution is segregated in the grain boundary to reduce the strength or bendability. Accordingly, the Sn content is specified to be 0.01 to 3.0%, preferably 0.1 to 2.0%.
  • P is an element necessary for enhancing the strength or stress relaxation resistance characteristic by forming a fine precipitate with Ni. Also, P acts as a deoxidizing agent. A content of less than 0.01% causes shortage in the P-based fine precipitate particle and therefore, a content of 0.01% or more is necessary. However, if this element is excessively contained to exceed 0.3%, an Ni-P intermetallic compound precipitated particle is coarsened, which leads to reduction not only in the strength or stress relaxation resistance characteristic but also in the hot workability. Accordingly, the P content is specified to be 0.01 to 0.3%, preferably 0.02 to 0.2%.
  • Fe, Zn, Mn, Si and Mg are impurities that readily intermix from a molten raw material such as scrap. These elements each produces an effect when contained but generally decreases the electrical conductivity. Also, if the content is increased, ingot making in a shaft furnace becomes difficult. Accordingly, in the case of obtaining a high electrical conductivity, the contents are specified to be 0.3% or less of Fe, 0.05% or less of Zn, 0.1% or less of Mn, 0.1% or less of Si and 0.3% or less of Mg. In other words, the contents lower than these upper limits are allowable in the embodiment of the present invention.
  • Fe elevates the recrystallization temperature of the copper alloy, similarly to Sn. However, if its content exceeds 0.5%, the electrical conductivity decreases. The content is 0.3% or less.
  • Zn prevents separation of tin plating.
  • its content exceeds 1%, the electrical conductivity decreases and a high electrical conductivity cannot be obtained.
  • the content is 0.05% or less.
  • the temperature region from about 150 to 180°C where the alloy sheet is used as an automotive terminal, the effect of preventing separation of tin plating can be obtained even with a content of 0.05% or less.
  • Mn and Si have an effect as a deoxidizing agent. However, if the content thereof exceeds 0.1%, the electrical conductivity decreases and a high electrical conductivity cannot be obtained. In the case of ingot making in a shaft furnace, the contents are preferably 0.001% or less of Mn and 0.002% or less of Si.
  • Mg has an activity of enhancing the stress relaxation resistance characteristic. However, if its content exceeds 0.3%, the electrical conductivity decreases and a high electrical conductivity cannot be obtained. In the case of ingot making in a shaft furnace, the content is preferably 0.001% or less.
  • the copper alloy according to the embodiment of the present invention is allowed to further contain at least one member selected from the group consisting of Ca, Zr, Ag, Cr, Cd, Be, Ti, Co, Au and Pt in an amount of 1.0% or less as a total amount of these elements.
  • These elements have an activity of preventing coarsening of the grain but, if the amount of these elements exceeds 1.0% in total, the electrical conductivity decreases and a high electrical conductivity cannot be obtained. Also, ingot making in a shaft furnace becomes difficult.
  • Hf, Th, Li, Na, K, Sr, Pd, W, S, C, Nb, Al, V, Y, Mo, Pb, In, Ga, Ge, As, Sb, Bi, Te, B and Misch metal are also impurities, and the amount of these elements is limited to 0.1% or less in total.
  • the production method of the copper alloy sheet according to the embodiment of the present invention is described below.
  • the production method itself may be an ordinary method except for the conditions in the finish annealing step. That is, a molten copper alloy after adjusting the component composition is subjected to casting, ingot scalping, soaking and hot rolling and then repeatedly to cold rolling and annealing, whereby a final (product) sheet is obtained.
  • preferred production conditions are present for allowing the copper alloy sheet according to the embodiment of the present invention to obtain necessary properties such as strength, stress relaxation resistance characteristic and bendability, and these are described below.
  • the time required is preferably as short as possible, such that the time required from the completion of addition of alloy elements to the initiation of casting in the copper alloy melting furnace is within 1,200 seconds and further, the time required from the extraction of ingot out of the ingot heating furnace to the completion of hot rolling is within 1,200 seconds.
  • Hot rolling may be performed in an ordinary manner.
  • the inlet-side temperature of hot rolling is approximately from 600 to 1,000°C, and the finishing temperature is approximately from 600 to 850°C. After the hot rolling, water cooling or standing to cool is performed.
  • cold rolling and annealing are repeatedly performed to obtain a copper alloy sheet having a product sheet thickness.
  • the annealing and cold rolling may be repeated according to the final (product) sheet thickness.
  • the working ratio is selected so that a working ratio of approximately from 30 to 80% can be obtained in the final finish rolling.
  • intermediate recrystallization annealing may be appropriately interposed.
  • the finish annealing temperature is preferably performed at a maximum peak temperature of 500 to 800°C in terms of the substantial temperature of the sheet, and the holding time in this temperature range is preferably from 10 to 60 seconds.
  • the cold rolling ratio per pass of the final cold rolling is specified to be from 10 to 50%.
  • the rolling is preferably performed usually in 3 or 4 passes while avoiding an excessively small or large number of passes.
  • the cold rolling ratio per pass of the final cold rolling is less than 10%, the sum of distribution densities of B orientation, S orientation and Cu orientation is liable to be less than 30% and the work-hardened amount in the cold rolling has a high possibility of becoming insufficient. In turn, it is likely impossible to satisfy the above-described high strength or enhance the stress relaxation resistance characteristic or bendability.
  • the final annealing is performed in a continuous heat-treating furnace, whereby the texture specified in the embodiment of the present invention can be composed and the stress relaxation resistance characteristic and bendability can be enhanced while maintaining the high strength. That is, in the continuous heat-treating furnace, the tension imposed on the sheet when passing can be controlled and in turn, the texture of the copper alloy sheet can be controlled to a rolled texture where the distribution density of B orientation is 40% or less and the sum of distribution densities of B orientation, S orientation and Cu orientation is from 30 to 90%.
  • the tension imposed on the sheet when passing in the continuous heat-treating furnace greatly affects the distribution density of Brass orientation (B orientation).
  • the tension imposed on the copper alloy sheet when passing during final annealing in the continuous heat-treating furnace is controlled in the range of 0.1 to 8 kgf/mm 2 . If the tension on passing of the sheet is out of this range, there is a high possibility that the texture specified in the embodiment of the present invention is not composed.
  • the temperature of the final annealing in the continuous heat-treating furnace is preferably from 100 to 400°C. If the annealing temperature is a temperature condition of less than 100°C, this is the same as not performing the low-temperature annealing and the texture/properties of the copper alloy sheet have a high possibility of scarcely changing from the state after the final cold rolling. Conversely, if the annealing is performed at an annealing temperature exceeding 400°C, this incurs recrystallization, excessive occurrence of a rearrangement or recovery phenomenon of dislocations or coarsening of the precipitate and therefore, the texture specified in the embodiment of the present invention may not be composed. Also, the strength is highly likely to decrease.
  • Copper alloy thin sheets varied in the texture with respect to a distribution density of Brass orientation and a sum of distribution densities of Brass orientation, S orientation and Copper orientation, were produced by controlling the cold rolling ratio (rolling reduction) per pass at the final cold rolling and the tension imposed on the copper alloy sheet when passing at the final annealing in a continuous heat-treating furnace. These copper alloy thin sheets each was evaluated for various properties such as electrical conductivity, tensile strength, 0.2%-proof stress, stress relaxation resistance characteristic and bendability.
  • a copper alloy having a chemical component composition shown in Table 1 (the balance of the composition excluding the element amounts shown is Cu) was melted in a coreless furnace and then subjected to ingot making by a semicontinuous casting method (cold solidification rate of casting: 2°C/sec) to obtain an ingot of 70 mm (thickness) ⁇ 200 mm (width) ⁇ 500 mm (length).
  • the obtained ingots were rolled in common under the following conditions to produce a copper alloy thin sheet.
  • each ingot was scalped and heated, the ingot was heated at 960°C in a heating furnace and immediately hot-rolled at a hot rolling finishing temperature of 750°C into a 16 mm-thick sheet, and the sheet was quenched in water from a temperature of 650°C or more.
  • the time required from the completion of addition of alloy elements to the initiation of casting in the melting furnace was set to 1,200 seconds or less commonly among respective Examples, and the time required from the extraction out of the heating furnace to the completion of hot rolling was set to 1,200 seconds or less commonly among respective Examples.
  • the sheet was subjected to cold rolling, continuous finish annealing, cold rolling and strain relief annealing in this order to produce a copper alloy thin sheet. That is, the sheet after primary cold rolling (rough cold rolling, intermediate cold rolling) was scalped. Finish annealing of the sheet was performed in an annealing furnace at the maximum peak temperature of 600°C in terms of the substantial temperature of the sheet by holding the sheet at this temperature for 60 seconds.
  • low-temperature annealing was performed in a continuous annealing furnace by making constant the substantial temperature (maximum peak temperature) at 350°C and varying the tension imposed on the copper alloy sheet when passing to obtain a 0.25 mm-thick copper alloy thin sheet.
  • the balance of the composition excluding the element amounts shown is Cu, and the content of elements of Group A, that is, Ca, Zr, Ag, Cr, Cd, Be, Ti, Co, Au and Pt, as other impurity elements was 1.0 mass% or less in total of these elements.
  • the content of elements of Group B was 0.1 mass% or less in total of these elements.
  • a test specimen for the observation of texture was sampled from the obtained copper alloy sheet and after mechanical polishing and buff polishing, the surface was regulated by electrolytic polishing. Measurement of each of the obtained test specimens by the above-described method was performed at intervals of 1 ⁇ m with respect to a region of 500 ⁇ m ⁇ 500 ⁇ m. The measurement and analysis were performed, as described above, by using FESEM manufactured by JEOL Ltd. and the EBSP measurement/analysis system manufactured by TSL and using an analysis software for the system, whereby the distribution density of B orientation and the sum of distribution densities of B orientation, S orientation and Cu orientation were determined.
  • test specimen was sampled from the copper alloy thin sheet and machined to produce a JIS No. 5 tensile test specimen such that the longitudinal direction of the test specimen runs in the direction orthogonal to the rolling direction of the sheet material.
  • the proof stress is tensile strength corresponding to a permanent elongation of 0.2%.
  • a sample was extracted from the copper alloy thin sheet and measured for the electrical conductivity.
  • the sheet was worked into a strip-like test specimen of 10 mm (width) ⁇ 300 mm (length) by milling and measured for the electrical resistance by a double bridge-type resistance measuring apparatus according to the measuring method of electrical conductivity of nonferrous metal materials specified in JIS-H0505, and the electrical conductivity was calculated according to the average cross-sectional area method.
  • the copper alloy thin sheet was evaluated for the stress relaxation resistance characteristic in the orthogonal direction involving severer stress relaxation than in the parallel direction, with respect to the rolling direction by measuring the stress relaxation ratio in this direction.
  • the stress relaxation ratio measuring test a sample where the stress relaxation ratio in the direction orthogonal is less than 10% is judged as passed in terms of the stress relaxation resistance characteristic.
  • a test specimen was sampled from the copper alloy thin sheet and measured using the cantilever system shown in Fig. 1 .
  • L was determined such that a surface stress corresponding to 80% of the proof stress of the material was loaded on the material.
  • the specimen was taken out, and the permanent distortion ⁇ after removing the deflection d was determined.
  • the bending test of the copper alloy sheet sample was performed according to Japan Copper and Brass Association Technical Standards.
  • the sheet material was cut into a size of 10 mm (width) ⁇ 30 mm (length) and while applying bending in Bad Way (where bending axis is parallel to the rolling direction), the presence or absence of cracking in the bent part was observed through an optical microscope at a magnification of 50.
  • the bending was performed under the conditions such that the ratio R/t of the minimum bend radius R to the sheet thickness t (0.25 mm) of the copper alloy sheet is as small as possible and becomes almost 0.
  • the bendability was rated A when cracking was not observed, rated B when fine cracking was generated, and rated C when relatively large cracking was generated. Usually, a smaller R/t is rated as excellent bendability.
  • the copper alloy sheets are produced also within preferred conditions of the production method, such as cold rolling ratio (rolling reduction) per pass at the final cold rolling and the tension imposed on the copper alloy sheet when passing at the final annealing in a continuous heat-treating furnace.
  • cold rolling ratio rolling reduction
  • the distribution density of B orientation is 40% or less and at the same time, the sum of distribution densities of B orientation, S orientation and Cu orientation is from 30 to 90%.
  • the copper alloy sheets of Inventive Examples 44 to 53 of Table 2 have, as terminal/connector properties, an electrical conductivity of 30% IACS or more and a stress relaxation ratio of less than 10% in the orthogonal direction involving severer stress relaxation, with respect to the rolling direction.
  • the bendability is excellent.
  • the copper alloy sheets of Inventive Examples further have, as mechanical properties, a 0.2%-proof stress of 500 MPa or more. That is, the copper alloy sheets of Inventive Examples are assured of high electrical conductivity and strength and excellent particularly in the stress relaxation resistance characteristic and bendability, revealing that the copper alloy sheet satisfies all of these properties at the same time.
  • Inventive Example 49 of Table 2 (alloy No. 36 of Table 1), the Ni content is the upper limit of 3.0%; in Inventive Example 50 (alloy No. 37 of Table 1), the Sn content is the lower limit of 0.01%; in Inventive Example 51 (alloy No. 38 of Table 1), the Sn content is the upper limit of 3.0%; in Inventive Example 52 (alloy No. 39 of Table 1), the P content is the lower limit of 0.01%; and in Inventive Example 53 (alloy No. 40 of Table 1), the P content is the upper limit of 0.3%.
  • Comparative Examples 56 to 61 of Table 2 the copper alloy sheets are produced within preferred conditions of the production method such as rolling speed in final cold rolling and sheet passage rate in final annealing. Accordingly, in Comparative Examples 56 to 61, the Cu-Ni-Sn-P-based copper alloy sheet has the texture specified in the embodiment of the present invention. Nevertheless, in these Comparative Examples, due to use of alloy Nos. 43 to 48 of Table 1 which are a copper alloy out of the composition range of the embodiment of the present invention, any one of the electrical conductivity, strength, stress relaxation resistance characteristic and bendability is significantly inferior to Inventive Examples.
  • Comparative Example 56 of Table 2 the Ni content deviates below the lower limit (alloy No. 43 of Table 1) and therefore, the strength and stress relaxation resistance characteristic are low.
  • Comparative Example 57 the Ni content deviates above the upper limit (alloy No. 44 of Table 1) and therefore, the balance between strength and electrical conductivity or the bendability is low.
  • Comparative Example 58 the Sn content deviates below the lower limit (alloy No. 45 of Table 1) and therefore, the strength is excessively low.
  • the Sn content deviates above the upper limit (alloy No. 46 of Table 1) and therefore, the electrical conductivity and bendability are low.
  • Comparative Example 60 the P content deviates below the lower limit (alloy No. 47 of Table 1) and therefore, the strength and stress relaxation resistance characteristic are low.
  • Comparative Example 61 the P content deviates above the upper limit (alloy No. 48 of Table 1) and therefore, cracking occurred during hot rolling, failing in characterization.
  • Comparative Examples 62 and 63 of Table 2 a copper alloy within the composition range of the embodiment of the present invention in Table 1 is used (alloy Nos. 33 and 34) and other production conditions are also within the preferred range, similarly to Inventive Examples. Nevertheless, the cold rolling ratio (rolling reduction) per pass at the final cold rolling or the tension imposed on the copper alloy sheet when passing at the final annealing in a continuous heat-treating furnace are out of the preferred range. In Comparative Example 62, the tension imposed on the sheet at the final annealing is substantially not present and is too small, and in Comparative Example 63, the cold rolling ratio per pass at the final cold rolling is too small and at the same time, the tension imposed on the sheet at the final annealing is too large.
  • Comparative Examples 62 and 63 the texture of the Cu-Ni-Sn-P-based copper alloy sheet deviates from the texture specified in the embodiment of the present invention. Accordingly, in these Comparative Examples, the stress relaxation resistance characteristic in the direction orthogonal to the rolling direction is extremely inferior to Inventive Examples. Furthermore, the bendability is significantly poor as compared with Inventive Examples.
  • Element Group A the total content of Ca, Zr, Ag, Cr, Cd, Be, Ti, Co, Au and Pt.
  • Other Element Group B the total content of Hf, Th, Li, Na, K, Sr, Pd, W, S, C, Nb, Al, V, Y, Mo, Pb, In, Ga, Ge, As, Sb, Bi, Te, B and Misch metal. Table 2 Class No. Alloy No.
  • a Cu-Ni-Sn-P-based alloy sheet satisfying the stress relaxation resistance characteristic in the direction orthogonal to rolling and being excellent in bendability and also in other properties required for a terminal or a connector can be provided.
  • connection component such as automotive terminal or connector.

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Claims (1)

  1. Kaltgewalztes Kupferlegierungsblech mit einer 0.2%-Dehngrenze von 500 MPa oder mehr, bestehend aus, in Form von Masse-%, 0,3 bis 3,0% von Ni, 0,01 bis 3,0% von Sn und 0,01 bis 0,3% von P, und gegebenenfalls aus mindestens einem Element, ausgewählt aus der Gruppe, bestehend aus, in Form von Masse-%, 0,3% oder weniger von Fe, 0,05% oder weniger von Zn, 0,1% oder weniger von Mn, 0,1% oder weniger von Si und 0,3% oder weniger von Mg, gegebenenfalls aus mindestens einem Element, ausgewählt aus der Gruppe, bestehend aus Ca, Zr, Ag, Cr, Cd, Be, Ti, Co, Au und Pt, in einer Gesamtmenge von 1,0 Masse-% oder weniger, und gegebenenfalls aus mindestens einem Element, ausgewählt aus der Gruppe, bestehend aus Hf, Th, Li, Na, K, Sr, Pd, W, S, C, Nb, AI, V, Y, Mo, Pb, In, Ga, Ge, As, Sb, Bi, Te, B und Mischmetall, in einer Gesamtmenge von 0,1 Masse-% oder weniger, wobei der Rest Kupfer ist, wobei das Kupferlegierungsblech eine Textur aufweist, in der eine Verteilungsdichte der Messingausrichtung 40% oder weniger beträgt und eine Summe der Verteilungsdichten der Messingausrichtung, der S-Ausrichtung und der Kupferausrichtung 30 bis 90% beträgt, gemessen durch ein Kristallorientierungsanalyseverfahren unter Verwendung eines Elektronenrückstreumusters (EBSP) durch ein Feldemissions-Rasterelektronenmikroskop (FESEM), und wobei das Kupferlegierungsblech, als Anschluss-Nerbindungsteileigenschaften, eine elektrische Leitfähigkeit von 30% IACS oder mehr aufweist.
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JP2007205630A JP4324627B2 (ja) 2007-08-07 2007-08-07 強度−延性バランスに優れた銅合金板
JP2007232641A JP4210703B1 (ja) 2007-09-07 2007-09-07 耐応力緩和特性と曲げ加工性とに優れた銅合金板
JP2007252036A JP4210705B1 (ja) 2007-09-27 2007-09-27 耐応力緩和特性とプレス打ち抜き性とに優れた銅合金板
JP2007252037A JP4210706B1 (ja) 2007-09-27 2007-09-27 耐応力緩和特性に優れた銅合金板
PCT/JP2008/063320 WO2009019990A1 (ja) 2007-08-07 2008-07-24 銅合金板
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US20110223056A1 (en) 2011-09-15
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EP2695958B1 (de) 2018-12-26
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EP2184371B1 (de) 2016-11-30
EP2695957B1 (de) 2018-11-28
CN101743333A (zh) 2010-06-16
EP2695958A2 (de) 2014-02-12
KR101227315B1 (ko) 2013-01-28
EP2695956A2 (de) 2014-02-12
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