EP1889934B1 - Copper alloy plate and process for producing the same - Google Patents

Copper alloy plate and process for producing the same Download PDF

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Publication number
EP1889934B1
EP1889934B1 EP06766490A EP06766490A EP1889934B1 EP 1889934 B1 EP1889934 B1 EP 1889934B1 EP 06766490 A EP06766490 A EP 06766490A EP 06766490 A EP06766490 A EP 06766490A EP 1889934 B1 EP1889934 B1 EP 1889934B1
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copper alloy
mass
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content
stress relaxation
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German (de)
English (en)
French (fr)
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EP1889934A1 (en
EP1889934A4 (en
Inventor
Yasuhiro c/o Kobe Corporate Research Lab. ARUGA
Koya c/o Chofu Plant in NOMURA
Katsura c/o Kobe Corporate Research Lab KAJIHARA
Yukio c/o Chofu Plant SUGISHITA
Hiroshi c/o Chofu Plant SAKAMOTO
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Kobe Steel Ltd
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Kobe Steel Ltd
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Priority claimed from JP2005168591A external-priority patent/JP3871064B2/ja
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Priority to EP11002839.6A priority Critical patent/EP2366807B1/en
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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
    • C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/02—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
    • 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

Definitions

  • the present invention relates to a copper alloy plate which is excellent in bending formability, shear stamping workability and stress relaxation resistance and which is suitable for use particularly as an automotive terminal, an automotive connector and the like, and also to a method for manufacturing such a copper alloy plate.
  • connection parts such as automotive terminals and automotive connectors are demanded to be manufactured at low costs but yet remain reliable in their capabilities even in a high-temperature environment as that inside an engine room these days.
  • One of the most important properties to secure the demanded reliability even in a high-temperature environment is a capability of maintaining locking at a contact point, which is usually called a "stress relaxation resistance".
  • stress relaxation resistance a capability of maintaining locking at a contact point
  • Copper alloys superior in stress relaxation resistance are a Cu-Ni-Si alloy, a Cu-Ti alloy, a Cu-Be alloy and the like, as already known. Containing strongly oxidizing elements (such as Si, Ti and Be), these alloys will not melt inside a large-scale melting furnace which opens wide to the atmosphere and are therefore inevitably expensive to make.
  • an alloy primarily made of Cu-Ni-Sn-P containing a relatively small amount of additive elements can be made as an ingot inside a shaft furnace at a high productivity and therefore demands only an extremely low cost.
  • a Cu-Ni-Sn-P alloy as well, various proposals have been made in an effort to improve its stress relaxation resistance. This is a very promising alloy system which could be capable of exhibiting a stress relaxation resistance equivalent to that of a Cu-Be alloy depending upon a manufacturing method and the amount of additive elements.
  • Patent Document 1 JPB 2844120 discloses a method of making a copper-based alloy for use as a connector which exhibits an excellent stress relaxation resistance.
  • Ni-P intermetallic compounds are dispersed finely and uniformly in the matrix of a Cu-Ni-Sn-P alloy to thereby enhance the electric conductivity while at the same time improving the stress relaxation resistance and other properties, and this patent document describes that it is necessary to strictly control the start of cooling during hot rolling, the temperature at the end point of hot rolling, the cooling temperature during hot rolling and also the temperature and the duration of a 5-720 minute heat treatment which is carried out in the middle of cold rolling which follows hot rolling, in order to obtain desired characteristics.
  • JP 2000-129377 A describes a copper base alloy having a composition, which consists of, by weight, 0.5 to 3.0 % Ni, 0.5 to 2.0 % Sn, 0.025 to 1.0 % P, the balance being Cu with inevitable impurities, and optionally contains 0.01 to 2.0 % Zn, and wherein the ratio between the Ni wt.% and the P wt.% has a value of less than 20.
  • JASO-C400 the standard set by The Society of Automotive Engineers of Japan, requires with respect to the stress relaxation resistance that the stress relaxation ratio after holding at 150 degrees Celsius for 1,000 hours is 15 % or lower.
  • Fig. 1 in the sections (a) and (b), show a stress relaxation resistance testing machine. Using this testing machine, a test specimen 1 cut out in a rectangular shape is fixed at its one end to a rigid body test bench 2 and then cantilevered at the other end and consequently bent (the amount of bending is d), and after maintaining this state at a predetermined temperature for a predetermined period of time, unloading is done at a room temperature and the amount of post-loading bending (permanent strain) ⁇ is calculated.
  • the stress relaxation ratio of a copper alloy plate is anisotropic and has a different value depending upon how the longitudinal direction of a test specimen extends relative to the rolling direction of the copper alloy plate.
  • the stress relaxation ratio is lower when the longitudinal direction is parallel to the rolling direction than when the longitudinal direction is perpendicular to the rolling direction.
  • the JASO standard mentioned above does not specify this direction, which has led to an understanding that the stress relaxation ratio needs be 15 % or less in any one of the parallel direction and the perpendicular direction to the rolling direction.
  • the recent years nevertheless have seen people believing that a high stress relaxation resistance in the perpendicular direction to the rolling direction of a copper alloy plate is desirable.
  • Fig. 2 shows a cross sectional structure of a typical box-shaped connector (female terminal 3).
  • an upper holder section 4 supports a push part 5 in a cantilever posture, and insertion of a male terminal 6 elastically deforms the push part 5, whereby the reaction force to the deformation fixes the male terminal 6.
  • Denoted at 7 is a wire connecting part and denoted at 8 is a fixing segment in Fig. 2 .
  • the longitudinal direction of the female terminal 3 i.e., the longitudinal direction of the push part 5 is directed perpendicular to the rolling direction.
  • the push part 5 is demanded to exhibit a particularly high stress relaxation resistance against bending (elastic deformation) of the push part 5 along the longitudinal direction of the push part 5.
  • the copper alloy plate must exhibit a particularly high stress relaxation resistance along the perpendicular direction to its rolling direction.
  • Ni-P intermetallic compounds size easily become coarse by a heat treatment during copper alloy production and bending formability of the copper alloy, which is evidence of an accurate terminal shape, deteriorates although its stress relaxation resistance is high enough to meet the requirement set by the present automotive technologies and that stamping-induced flashes are large which will wear away metal dies for press working of terminals.
  • the upper holder section 4 supports the push part 5 in a cantilever posture, and insertion of the male terminal 6 elastically deforms the push part 5, whereby the reaction force to the deformation fixes the male terminal 6.
  • denoted at 7 is the wire barrel part and denoted at 8 is the fixing segment.
  • the present invention aims at achieving a high stress relaxation resistance represented by a stress relaxation ratio of 15 % or lower along the perpendicular direction to the rolling direction of a Cu-Ni-Sn-P alloy.
  • the object of the present invention is to obtain a copper alloy plate made of a solid solution copper alloy mainly containing Cu-Ni-Sn for manufacturing of electric connection components which exhibits an excellent bending formability along the perpendicular and vertical direction to the rolling direction and also exhibits an excellent shear stamping workability.
  • a copper alloy plate made of a copper alloy exhibiting an excellent stress relaxation resistance is characterized in that it contains Ni: 0.1 through 3.0 % (i.e., mass% which will be equally applied below), Sn: 0.01 through 3.0 % and P: optionally further containing Fe: 0.5 % or less, Zn: 1 % or less, Mn: 0.1 % or less, Si: 0.1 % or less, Mg: 0.3% or less, one or more elements selected from the group consisting of Ca, Zr, Ag, Cr, Cd, Be, Ti, Co, Au and Pt in the total amount of 1 % or less, and one or more elements selected from the group consisting 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 metals in the total amount of 0.1 % or less and 0.01
  • the extracted residues method requires that 10 g of the copper alloy is immersed in 300 ml of a methanol solution which contains 10 mass% of ammonium acetate, and using the copper alloy as the anode and platinum as the cathode, constant-current electrolysis is performed at the current density of 10 mA/cm 2 , and the solution in which the copper alloy is thus dissolved is subjected to suction filtration using a membrane filter of polycarbonate whose filter mesh size is 0.1 ⁇ m, thereby separating and extracting undissolved residues on the filter.
  • Ni content in the extracted residues is identified through analysis by ICP after dissolving the undissolved residues separated and left on the filter into a solution prepared by mixing aqua regia and water at the ratio of 1 : 1. Further, the size of Ni-containing oxides, crystalloids and precipitates is ⁇ 0.1 ⁇ m, and the copper alloy plate is being made by the following method.
  • a method of making a copper alloy plate exhibiting an excellent stress relaxation resistance is a method of making a plate of the copper alloy described in the summary above and is characterized in that while a copper alloy plate is being made through casting of the copper alloy, hot rolling, cold rolling and annealing, the time needed until the start of casting since completion of addition of alloy elements to melting furnace is 1,200 seconds or shorter and the time needed until the end of hot rolling since ejection of an ingot from an ingot heating furnace is 1,200 seconds or shorter.
  • a copper alloy mainly containing Cu-Ni-Sn-P exhibits a high stress relaxation resistance represented by a stress relaxation ratio of 15 % or lower along the perpendicular direction to the rolling direction. It is also possible to obtain a copper alloy exhibiting excellent characteristics, such as the bending property, the electric conductivity (of about 30%IACS or more) and the strength (i.e., a proof stress of about 480 MPa or more), suitable as a terminal or connector.
  • the inventors of the present invention studied the reason why a conventional solid solution copper alloy in which precipitation of Ni-P compounds is suppressed described earlier almost exhibits a high stress relaxation resistance represented by a stress relaxation ratio of 15 % or lower along the parallel direction to the rolling direction but fails achieving this along the perpendicular direction to the rolling direction.
  • coarse oxides, crystalloids and precipitates of Ni of a certain size or larger correspond to the amount of Ni in extracted residues separated and left on a filter whose filter mesh size is 0.1 ⁇ m referred to in the summary above of the present invention. If the Ni content in the extracted residues is suppressed down to 40 % or less of the Ni content in the copper alloy described above, a high stress relaxation resistance represented by a stress relaxation ratio of 15 % or lower is achieved along the perpendicular direction to the rolling direction. At the same time, an excellent bending property, an excellent electric conductivity and an excellent strength are attained.
  • Ni compounds such as coarse oxides, crystalloids and precipitates of Ni having a certain size exceeding 0.1 ⁇ m makes it possible to ensure the amount of fine Ni compounds of 0.1 ⁇ m or smaller (including nano-level fine Ni clusters or finer Ni clusters), the amount of solute Ni in solid solutions (hereinafter referred to "solute Ni"), etc.
  • a Ni cluster means a group of atoms as they are before crystallization when viewed at the atomic structure level.
  • Uniform and fine dispersion alone of Ni-P intermetallic compounds in the matrix of a Cu-Ni-Sn-P alloy according to Patent Document 1 does not make it possible to improve the stress relaxation resistance in the perpendicular direction to the rolling direction, and therefore, it is necessary to ensure the amount of fine Ni compounds of 0.1 ⁇ m or smaller and the amount of solute Ni described above. However, it is not possible to directly measure fine Ni compounds of 0.1 ⁇ m or smaller and the amount of solute Ni.
  • the present invention is characterized in suppressing coarse Ni compounds of exceeding 0.1 ⁇ m described above and indirectly ensuring the amount of fine Ni compounds of 0.1 ⁇ m or smaller and the amount of solute Ni.
  • the amount of fine Ni compounds of 0.1 ⁇ m or smaller and the amount of solute Ni measured in absolute amounts have already decreased through preceding steps.
  • the insufficient absolute amounts of the fine Ni compounds of 0.1 ⁇ m or smaller and solute Ni still make it difficult to improve the strength and the stress relaxation resistance.
  • the chemical composition of the copper alloy according to the present invention will be described.
  • the premise with respect to the chemical composition of the copper alloy in the present invention is that the copper alloy is a Cu-Ni-Sn-P alloy which can be cast as an ingot in a shaft furnace therefore with high productivity at a greatly reduced cost.
  • the copper alloy basically contains Ni: 0.1 through 3.0 %, Sn: 0.01 through 3.0 % and P: 0.01 through 0.3 %, optionally further containing Fe: 0.5 % or less, Zn: 1 % or less, Mn: 0.1 % or less, Si: 0.1 % or less, Mg: 0.3% or less, one or more elements selected from the group consisting of Ca, Zr, Ag, Cr, Cd, Be, Ti, Co, Au and Pt in the total amount of 1 % or less, and one or more elements selected from the group consisting 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 m
  • Ni is an element which is necessary to create fine precipitates with P and improve the strength and the stress relaxation resistance. Even with the manufacturing method according to the present invention which is the most proper, the Ni content of less than 0.1 % will result in an insufficient amount of fine Ni compounds of 0.1 ⁇ m or smaller and the amount of solute Ni measured as absolute amounts. Hence, the content must be 0.1 % or more for the benefit of Ni to be felt effectively.
  • Ni content is set within the range of 0.1 through 3.0 %, or preferably 0.3 through 2.0 %.
  • Sn dissolves as solid solutions in a copper alloy and enhances the strength. Further, Sn precipitates suppress recrystallization-induced softening during annealing. While annealing at a high temperature is necessary for positive creation of Sn precipitates in the copper alloy according to the present invention, if the Sn content is less than 0.1 %, it is not possible to suppress recrystallization-induced softening during annealing, thus leading to a decreased strength. Hence, when the Sn content is less than 0.1 %, the strength needs be enhanced by means of facilitated rolling reduction during final cold rolling after annealing or by otherwise appropriate approach. This however will slightly decrease the electric conductivity, the stress relaxation resistance, etc.
  • the Sn content of less than 0.01 % i.e., too little Sn, will result in too low a strength even despite enhanced rolling reduction during final cold rolling after annealing and make it impossible for the balance between these characteristics to achieve a desired level.
  • the content over 3.0 % will lower the electric conductivity and make it impossible to attain the electric conductivity of 30%IACS or higher.
  • the Sn content is set within the range of 0.01 through 3.0 %, or preferably 0.1 through 2.0 %, or more preferably 0.3 through 2.0 %.
  • P is an element which is necessary to create fine precipitates with Ni and improve the strength and the stress relaxation resistance.
  • the P content of less than 0.01 % will result in a shortage of P-based fine precipitated particles, and hence, the content needs be 0.01 % or more.
  • An excessive content beyond 0.3 % will however coarsen precipitated particles of Ni-P intermetallic compounds and deteriorate not only the strength and the stress relaxation resistance but the workability of hot working as well. For this reason, the Sn content is set within the range of 0.01 through 0.3 %, or preferably 0.02 through 0.2 %.
  • Fe, Zn, Mn, Si and Mg can be easily mixed from materials for melting such as scraps. These elements, although respectively effective in some respects, generally decrease the electric conductivity. Further, higher contents of these will make ingot making difficult in a shaft furnace. Hence, to achieve the electric conductivity of 30% IACS or higher, Fe should be 0.5 % or less, Zn should be 1 % or less, Mn should be 0.1 % or less, Si should be 0.1 % or less and Mg should be 0.3 % or less. In other words, any concentrations equal to or lower than these upper limits are acceptable in the present invention.
  • Fe increases the recrystallization temperature of a copper alloy.
  • Sn content exceeding 0.5 % will decrease the electric conductivity and the electric conductivity of 30%IACS will not be achieved.
  • the Sn content is preferably 0.3 % or less.
  • the Zn prevents spalling of a tin plating.
  • the Zn content exceeding 1 % will decrease the electric conductivity and the electric conductivity of 30%IACS will not be achieved.
  • the Zn content is preferably 0.05 % or less.
  • the Zn content of even 0.05 % or less prevents spalling of a tin plating.
  • Mn and Si serve as deoxidizers. However, a content exceeding 0.1 % will decrease the electric conductivity and the electric conductivity of 30%IACS will not be achieved. Further, for ingot making in a shaft furnace, it is desirable that the Mn content is 0.001 % or less and the Si content is 0.002 % or less.
  • Mg functions to improve the stress relaxation resistance.
  • the Mg content exceeding 0.3 % however will decrease the electric conductivity and the electric conductivity of 30%IACS will not be achieved.
  • the Mg content is preferably 0.001 % or less.
  • the copper alloy according to the present invention may contain additional elements of Ca, Zr, Ag, Cr, Cd, Be, Ti, Co, Au and Pt in the total amount of 1.0 % or less. Although preventing coarsening of crystal grains, these elements, when contained in the total amount which exceeds 1.0 %, decrease the electric conductivity and the electric conductivity of 30% IACS can not be attained. This also makes ingot making in a shaft furnace 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 metals are impurities and should therefore be suppressed down to the total amount of 0.1 % or less.
  • the present invention suppresses coarse Ni oxides, crystalloids and precipitates (Ni compounds) which are larger than the 0.1- ⁇ m size and attains a high stress relaxation resistance represented by a stress relaxation ratio of 15 % or lower along the perpendicular direction to the rolling direction.
  • the amount of such coarse Ni compounds having this size or larger are defined as the Ni content in extracted residues separated and left on a filter whose filter mesh size is 0.1 ⁇ m.
  • the Ni content in the extracted residues is regulated down to 40 % or less of the Ni content in the copper alloy.
  • the proportion of the Ni content in the extracted residues in the Ni content in the copper alloy reaches or exceeds 40 %, the amount of the coarse Ni compounds described above will increase. This will therefore result in an insufficient amount of fine Ni compounds of 0.1 ⁇ m or smaller and an insufficient amount of solute Ni. Hence, the stress relaxation resistance and the strength along the perpendicular direction to the rolling direction will decrease. Further, since fracture will start at these coarse compounds, the bending formability as well will deteriorate.
  • the copper alloy weighting 10 g is immersed in 300 ml of a methanol solution which contains 10 mass% of ammonium acetate, and using the copper alloy as the anode and platinum as the cathode, constant-current electrolysis is performed at the current density of 10 mA/cm 2 .
  • the solution in which the copper alloy is thus dissolved is subjected to suction filtration using a membrane filter of polycarbonate whose filter mesh size is 0.1 ⁇ m, thereby separating and extracting undissolved residues on the filter.
  • the filter mesh size of 0.1 ⁇ m of this filter is currently the finest filter mesh size.
  • solute Ni already existing in the copper matrix have been dissolved, while coarse Ni compounds larger than 0.1 ⁇ m and fine Ni compounds of 0.1 ⁇ m or smaller are dispersed without getting dissolved.
  • the undissolved residues separated and left on the filter whose filter mesh size is 0.1 ⁇ m are only the coarse Ni compounds which are larger than 0.1 ⁇ m.
  • solute Ni dissolved in advance and the fine Ni compounds of 0.1 ⁇ m or smaller pass through the filter together with the solution.
  • Ni content in the residues thus extracted and separated is identified through analysis by ICP after dissolving the undissolved residues separated and left on the filter into a solution prepared by mixing aqua regia and water at the ratio of 1 : 1.
  • the process per se for making the copper alloy according to the present invention may be any ordinary method.
  • a final (product) plate is obtained through repetition of casting a molten copper alloy whose chemical composition has been adjusted, facing of the surfaces of the resulting ingot, soaking, hot rolling, cold rolling and annealing.
  • Control of the mechanical properties such as the strength level is achieved by means of controlled precipitation of fine products of 0.1 ⁇ m or smaller mainly in accordance with a cold rolling condition and an annealing condition.
  • the optimal method of making the copper alloy according to the present invention requires that during a stage of obtaining the copper alloy plate through copper alloy casting, hot rolling, cold rolling and annealing, the time since the completion of addition of the alloy elements into melting furnace until the start of casting is 1,200 seconds or shorter and that the time since ejection of an ingot from an ingot heating furnace until the end of hot rolling is 1,200 seconds or shorter.
  • coarse Ni compounds are suppressed on the further upper stream side at the manufacturing steps.
  • melting and casting per se may be performed by an ordinary method such as continuous casting and semi-continuous casting.
  • casting completes preferably within 1,200 seconds or less since the completion of addition of the elements to the melting furnace, or more preferably, within 1100 seconds or less, and the cooling/solidification rate is preferably 0.1 °C /sec or faster, or more preferably 0.2 °C/sec or faster.
  • the long time requires before casting however has been found to promote creation and coarsening of oxides containing Ni and lower the yield of the additive elements.
  • the time since the completion of addition of alloy elements into a melting furnace until the start of casting is shortened down to 1,200 seconds or shorter, or more preferably, to 1100 seconds or shorter.
  • the shortening of the time required until casting can be achieved by predicting the composition as it is after additional loading of the raw materials from the past results of melting and by shortening the time necessary for re-analysis, etc.
  • the time since ejection of an ingot from the heating furnace until the end of hot rolling is the waiting time which the ingot removed from the heating furnace following heating in the furnace must wait for before the start of hot rolling.
  • the total time required since ejection from a heating furnace until the end of hot rolling is actively controlled down to 1,200 seconds or shorter.
  • Such time control can be attained by means of quick transportation of an ingot from the heating furnace to the hot rolling line and through use of a small slab rather than a large slab which will extend the hot rolling time.
  • Hot rolling may be performed by an ordinary method.
  • the inlet temperature for hot rolling is from 600 to 1,000 degrees Celsius approximately, and the finishing temperature for hot rolling is from 600 to 850 degrees Celsius approximately. Hot rolling is followed by water cooling or standing for cooling.
  • cold rolling and annealing is performed, whereby a copper alloy plate or the like having the thickness as a product plate is made.
  • Annealing and cold rolling may be repeated depending upon the thickness of the final (product) plate.
  • the rolling reduction is selected so that the rolling reduction of approximately 30 through 80 % will be obtained during final finishing rolling.
  • Annealing for recrystallization may be performed in the middle of cold rough rolling as needed.
  • Annealing of the copper alloy plate as it is after cold rough rolling may be continuous annealing or batch annealing.
  • the holding temperature must naturally be high in the case of continuous annealing (which takes only a short time) but low in the case of batch annealing (which demands a long time).
  • 500 - 800 °C, X 10 - 60 seconds is preferable for continuous annealing and 300 - 600 °C ⁇ 2 - 20 hours is preferable for batch annealing (long time).
  • the annealing is preferably followed by rapid cooling at the cooling rate of 10 °C/sec or faster.
  • Stress-relief annealing or stabilizing annealing after final finishing cold rolling is performed preferably at the actual temperature of 250 through 450 degrees Celsius for 20 through 40 seconds. This is because this will eliminate strain which has introduced during final finishing rolling but will not accompany softening of the materials or accordingly greatly reduce the strength.
  • a copper alloy plate according to the present invention will now be described.
  • the composition of the copper alloy according to the present invention will be described first.
  • Ni is an element which dissolves as solid solutions in the copper alloy, and accordingly enhances the stress relaxation resistance and improves the strength.
  • the Ni content is 0.4 % or less, this effect is not promised, but the Ni content exceeding 1.6 % will work with P, another additive element present at the same time, and easily precipitate intermetallic compounds, thereby reducing solute Ni and deteriorating the stress relaxation resistance.
  • the Ni content is set to 0.4 through 1.6 %. The range of 0.7 to 0.9 % is more desirable.
  • Sn is an element which dissolves as solid solutions in the copper alloy and accordingly improves the strength due to work hardening.
  • this element serves also as an element which contributes to the heat resistance as well.
  • the.Sn content of 0.4 % or less will decrease the heat resistance and facilitate recrystallization-induced softening during annealing, and therefore result in failure of sufficiently increasing the annealing temperature.
  • the Sn content exceeding 1.6 % will lower the electric conductivity and the electric conductivity of 30%IACS will not be achieved in the copper alloy plate, namely, a final product.
  • the Sn content is set to 0.4 through 1.6 %.
  • the range of 0.6 to 1.3 % is more desirable.
  • High-temperature annealing brings about another advantage that a sufficient amount of solute Ni necessary for improvement of the stress relaxation resistance is secured.
  • P is an element which creates Ni-P precipitates at the manufacturing steps and accordingly improves the heat resistance during annealing. This makes it possible to perform annealing at a high temperature and improve the bending formability and the shear stamping workability.
  • P content is less than 0.027 %, P tends to combined with Ni which is added in a greater amount than the P content, and creates strong Ni-P intermetallic compounds, whereas addition of P in the amount exceeding 0.15 % further increases the amount of precipitated Ni-P intermetallic compounds, either one of which fails to permit the Ni-P intermetallic compounds to dissolve again as solid solutions during annealing, loads to a deteriorated bending formability and a deteriorated shear stamping workability and results in a failure to secure enough solute Ni which are necessary to improve the stress relaxation resistance.
  • the P content is set to 0.027 through 0.15 %. 0.05 through 0.08 % is more preferable.
  • the Ni/P ratio is set to 15 or smaller, to thereby improve the heat resistance owing to Ni-P precipitates for realizing dissolution of Ni as solid solutions and for pinning of dislocations in matrix at a high annealing temperature while at the same time ensuring decomposition and dissolution as solid solutions of the Ni-P precipitates during recrystallization-induced softening which is caused by annealing.
  • the Ni/P ratio is set to 15 or larger, the heat resistance becomes insufficient, and therefore, annealing must be performed at a relatively low temperature, the bending formability and the shear stamping workability do not improve and a sufficient stress relaxation resistance is not obtained.
  • Fe is an element which suppresses coarsening of recrystallized grains during annealing. Addition of Fe in the amount of 0.0005 % or more to the copper alloy makes it possible to heat up the copper alloy to a high temperature during annealing, sufficiently dissolve the additive elements as solid solutions and at the same time suppress coarsening of recrystallized grains. The Fe content beyond 0.15 % however will decrease the electric conductivity and the electric conductivity of 30% IACS will not be achieved.
  • the copper alloy according to the present invention may further contain accessory constituent of Zn, Mn, Mg, Si, etc.
  • Zn preventing spalling of a tin plating
  • Zn may be added in the amount of 1 % or less however, to the extent that Zn is used in a temperature range (approximately from 150 degrees Celsius to 180 degrees Celsius) for use as an automotive terminal, addition of Zn in the amount of even 0.05 % or less is enough.
  • the Zn content is preferably 0.05 % or less.
  • Mn and Si may be added as deoxidizers, each in the amount of 0.01 % or less. Mn and Si however are preferably added in the amount of 0.001 % or less and in the amount of 0.002 % or less, respectively.
  • Mg has a function of improving the stress relaxation resistance, and therefore, may be added in the amount of 0.3 % or less.
  • the Mg content is preferably 0.001 % or Less.
  • Pb is an impurity and should preferably be limited to 0.001 % or less.
  • the copper alloy plate according to the present invention has a structure that precipitates of Ni-P intermetallic compounds are dispersed in the copper alloy.
  • particles whose diameters are beyond 60 nm cause cracking during bending at small R/t (R: bend radius, t: plate thickness), and the presence if any of such particles will deteriorate the bending formability.
  • R/t bend radius
  • t plate thickness
  • the diameters (lengths of the major axis) of the circumscribed circles of the precipitated particles are used as the diameters of precipitates referred to in the present invention.
  • particles whose diameters are 60 nm or smaller which do not deteriorate the bending formability it is desirable that there are on the average twenty such particles within the scope of 500 nm x 500 nm and it is more desirable that there are thirty or more such particles.
  • the copper alloy plate according to the present invention can be made by performing hot rolling and cold rough rolling after homogenizing treatment of an copper alloy ingot, thereafter performing finishing continuous annealing of the copper alloy plate as it is after cold rough rolling, and further performing cold rolling and stabilizing annealing.
  • the copper alloy according to the present invention is not a precipitation hardened copper alloy and therefore does not require any particularly strict control of conditions during homogenizing treatment, hot rolling and cold rough rolling.
  • homogenizing treatment may be performed at 800 through 1,000 degrees Celsius for 0.5 to 4 hours
  • hot rolling may be performed at 800 through 950 degrees Celsius
  • hot rolling may be followed by water cooling or standing for cooling.
  • cold rough rolling the rolling reduction is selected so that the rolling reduction of approximately 30 through 80 % will be obtained during final finishing rolling.
  • Annealing for recrystallization may be performed in the middle of cold rough rolling as needed.
  • transition of the precipitated phase takes place during a few dozens of seconds of annealing over 650 degrees Celsius. As described earlier, if a holding temperature is low, relatively many coarse precipitates are observed. The thermodynamic principle is that a further increased holding temperature will usually further aggregate and coarsen precipitates. However, in the case of the alloy system according to the present invention, transition of the precipitated phase takes place from around 600 to 650 degrees Celsius: Coarse precipitates created in a low temperature region whose one end is a temperature near 600 to 650 degrees Celsius are decomposed and dissolve as solid solutions, and a new phase which precipitates fine Ni-P compounds appears. These precipitates contribute to improvement of the bending formability and reduction of stamping-induced flashes.
  • high-temperature and short annealing held at a actual temperature exceeding 650 degrees Celsius for the period of 15 through 30 seconds makes it possible to obtain a structure in which precipitates of Ni-P intermetallic compounds are properly dispersed in the copper alloy.
  • Annealing is preferably followed by rapid cooling at the cooling rate of 10 °C/sec or faster.
  • the annealing temperature described above secured under this high-temperature/short condition promises another advantage that the precipitates of the Ni-P intermetallic compounds precipitated while the temperature rose dissolve as solid solutions and sufficient solute Ni needed for improvement of the stress relaxation resistance are obtained.
  • Stabilizing annealing after final finishing rolling is preferably performed at 250 through 450 degrees Celsius for 20 through 40 seconds. This is because this will eliminate strain which has introduced during final finishing rolling but will not accompany softening of the materials or accordingly greatly reduce the strength.
  • Test specimens weighting 10 g for measurement of extracted residues were taken out of thus obtained copper alloy thin plates, and by the method described earlier, the Ni contents in the extracted residues separated by meshes whose filter mesh size was 0.1 ⁇ m were identified through analysis by ICP described earlier. The proportions (%) of these in the Ni content in the copper alloys were then calculated. Table 2 shows the results.
  • test specimen was cut out from the copper alloy plate and subjected to a tensile test, electric conductivity measurement, stress relaxation ratio measurement and a bending test. Table 2 also shows these results.
  • Test specimens were cut out from the copper alloy thin plates, and JIS5-tensile test specimens were made by machining so that the longitudinal direction of the test specimens became perpendicular to the rolling direction of the plate members.
  • JIS5-tensile test specimens were made by machining so that the longitudinal direction of the test specimens became perpendicular to the rolling direction of the plate members.
  • mechanical properties were measured.
  • the yield stress is the tensile strength corresponding to permanent elongation of 0.2 %.
  • Specimens were taken from the copper alloy thin plates described above, and the electric conductivities were measured.
  • the electric conductivities of the specimens of the copper alloy plates strip-shaped test specimens which were 10 mm wide and 300 mm long were processed by milling the electric resistance values were measured using a double-bridge type resistance measurement machine in accordance with the method of measuring the electric conductivity of a nonferrous metal material defined in JIS-H0505, and the electric conductivities were calculated by an average cross sectional area size method.
  • test specimens were taken from the copper alloy thin plates described above and measured in a cantilever posture as shown in Fig. 1 .
  • L was determined so that surface stress corresponding to 80 % of the yield stress of the material would be applied upon the material.
  • Ni compounds such as coarse oxides, crystalloids and precipitates of Ni of 0.1 ⁇ m or larger, were suppressed such that the proportions of the Ni contents in the extracted residues separated by the extracted residues method described earlier in the Ni contents in the copper alloys would be 80 % or smaller. It is therefore inferred that the amounts of fine Ni compounds of 0.1 ⁇ m or smaller (including fine Ni clusters at the nano level or smaller Ni clusters), the amounts of solute Ni and the like were ensured.
  • the (reference) examples 101 through 116 of the invention thus each attained a high stress relaxation resistance represented by a stress relaxation ratio of 15 % or lower along the perpendicular direction to the rolling direction. Further, exhibiting an excellent bending property and strength, these achieve superior properties for use in terminals, connectors, etc.
  • Fe, Zn, Mn, Si and Mg were each in a great amount exceeding the upper limits described earlier as denoted at the alloy numbers of 6 to 10 in Table 1.
  • the total content of the elements Ca, Zr, Ag, Cr, Cd, Be, Ti, Co, Au and Pt was large and exceeded the upper limit of 1.0 mass% described earlier as denoted at the alloy number 11 in Table 1.
  • 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 metals was large and exceeded the upper limit of 1.0 mass% described earlier as denoted at the alloy number 12 in Table 1.
  • the Sn content was as low as less than 0.1 %, and despite an attempt to improve the strength by setting rolling reduction during finishing cold rolling relatively high in the manner described earlier, annealing-induced softening made the stiffness relatively weak as compared to the other (reference) examples of the present invention.
  • the time required since the completion of addition of the alloy elements into the melting furnace until the start of casting was too long, exceeding 1,200 seconds.
  • the time since ejection from the heating furnace until the end of hot rolling was too long, exceeding 1,200 seconds.
  • the comparative examples 123 through 126 are remarkably inferior in terms of stress relaxation resistance along the perpendicular direction to the rolling direction to the (reference) examples of the present invention.
  • the comparative examples 117 through 122 shown in Table 2 used copper alloys not falling under the compositions according to the present invention denoted at the alloy numbers of 14 to 19 in Table 1. Hence, although the manufacturing conditions were within the preferable ranges, they were remarkably inferior to the (reference) examples of the present invention in terms of either the proportion of the Ni content in the extracted residues in the Ni content in the copper alloy, the stress relaxation resistance, the bending property, the electric conductivity or the strength.
  • the Ni content in the copper alloy according to the comparative example 117 was lower than the lower limit (denoted at the alloy number 14 in Table 1). Hence, the strength and the stress relaxation resistance were low.
  • the Ni content in the copper alloy according to the comparative example 118 was higher than the upper limit (denoted at the alloy number 15 in Table 1). Hence, the strength, the stress relaxation resistance and the bending formability were inferior.
  • the Sn content in the copper alloy according to the comparative example 119 was lower than the lower limit (denoted at the alloy number 16 in Table 1). Hence, in the comparative example 119, despite an attempt to improve the strength by setting rolling reduction during finishing cold rolling relatively high in the manner described earlier, annealing-induced softening made the strength too weak.
  • the Sn content in the copper alloy according to the comparative example 120 was higher than the upper limit (denoted at the alloy number 17 in Table 1) . Hence, the electric conductivity was low.
  • the P content in the copper alloy according to the comparative example 121 was lower than the lower limit (denoted at the alloy number 18 in Table 1). Hence, the strength and the stress relaxation resistance were low.
  • the P content in the copper alloy according to the comparative example 122 was higher than the upper limit (denoted at the alloy number 19 in Table 1). Hence, the strength, the stress relaxation resistance and the bending formability were inferior.
  • Copper alloys covered with charcoal were molten in the atmosphere inside a Kryptol furnace, thereby obtaining ingots (No. 201 through No. 209) which were 45 mm thick and had the compositions shown in Table 3.
  • hot rolling was performed, which made the ingots 15 mm thick
  • quenching was then performed from 830 degrees Celsius or a higher temperature, the both surfaces were thereafter faced 1 mm each, thereby obtaining the thicknesses of 13 mm, and cold rough rolling was conducted, whereby the thicknesses shown in Table 3 were obtained.
  • Measurement of the electric conductivity was in accordance with the method of measuring the electric conductivity of a nonferrous metal material defined in JIS-H0505, and the electric conductivities were measured by a four-terminal method using a double bridge.
  • Measurement of the hardness was in accordance with the micro-tensile test method defined in JIS-Z2251, and the Vickers hardness was measured with a test load of 100 g (0.9807 N).
  • JIS5-tensile test specimens were prepared by machining so that the longitudinal direction of the test specimens became parallel (LD) and perpendicular (TD) to the rolling direction of the plate members, and the mechanical properties were measured through a tensile test in accordance with JIS-Z2241.
  • the yield stress is the tensile strength corresponding to permanent elongation of 0.2 %.
  • AKASHI spring elastic bending limit testing machine manufactured by AKASHI (MODEL: APT)
  • LD parallel
  • TD perpendicular
  • the stress relaxation ratio was measured in a cantilever test as shown in Fig. 1 .
  • L was determined so that surface stress corresponding to 80 % of the yield stress of the material would be applied upon the material.
  • the circle stamping test complying with JCBAT310 (the method of a shearing test of a thin bar of copper and a copper alloy) set by the Japan Copper and Brass Association was conducted, measuring the shear-induced flash height.
  • JCBAT310 the method of a shearing test of a thin bar of copper and a copper alloy set by the Japan Copper and Brass Association was conducted, measuring the shear-induced flash height.
  • a stamping press having the punch diameter of 10.000 mm ⁇ and the die diameter of 10.040 mm ⁇
  • the shear rate was 50 mm/min. Flashes created at the periphery of the punched circular hole were measured at four places which were apart from each other by 90 degrees around the circumference, and an average value was used as the flash height.
  • Samples were finished into thin films for TEM observation, by an electro-polished thin film method (twin jet method).
  • TEM H-800 having the accelerating voltage of 200 kV
  • Hitachi, Ltd. images were taken at 40,000 magnifications and 100,000 magnifications, and printed on photographic printing papers after further enlarged 1.5 times.
  • the number of precipitates whose diameters were beyond 60 nm was counted in a square scope of 1,000 nm ⁇ 1,000 nm on the photographic printing papers on which the images were magnified 60,000 times, and the number of precipitates whose diameters were from 5 nm to 60 nm was counted in a square scope of 500 nm ⁇ 500 nm on the photographic printing papers on which the images were magnified 150,000 times. These were observed in multiple scopes and an average value was calculated.
  • the precipitated particles above observed within the scopes were all spherical.
  • No. 201 through No. 207 in which precipitates whose diameters were beyond 60 nm were not found were excellent in terms of bending formability along both the LD and the TD directions.
  • No. 201 through 204 and No. 208 in which twenty or more precipitates whose diameters were from 5 nm to 60 nm were observed within the scopes of 500 nm ⁇ 500 nm, the average flash height was low, and the flash height was particularly low in No. 201 through No. 204.
  • the stress relaxation rates were 15 % or lower along both the LD and the TD directions.
  • the annealing temperature was 600 degrees Celsius which was below 650 degrees Celsius, and therefore, coarse precipitates beyond 60 nm did not get decomposed sufficiently or became solid -solutions again but were partially left remaining, which deteriorated the bending formability.
  • some fine precipitates were created due to the large amounts of added Ni, which suppressed the flash height low.
  • the total amount of Ni-P precipitates was great and the amount of Ni becoming solid solutions again was insufficient, it was not possible to ensure enough solute Ni needed for improvement of the stress relaxation resistance, and the stress relaxation rate was high along the TD direction.
  • a copper alloy plate made of a Cu-Ni-Sn-P alloy which exhibits a high stress relaxation resistance along the perpendicular direction to the rolling direction and which is excellent in strength, electric conductivity and bending formability.
  • This permits application to connection components such as automotive terminals and automotive connectors which demand a favorable stress relaxation resistance along the perpendicular direction to the rolling direction.

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Abstract

　Ｎｉ：０．１～３．０％（質量％、以下同じ）、Ｓｎ：０．０１～３．０％、Ｐ：０．０１～０．３％を各々含有し、残部銅および不可避的不純物からなる銅合金であって、抽出残渣法により目開きサイズ０．１μｍのフィルター上に抽出分離された抽出残渣におけるＮｉ量が、銅合金のＮｉ含有量に対する割合で４０％以下であることを特徴とする耐応力緩和特性に優れた銅合金であって、抽出残渣法は、１０質量％の酢酸アンモニウム濃度のメタノール溶液３００ｍｌに、１０ｇの前記銅合金を浸漬し、この銅合金を陽極とする一方、白金を陰極として用いて、電流密度１０ｍＡ／ｃｍ２で定電流電解を行い、この銅合金を溶解させた溶液を、目開きサイズ０．１μｍのポリカーボネート製メンブレンフィルターによって吸引ろ過し、このフィルター上に未溶解物残渣を分離抽出するものであり、また、抽出残渣中のＮｉ量は、フィルター上の未溶解物残渣を王水と水とを１対１の割合で混合した溶液によって溶解した後に、ＩＣＰ発光分光法によって分析して求めるものである、銅合金である。
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CN107208191B (zh) * 2015-04-24 2020-03-13 古河电气工业株式会社 铜合金材料及其制造方法
JP6608675B2 (ja) * 2015-11-02 2019-11-20 Ｄｏｗａメタルテック株式会社 放熱板およびその製造方法
KR102226988B1 (ko) * 2016-10-05 2021-03-11 가부시키가이샤 고베 세이코쇼 방열 부품용 구리 합금판, 방열 부품, 및 방열 부품의 제조 방법
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EP1889934A1 (en) 2008-02-20
KR100968997B1 (ko) 2010-07-09
KR20080007403A (ko) 2008-01-18
WO2006132317A1 (ja) 2006-12-14
CN101693960B (zh) 2011-09-07
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EP1889934A4 (en) 2009-09-30
US20090116996A1 (en) 2009-05-07
KR20100003376A (ko) 2010-01-08

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